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Haytons Stream catchment water quality investigation

Report No. R09/105 ISBN 978-1-877542-57-2

Prepared for Environment Canterbury by

Jonathan Moores Jennifer Gadd Janine Wech Marty Flanagan NIWA October 2009

Report R09/105 ISBN 978-1-877542-57-2 58 Kilmore Street PO Box 345 Christchurch 8140 Phone (03) 365 3828 Fax (03) 365 3194 75 Church Street PO Box 550 Timaru 7940 Phone (03) 687 7800 Fax (03) 687 7808 Website: www.ecan.govt.nz Customer Services Phone 0800 324 636

© All rights reserved. This publication may not be reproduced or copied in any form without the permission of the client. Such permission is to be given only in accordance with the terms of the client's contract with NIWA. This copyright extends to all forms of copying and any storage of material in any kind of information retrieval system.

Haytons Stream Catchment Water Quality Investigation Jonathan Moores Jennifer Gadd Janine Wech Marty Flanagan NIWA contact/Corresponding author

Jonathan Moores

Prepared for

Environment Canterbury NIWA Client Report: AKL-2009-051 October 2009 NIWA Project: ECY09101 National Institute of Water & Atmospheric Research Ltd 269 Khyber Pass Road, Newmarket, Auckland P O Box 109695, Auckland, New Zealand Phone +64-9-375 2050, Fax +64-9-375 2051 www.niwa.co.nz

Contents Executive Summary iv

1. Introduction 1 1.1 Background 1 1.2 Previous Studies 2 1.3 Project Brief 2 1.4 Content of this Report 3

2. Methods 4 2.1 Overview 4 2.2 Catchment Description 4 2.3 Sampling Sites 7 2.4 Sample Collection 10 2.4.1 Water Samples 10 2.4.2 Sediment Sampling 13 2.5 Sample Analysis 13 2.5.1 Water Samples 14 2.5.2 Sediment samples 15 2.6 In situ Measurement of Physicochemical Parameters 15 2.6.1 Field Observations 15 2.6.2 Data sondes 16 2.7 Rainfall data 16

3. Results 17 3.1 Rainfall and Stream Flow Conditions 17 3.2 Field observations 19 3.3 Stream Water Quality 23 3.3.1 In situ Physico-chemical measurements 23 3.3.2 pH 25 3.3.3 TSS 27 3.3.4 Ammoniacal-Nitrogen 28 3.3.5 NOx-Nitrogen 30 3.3.6 Dissolved Reactive Phosphorus 32 3.3.7 Biochemical Oxygen Demand 34 3.3.8 Copper 35 3.3.9 Lead 37 3.3.10 Zinc 39

3.3.11 Other Metals/Metalloids 42 3.3.12 Indicator Bacteria 45 3.3.13 PAHs 47 3.3.14 Additional Contaminants Measured in Stage 1 Only 50 3.4 Sediment quality 51 3.5 Data Sonde Results 56 3.5.1 Data Quality 56 3.5.2 Rainfall and Stream Water Level 57 3.5.3 Water temperature 59 3.5.4 Dissolved oxygen 60 3.5.5 Conductivity 60 3.5.6 Turbidity 60 3.5.7 Ammoniacal-N 61 3.5.8 Evidence of dry and wet weather contamination 61

4. Discussion 66 4.1 Extent of Water Contamination 66 4.1.1 Comparison to water quality guidelines 66 4.1.2 Comparison to other urban streams 68 4.2 Extent of Sediment Contamination 71 4.3 Possible Sources of Contaminants 72 4.3.1 Ammoniacal-N 72 4.3.2 DRP 76 4.3.3 NOx-N 78 4.3.4 Fluoride 78 4.3.5 Metals 78 4.3.6 TSS 81 Effectiveness of Wigram Retention Basin 81 4.4 Effects on Heathcote/Opawaho River 82

5. Conclusions 89

6. Recommendations 91

7. Acknowledgements 91

8. References 93

Appendix 1 - Photographs of Sampling Locations 96

Appendix 2 – Analytical Methods 102 Water Samples 102 Sediment Samples 103

Appendix 3 – Field Observations and in situ physico-chemical measurements 104

Appendix 4 – Analytical Results 106

Reviewed by: Approved for release by:

Alastair Suren Ken Becker Senior Freshwater Ecologist Regional Manager

Executive Summary

Haytons Stream is a tributary of the Heathcote/Opawaho River, Christchurch, which has degraded water quality with respect to sediment, nutrients, metals and bacteria. The stream drains a mixed land use catchment in south-west Christchurch and has been identified as a source of contaminants into the upper reaches of the Heathcote/Opawaho River. This study aimed to assess the extent of contamination in Haytons Stream; sources of contaminants; and the effect of the stream on the Heathcote/Opawaho River.

Stage 1 included collection of water samples from 9 locations within the catchment including its tributary Paparua Stream, and upstream and downstream of the confluence with the Heathcote/Opawaho River (11 locations in total). The locations selected included sites upstream and downstream of residential and industrial land use. Water samples were collected during dry and wet weather, and analysed for a wide range of contaminants associated with stormwater. In addition, a suite of contaminants indicative of contaminated land were assessed in the dry weather samples. Sediment samples were collected from all sites (excluding one where insufficient sediment had deposited) and analysed for stormwater contaminants. Stage 2 involved further sampling during dry and wet weather at seven key locations, reduced from the 11 sites in stage 1. Autosamplers were used to collect water samples over two wet weather events and grab samples were collected during dry weather. Samples were analysed for a restricted suite of parameters, indicative of stormwater and industrial discharges.

In Paparua Stream, water quality generally declined from the headwaters and at locations downstream of residential land use, to the site downstream of industrial land use. Overall, for Haytons Stream, with a catchment of industrial land use, the results showed poorer water quality than in Paparua Stream. Water quality was generally poorest at sites in Haytons Stream located at Gerald Connolly Place and at Symes Road. For some parameters, such as ammoniacal-N, DRP, TSS and total metals, there was an improvement in water quality downstream of the confluence with Paparua Stream and downstream of the Wigram Retention Basin.

Higher concentrations were detected during wet weather sampling for many parameters, including TSS, total metals (which includes particulate forms) and indicator bacteria, as expected for a stream receiving high inputs of urban stormwater. Dissolved metal concentrations did not change substantially during wet weather. Furthermore, elevated concentrations of ammoniacal-N, NOx-N, DRP, BOD and zinc were measured during both dry and wet weather sampling, indicating that sources of these contaminants are not restricted to urban stormwater. Possible sources of DRP and NOx-N include industries such as fertiliser manufacture. Ammoniacal-N was also elevated elsewhere in the catchment on some occasions, and appears to be the result of intermittent discharges. There are no clear sources of BOD, with elevated concentrations throughout the lower part of the catchment. Zinc

Haytons Stream Catchment Water Quality Investigation iv

was also elevated throughout the lower catchment with roof runoff identified as a likely source during wet weather.

Sediment sampling indicated elevated concentrations of zinc in most samples, including all those downstream of the residential and industrial land use. Median zinc concentrations exceed those measured at other locations in Christchurch. Other parameters varied in concentration between sites with no clear source. Although very elevated at some locations, PAH concentrations were below sediment quality guidelines.

Sampling in the Heathcote/Opawaho River showed a clear increase in ammoniacal-N, DRP, BOD, zinc and nickel concentrations downstream of the confluence with Haytons Stream. The specific sources of these contaminants should be isolated and where possible, removed or minimised, to reduce the adverse effects on the downstream receiving waters of the Heathcote/Opawaho River.

Haytons Stream Catchment Water Quality Investigation v

1. Introduction

1.1 Background

Haytons Stream is a headwater tributary of the Heathcote/Opawaho River in the western part of Christchurch. The results of previous water quality monitoring indicate that the stream is a source of contaminants which are contributing to the degradation of the main river (Pattle Delamore Partners (PDP), 2007). These contaminants include nutrients, bacteria, suspended solids and, potentially, heavy metals, reflecting the predominantly urban land use of Haytons Stream catchment.

Environment Canterbury (ECan) contracted NIWA to undertake an investigation of water and sediment contamination of Haytons Stream and its effects on the quality of the Heathcote/Opawaho River. The aims of the project were to investigate:

• the extent of contamination of the water and sediments of Haytons Stream;

• the location of primary contaminant sources during dry and wet weather; and

• the effects on the water and sediment quality of the Heathcote/Opawaho River.

The project seeks to provide information that will assist ECan and its partners in a number of ways:

• To help guide ECan and Christchurch City Council (CCC) in their functions of planning, managing and regulating the collection, treatment and discharge of stormwater in the catchment;

• To help ECan pollution prevention and consent compliance staff with identifying and resolving any key point source discharges of contaminants; and

• To contribute towards the objectives of the ECan’s Improving Urban Waterway Health project1, for instance by raising community awareness and participation in addressing water quality issues facing Christchurch’s urban streams.

1 http://ecan.govt.nz/get-involved/local-projects-community-groups/Pages/improving-urban-waterway-health

Haytons Stream Catchment Water Quality Investigation 1

1.2 Previous Studies

CCC holds over 15 years worth of water quality data collected at sampling sites in the Heathcote/Opawaho River catchment, including at two sites in Haytons Stream catchment, one at Wigram Rd and one downstream of the Wigram Retention Basin. Analyses of these data indicate that Haytons Stream is a source of contaminants to the main river, particularly suspended solids, BOD, nutrients and microbiological contaminants (PDP, 2007). The elevated concentrations of nutrients are likely to be the result of discharges from industrial activities, including fertiliser production, in the catchment (PDP, 2007). The heavy metals zinc, copper and lead have also been detected at elevated concentrations in Haytons Stream, although there is a lack of data to determine the effect of these on the water quality of the Heathcote/Opawaho River (ECan, 2008).

Brown et al. (1996) investigated the stormwater quality of the Wigram Retention Basin which is located immediately upstream of the confluence of Haytons Stream with the Heathcote/Opawaho River. Elevated concentrations of dissolved reactive phosphorus (DRP) and ammonia were measured in water samples collected upstream and downstream of the retention basin. Samples collected at the point of discharge from the Ravensdown Fertiliser factory located in the mid-catchment suggested that this was the primary source of elevated nutrient concentrations. While the retention basin was found to be effective for the removal of suspended solids, there was considerable variation in its performance in treating other contaminants. For instance, during some storm events sampled there was a net export of nitrate and some dissolved metals from the retention basin to the Heathcote/Opawaho River (Brown et al., 1996).

1.3 Project Brief

The project brief set out three objectives for the project (ECan, 2008):

1. To undertake monitoring of water quality during dry and wet weather at a suitable number of locations in Haytons Stream to monitor inputs from various land uses and potential dischargers, and also in the Heathcote River, above and below Haytons Stream inflow to determine the effect on receiving water quality.

2. To investigate sediment quality at suitable locations on Haytons Stream and the Heathcote River to determine the extent to which historical contamination may be affecting the current aquatic environment.

3. Prepare a report on the findings.


The brief also stated that:

“the determinands that should be analysed for should take into account the range of contaminants typically found in residential and industrial stormwater as well as the activities of industries in the catchment. For the water quality monitoring the first round of sampling should include analysis for a wide range of contaminants to determine their presence or absence and whether they are detected in the downstream receiving environment (Heathcote River) as a result of the inflow from Haytons Stream. Analysis should then be scaled back to those contaminants that are detected and are considered problematic in the immediate and downstream receiving environment.

The location of monitoring sites shall be determined in consultation with Environment Canterbury staff.”

1.4 Content of this Report

Chapter 2 of this report describes the study field programme, including the location of sampling sites, methods of sample collection and sample analyses. Chapter 3 presents the results of sample analyses and describes aspects of their spatial and temporal variability. In Chapter 4, the variations in water and sediment quality are discussed in relation to catchment land use and the location of industrial activities. Conclusions and recommendations for further work are described in Chapter 5.



2. Methods

2.2 Catchment Description

The study adopted a two-stage sampling programme: the first comprised a spatially extensive round of sampling; and the second targeted sites and conditions likely to yield the most information on the sources and extent of stream contamination. Table 1 provides an overview of the key aspects of each of Stages 1 and 2 while further details are given below in Sections 2.2 to 2.6.

2.1 Overview

Haytons Stream catchment covers an area of approximately 13 km2 within which there are two main subcatchments; Paparua Stream and Haytons Stream (see Figure 1). Paparua Stream drains the northern part of the catchment, with its baseflow augmented by flow conveyed by a water race from the Waimakariri / Paparua irrigation scheme. Farmland and new subdivisions occupy the upper Paparua Stream catchment, giving way to residential areas and the Riccarton racecourse in the middle reaches. In its lower reaches the stream is piped for around 1400 m, before re-emerging in an industrial area immediately upstream of its confluence with Haytons Stream.

Haytons Stream drains the southern part of the catchment, but is relatively limited in its extent compared to Paparua Stream. Haytons Stream emerges from the reticulated stormwater network in an area of industrial land, located approximately centrally within the catchment as a whole. The stream runs through an open channel for a distance of around 600 m before re-entering the pipe network for a similar distance. It then remerges, again in an area of industrial land use, around 900 m upstream of its confluence with Paparua Stream.

Below the confluence adjacent to Haytons Rd, Haytons Stream runs through areas of industrial and pastoral land prior to entering the Wigram Retention Basin (WRB). The outlet from the retention basin discharges almost directly into the main Heathcote/Opawaho River.

Table 1 Overview of sampling programme.

Stage 2 Stage 1

Water Sampling Sediment Sampling

Sampling Sites Eleven sites, distributed in relation to variations in catchment land use and key industrial activities

Seven sitesa, distributed in relation to catchment land use and confluence with the Heathcote/Opawaho River.

Ten sites – all but one of the Stage 1 water sampling sites.

Analytical Parameters (refer to Section 2.5 for details)

• In situ physicochemical parameters • pH • suspended solids • heavy metals • nutrients • biochemical oxygen demand • microbiological indicators • hydrocarbons

• In situ physicochemical parameters • pH • suspended solids • key heavy metals • nutrients • biochemical oxygen demand • microbiological indicators • site specific contaminants:

hydrocarbons, other heavy metals

• nutrients • key heavy metals • hydrocarbons • total organic carbon

Sampling Methods Two sets of grab samples, one each during dry and wet weather conditions.

Two sets of dry weather grab samples.

Two wet weather events sampled by automatic water sampler, with three samples from each site analysed.

Collection of stream bed sediments.

Note: (a) An eighth site was sampled during the two additional dry weather runs (see Section 2.3)



Figure 1 Aerial photograph of Haytons Stream catchment showing catchment boundary (solid red line), sub-catchment boundary between Paparua and Haytons Streams (dashed red line), land use (dense areas of yellow lines indicate residential property boundaries; industrial areas are occupied by larger white/grey roofed buildings) and location of other features named in the text. (source of photograph: Christchurch City Council).

Paparua Stream

Haytons Stream

N

1 km

Confluence of Haytons Stream and

Heathcote River

Paparua water race

Riccarton

Racecourse

Main South Rd

Waterloo Rd

Carm

en R

d

Sockburn roundabout

Confluence of Paparuaand Haytons Streams

Wigram retention basin

Haytons Rd


Sites were selected in consultation with ECan and Christchurch City Council (CCC) staff. The location of sampling sites is described in Table 2 and shown in Figure 2. Photographs of each site are presented in Appendix 1.

During Stage 2, wet weather water sampling was conducted at seven sites, with site selection guided by the results of the Stage 1 sampling. At six sites, automatic water samplers were installed and operated by NIWA. At a seventh site, the automatic water sampler was installed and operated by CCC (site HAS-DWB, downstream of the WDB). In addition, dry weather samples were collected at these seven sites and at site HAS-SYR.

2.3 Sampling Sites

The Heathcote/Opawaho River begins in the vicinity of Wigram Aerodrome, approximately 3-4 km upstream of the confluence with Haytons Stream. The river is said to be spring-fed (Robb 1988), though most springs arise downstream around Henderson’s basin and flow into tributaries such as Cashmere Stream. ECan’s GIS system notes one spring downstream of Aidanfield Road, about 800 m upstream of the confluence with Haytons Stream. The headwaters near Wigram Road and upstream are not constantly flowing (pers. obs) and are likely to be rain-fed.

During Stage 1, water samples were collected at 11 sites distributed through the catchment in order to characterise water quality in areas of varying land use and types of industrial activity. These included sites:

• On the Heathcote/Opawaho river, upstream and downstream of the confluence with Haytons Stream.

• Upstream and downstream of the WRB, which previous monitoring had suggested may be a key contaminant source (ECan, 2008); and

• Upstream and downstream of specific point discharges of concern (ie key industries); and

• Downstream of industrial land;

• Downstream of residential land;

• Upstream of the urban area;

Table 2 Sampling sites in Haytons Stream catchment.

Approx Map Ref Site name

Easting

NorthingWaterway Location Purpose Stage 1 &

sediments Stage 2

PAS-BUR 2470770 5742480 Paparua water race Buchanans Rd Baseline site x -

PAS-CAR 2472320 5742010 Paparua Stream Carmen Rd Residential area x x

PAS-RAR 2473370 5741470 Paparua Stream Racecourse Rd Additional residential area and uppermost entry point of industrial discharges x

-

PAS-HTR 2474480 5740130 Paparua Stream Hayton Rd Outlet of Paparua subcatchment, immediately u/s of confluence with Haytons Stream x x

HAS-GCP 2473040 5740690 Haytons Stream Gerald Connolly Place Industrial area x x

HAS-SYR 2473610 5740370 piped tributary of Haytons Stream Symes Rd Industrial, including fertiliser manufacture x xa

HAS-HTR 2474490 5740090 Haytons Stream Hayton Rd Outlet of Haytons subcatchment, immediately u/s of confluence with Paparua Stream x x

HAS-UWB 2475670 5739500 Haytons Stream u/s Wigram retention basin Whole catchment, upstream of influence of retention basin x -

HAS-DWB 2476050 5739250 Haytons Stream d/s Wigram retention basin Whole catchment, downstream of influence of retention basin x xb

HER-UHD 2476010 5739060 Heathcote River u/s Haytons Stream confluence Main river, upstream of influence of Haytons subcatchment x x

HER-DHD 2476090 5739270 Heathcote River d/s Haytons Stream confluence Main river, downstream of influence of Haytons subcatchment x x

Notes a dry weather sampling only b automatic water sampler operated by CCC



Figure 2 Location of sampling sites showing streams (blue lines), stormwater network (green lines), catchment boundary (solid red line) and sub-catchment boundary between Paparua and Haytons Streams (dashed red line).

PAS-BUR

PAS-CAR

HAS-GCP

HAS-SYR

HAS-UWB

HAS-DWB

HER-DHD

HER-UHD

PAS-RAR

HAS-HTR

PAS-HTR

Additional water quality data was collected by the installation of data sondes in Haytons and Paparua Streams upstream of their confluence at Haytons Rd. Sediment samples were collected at each of the Stage 1 water sampling sites other than at one site (Haytons Stream at Symes Rd) at which the stream flows through an underground concrete stormwater pipe.

2.4 Sample Collection

2.4.1 Water Samples

Stage 1

Two sets of water ‘grab’ samples were collected during Stage 1: one set during dry weather and one during wet weather conditions. Sample collection and handling was in accordance with standard protocols for the subsequent analyses. This included the collection of 6 samples at each sampling site using containers provided by the analytical laboratory, as follows:

• Samples collected for total metals analyses were collected in acid-washed polyethylene containers to avoid potential contamination by trace metals present in glass (Batley, 1989);

• Samples collected for dissolved metals analysis were field filtered through acid-washed filter membranes (see below);

• Samples collected for hydrocarbon analyses were collected in glass containers to avoid loss of hydrocarbons by sorption to walls of plastic bottles;

• Samples collected for microbiological analysis were collected in sterile polyethylene containers;

• Samples collected for TSS and nutrients were collected in unpreserved polyethylene containers;

• Samples collected for BOD were collected in additional unpreserved polyethylene containers.

The sample containers as supplied contained the appropriate preservative for the test required. In order to prevent loss of preservatives during sampling, samples were collected in separate polyethylene / glass bottles (clean bottles for each site) and


transferred to the relevant bottles containing the preservatives to be submitted to the analytical laboratory. Samples submitted for microbiological analyses were collected directly into the sterile sample bottles, on the recommendation of the analytical laboratory.

Samples for dissolved metal analysis were field filtered with 0.45 µm pore cellulose ester syringe filters. These were acid-washed with nitric acid prior to use (as were the sterile syringes). Handling of sample bottles and filtering equipment was by way of the clean-hand technique: a fresh pair of latex gloves were used for each sample, care was taken to ensure that the sample was not contaminated by touching the ends of the syringe, filter or the mouth of the bottle (and lid). Filtered and unfiltered method blanks were included in each sampling round to check quality control.

On completion of each sampling run, samples were catalogued, labelled and delivered to Hills Laboratories in Christchurch for analysis within the respective critical time for each (for instance, 24 hours for microbiological tests). During the period of sample collection and transport to the lab, samples were stored in chilly bins containing pre-chilled ice-bricks. A Chain of Custody form was completed on delivery of the samples, copies of which are held by NIWA.

Stage 2

During Stage 2, two further sets of wet weather samples were collected by automatic water samplers deployed at seven of the sites. Six Mannings samplers and one Liquiport sampler (at HAS-DWB site, sampler provided and operated by CCC) were installed in secure cabinets adjacent to the stream at each site. PumpPro liquid water level sensors controlled by NIWA Ecologger data loggers were installed at the six Mannings sites to measure stream water level in order to trigger sample collection2. Water levels were recorded at these six sites to a stage resolution of 1 mm at 5 minute intervals.

Each logger was programmed to trigger collection of a first water sample following a rise in stream water level above a threshold determined from the low flow water level preceding rainfall, with subsequent samples collected on a time-proportional basis. Sampler intakes were located so as to ensure sample collection from freely flowing, well-mixed waters. The water samplers were set up for sampling before forecasted rainfall events by stocking with plastic acid-washed sampling bottles, and with pairs of plastic and glass bottles at one site (HAS-GCP) where samples were required for hydrocarbon analysis.

2 The Liquiport sampler has its own water level sensor.


Prior to installing the automatic samplers, all hosing, bottles and caps were detergent soaked for a minimum of 24 h in a solution of Decon 90® phosphate-free detergent, then rinsed in distilled water. Following this, bottles and caps were then soaked in 10% HCl for at least 24 h followed by rinsing in distilled water then deionised water before being allowed to air dry. When dry, caps were attached to bottles ready for deployment (when they were removed they were placed into a fresh snap-lock plastic bag until sampling was complete). Hoses were flushed with at least 1 L of HCl, followed by at least 10 L of distilled water and left to drain. Ends of hoses were protected from contamination by taping small snap-lock plastic bags around each end. These were removed once in the field.

The automatic samplers collected water samples during two storm events, with three samples from each site selected for analysis during each of these events (see Section 3.1). During each of these events the samplers were configured to collect samples at hourly intervals, reflecting the duration of rainfall forecasted by EcoConnect, NIWA’s meteorological forecasting system. In order to provide sufficient volume of water required for the range of analyses required, the auto-samplers were configured to fill pairs of sample bottles each time sample collection was triggered, i.e. two samples one immediately after the other. Sampling took approximately 2 minutes per bottle (including pre-purging the line, filling the bottle and post-sampling flushing of the line). Each pair of samples therefore took approximately 4 minutes to collect, followed by an interval of 56 minutes before the collection of the next samples was triggered.

During each visit to set up or collect samples, water level data were collected by unloading the logged measurements onto a laptop computer. Additional visits were made regularly to collect these data at times when the samplers were not activated. During each visit to the site, field staff inspected all instrumentation including comparison of observed and logged water levels, measurement of battery voltages and observation of equipment condition.

Water level data collected from the logger were transferred to NIWA’s TIDEDA hydrological database. Following the collection of samples, the time series of water levels and sampling time were reviewed in order to check that the collected samples were well distributed throughout the relevant event hydrograph. Providing that this was the case, the samples were retained for processing and analysis. Processing comprised filtering for dissolved metals and transfer to the various containers provided by the analytical laboratory. All samples were transported to / from NIWA in chilly bins and were stored in a refrigerator until processed. All sample collection and processing occurred within the same working day with a maximum interval between retrieving samples from a sampler and completing processing of approximately 6 hours.


The samples selected for analysis were transferred to containers provided by the analytical laboratory in accordance with the requirements set out in relation to Stage 1 samples above.

In addition, two further sets of grab samples were collected during dry weather conditions following the methods described in relation to Stage 1 above.

2.4.2 Sediment Sampling

Sediment sampling methods were employed with the dual aims of capturing the spatial heterogeneity of sediments at each sampling site and ensuring capture of sufficient fine material (< 2 mm) for subsequent analyses. Samples were collected by making multiple sweeps of an acid-washed plastic container across the stream bed. While core samplers are the standard method for collection of estuarine and coastal sediments, these are very difficult to use in streams due to a) the continuous presence of overlying water; b) the heterogeneous substrates encountered; and c) the shallow depth of sediment to be collected. These factors can result in cores not holding together during extraction and loss of fine sediments into the water.

Sweep sediment samples were composited in a plastic bucket lined with a plastic bag (a new bag for each site). The coarsest material (approx > 5mm) was removed by hand (wearing gloves). The sample was allowed to stand for around 30 minutes in order to promote settlement of fine materials before excess water was decanted. The use of a similar period at each site represented an attempt to ensure consistency in any loss of very fine suspended particles occurring during the decanting process.

The sediments were homogenised and sub-sampled into 2 containers (one plastic, one glass) provided by the analytical lab. Samples were transported to the lab in a chilly bin containing pre-chilled ice-bricks.

2.5 Sample Analysis

All analyses were conducted by Hill Laboratories at their Christchurch and Hamilton laboratories. The analyses undertaken are described below while Appendix 2 lists the relevant sample preparation and analytical methods employed. Hill Laboratories are IANZ accredited for each of these tests.


2.5.1 Water Samples

Stage 1

Water samples collected during Stage 1 of the sampling programme were analysed for a broad range of parameters, based on the contaminants typically found in urban stormwater and streams. All Stage 1 samples were analysed for the following:

• Total suspended solids (TSS) • pH • Nutrients: total ammoniacal nitrogen (NH4-N), Nitrate-nitrite nitrogen (NOx-

N) and dissolved reactive phosphorus (DRP) • Carbonaceous biochemical oxygen demand (cBOD) • Bacteriological indicators: E. coli and Faecal coliforms • Metals (total and dissolved): zinc, copper, lead, cadmium, nickel, arsenic,

chromium • Hydrocarbons: Total Petroleum Hydrocarbons (TPHs), Polycyclic Aromatic

Hydrocarbons (PAHs)

BOD was assessed by analysis of carbonaceous BOD5, which excludes the oxygen demand contributed by nitrogenous substances. Although nitrogenous substances, such as ammonia, in water samples contribute additional oxygen demand, the amount of this measured in a BOD5 test depends on the presence of nitrifying bacteria in the water samples. By contrast, samples are seeded with heterotrophic bacteria that degrade the carbonaceous substances, meaning the oxygen demand is proportional to the amount of carbonaceous substances present. The cBOD5 test is therefore more reliable and a better measure of oxygen demand from pollution. cBOD5 measurements will be lower than total BOD5, particularly when there are high levels of nitrogenous substances present.

In addition, the set of dry weather samples collected during Stage 1 were analysed for a number of additional parameters, with the aim of investigating the potential effects on stream base flow of the migration of contaminants from contaminated land3. These additional parameters were:

• Total cyanide • Fluoride • Chloride • A suite of volatile organic compounds (VOCs)

3 For ECan Contaminated Sites Team


Stage 2

Following review of the results of Stage 1 of the sampling programme, the range of analyses of Stage 2 samples was narrowed down to the following parameters, based on their presence / absence and variations in concentrations between sites:

• Total suspended solids (TSS) • pH • Nutrients: total ammoniacal nitrogen (NH4-N), Nitrate-nitrite nitrogen (NOx-

N) and dissolved reactive phosphorus (DRP) • Carbonaceous biochemical oxygen demand (cBOD5) • Bacteriological indicators: E. coli and Faecal coliforms • Metals (total and dissolved): zinc, copper, lead

In addition, wet and dry weather samples from three sites (HAS-HTR, HER-UHD and HER-DHD) were analysed for the additional metals aresenic, cadmium, chromium and nickel (total and dissolved), based on their presence in Stage 1 samples collected at HAS-HTR and to investigate the extent of their transport of them to the Heathcote River. The wet samples from one site (HAS-GCP) were analysed for PAHs, again based on their presence in Stage 1 wet weather samples collected at that site.

2.5.2 Sediment samples

Samples of stream sediment were analysed for the following parameters (< 2mm fraction following sieving by analytical laboratory):

• Nutrients: eg Ammonium (NH4-N), Nitrate-nitrite nitrogen (NOx-N) and Total recoverable phosphorus (TRP)

• Metals: zinc, copper and lead • Hydrocarbons: Total Petroleum Hydrocarbons (TPHs), Polycyclic Aromatic

Hydrocarbons (PAHs) • Total organic carbon (TOC).

2.6 In situ Measurement of Physicochemical Parameters

2.6.1 Field Observations

Coinciding with the collection of water grab samples, the following physicochemical parameters were measured in situ with TPS WP-81 and TPS WP 82Y multi-parameter water quality probes: temperature, dissolved oxygen (DO) saturation, conductivity and pH. Meters were calibrated in the field at the start of each sampling round. For pH calibration, the buffers used were 4, 7 and 10. Conductivity solution for calibration was KCl 1408 µScm-1. DO probes were calibrated in air (saturation 100%).


Water clarity was measured with a water clarity tube. Observations of water colour, odour and the presence of a foam or sheen were recorded.

2.6.2 Data sondes

As part of Stage 2 of the field programme, two Manta 2 data sondes were deployed at the PAS-HTR and HAS-HTR sites with the aim of continuous measurement of water temperature, DO, conductivity, pH and turbidity in the two streams immediately upstream of their confluence. In addition to these parameters, the sondes also measured ammoniacal-N.

The sondes were calibrated, tested and found to be performing satisfactorily at NIWA’s Water Quality Laboratory in Hamilton prior to dispatch to Christchurch. However, following deployment it became apparent that the sondes were not performing satisfactorily in the field, particularly in relation to pH. They were removed and measures taken to identify and remedy their poor performance. A replacement instrument was obtained for one of the sondes and the two were redeployed. As a result of these problems, the period over which sondes were deployed is not concurrent with that during which the Stage 2 samples were collected.

2.7 Rainfall data

Rainfall data was not collected as part of this study. Telemetered rainfall information was available from two existing rain gauges in the catchment: College of Education (site no. 325507) and WRB (site no. 325508). These sites are operated by NIWA under contract to CCC who gave permission for use of the data in this study. Rainfall data from these sites provided a near real time check on the progress of events at each sampling site while also allowing characterisation of the rainfall depths and durations associated with each event sampled.



Table 3 Antecedent weather and rainfall characteristics associated with each sampling run.

3. Results

3.1 Rainfall and Stream Flow Conditions

Table 3 summarises antecedent weather conditions and characteristics of rainfall associated with each sampling run. Figure 3 shows the timing of each sampling run in relation to the distribution of rainfall over the period March to July 2009. Both dry and wet weather sampling runs were undertaken following a period of at least 3 days of dry weather (ignoring isolated showers of < 1 mm), ensuring that:

• In the case of dry weather runs, the stream water quality was unlikely to be influenced by stormwater discharges; and

• In the case of wet weather runs, sufficient time had passed since the previous rain event to allow the build up of contaminants on impermeable surfaces over which rainfall runoff occurred.

Figure 4 shows the timing of grab sample collection during the Stage 1 wet weather sampling run of 29 April. Samples were collected over a 2.5 hr period following four hours of rain falling at 0.4-1.4 mm/hr intensity.

Sampling Run Date Time since last raina, b (days)

Rainfall deptha (mm)

Rainfall durationa (hours)

Stage 1 dry 20 March 2009 8 - -

Stage 1 wet 29 April 2009 9 18 19

Stage 2 dry #1 4 June 2009 4 - -

Stage 2 wet #1 3 July 2009 3 16 10

Stage 2 dry #2 22 July 2009 9 - -

Stage 2 wet #2 24 July 2009 11 7.5 6

Notes a Rainfall data taken from CCC’s College of Education rain gauge (site no. 325507). b Ignoring showers < 1mm depth


Figure 3 Daily rainfall at the College of Education rain gauge (site no. 325507) over the period 1 March to 31 July 2009. Arrows indicate the timing of sample collection (red = dry weather; blue = wet weather).

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rly ra

infa

ll (m

m)

12:00 13:00 14:00 15:00 16:00 17:00 18:00 19:00 20:00 21:00 22:00 23:0011:00

period over which samples were collected

Hou

rly ra

infa

ll (m

m)

Figure 4 Hourly rainfall at the College of Education rain gauge (site no. 325507) over the period 1100 hrs to 2300 hrs, 29 April 2009, showing the period over which samples were collected.

As described in Section 2.4.1, three samples collected at each site during the Stage 2 wet weather runs were selected for analysis based on a review of the event hydrographs4. Samples were selected in order to allow characterisation of stream water quality during the early, peak and receding stages of each of the two events sampled (see Figures 5 and 6). Note that while the period of rising and peak flows at sites in the Heathcote/Opawaho River occurred several hours after the recession of flows in Haytons Stream, it coincides closely with the period of rising and peak water levels in the WRB. This is important, because it means that the period over which samples were collected from the Heathcote/Opawaho River coincided with the period over which stormwater-generated flows from Haytons Creek were discharged to the main river, due to the attenuating influence of the retention basin.

3.2 Field observations

Observations of odour, sheen, water colour and clarity were made while collecting water and sediment samples. At most sites there were no odours or sheens observed, but odour or sheen was observed at three sites (Table 4). On the 22 July, white particulate material was observed on the water surface at HAS-GCP and the water had very poor clarity (see Figure 7). The Pollution Hotline was alerted and investigated but could not find the source of the pollution (D. Pilbrow, ECan, pers comm.). It was suggested that the cause was someone washing paint into the stormwater system. Appendix 3 contains the full set of field observations.

4 No samples were collected at the outlet of the Wigram Retention Basin (HAS-DWB) during the first wet weather event in Stage 2. Six samples collected at this site during the second wet weather event were analysed: five of these were composite samples derived from combining successive samples collected at half hourly intervals, while the sixth was a grab sample collected around 5 hours following the event peak.


0

1000

Sta

ge m

m20090702:1200 02:18 03:00 03:06 03:12 DD:HH

site 2 PAS CAR at Carmen Rd Stage mm

0

1000

age

mm

St

20090702:1200 02:18 03:00 03:06 03:12 DD:HHsite 4 PAS HTR at Haytons Rd Stage mm

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ge m

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20090702:1200 02:18 03:00 03:06 03:12 DD:HHsite 5 HAS GCP at Gerald Connolly Pl Stage mm

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ge m

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20090702:1200 02:18 03:00 03:06 03:12 DD:HHsite 7 HAS HTR at Haytons Rd Stage mm

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20090702:1200 02:18 03:00 03:06 03:12 DD:HHsite 66642 Wigram Retention Pondw ater-level (HWE) Level mm

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ge m

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20090702:1200 02:18 03:00 03:06 03:12 DD:HHsite 10 HER UHD at US Heathcote River Stage mm

0

1000

Sta

ge m

m

20090702:1200 02:18 03:00 03:06 03:12 DD:HHsite 11 HER DHD at DS Heathcote River Stage mm

Figure 5 Stage 2, wet weather event 1: Stream water level hydrographs with the timing of each

No samples were collected at the outlet of the Wigram Retention Basin (HAS-DWB) during Stage 2 event 1 due to instrument failure.

sample selected for processing shown by hollow circles.

Note:


0

1000mS

tage

m723:20090 2200 24:02 24:04 24:06 24:08 24:10 24:12 24:14 DD:HH

sit Car m

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e 2 PAS CAR at men Rd Stage m

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tage

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e 4 PAS HT ons Rd Stage mm

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24:02 24:04 24:06 24:08 24:10 24:12 24:14 DD:HHsite 5 HAS GCP at Gerald Connolly Pl Stage mm

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20090723:2200 24:02 24:04 24:06 24:08 24:10 24:12 24:14 DD:HHsite 66642 Wigram Retention Pondw ater-level (HWE) Level mm

600

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ge m

m

20090723:2200 24:02 24:04 24:06 24:08 24:10 24:12 24:14 DD:HHsite 10 HER UHD at US Heathcote River Stage mm

500

600

700

Sta

ge m

m

20090723:2200 24:02 24:04 24:06 24:08 24:10 24:12 24:14 DD:HHsite 11 HER DHD at DS Heathcote River Stage mm

Figure 6 Stage 2, wet weather event 2: Stream water level hydrographs with the timing of each sample selected for processing shown by hollow circles.

Note: Six samples from the outlet of the Wigram Retention Basin (HAS-DWB) were selected for analysis during this event to provide six samples in total over the two events.


Table 4

Site Date Observation

Observations of odour, sheens or unusual colours.

PAS-RAR 20 March Oily sheen

HAS-GCP 20 March Oily sheen

29 April Strong petrochemical odour

4 June Patches of oily sheen (see Figure 8)

22 July Small patches of oily sheen; patches of white particulate material on surface (possibly paint); water opaque and cloudy.

PAS-HTR 22 July Small patches of oily sheen

Appearance of Haytons Stream at Gerald Connolly Place, 22 July 2009, showing presence of white substance emerging from upstream piped section.

Figure 7

Figure 8 Appearance of Haytons Stream at Gerald Connolly Place, 4 June 2009, showing presence of oily sheen.


3.3 Stream Water Quality

This section describes the results of sampling at the nine sites located within Haytons Stream catchment. The results of sampling at the two sites on the Heathcote River upstream and downstream of Haytons Stream confluence are described in Section 4.4. The full set of results are contained in Appendices 3 and 4.

3.3.1 In situ Physico-chemical measurements5

Temperature

Water temperature varied from about 4 to 16 ºC during the dry weather sampling, with the higher temperatures measured in March (top of bars in Fig. 9) and lower temperatures measured in June and July (middle and bottom of bars). There was little difference between sites (Fig. 9), with the exception of HAS-DWB, where temperatures were generally higher. Temperatures were slightly higher during wet

similar time of year,

Conductivity

olved ions in a water body. These dissolved ions include mineral salts, such as calcium and magnesium; and nutrients, such as ammonia, nitrate and phosphate ions. Dissolved copper, lead and

concentrations too low to contribute to increased conductivity.

weather sampling when comparing to dry weather sampling at a due to the heating of runoff by flow over warm impervious surfaces. Temperatures during wet weather did not reach the maximum temperatures measured during dry weather in March.

Conductivity is an indicator of the concentration of diss

zinc are typically at

Conductivity was higher and more variable during dry weather sampling than during wet weather (Fig. 10). The higher conductivity may be due to minerals and nutrients in groundwater-sourced water. Conductivity decreased with the addition of rain water during storm events, as rain water typically has very low concentrations of dissolved ions. The highest conductivity measured was at HAS-HTR on the 22nd July (893 µS cm-1) and coincides with a very high ammoniacal-N measurement (see Section 3.3.4 below). Apart from this measurement, conductivity was relatively similar across all sites in Haytons Stream. Conductivity was generally lower upstream in Paparua Stream.

5 Measurements of temperature, conductivity, DO and pH were not taken in the field at the time that wet weather samples were collected by automatic water sampler. However, measurements of these parameters were made in samples collected by the automatic samplers once returned to the lab and these are included here (‘wet stage 1 & 2’) for comparison with the in situ measurements collected during grab sample runs.


0

5

10

15

20D

ry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

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Wet Dry

Wet

PAS-BUR PAS-CAR PAS-RAR PAS-HTR HAS-GCP HAS-SYR HAS-HTR HAS-UWB HAS-DWB

Tem

pera

ture

(o C)

Wet stage 2 Wet stage 1Dry 20 Mar Dry 4 JunDry 22 July

Figure 9 Stream water temperature in Haytons Stream catchment. Note for this plot and others following in this section: Data from Stage 1 and dry

pling are represented by a point. For sites assessed in Stage 2, data from er sampling are represented by bars. The bars indicate the maximum (top

weather samthe wet weathof bar), median (horizontal line) and minimum values (bottom of bar). No. samples = 6 for wet weather sampling (2 storm events).

0

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Dry

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Wet


Con

duct

ivity

( µ

S c

m-1

)

Wet stage 2 Wet stage 1Dry 20 Mar Dry 4 JunD

Figure 10 Stream water conductivity in Haytons Stream catchment.

ry 22 July


Dissolved Oxygen

Dissolved oxygen saturation was extremely variable at most sites (Fig. 11), with low saturation measured at most sites, particularly during dry weather sampling. The minimum recorded was 22% at HAS-UWB during dry weather (20th March). A low value of 32% was recorded at HAS-GCP on 22nd July, during the observed pollution event. An elevated cBOD5 value was also recorded at that time (see section 3.3.7 below). Greater dissolved oxygen saturation during wet weather may be due to the inputs of water with higher dissolved oxygen saturation (rain water) and higher water velocities in the streams causing increased water turbulence and entrainment of oxygen.

0

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Dis

solv

ed o

xyge

n sa

tura

(%)

tion


Figure 11

3.3.2

ring dry weather m, with values

, during both dry and wet weather sampling. The maximum pH of 8.8 was measured at HAS-GCP

Dissolved oxygen saturation in Haytons Stream catchment.

pH

The median pH was generally 7.2-8.0 across all sites measured dusampling (Fig. 12). The range in values was greater in Haytons Streafrom 6.9 to 8.6 measured. The pH was lower at all sites during wet weather sampling, with most values less than 7.5, and all minimum and median values 7.2 or lower. The decrease in pH during wet weather is caused by the addition of rainfall, which is slightly acidic due to the natural dissolution of carbon dioxide in the atmosphere into rain drops.

There were a number of elevated pH measurements in Haytons Stream



on the rise of the 24th July storm event, and pH 8.3 was measured at HAS-HTR at the same time. These two samples also contained extremely elevated concentrations of ammonia suggesting an illegal discharge into the stream at that time. In fact, most of the pH measurements above 8.0 in Haytons Stream coincided with extremely high ammoniacal-N concentrations (see Fig. 13). These ammoniacal-N measurements are discussed further in Section 3.3.4. When these values are excluded, there is little difference in the pH between Paparua Stream and Haytons Stream (as shown by the similar median and minimum values in Fig. 12).

6.0

6.5

7.0

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8.5

9.0

Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet


pH


Figure 12 Stream water pH in Haytons Stream catchment.

6.0

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9.5

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HAS-GCP HAS-HTR HAS-SYR

pH

0

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40

60

80

100

120

Am

mon

iaca

l-N (g

m -3

)

Ammoniacal-N140

pH

Figure 13 Relationship of pH and ammoniacal-N at sites in Haytons Stream.

3.3.3 TSS

Total suspended solids concentrations were variable throughout the catchment, with higher concentrations measured during wet weather sampling at most sites (Fig. 14). During dry weather sampling TSS concentrations were regularly less than the detection limit of 3 g m-3, and consistently lower than 50 g m-3, with the exception of an elevated measurement of 470 g m-3 at HAS-GCP. This measurement occurred on the 22 July (associated with the pollution incident described in Section 3.2) and was due to the presence of white particulate material. During wet weather sampling, minimum concentrations were generally 10-30 g m-3, and maximum concentrations 100-200 g m-3. Although TSS concentrations were elevated at PAS-HTR and HAS-HTR, concentrations were lower downstream of the Wigram Retention Basin, with a maximum of 34 g m-3 measured, indicating the basin is achieving sediment removal.

0

100

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PAS-B HAS-GCP HAS-SYR HAS-HTR HAS-UWB HAS-DWBUR PAS-CAR PAS-RAR PAS-HTR

TSS

(g m

-3)


Figure 14

e.

Total suspended solids concentrations in Haytons Stream catchment.

TSS concentrations over two wet weather events sampled in Stage 2 are shown in Fig. 15. In most cases, these indicate higher concentrations during the rise and peak of each storm event (samples 1 and 2) compared to the recession of the storm event (sample 3). Samples from HAS-DWB did not show this pattern during the second storm event, as the retention pond reduces both peak flows and peak TSS concentrations. This site was not sampled during the first storm event due to instrument failur


(a)

0

50

100

PAS-CAR PAS-HTR HAS-GCP HAS-HTR HAS-DWB

Stage 2 sampling sites

TSS

(g15

200

m0- 3

)

250Sample 1Sample 2Sample 3

0

50

100

150

SS

(g m

- 3 )

200



T

Sample 1Sample 2Sample 3Sample 4Sample 5Sample 6

(b)

Figure 15 Total suspended solids concentrations at Stage 2 sampling sites during two wet

weather events (a) 3 July and (b) 24 July.

3.3.4 Ammoniacal-Nitrogen

Ammoniacal-N concentrations (Fig. 16) were relatively low in Paparua Stream (mean values ≤ 0.1 g m-3), though elevated results were detected immediately upstream of the confluence with Haytons Stream (PAS-HTR) during dry weather (concentrations of 14 g m-3 on 4 June and 3 g m-3 on 3 July). Substantially higher concentrations were measured in the middle reaches of Haytons Stream during both dry and wet weather

yed in full in Fig. 17 below. Concentrations were much lower downstream of the confluence with Paparua Stream, sampling. This data is discussed further and displa

and downstream of the Wigram Retention Basin (Fig. 16).

A number of samples, particularly in Haytons Stream, contained ammoniacal-N at concentrations from 14-100 g m-3. These ammoniacal-N concentrations are extremely elevated compared to concentrations found in natural waterways (0.01-0.1 g m-3, see


Meredith & Hayward 2002) and are well above values that could cause toxicity. Guidelines to prevent toxicity to freshwater fish generally suggest maximum ammoniacal-N concentrations around 1 g m-3 (depending on pH, ANZECC (2000)). This is discussed further in Section 4.1.1.

0

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40

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120

Dry

We Dry

We Dry

We Dry

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We Dry

We Dry

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Wet t t t t t t t t

PAS-B PAS-HTR HAS-GCP HAS-SYR HAS-HTR HAS-UWB HAS-DWBUR PAS-CAR PAS-RAR

Am

mon

iaca

l-N (g

m -3

)


Figure 16 Ammoniacal-N concentrations in Haytons Stream catchment.

R and 2.6 g m at HAS-HTR. On the 22 July, when ammoniacal-N concentrations were again elevated at HAS-GCP (24 g m-3) concentrations were also elevated at HAS-SYR (57 g m-3) and at HAS-

-3 r more of either

The site with most consistently elevated ammoniacal-N concentrations was HAS-GCP, measuring 2.5-33 g m-3 during dry weather sampling and up to 33 g m-3 during wet weather sampling (Fig. 16). The maximum dry weather concentration was 33 g m-

3 on 20th March. Downstream sites measured substantially lower concentrations at that time (Fig. 16), with 0.46 g m-3 recorded at HAS-SY -3

nd

HTR, reaching an extreme value of 100 g m . These results suggest one oplumes of ammonia moving downstream, originating from sources upstream HAS-GCP or HAS-SYR or both.

During the wet weather sampling, ammoniacal-N concentrations were elevated at HAS-GCP on 24th July, measuring 33 g m-3 in the sample collected on the rise of the storm. Samples from the peak and recession of that storm, collected two and four hours later (see Fig. 16), measured 0.29 and 0.46 g m-3 respectively, indicating the plume of elevated concentrations was short-lived. Again, the plume appears to have moved downstream to HAS-HTR, with 54 g m-3 measured in the first sample (rise of storm), decreasing to 8.2 and 3.6 g m-3 in subsequent samples (peak and recession of storm). Samples were not collected from HAS-SYR on these dates.


The elevated ammoniacal-N concentrations were not constant, with all samples below 2.5 g m-3 during wet weather sampling on 3rd July.

0

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100

0

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40A

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onia

cal-N

(g m

-3 )

1 2 3 1 2 3

20-Mar 4-Jun 22-Jul 29-Apr 3-Jul 24-Jul

Dry Wet

HAS-GCP

HAS-SYR

HAS-HTR

Figure 17

3.3.5 NOx-Nitrogen

sampling, there was little difference in NOx-N concentrations (Fig. 18). At HAS-

Ammoniacal-N concentrations in the middle reaches of Haytons Stream by sampling event, indicating the elevated concentrations during both dry and wet weather sampling. Note samples were not collected at HAS-SYR on the 3rd or 24th July.

For most sites with more than one measurement during both dry and wet weather


HTR, the maximum and median NOx-N concentrations were higher during dry weather than wet weather. At HAS-SYR, all dry weather NOx-N concentrations were higher than the wet weather concentrations, however only one sample was collected under the wet weather conditions. The elevated NOx-N at Symes Road may be due to oxidation of ammoniacal-N, also elevated at this site; or alternatively, there may be an additional source of NOx-N at this site.

There was a general increase in NOx-N concentrations from upstream to downstream, with highest concentrations measured during dry weather sampling at HAS-SYR and HAS-HTR. During wet weather sampling, concentrations were highest downstream of the Wigram Retention Basin, showing little or no removal within the basin.

0.0

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Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet


NO

x-N

(g m

-3)


Figure 18

ations over two wet weather events sampled in Stage 2 are shown in Fig. 19. For most sites, except the upper Paparua Stream (PAS-CAR) and downstream of the retention basin (HAS-DWB), higher concentrations were measured on the rise

nt (sample 1) compared to the peak and recession (samples 2 and 3).

NOx-N concentrations in Haytons Stream catchment.

NOx-N concentr

of each storm eveAt HAS-DWB concentrations were very similar in all samples, ranging from 1.5-1.6 g m-3, and were substantially higher than most concentrations measured upstream. A potential source of this NOx-N is oxidation of ammoniacal-N to nitrite-N and nitrate-N (nitrification) within the pond. This is supported by the lower concentrations of ammoniacal-N exiting the pond compared to those entering it (see Section 3.3.4).


0.0

0.1

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NO

x-N

(g m

- 3 )

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(a)

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g m

Sample 1Sample 2Sample 3Sample 4Sample 5Sample 61.2

1.4

-3 )

0.0

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NO

x-N

(

(b)

Figure 19 centrations at Stage 2 sampling sites during two wet weather events (a) 3 July and (b) 24 July.

3.3.6 Dissolved Reactive Phosphorus

As with ammoniacal-N, dissolved reactive phosphorus (DRP) concentrations were low in the upper reaches of Paparua Stream, with most samples measuring concentrations less than 0.05 g m-3 (Fig. 20). DRP was higher further downstream in Paparua Stream (PAS-HTR) during both dry and wet weather, with a maximum of 0.30 g m-3 measured during dry weather sampling on 4 June.

NOx-N con


0

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2

3

4

5

6

7

8

9

10

Dry

Wet Dry

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Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet


DR

P (g

m -3

)


Figure 20 Dissolved Reactive Phosphorus concentrations in Haytons Stream catchment.

t ream, DRP concentrations were in the same range as Paparua Stream g eather sampling at HAS-GCP, with slightly higher concentrations

ain highly elevated at HAS-HTR, but were substantially lower downstream of the confluence with Paparua Stream and downstream of the Wigram Retention Basin, though concentrations remained above the background levels seen in Paparua Stream.

DRP concentrations remained elevated throughout the two storm events measured at HAS-HTR (Fig. 21), with concentrations from 1.1 to 1.6 g m-3 (event 1) and 4.3 to 1.3 g m-3 (event 2), suggesting a constant discharge of DRP, rather than a short-lived pulse. Samples were not collected at HAS-SYR for these two storms.

In Hay ons Stdurin dry wmeasured there during wet weather sampling (maximum 0.54 g m-3). Substantially higher concentrations were measured during both dry and wet weather sampling at HAS-SYR, with DRP ranging from 1.1 to 8.8 g m-3. These concentrations are about an order of magnitude higher than concentrations at HAS-GCP and are values rarely seen in natural waterbodies.(Meredith & Hayward 2002). Such elevated DRP concentrations could lead to eutrophication, with excess growth of algae and macrophytes, and potential algal blooms. This is most likely to occur in ponded waters, such as the retention pond, or slow moving sections of the Heathcote River. Downstream of HAS-SYR, DRP concentrations rem


0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8



DR

P (g

m -3

)


(a)

2.0

3.0

3.5

4.0

4.5

5.0

DR

-3 )

2.5

P (g

m

0.0

0.5

1.0

1.5




(b)

Figure 21 rations at Stage 2 sampling sites during two wet weather events (a) 3 July and (b) 24 July.

3.3.7

2 g m-3) and was lower again further downstream at HAS-HTR (7.2 g m-3). This latter value is unlikely to represent dilution or degradation of the

cBOD5 was also highest at HAS-GCP in the other two samples collected during dry weather when compared to other sites and was also generally higher during wet weather sampling (Fig. 22). Overall, during dry and wet weather sampling, the lowest

DRP concent

Biochemical Oxygen Demand

Carbonaceous BOD5 was highest at HAS-GCP, with an extremely elevated value of 450 g m-3 recorded during dry weather sampling on 22 July (date of pollution incident). The elevated cBOD5 may be due to the paint observed in the water, or other chemicals associated with that pollution incident, such as solvents. At HAS-SYR, cBOD5 was lower (1

pollution observed at HAS-GCP, as observations suggested that the pollution plume had not reached HAS-HTR at the time of sampling.


cBOD5 concentrations were measured in the upper Paparua Stream and concentrations were only slightly higher, at HAS-DWB, downstream of the Wigram Retention Basin.

0

10

20

30

40

50

Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

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Wet


c B

OD

5 (g

m -3

)


450 g m-3

Figure 22 cBOD5 concentrations in Haytons Stream catchment.

Note: Maximum value of 450 g m-3 is not shown on the plot to ensure other data points are visible.

Analysis of the results during the two storm events sampled (Fig. 23) shows that at most sites, cBOD5 concentrations were highest on the rise of the storm, dropping slightly during the peak and dropping further on the recession of the storm. This suggests the substances with oxygen demand are readily transported into the stormwater and stream system. At HAS-DWB, concentrations were fairly similar through the one storm event sampled, demonstrating the dampening effect of the retention basin.

3.3.8 Copper

Total copper concentrations were about 2-6 times higher than dissolved copper ing dry weather

sampling (Fig. 24). This indicates that the majority of the copper is in particulate form, with increases in particulate copper during wet weather events. A comparison of the dry and wet weather sampling shows slightly higher dissolved copper concentrations at most sites during wet weather sampling, and a more apparent increase in total copper during wet weather sampling.

concentrations during wet weather sampling, but 1-2 times higher dur


0

2

4

6

8

10

12

14



cBO

D5

(g m

-3 )


(a)

0

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4

6

8

10

12

14

16

18



cBO

D5

(g m

-3

Sample 1Sample 2Sample 3Sample 4

)

Sample 5Sample 6

(b)

Figure 23 cBOD5 concentrations at Stage 2 sampling sites during two wet weather events (a) 3

July and (b) 24 July.

Copper concentrations (dissolved and total) showed a general increase in Paparua

hest concentrations were measured at HAS-GCP (dry weather sampling) and HAS-HTR (wet weather sampling). These differences were more

d copper. Total copper concentrations were upstream sites, during both dry and wet weather

Stream from the upper catchment sites to the confluence with Haytons Stream. In Haytons Stream, the hig

apparent for total copper than dissolvelower at the outlet from WRB thansampling, while dissolved copper concentrations were within the range measured upstream.


0

0.001

0.002

0.003

0.004

0.005

0.006

0.007

0.008

Dry

Wet Dry

Wet Dry

Wet Dry

Wet

Wet

Wet Dry

Wet Dry

Dry

Wet Dry

Wet Dry

PAS -CAR PA PAS-HTR HAS-SYR HAS-UW DWB-BUR PAS S-RAR HAS-GCP HAS-HTR B HAS-

Dis

solv

ed c

oppe

r (g

m -3

)


0.000

0.005

0.010

0.015

0.020

0.025

0.030

0.035

0.040

0.045

0.050

Dry

Wet Dry

Wet Dry

Dry

Wet Dry

Wet et Dry

Wet

Wet

Wet Dry

Wet Dry

W Dry


Tota

l cop

per (

g m

-3)


Figure 24 Dissolved and total copper concentrations in Haytons Stream catchment.

3

al lead concentrations were substantially higher during wet weather sampling than dry weather sampling,

.3.9 Lead

Total lead concentrations were substantially higher than dissolved lead concentration, during both dry and wet weather sampling, indicating the majority of the lead in the stream samples was in particulate form. Similar to copper, dissolved lead concentrations were similar during both dry and wet weather sampling, with the exception of results for PAS-HTR (Fig 25). At all sites, tot


indicating the added load of particulate lead during storm events. At PAS-HTR, total lead concentrations also increased during wet weather sampling, and were substantially higher than dissolved concentrations.

0.0000

0.0005

0.0010

0.0015

0.0020

Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet


Dis

solv

ed le

ad (g

m -3

)


0.00

0.02

0.04

0.06

0.08

0.10

Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet


Tota

l lea

d)


(g m

-3

Figure 25 Dissolved and total lead concentrations in Haytons Stream catchment. 6

6 An elevated value of 0.024 g m-3 for dissolved lead was measured upstream in Paparua Stream at PAS-CAR but was not included as the concentration of total lead in that sample was substantially less, indicating contamination of the sample for dissolved analysis.


Dissolved lead concentrations were generally lower in the upper Paparua Stream and higher at sites downstream of the industrial land use (PAS-HTR, HAS-GCP, HAS-HTR). This trend was more apparent for total lead, with concentrations during both dry and wet weather sampling being highest downstream of industrial land use. Lower concentrations were measured downstream of the WRB, indicating removal in the basin.

3.3.10 Zinc

At most sites there were no, or minor differences between dry and wet weather concentrations of dissolved or total zinc (Fig. 26), however at PAS-CAR and HAS-HTR both dissolved and total zinc increased during wet weather events. Total zinc concentrations were similar to or up to two times higher than dissolved zinc, indicating that compared to copper and lead, a much lower proportion of zinc is found in particulate form.

le of the catchment. This difference was more apparent than with copper and lead, and occurred during both dry

r both dissolved and total forms of zinc. Dissolved and nstream of the WRB than immediately or

As with copper and lead, zinc concentrations were lowest upstream in Paparua Stream, and highest downstream of industrial land use in the midd

and wet weather sampling fototal zinc concentrations were lower dowfurther upstream.

Unlike TSS or cBOD5, dissolved zinc concentrations did not demonstrate a consistent pattern in the samples collected over each storm (Fig. 27). At PAS-HTR and HAS-GCP, concentrations were highest during the rise of the storm on the 24th July, decreasing in the peak and recession samples. However, this pattern was not apparent in samples collected from the 3rd July storm event.

The total zinc concentrations over the two storm events (Fig. 28) more closely reflected the pattern in TSS concentrations, being highest at the start of the storm event, and lowest at the end. Again, concentrations downstream of the retention pond were similar across all samples during the event of 24 July.


0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet


Dis

solv

ed z

inc

(g m

-3)


0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet

PA UR PAS-CAR PAS-RAR PAS-HTR HAS-GCP HAS-SYR HAS-HTR HAS-UWB HAS-DWBS-B

Tota

l zin

c (g

m -3

)


Figure 26 Dissolved and total zinc concentrations in Haytons Stream catchment.


0.0PAS-CAR PAS-HTR HAS-GCP HAS-HTR HAS-DWB


0.1

0.4

0.2

0.3D

isso

lved

zin

c (g

m-3

)

0.5Sample 1Sample 2Sample 3

(a)

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9



Dis

solv

ed z

inc

(g m

-3 )


(b)

Figure 27 Dissolved zinc concentrations at Stage 2 sampling sites during two wet weather events

(a) 3 July and (b) 24 July.


0.0

0.5

1.0

1.5

2.

3.0

S R P H S P A T -DWB

e a n e

Tota

l zin

c ( 2.g

m-3

)0

5

3.5

PA -CA AS- TR HA

2 s

-GC

mpli

H

s

S-H R HAS

Stag g sit


(a)

0.0

50.

1.0

1.

2.0

3.0



To (g

m-3

)

5

2.5

tal z

inc

Sample 1Sam 2pleSam 3pleSam 4pleSam 5pleSample 6

(b)

Figure 28 o z c r n t g t e e er events (a)

J and (b) 24 July.

1 t t M a d

Dissolved and total arsenic, cadmium, chromium and nickel were each during Stage 1 sampling, during both dry and wet weather. During drysampling, the concentrations of dissolved forms were below detection at all sites in Paparua Stream (Table 5). Dissolved arsenic, cadmium, chromium and nic were detected in samples from at least one site in Haytons Stream. During we ather sampling (Table 5), dissolved cadmium and nickel remained below detection in Paparua Stream, whereas dissolved arsenic and chromium were measurable, albeit at lower concentrations than in Haytons Stream

T3

tal uly

inc con ent atio s a Sta e 2 sampling si es during two w t w ath

3.3. 1 O her Me als/ et lloi s

measured weather

kelt we

.


Table 5 Dissolved arsenic, cadmium, chromium and nickel concentrations (g m-3) measured in n 20th March and wet

weather sampling on 29 April. Hayto s Stream catchment during dry weather sampling on

th

Arsenic Cadmium Chromium Nickel

Dry weather

PAS-BUR < 0.0010 < 0.000050 < 0.00050 < 0.00050

< 0.00050

HAS-GCP < 0.0010 0.000059 < 0.00050 < 0.00050

< 0.000050 < 0.00050 0.00063

Wet weather

PAS-CAR < 0.0010 < 0.000050 < 0.00050 < 0.00050

PAS-RAR < 0.0010 < 0.000050 < 0.00050 < 0.00050

PAS-HTR < 0.0010 < 0.000050 < 0.00050

HAS-SYR < 0.0010 0.00015 0.00088 0.00079

HAS-HTR 0.0031 0.000061 < 0.00050 0.0012

HAS-UWB 0.0019 < 0.000050 < 0.00050 0.0021

HAS-DWB 0.0025

PAS-BUR < 0.0010 < 0.000050 < 0.00050 < 0.00050

PAS-CAR 0.0016 < 0.000050 0.00076 < 0.00050

RAR 0.001 000050 010 50

0.0018 0.000050 0.0011 050

0.0020 0.000050 0.0025 0.0006

0.0049 0.00040 0.0021 33

0.0028 0.00014 0.0023 13

0.0023 0.000057 0.0014 10

0.0021 0.000050 0.00050 069

PAS- 5 < 0. 0.0 < 0.000

PAS-HTR < < 0.00

HAS-GCP <

HAS-SYR 0.00

HAS-HTR 0.00

HAS-UWB 0.00

HAS-DWB < < 0.00

s of these metals oids showed a very similar pattern, with total arsenic, chromium and nickel usually only detected in Paparua Stream during wet

eather sampling (Figs. 29, 31-32) and cadmium regularly below the detection limit during both dry and wet weather sampling (Fig. 30). Additional sampling during dry

Total form and metall

w

weather at HAS-SYR and during wet weather at HAS-HTR demonstrates a range in concentrations, but does not suggest major contamination.


0.000

0.002

0.004

0.006

0.008

0.010

Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet


Tota

l ars

enic

(g m

-3 )

Wet stage 1&2 Wet stage 1 onlyDry 20 Mar Dry 4 JunDry 22 July

Detection limit

Total arsenic concentrations in Haytons Stream catchment. Note the detection limit is shown on this figure as m

Figure 29 any values were below this limit.

0.000

0.001

0.001

0.002

0.002

0.003

Dry

Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet

Wet Dry

Wet


Tota

l cad

miu

m (g

m -3

)


Detection limit

Figure 30 Total cadmium concentrations in Haytons Stream catchment. Note the detection limit is shown on this figure as many values were below this limit.


0.000

0.005

0.010

0.015

0.020

0.025

0.030

0.035

Dry

Wet Dr

Wet Dr

Wet Dr

Wet Dr

Wet Dr

Wet Dr

Wet Dr

Wet Dr

Wety y y y y y y y


Tota

l chr

omiu

m (g

m -3

)

Wet stage 1&2 Wet stage 1 onlyDry 20 Mar Dry 4 JunD

De

ry 22 July

tection limit

Total chromium concentrations in Haytons Stream catchment. Note the detection limit is shown on this figure as many values were below this limit.

Figure 31

0.000

0.002

0.004

0.006

0.008

0.010

Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet


Tota

l nic

kel (

g m

-3 )


Detection limit

Figure 32 Total nickel concentrations in Haytons Stream catchment. Note the detection limit is shown on this figure as many values were below this limit.

3.3.12 Indicator Bacteria

Faecal coliforms and E. coli are bacteria that indicate the likely presence of faecal material, as both organisms are found in the guts of mammals, including humans, pets


and livestock. This means there are multiple sources of these bacteria in urban areas, such as roof runoff, which may contain bird dro unoff from lawns where cats or dogs have defecated. In addition, water fowl such as ducks, increase the bacteria counts in streams. Extremely elevated values of indicator bacteria (>100,000 cf 0 m ) can suggest the presence of raw sewage from leaks or overflows.

Faecal coliforms and E. coli estimated counts were identical for most samples and sa ng nts, with only three exceptions, where E. coli numbers were slightly lower than faec o rm T void repetition, only e ults for E. coli are presented. Faecal coliform results can be found in the Appendix 4.

There was no clear trend in bacteria counts within the catchment, with elevated values m red at all sites (Fig. 33). E. coli and faecal coliform numbers were substantially higher during wet weather sampling with maximum counts 2-15 times higher than during dr eat s l F a tes but HAS-HTR, the maximum count was fr s collected during wet weather sam ling on the 29 April. This may be related to the high rainfall depth of this storm and the longer antecedent dry period co s sampled.

ppings, and r

u 10

mpli

easu

om sam

mpared to other storm

L-1

eveal c lifo s. o a th res

y wple

her amp ing. or ll sip

0

5 000

10 000

15 000

20 000

25 000

Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet Dry

Wet


E. c

oli

(cf

u 10

0 m

L-1)

We e 2t stag We et stag 1Dr ulyy 22 J Dry 4 JunDr ary 20 M

60 000 cfu 100 mL-1 ж

Figure 33 E. coli nu ers in Haytons Stream catchment.

An elevated value of 60 000 E. coli 100 ml-1 was measured at HAS-UWB, well above the values measured at other sites. This site is in farmland and the stream may be affect d b matter from livestock. Further sampling at this location is required to asses h r c o io m currence or whether th ul s a o

mb

e

is res

y inputs of faecal

t was wone-

etheff.

fae al c ntaminat n is a co mon oc


Analysis of the results during the two storm events sampled does not show a consistent trend (Figure 34). During the first event, E. coli numbers were highest at the

of the storm at m , excep , whe murise of the storm. During the second event, higher numbers were measured at the end

m, except at -HTR and HAS-DWB. E. co bers were lower at the e retention p

peak ost sites t HAS-HTR n they were ch higher on the

of the stor HAS li numoutlet of th ond.

0

1 000

2 000

3 000

E. c

oli 4 000

5 000

(c

6 00

fu 1

00

0

0

8 000

0

0



m

7 00L-1)

9 00

10 00Sample 1Sample 2Sam

ple 3

(a)

0

1 000

2 000

3 000

4 000


E. c

oli

5 000

10 000


(cfu

100

mL

6 000

7 000

8 000

9 000

-1)


(b)

Figure 34 E. coli counts at Stage 2 sampling sites during two wet weather events (a) 3 July and

3

PAHs were measured at all sites during Stage 1 dry and wet weather sampling, and at AS-GCP only during an additional wet weather sampling event (24 July). During

dry weather sampling PAHs were detected only at HAS-UWB, with eight compounds detected totalling 0.12 µg m-3 (0.00012 g m-3). During wet weather sampling (29

(b) 24 July.

.3.13 PAHs

H



e t t at e t n to 9 compounds detected (Table 6). r at HAS-HTR to 0.85 µg m-3 at

HAS-GCP (Fig. 35). The peak concentration at HAS-GCP (29th April) was not associated with elevated concentrations of other parameters, such as total petroleum

o < 7 g m-3).

Additional sampling at HAS-GCP on 24 July to further investigate the previously levated result showed slightly lower concentrations (total 0.044-0.29 µg m-3) which

lower during s m mples a larger number of individual

compounds were measured (12) than in the Stage 1 sampling (9 compounds).

, ost frequently: phenanthrene, fluoranthene, pyrene and benzo[b]fluoranthene/benzo[j]fluoranthene. These PAHs are those typically found in stormwater samples

0.0000

0.000

0 4

0.0006

0.000

0 0

y et Dry et Dry et Dry et Dry et Dry

Wet Dry

Wet Dry

Wet Dry

Wet

Tota

l PA

Hs

(g m

-3 )

2

.000

8

.001

Dr

W W W W W

PAS-BUR PAS-CAR PAS-RAR PAS- HAS-HTR HAS-UWB HAS-DWBHTR HAS-GCP HAS-SYR

Wet stage 1&2

AT

prihe

l), Ptota

AHl PA

s wH

ercon

decen

ectrat

ed ion

fivange

sid f

es,rom

wit 0.

h o019

e µg m-3

hydr carbons (TPH), which were below detection ( 0.

ewere at th

maximum during the peak of the storm event and were 6-7 folde tor recession. However, in these sa

Of the 16 PAHs analysed four were detected m

and are representative of petrogenic sources.

Wet stage 1 only

Dry 20 March

Figure 35 Total PAHs (sum of detected compounds only) in Haytons Stream catchment.


Table 6 PAH concentrations measured in Haytons Stream catchment during Stage 1 and pling at HAS-GCP (all concentrations µg m-3).

HAS-UWB

20-Mar PAS-CAR

29-Apr PAS-HTR

29-Apr HAS-GCP

29-Apr HAS-SYR

29-Apr HAS-HTR

29-Apr HAS-GCP 24-Jul - 1

HAS-GCP 24-Jul – 2

HAS-GCP 24-Jul - 3

additional sam

Na 0 0 0 < 0.067 < 0.020 0.031 a < 0.040 phthalene < 0.04 < 0.040 < 0.04 0.40 a < 0.04

Ac 8 8 8 < 0.014 < 0.005 < 0.005 < 0.008

Ac 8 8 8 < 0.014 < 0.005 < 0.005 < 0.008

Flu 8 8 8 < 0.014 0.018 0.016 < 0.008

Ph < 0.014 0.024 0.023 < 0.008

Ant 8 8 < 0.014 < 0.005 < 0.005 < 0.008

Flu 8 0.02 < 0.014 0.03 0.038 0.016

Pyr 0.019 0.044 0.051 0.028

Chr 8 < 0.008 < 0.014 0.01 0.015 < 0.008

Be ne 8 8 < 0.008 < 0.014 0.01 0.015 < 0.008

Be ene 8 < 0.014 0.024 0.043 < 0.008

Be ene 8 8 < 0.008 < 0.014 0.008 0.012 < 0.008

Be BAP 8 0.008 < 0.014 0.009 0.017 < 0.008

Dib ace 8 8 < 0.008 < 0.014 < 0.005 < 0.005 < 0.008

Ind pyre 8 < 0.008 < 0.014 0.007 0.011 < 0.008

Be ene 8 0.013 < 0.014 0.014 0.022 < 0.008

Tot 0.019 0.20 0.29 0.044

enaphthene

enaphthylene

orene

enanthrene

hracene

oranthene

ene

ysene

nzo[a]anthrace

nzo[b]fluoranth

nzo[k]fluoranth

nzo[a]pyrene (

enzo[a,h]anthr

eno(1,2,3-c,d)

nzo[g,h,i]peryl

al PAHs

< 0.00

< 0.00

< 0.00

0.011

< 0.00

0.024

0.019

0.009

< 0.00

+ Benzo[j]fluoranthene 0.016

< 0.00

) 0.014

ne < 0.00

ne 0.011

0.015

0.12

< 0.008 < 0.00

< 0.008 < 0.00

< 0.008 < 0.00

0.013 0.011

< 0.008 < 0.00

0.013 < 0.00

0.014 0.015

< 0.008 < 0.00

< 0.008 < 0.00

0.011 < 0.00

< 0.008 < 0.00

< 0.008 < 0.00

< 0.008 < 0.00

< 0.008 < 0.00

0.01 < 0.00

0.061 0.026

< 0.008

< 0.008

0.14

0.16

0.013

< 0.00

< 0.00

< 0.00

0.021

< 0.008

< 0.008

0.083 0.018

< 0.008

< 0.008

0.013 0.008

< 0.008

< 0.008

< 0.008

< 0.008

< 0.008

0.85 0.047

b

Noa C above deb S compou

tes: oncentrations um of detected

tection limit are in bold for clarity. nds only.


3.3.1

luoride, chloride, TPH and a large suite of volatile organic compounds. None of the volatile organic compounds (including BTEX) were detected in any of the

les

of an oily sheen at two sites on the 20th March and one site on the 29th April.

sites, though fluoride was not. There is an old landfill on Racecourse Road which may be the source of this cyanide and chloride

Table 7

Chloride increased downstream within Haytons Stream and was highest at the outlet from Wigram Retention Basin. Fluoride concentrations were low in Paparua Stream and the upper site of Haytons Stream (HAS-GCP) but 25 times higher at HAS-SYR

samp .

TPH concentrations were below detection limits (0.7 g m-3) for total TPH (C7-C36) for all samples. Samples collected during wet weather sampling in Stage 1 (29 April) were also analysed for TPH, with the same result. This is despite the presence

Total cyanide (which includes hydrogen cyanide (HCN), free cyanide ions (CN-) and complexes of cyanide with metals) was detected in one sample, at PAS-RAR, though concentrations were low (Table 7). Chloride was also slightly elevated at this site compared to upstream and downstream

(Kingett Mitchell 2005a).

Cyanide, chloride and fluoride concentrations measured in Haytons Stream catchment during dry weather sampling on 20th March.

Site Total Cyanide Chloride Fluoride

PAS-BUR < 0.0010 1.2 0.054

PAS-CAR < 0.0010 1.2 0.070

PAS-RAR 0.0012 2.3 0.053

PAS-HTR < 0.0010 1.5 0.066

HAS-GCP < 0.0010 5.0 0.085

0.0010 7.6 2.5

HAS-UWB < 0.0010 6.5 0.75

B < 0.0010 12 0.60

HAS-SYR < 0.0010 4.5 2.1

HAS-HTR <

HAS-DW

4 Additional Contaminants Measured in Stage 1 Only

Samples collected during Stage 1 dry weather sampling were also analysed for cyanide, f

and HAS-HTR. Fluoride was approximately 3 times lower downstream of the confluence with Paparua Stream, probably due to dilution with the cleaner Paparua Stream (Table 7).

3.4 Sediment quality

The stream substrate was described during collection of the sediment samples and shows a wide variation, with sand/silt ranging from 0 to 45% in Haytons Stream catchment (Fig. 36). The proportion of sand/silt was much higher in the Heathcote River, at 95-100%. No sample could be collected at Symes Road due to a lack of sediment at this site, in a concrete stormwater drain. Sediment texture influences contaminant concentrations, as fine particles with high surface area tend to adsorb higher concentrations of metals, while coarse sands have low surface area and few binding sites for metals. Sediments with high proportions of organic carbon also tend to adsorb higher concentrations of organic contaminants and some metals (especially copper). As the texture of samples collected was not assessed in this study, the variation in stream substrate should be considered in interpreting the sediment quality results presented below.

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

PAS-BUR

PAS-CAR

PAS-RAR

PAS-HTR

HAS-GCP

HAS-SYR

HAS-HTR

HAS-UWB

HAS-DWB

HER-UHD

HER-DHD

Per

cent

age

subs

trate

type

Sand/Silt Gravel Pebbles Small Cobble Large Cobble Bedrock

Figure 36 Visual assessment of substrate at sediment sampling sites in Paparua Stream, Haytons Stream and Heathcote River. Note the bedrock at HAS-SYR was a concrete stormwater pipe.

Copper, lead, zinc, nutrients and hydrocarbons (TPH and PAHs) were measured in the sediments collected in Haytons Stream catchment (Tables 8-10). For many



parameters, there were no obvious differences in sediment quality within the catchment, or compared to the Heathcote River. This may be at least partly due to differences in the sediment texture, as a higher silt or mud content in some samples could higher in a higher metal content, even in the absence of contamination, due todifferences in the origin (and hence composition) of material comprising the different size fractions.

Zinc concentrations did show some trend, with substantially lower concentrations (86-90 mg kg-1) in the upper Paparua Stream (PAS-BUR and PAS-CAR). Much higher concentrations were found at PAS-RAR (380 mg kg-1) downstream of residential areas; and at PAS-HTR (1 900 mg kg-1), downstream of industrial land use and major roads. Zinc concentrations in Haytons Stream were also higher than in the upperPaparua Stream, at 290-450 mg kg-1. The lower concentrations in Paparua Stream are

sites. Overall, these results suggest enrichment of zinc in the sediments of the lower Paparua

m .

other locations, at 62 mg kg . This site had the highest proportion of sand and silt in the substrate and it is

Strea and in Haytons Stream

Copper concentrations ranged from 5.5 to 33 mg kg-1, with the highest concentration in Paparua Stream upstream of the confluence with Haytons Stream (PAS-HTR). Both zinc and phosphorus concentrations were also exceptionally high at this location compared to other sites. The lead concentration was also approximately double that of most other sites (excluding HER-UHD). The substrate assessment did not indicate higher silt content than other sites and TOC was not substantially higher than other samples, suggesting that these elevated values are not due to differences in texture, but are due to higher contamination levels at this site.

The lead concentration at HER-UHD was elevated compared to-1

likely that the sample collected also had a high proportion of sand and silt. In addition, this sample had much higher organic carbon content than other sediment samples (12%, c.f. 0.66-2.5% for all other samples).

unlikely to be due to differences in sediment texture (i.e., lower proportions of fine sediments) as the concentrations of copper and lead were similar to other


T nc tion ples yto r.

opp - hos arbon

able 8 Co

Sample Name

entra

C

s of metals and nutrients (mg kg-1 dry

er Lead Zinc

weight) in sediment sa

Ammonium

m

N

from Paparua Stream, Ha

NOx-N P

ns Stream and Heathcote Rive

phorus Total Organic C(%)

PAS-BUR 12 726 86 < 5.0 < 1.0 00 2.3

PAS-CAR

PAS-RAR

PAS-HTR

HAS-GCP

HAS-HTR

HAS-UWB

HAS-DWB

HER-UHD

HER-DHD

5.5 310

15 5.0 600

33 3,100

13 710

13 880

12 580

16 900

24 800

5.9 440

20 90

33 380

73 1,900

21 420

41 290

24 450

19 320

62 310

18 460

7.0

<

26

39

< 5.0

15

34

28

9.2

< 1.0

3.4

< 1.0

< 1.0

< 1.0

< 1.0

4.4

< 2.8

< 1.0

0.66

2.5

2.0

1.1

1.7

0.72

0.73

12

0.79

Table 9

14 C15 – C36 Total (C7 – C36)

Total petroleum hydrocarbon (TPH) concentrations (mg kg-1 dry weight) in sediment samples from Paparua Stream, Haytons Stream and Heathcote River.

Site C7 – C9 C10 – C

PAS-BUR < 11 < 20 < 30 < 60

PAS-CAR < 11 < 20 < 30 < 60

PAS-RAR < 16 < 23 94 95

PAS-HTR < 9.2 < 20 < 30 < 60

HAS-GCP < 17 < 23 100 100

HAS-HTR < 16 < 22 < 31 < 60

< 24 < 34 < 60 HAS-UWB < 17

HAS-DWB < 30 < 42 91 94

HER-UHD < 77 < 110 380 410

HER-DHD < 19 < 27 < 38 < 60

TPH concentrations were low in most samples, with only four samples containing TPH above the detection limits (Table 9). In three of these, the total TPH ranged from 94-100 mg kg-1 dry weight, while at HER-UHD, total TPH measured 410 mg kg -1 dry

in other samples the total ranged from 0.034 to 0.89 mg kg dry weight. PAHs showed a

am catchment, with s detected at downstream

weight.

The sample from HER-UHD also contained the highest concentration of PAHs (Table 10) with a total of 6.0 mg kg-1 dry weight. The sample from PAS-RAR also contained elevated concentrations with a total of 2.1 mg kg-1 dry weight, whereas

-1

general increase from upstream to downstream within Paparua Strehigher concentrations and more individual PAH compoundsites.

The profiles of individual PAH compounds were similar for all samples (Fig. 37), with the exception of the sample from HAS-GCP, which contained elevated naphthalene, unlike all other samples. Naphthalene was also detected in stormwater samples from this site (see Section 3.3.13).



Table 10 PAH concentrations (mg kg-1 dry weight) measured in sediments from Paparua Stream, Haytons Stream and Heathcote River.

PAS-BUR PAS-CAR PAS-RAR PAS-HTR HAS-GCP HAS-HTR HAS-UWB HAS-DWB HER-UHD HER-DHD

Naphthalene < 0.012 < 0.012 < 0.017 < 0.010 0.19 < 0.010 < 0.014 < 0.017 < 0.044 < 0.011

Acenaphthene < 0.0023 < 0.0023 0.005 0.0028 0.0037 < 0.0020 < 0.0027 < 0.0034 0.043 < 0.0022

Acen .00

Fluor .00 0.0

Phen 002 0.0

Anth .00 0.

Fluor 006 0.

Pyre 007 0.

Chry .003 0.

Benz 002 0.

BenzBenz 004 0.

Benz .00 0.

Benz 0033 0.0

Dibe .0023 0.0

Inde .0023 0.0

Benz 0035 0.048

Total .034 0.62

aphthylene < 0

ene < 0

anthrene 0.

racene < 0

anthene 0.

ne 0.

sene 0

o[a]anthracene 0.

o[b]fluoranthene + o[j]fluoranthene 0.

o[k]fluoranthene < 0

o[a]pyrene (BAP) 0.

nzo[a,h]anthracene < 0

no(1,2,3-c,d)pyrene < 0

o[g,h,i]perylene 0.

PAHs

23 0.0027 0.011

23 0.0043 0.011

9 0.034 0.16

23 0.0043 0.044

3 0.04 0.36

2 0.04 0.38

0.018 0.15

8 0.016 0.15

5 0.026 0.27

23 0.0099 0.097

0.016 0.17

0.0033 0.034

0.0098 0.12

0.016 0.17

0.24 2.1

0.0066 0.0041

0.0071 0.027

0.087 0.077

0.011 0.017

0.12 0.092

0.13 0.18

0.048 0.041

0.042 0.034

0.073 0.07

0.028 0.021

0.047 0.037

0.0091 0.009

0.031 0.026

0.044 0.059

0.69 0.89

0.0053 < 0.0027 0.0042

043 < 0.0027 0.0059

52 0.0082 0.03

011 < 0.0027 0.0059

096 0.019 0.047

10 0.025 0.056

041 0.0098 0.023

045 0.0068 0.021

081 0.015 0.041

03 0.0058 0.016

58 0.0085 0.026

12 < 0.0027 0.0056

37 0.0066 0.019

0.012 0.027

0.12 0.33

0.022 0.0038

0.1 0.0042

0.79 0.031

0.13 0.010

1.1 0.078

1 0.082

0.43 0.043

0.48 0.051

0.61 0.063

0.24 0.026

0.45 0.048

0.074 0.0077

0.25 0.024

0.32 0.031

6.0 0.50 a 0

Notea Su ly.

s:

m of detected compounds on

0.0

0.2

0.4

0.6en

tratio

n (m

0.8

1.0

Naphtha

lene

Acenap

hthene

Acenap

hthyle

ne

Fluoren

e

Phena

nthren

e

Anthrac

ene

Fluoran

thene

Pyrene

Chrysen

e

Benzo

[a]anth

racen

e

Benzo

[b]flu

oranth

ene

Benzo

[k]flu

oranthe

ne

Benzo

[a]pyre

ne

Dibenzo

[a,h]anthrac

ene

Inden

o(1,2,

3-c,d)

pyrene

Benzo

[g,h,i]p

erylen

e

PA

H c

onc

g kg

-1 d

ry w

ei

1.2

ght)

PAS-BURPAS-CARPAS-RARPAS-HTRHAS-GCPHAS-HTRHAS-UWBHAS-DWBHER-UHDHER-DHD

Figure 37 Profile of PAHs in sediment samples from Paparua Stream, Haytons Stream and Heathcote River.

3.5 Data Sonde Results

3.5.1 Data Quality

Data sondes were deployed at the HAS-HTR and PAS-HTR sampling sites to provide a continuous measure of water quality in each stream. Each sonde was deployed for two periods, totalling 59 days between 23rd July and 1st October at HAS-HTR and 39

evious unsatisfactory sonde was obtained. Both sondes were removed for the period 8th to 21st September 2009 for servicing.

The data sondes were fitted with sensors capable of measuring the following

Despite repeated efforts to establish causes of instrument failure (including fitting replacement sensors), measurement of pH was unsatisfactory and no pH results are presented here. Measurements of temperature, conductivity, DO and turbidity made by multi-parameter field meter were consistent with concurrent data sonde measurements, with the exception of DO in the case of the sonde on Paparua Stream (see below). No independent measurements of ammoniacal-N were made during the period that the sondes were deployed.

Ammonia and nitrate sensors are generally more suitable for indicating trends or relative changes rather than absolute concentrations of these contaminants (NIWA, 2008). Their performance is very much dependent on the characteristics of the water

days between 12th August and 1st October at PAS-HTR. Deployment at the latter site was delayed while a replacement for a pr

parameters: temperature, conductivity, DO concentration, DO saturation, pH, ammoniacal-N concentration and turbidity.


body being monitored, and the electrodes have a short 'life span' and are not reliable at low levels. Despite these limitations, the measurements of ammoniacal-N made by the sondes are reported here as, in combination with other measurements, they do provide information of some important aspects of water quality in Haytons and Paparua Streams.

3.5.2 Rainfall and Stream Water Level

Fig. 38 shows measurements of water temperature, conductivity, DO concentration, DO saturation, turbidity and ammoniacal-N along with the rainfall and stream water levels recorded over the period of datasonde deployment.

Other than a number of rain events in the second half of August and towards the latter part of September, conditions in the catchment were relatively dry. However, while the major peaks in the stream hydrographs corresponded with rain events, other smaller fluctuations in the water level record of both streams appear to be independent of weather conditions.

Haytons Stream where the daily variation in stream water level was of the order of 50 mm. At other times there were periods of around 2 days over which the stream water level fell, before returning rapidly to its original level (for instance 6-7 Sep and 13-14 Sep). Again, this feature is more evident in the record of Haytons Stream than Paparua

m water level recorders. They appear to be indicative of regular (daily) discharges to Haytons Stream for periods of five days, followed by periods of two days when discharges ceased and/or water may have been abstracted from the stream: in other words, a 7 day cycle of water discharge / use. Figure 39 provides an example of these changes in the stream water level over the period 31 August to 21 Sep.

Fluctuations in the record of Paparua Stream are less regular but also include some more sustained reductions, perhaps relating to the way in which the water race feeding the stream was managed.

.

During dry spells there was a diurnal rise and fall in water level, more noticeably in

Stream. The scale of these water level changes falls well outside the range of measurement error associated with the strea


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Paparua

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1400

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Turb

U) .

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800

idity

(NT

Haytons

Paparua

Figure 38 ity, turbidity and ammoniacal-N measured in Haytons Rainfall at College rain gauge and water level, temperature, dissolved oxygen, conductiv

and Paparua Streams at Haytons Rd, 23 July to 1 October 2009.



031/08 1/09 2/09 3/09 4/09 5/09 6/

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09 9 20/09 21/09 22/09

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3

5

ainf

all (

mm

/h

Water level

Rainfall

Figure 39

Water temperature followed a rising trend over the period of measurement, as would be expected with the transition from winter to warmer spring air temperatures (Figure 38). While both streams had a mean temperature of around 9 oC during the period of concurrent measurement, the diurnal variation was much greater in Haytons Stream (typically 4-8 oC) than Paparua Stream (1-2 oC). Given the similarity in mean temperatures, the differences in diurnal variation appears to reflect differences in the characteristics of the streams which control heating and heat loss, rather than a discharge of warm water to Haytons Stream. Paparua Stream is piped for 1400 m immediately upstream of the point at which the data sonde was deployed. Compared to Haytons Stream, it is therefore protected from heating by direct solar radiation during the day and insulated against radiative heat loss at night.

In addition, there was no clear relationship between water temperature and the apparent weekly cycle of changes in the water level of Haytons Stream (see Section 3.5.2). The diurnal pattern of rising then falling temperatures occurred irrespective of water level: i.e. continuing during weekends despite a fall in the stream water level. During weekdays the stream water temperature began to rise during the morning, in advance of the rise in stream water level which typically occurred in the afternoon. This further suggests that differences in the temperature regime of the two streams are not the result of a discharge of warm water to Haytons Stream.

Water level in Haytons Stream at Haytons Rd and rainfall at College rain gauge, 31 August to 21 September 2009. Weekend days are shaded.

5.3 Water temperature 3.

3.5. Dis o

Mean DO t n and % sat i meas ents r in Haytons St than in d d contrast with results reported in Section 3.3.1. However, there is clear evidence of downwards drift in the measure n A H o A u w a more rapid decrease after the sondes were redeployed following servicing ( ig. 38). Excluding measurements after 25 August, m n n o n u on were both sl y higher P r S c p d 9.2 g m-3 and 79% at HAS-HTR.

A h tem re, diurnal variations in DO were more marked in Haytons Stream th n Pap a , h e g e e a m m ma increasing in latter par p s m . orning and maxima in the late afternoon cl photosynthesis a a h , r o relationship between the diurnal cycle of DO and the changes in water level in Haytons Stream de ed in n

3.5. Conductivity

M cond over the period of concurrent measurement was higher in Haytons Stream (260 µ n e ) h lts were consistent with the results of measure n k d m these sites (Section 3.3.1).

Th re o x m h as t S-HT ite, with conductivit o 0 µ m o x c ments of elevated conductivity were recorded for periods ranging from 5 minutes to two continuous p y g 2 s h aximum conductivit rement, 3411 µS cm-1 was recorded during the latter event. While neither of the e e e i it gnificant rainfall, several of the shorter ‘spikes’ in 13 August, between 15-18 August a o 5 t een wet an y, turbidity and ammoniacal-N are de f

3.5. urbid

Mean turbidity e c u e r Haytons Stream (58 NTU) than in Paparua Stream (26 NT sults we w e higher S co o m u a l o R than in se collec P - e . . t t e ally low

4

ream

ightl

s witan i the

scrib

5

ean

ere we

d dry weather conditions and conductivitscribed

6 T

ith th tho

solv

con

ed

cen Pap

xygen

ratioarua

urat on uremcord

weonsi

re here

ighe, in Stream when the entire re is c

me

in

t of DO at P S- TR from ar und 25 ug st, F

ith

eam, a

DOt 9.8

co g m

centratind 8

n a4%

d %om

satare

rati to apa ua trea -3 a

peraru

atu Strt of

eamthe

witerio

thd of

ranmea

e bure

tweent

n d DO

ily min

iniima

a aoccu

nd mrred

aximid-m

, consistent eget

with the diurnal cwit

y the

e of respiration ande w by

ctio

quatic v tion. As temperature as n

Se 3.5.2.

uctivityS cm-1) tha in Paparua

meStrt ta

am en

(87 urin

µS g sa

cm-1

ple. T collection from

ese resu

R s

e m

h si

betw

re consistent

ner

a ny in

um exc

ber ess

f ef 1

tre00

ely higS c

men si

urem oc

entsasions (Fig. 38). Measure

a the HA-1

eriods of ty m

s

hree da s: 10-13 Au ust and 24- 6 Augu t. Teasu extend d p riods of elevated

conductivity did: for instance those on conduct vity coincided w

nd n 2 -26 August. The rela ionships

urther in Section 3.5.8.

ity

ov r the period of onc rrent m asuU). These re

ement was higher in

TSted

ncenAS

tratiHTR

ns (S

easctio

redn 3

in s3.3)

mp In

es ccon

llecrast

ted at HAS-HTto at he g


turbidity in Paparua Stream, a number of elevated measurements were recorded early in the deployment period (13-16 August), coinciding with rainfall and relatively high stream water levels (Fig. 38). Turbidity in Paparua Stream remained much lower (< 100 NTU) during subsequent storm events.

Elevated turbidity in Haytons Stream also corresponded with rainfall events (see, for instance, the second period of sonde deployment). Superimposed on this are a number of short lived ‘spikes’ in the turbidity record (approximate range 100-400 NTU), often

ot correspond with changes in other

3

There were several periods of elevated ammoniacal-N recorded at both sites, with

.

3

R over the 10 and 11 August. While there was an absence of rainfall over this period, the water level record indicates two possible discharges. Three small

th

r the period 15 to 19 August. In this case, all increases in turbidity, ammoniacal-N and conductivity appear to have

as short as a single measurement. These do nparameters measured, suggesting they are either the function of measurement error or perhaps the result of temporary sensor fouling or blockage.

.5.7 Ammoniacal-N

The mean concentration of ammoniacal-N over the period of concurrent measurement was 0.7 g m-3 at both sites. The maximum concentrations were 7.2 g m-3 at HAS-HTR and 8.0 g m-3 at PAS-HTR. These results were of the same order as those measured in grab samples at PAS-HTR but much lower than the maximum concentrations measured in samples collected at HAS-HTR prior to sonde deployment (see Section 3.3.4). However, for reasons described in Section 3.5.1, the absolute values of ammoniacal-N measured by the sondes are considered to be of uncertain reliability and more emphasis has been placed on interpreting relative changes in concentrations over time.

those at PAS-HTR tending to fall to ‘baseline’ concentrations more rapidly than those at HAS-HTR (Fig. 38). Increases in ammoniacal-N concentrations sometimes corresponded with rainfall, but not always, and this was the case at both sites. The examples in the following section demonstrate these findings in more details

.5.8 Evidence of dry and wet weather contamination

Fig. 40 traces the gradual increase and then fall in ammoniacal-N and conductivity at HAS-HT th th

spikes in turbidity around the 12 August possibly indicate unrelated later discharges or sensor fouling. Rainfall on the 13th then resulted in a water level rise of around 500 mm and a corresponding rapid rise then fall in turbidity, ammoniacal-N and conductivity.

Fig. 41 shows changes in these same variables ove th th


corresponded with rising stream water levels following rainfall. In contrast, Fig. 42 plots a large rise in conductivity and ammoniacal-N on 24th August that corresponded with relatively minor changes in stream water level and turbidity. This occurred on a Monday, with the large rise in conductivity and ammoniacal-N coinciding with the ‘recovery’ of the stream water level following two days of falling water levels over the

h daily increases in water level are present in the data, at other times conductivity fell

nciding with another rise in the stream water level unrelated to rainfall. The changes in water quality during each of the three periods of data described here

meters during a storm event around midnight on 25th August (Fig. 44). A subsequent increase in conductivity on

ollowing two days, again possibly indicating the influence of controls on water entering the catchment via the

weekend. This appears to confirm that the daily water level rises described in Section 3.5.2 are indeed the result of discharges to the stream.

However, the daily rise and fall in the stream water level on weekdays was only occasionally associated with elevated conductivity and ammoniacal-N. While other less extreme examples of elevated conductivity and ammoniacal-N corresponding wit

and then recovered in an inverse relationship with water level. The data record also contains evidence of relatively small increases in turbidity corresponding with daily water level increases and lower turbidity at weekends. In combination, these results are suggestive of a daily discharge to the stream which often increases turbidity but is only intermittently a source of ammoniacal-N.

Following rainfall, a much larger rise in water level and turbidity around midnight on the 25th August resulted in a lesser and relatively short lived spike in both conductivity and ammoniacal-N (Fig. 42). Both parameters then increased again later on the 26th August, coi

support the findings presented in Section 3.3.4 that contamination of Haytons Stream with ammoniacal-N can occur during both wet and dry weather conditions.

Figs. 43, 44 and 45 show similar data for Paparua Stream. Between 15th and 19th August increases in turbidity, conductivity and ammoniacal-N followed rainfall and coincided with a rise in stream water levels, other than a late peak in conductivity on the 19th (Fig. 43). There was also a spike in all three para

the 27th followed a much smaller rise in water level but was unrelated to rainfall – possibly this corresponded with a change in the origin of stream water from locally derived rainfall runoff to baseflow sourced from outside the catchment (via the water race crossing the catchment divide).

Fig. 45 shows a period of elevated conductivity and ammoniacal-N following a rise in stream water level, but again apparently unrelated to rainfall. The stream remained at approximately the same (higher) water level over the f

water race. However, the rise in conductivity and ammoniacal-N was not clearly related to the change in water level, possibly suggesting an independent origin. As


with Haytons Stream, these results appear to confirm that contamination of Paparua Stream with ammoniacal-N can occur during both wet and dry weather conditions.

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Figure 40 infall at College rain gauge, 10-13 August 2009.

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Water level, conductivity, turbidity and ammoniacal-N in Haytons

Figure 41 Stream and rainfall at College rain gauge, 15-19 August 2009.


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NH4-N

Figure 42 y, turbidity and ammoniacal-N in tons Stream and rainfall e, 24-28 August .

Water level, conductivit Hayat College rain gaug 2009

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Figure 43

N

Water level, conductivity, turbidity and ammoniacal-N in Paparua Stream and rainfall at College rain gauge, 15-19 August 2009.


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Figure 44 Water level, conductivity, turbidity and ammoniacal-N in Paparua Stream and rainfall

at College rain gauge, 24-28 August 2009.

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5

6

ll (m

m/h

r)

water level

turbidity

rainfall

0

20

40

60

80

100

120

140

160

180

200

3/09 12:00

Con

duct

ivity

(uS

/cm

)

4.5

5

4/09 0:00 4/09 12:00 5/09 0:00 5/09 12:00 6/09 0:00 6/09 12:00 7/09 0:00 7/09 12:00 8/09 0:00 8/09 12:000

0.5

1

1.5

2

2.5

3

3.5

4

NH

4-N

(mg/

l) .

conductivity

NH4-N

Water level, conductivity, turbidity and ammoniacal-N in Paparua Stream and rainfall at College rain gauge, 4-7 September 2009.

Figure 45


4. Discussion

4.1 Extent of Water Contamination

4.1.1 Comparison to water quality guidelines

The proposed Natural Resources Regional Plan (PNRRP) for Canterbury contains water quality standards for different classifications of water bodies (ECan 2004). The upper reaches of Paparua Stream (encompassing PAS-BUR, PAS-CAR and PAS-RAR) and the lower section of Haytons Stream (downstream of Wigram Road, encompassing sites HAS-UWB and HAS-DWB) are classified as “Urban”, while the remainder of the waterways are not identified on the planning maps. The Heathcote River is classed as “Lowland” in the upper reaches (from the headwaters to Aidanfield Drive) and “Urban” downstream to its mouth. The two sites in this study that were

dard for

Table 11

Parameter Standard

located in the Heathcote River were within the stretches classed as “Urban”.

Water quality standards for urban waterways are presented in Table 11 and are compared to the data collected in this study in Table 12. There is no stanindicator bacteria in the class: urban streams. Guidelines from the Ministry for the Environment and Ministry of Health recommend a maximum E. coli count of 260 for bathing water quality (MfE/MoH 2003).

Water quality standards for Class: urban streams (ECan 2004).

Dissolved oxygen saturation Shall exceed 80% at any time; and shall exceed 90% during daylight hours and at all times from May to September inclusive

Water temperature Shall not exceed 20oC as a daily maximum temperature; shall not exceed 11oC September inclusive

as a daily maximum temperature from May to

pH Shall be within the range 6 to 9

Total ammonia Shall not exceed 0.9 g m-3

Toxicants (including metals), measured as total fraction

Shall not exceed the 90% ANZECC trigger value

The comparison shows that standards for dissolved oxygen, copper, lead, zinc and E. coli were the most frequently exceeded in the catchment. No samples exceeded the standard for pH, total arsenic or total nickel. Compared with Haytons Stream, fewer samples from Paparua Stream exceeded standards.


Table 12 Comparison of water quality in Haytons Stream catchment with PNRRP standards for urban stream ica samples exceeded the standard.

DO Temp NH4-N Cadmium Chromium Copper inc

s a. Values in bold ind

Lead Z

te greater than 50% of

E. coli

Standard >90 % <11 ºC <0.9 g m-3 <0.4 mg m-3 <0.006 g m-3 <0.0018 g m-3 <0.0 5 g L-1056 g m-3 <0.01 m-3 <260 cfu 100m

Site Excd. Min. Excd. Max. Excd. Max. Excd. Max. Excd. Max. Excd. Max. Excd. Max. Excd. Max. Excd. Max.

PAS-BUR 2 / 2 71 2 / 2 14 0 / 2 <0.01 0 / 2 0.052 0 / 2 0.003 1 / 2 0.0046 0 / 2

PAS-CAR 1 / 7 65 2 / 7 15 0 / 10 0.27 0 / 2 0.052 0 / 2 0.0012 8 / 10 0.011 3 / 10 0

PAS-RAR 2 / 2 74 2 / 2 15 0 / 2 0.052 0 / 2 0.052 0 / 2 0.002 1 / 2 0.0064 0 / 2 0

PAS-HTR 2 / 6 69 2 / 6 16 2 / 10 14 0 / 2 0.076 0 / 2 0.0026 9 / 10 0.025 7 / 10 0

HAS-GCP 4 / 7 32 2 / 7 16 4 / 10 33 0 / 2 0.1 0 / 2 0.0044 10 / 10 0.029 7 / 10 0

HAS-SYR 2 / 4 49 2 / 4 14 2 / 4 57 1 / 4 1 0 / 4 0.0052 3 / 4 0.012 1 / 4 0

HAS-HTR 5 / 10 52 1 / 10 13 9 / 10 100 4 / 8 2 6 / 8 0.031 10 / 10 0.044 8 / 10

HAS-UWB 2 / 2 22 2 / 2 18 1 / 2 0.91 0 / 2 0.14 0 / 2 0.0027 2 / 2 0.0084 2 / 2 0

HAS-DWB 2 / 4 60 2 / 4 17 2 / 10 1.7 0 / 2 0.052 0 / 2 0.0007 10 / 10 0.004 0 / 10 0.24

HER-UHD 7 / 7 38 3 / 7 14 0 / 10 0.098 0 / 8 0.071 0 / 8 0.0024 6 / 10 0.010 1 / 10 0.07 0

HER-DHD 4 / 7 45 3 / 7 15 1 / 10 1.2 0 / 8 0.11 0 / 8 0.0026 5 / 10 0.0066 1 / 10 0.25 0

0.006 1 / 2

0.022 8 / 10

0.006 1 / 2

0.049 10 / 10

0.047 10 / 10

0.0058 4 / 4

0.091 10 / 10

0.010 2 / 2

0.003 10 / 10

0.010 5 / 10

0.0086 9 / 10

0.02 1 / 2 2 400

0.24 5 / 10 12 00

0.12 2 / 2 10 00

0.70 8 / 10 19 00

0.20 6 / 10 10 00

0.44 2 / 4 20 00

3.1 7 / 10 9 300

0.39 2 / 2 60 00

2 / 10 2 100

8 4 / 10 10 00

5 / 10 12 00

Notes: a Number of samples exceeding standard / total no. samples measured. Maximum concentration detected.


While the standard for ammonia was exceeded less frequently than other pa eters (Table 12), the scale of the exceedances is of considerable concern, with m ured values over 100x higher than the standard. The standard of 0.9 g ammoniacal-N in waters of pH 8.0 is based on protecting aquatic ecosyste from toxic effects of ammonia and the maximum values of 14-100 g m-3 in Hayton ream are likely to result in acute toxic effects to any biota exposed (Richardson 199

4.1.2 Comparison to other urban streams

PDP (2007) analysed water quality data for Christchurch urban streams from 1992 to 2006 and showed that Haytons Stream had higher dissolved oxygen, BOD, a onia, DRP and occasionally pH, than other sites in the Heathcote or Avon River catchments. Conductivity was lower than at other Heathcote River sites, but within the same range as values measured in the Avon River catchment. NOx-N concentrations were also lower than at other Heathcote River sites and, in addition, were lower than most sites in the Avon River catchment. Suspended solids were at similar concentrations in Haytons Stream to other sites in the Heathcote River catchment, which were generally higher than in the Avon River catchment. Metals data was available for only Haytons Stream and Curletts Drain, and showed similar median concentrations of most metals, though maximum concentrations tended to be higher in Haytons Stream, either at Wigram Road or downstream of the Wigram Retention Basin, than in Curletts Drain. Faecal coliforms and E. coli numbers in Haytons Stream were similar to oth te in the Heathcote catchment, while these bacteria were at slightly lower concentr ns at the outlet of Wigram Retention Basin.

The results of this study corroborate the results summarised above for BOD, a onia, DRP and pH, and in particular, confirm that ammoniacal-N and DRP are substantially higher than at other locations within the Christchurch urban area. How , the additional results did show some differences and these are discussed below.

The additional results indicate lower DO saturation in Haytons Stream catchm than previously measured (PDP 2007). In particular, during dry weather, DO satura was at least as low as other sites in the Heathcote River catchment, and, at ti was lower.

Conductivity was substantially higher in this study compared to the previ a, particularly during dry weather sampling. The values measured in this study in the range of those measured at other sites upstream and downstream in the Heathcote River and in its tributaries. A single value of 890 µS/cm measured at HAS-HTR during dry weather sampling (22 July) was higher than values reported in PDP (2007) for both the Heathcote and Avon river catchments.

rameas

ms s St7).

mm

at

er siatio

mm

ever

enttionmes

ous dat were

m-3 for total



NOx-N concentrations in the upper catchment (Paparua Stream and HAS-GCP) were in the range measured previously, however higher concentrations were measured at the Symes Road site and downstream. The concentrations at Symes Road were at the

r catchment.

y higher during wet weather sampling and were higher than previously measured in Haytons Stream (PDP 2007). TSS concentrations

r than previously measured in Haytons Stream during dry weather sampling, and remained

y measured.

Up until the end of 2006, metals were not measured in the Heathcote and Avon Rivers, unlike the other parameters discussed above. Metals have been measured in Curletts Drain (in the Heathcote catchment) and the Halswell Retention Basin (in the nearby Halswell catchment), both of which drain catchments with industrial land use. In addition, copper, lead and zinc were recently measured in the Cashmere Stream and its tributaries, draining residential, industrial and agricultural land use (EOS Ecology, 2006, cited in Golder Kingett Mitchell 2007).

When data for Haytons Stream is compared to other locations, copper and lead concentrations were about the same in Haytons Stream as in Cashmere Stream and tributaries during dry weather, and slightly higher during wet weather. Zinc concentrations in Haytons Stream during both dry and wet weather were substantially higher than those in Cashmere Stream and tributaries. This comparison suggests that the industrial land use contributes additional zinc to the Heathcote River. Copper, lead and zinc concentrations in Haytons Stream are about the same as those in Curletts Drain and slightly lower than in Halswell Retention Basin.

Comparative data from storm event monitoring is also available for metal concentrations in urban streams and reticulated stormwater networks in Auckland

upper end of the range measured at other sites in the Heathcote Rive

TSS concentrations were substantiall

were frequently above 100 g m-3 during wet weather sampling, which was the maximum value reported for the Heathcote River and tributaries (PDP 2007). However, TSS concentrations were substantially lower downstream of the Wigram Retention Basin and within the range observed at other sites previously (PDP 2007).

Median copper, lead and zinc concentrations were higher in the current study than the previous monitoring, particularly at sites in Haytons Stream upstream of the Wigram Retention Basin. Median cadmium and nickel concentrations were lowe

lower at most sites during wet weather sampling. The maximum measured concentrations in this study were substantially lower than the previous results for cadmium and nickel, and slightly lower for copper. At most sites, the maximum lead and zinc concentrations were within the range measured previously, though at HAS-GCP and HAS-HTR the maximum zinc concentration was higher than previousl

(NIWA, 2009). The urban streams monitored in Auckland drain mixed land-use catchments while sites on stormwater networks aimed to characterise stormwater quality discharged from specific types of land-use (i.e. catchment areas of solely residential, commercial or industrial land use).

The data indicates median total copper concentrations range from 0.006 to 0.017 g m-3 in streams under storm flow conditions, similar to the median concentrations in Haytons Stream. The 90th percentile concentrations of 0.019 – 0.061 g m-3 in the Auckland streams were also similar maximum concentrations in Haytons Stream. Slightly higher median and 90th percentile concentrations were measured in Auckland stormwater, with median values 0.008-0.033 g m-3, and 90th percentile 0.033-0.13 g m-

3.

Zinc concentrations at most sites in Haytons Stream were also similar to those in Auckland urban streams, where median total zinc concentrations were 0.05-0.23 g m-3

(NIWA 2009). At HAS-HTR, the median total zinc was somewhat higher at 0.66 g m-

3, but within the range for reticulated stormwater networks in commercial and industrial catchments in Auckland (range of medians 0.22-0.91 g m-3). Maximum concentrations were not reported for the Auckland data, but 90th percentile values were less than 0.5 g m-3 for urban streams and 0.25-2.9 g m-3 for stormwater. These are slightly below the maximum concentration of 3.2 g m-3 measured at HAS-HTR.

Dissolved zinc concentrations in upper Paparua Stream (median 0.08 g m-3, maximum 0.13 g m-3 during wet weather at PAS-CAR) were similar to Auckland urban streams (median concentrations 0.01-0.09 g m-3, 90th-percentiles 0.02-0.14 g m-3). However, sites in Haytons Stream and lower Paparua Stream (median concentrations -0.40 g m-3, maximum concentrations 0.15-0.80 g m-3) were almost a factor of ten higher than in Auckland urban streams but were within the range for storm (median concentrations 0.01-0.74 g m-3, 90th-percentiles 0.05-1.9 g m-3, NIWA 2009). Overall, zinc concentrations in the upper Paparua Stream are similar to Auckland urban streams, while concentrations in Haytons Stream and the lower Paparua Stream are similar to stormwater from commercial and industrial catchments.

Total lead concentrations were not measured in Auckland stormwater and str though particulate lead concentrations should provide a close comparison, as up to 98% of lead is attached to particulates (Timperley et al 2003). Total lead concentrations in Haytons Stream (median concentrations 0.004-0.029 , maximum concentrations 0.003-0.091 g m-3) were within the general ran f particulate lead in Auckland urban streams (median concentrations 0.003-0.016 , 90th-percentiles 0.008-0.079 g m-3). Lead concentrations in Auckland stormwater were generally slightly higher than in the urban streams (NIWA 2009).

0.10

water

eams,

g m-3

ge og m-3


Haytons Stre

am Catchment Water Quality Investigation 71

4.2 Extent of Sediment Contamination

An indication of the quality of sediments from Haytons Stream catchment and the

Table 13

-high,

r (mg kg-1)

Lead (mg kg-1)

Zinc (mg kg-1)

Heathcote River (upstream and downstream of the confluence) can be made by comparison to sediment quality guidelines. Comparison of copper, lead and zinc concentrations to the ANZECC sediment quality guidelines (Table 13) shows no exceedance of the ISQG-low for copper, two exceedances for lead and eight exceedances for zinc. Of the samples that exceeded the ISQG-low for zinc, four samples also exceeded the ISQG-high. This suggests the potential for adverse effects in biota living in or near sediments in these four locations from the high zinc concentrations.

Comparison of metals in sediment samples with ANZECC sediment quality guidelines. Values shaded yellow indicate exceedance of the ANZECC ISQG-low, values shaded red indicate exceedance of the ANZECC ISQG

Coppe

ANZECC ISQG-low 65 50 200

ANZECC ISQG-high 270 220 410

Sample Site

PAS-BUR 12 26 86

PAS-CAR 5.5 20 90

PAS-RAR 15 33 380

PAS-HTR 33 73 1 900

HAS-GCP 13 21 420

HAS-HTR 13 41 290

HAS-UWB 12 24 450

HAS-DWB 16 19 320

HER-UHD 24 62 310

HER-DHD 5.9 18 460

Concentrations of individual PAHs and grouped (low molecular weight, high molecular weight) PAH in the sediments were below the sediment quality guidelines when normalised to the concentration of organic carbon in the samples. There are no guidelines for concentrations of nutrients or TPH in sediments.

Haytons Stre

am Catchment Water Quality Investigation 72

Copper, lead and zinc in the sediments from Haytons Stream are compared to sediments in other Christchurch streams in Fig. 46. Data for the Avon and Styx Rivers is from a survey in 1980/1981, and studies have shown that zinc concentrations in sediment have increased, and lead concentrations decreased since this time (Kingett Mitchell 2005b). However, that survey still represents the largest survey of sediments in Christchurch, and more recent data from the Styx River is not yet publiclyavailable.

The data shows that overall, Haytons Stream sediments are not substantially morecontaminated with copper and lead than other streams, with median and maximum copper and lead concentrations lower than most other locations around Christchurch.However, the median zinc concentration measured in Haytons Stream was higher than most other Christchurch streams, with the exception of others with industrial land use in the catchment (Heathcote and Avon). The maximum measured in Haytons Stream sediment was the highest of all sites.

4.3 Possible Sources of Contaminants

As described within Section 3.3, water quality is higher in the upper Paparua Streamand becomes degraded with distance downstream, with most parameters increasing in concentration. There are greater increases in most parameters downstream of theindustrial land use around Haytons Road, suggesting that industrial land use is the greater source of contamination. This site is also downstream of Main South Road, a heavily trafficked road (>50,000 vehicles per day). Within Haytons Stream, there is nogeneral trend in water quality, though all sites assessed were located downstream ofindustrial land use. For some parameters there was an improvement in water quality at HAS-UWB, most likely due to dilution with the cleaner water from Paparua Stream.

Potential sources of those contaminants showing noticeable differences between sites are discussed in the following sections.

4.3.1 Ammoniacal-N

Elevated concentrations of ammoniacal-N were measured in the catchment (see Fig.47), particularly at HAS-GCP, under both wet and dry weather sampling, suggesting there is a source of ammoniacal-N upstream of this site. It appears that this source isintermittent, as an elevated concentration of 33 g m-3 was measured at HAS-GCP during dry weather sampling on the 20 March, but concentrations were much lower downstream. It is possible that a discharge containing ammonia into HAS-GCP had just commenced and had not reached the downstream sites at the time of sampling. Furthermore, concentrations rapidly decreased during a storm event, with 33 g m-3 initially measured at HAS-GCP on 24th July, decreasing to 0.29 g m-3 30 minutes later.

Haytons Stream Catchment Water Qua

0

50

100

150

200

Cop

per (

mg

kg-1

)

0

200

400

600

800

Lead

(mg

kg-1

)

ns an an an ial

ial

ial

an

0

400

800

1200

1600

2000

Zinc

(mg

kg-1

)

Figure 46 Copper, leasediments fr

Note: Heathfrom Robb (

) ) ) ) ) ) ) =1

2)

ayto

urb

urb

urb

dent erc

ustr

urb

(n=8 =2

4

(n=7

(n=5 =7

7

(n=5

(n=7

lity Investigation 73

25%-75% Non-Outlier Ran Outliers Extremes

H

Hea

thco

te -

Hal

swel

l -

Oke

over

-

Avo

n - r

esi

Avon

- co

mm

Avon

- in

d

Styx

-

ge

er da

d and zinc in sediments from Haytons Stream compared to that in om other streams in Christchurch.

cote and Halswell data from Kingett Mitchell (2005b); Avon Riv ta 1988) and Okeover Stream data from Blakely & Harding (2005).

(n (n (n

On one occasion ammoniacal-N concentrations were higher at HAS-SYR (57 g m ) and HAS-HTR (100 g m

-3

Ammonia from sewage would be expected to be associated with elevated BOD, phosphorus and solids. The elevated ammoniacal-N concentrations in the

During dry weather, ammoniacal-N can accumulate in stagnant water bodies such as

hin the sediment in the catchpit and in the overlying stormwater. Studies have shown that ammonium concentrations in catchpits can reach up to 20 g m-3 after 20-25 days (Memon & Butler

flushed into the stormwater system following a rain event. This

rainfall and may occur as part of a regular daily discharge (see Section 3.5.8).

-3) than at HAS-GCP (24 g m-3), suggesting an alternative source discharging to the stormwater network upstream of Symes Rd. Ravensdown Fertiliser works, which is located upstream of HAS-SYR, has previously been suggested as a likely source of elevated ammonia in stormwater in Haytons Stream catchment (Brown et al 1996).

In addition to elevated concentrations measured in samples collected at HAS-GCP and HAS-SYR, ammoniacal-N was also elevated at PAS-HTR on one occasion, measuring 12 g m-3 during dry weather sampling. This suggests the presence of at least three sources of ammonia within the catchment.

Potential sources of ammonia in stormwater include degradation of organic matter containing nitrogen, inputs of sewage from overflows or leakage, flushing of catchpits where ammonia has been generated during dry weather, and illegal discharges or accidental spills of solutions containing ammonia (e.g., cleaning products or refrigerants).

catchment often coincided with elevated pH (see Fig. 48), sometimes elevated BOD and sometimes elevated suspended solids. Overall, the sampling data does not provide a clear picture of a single source of ammoniacal-N.

stormwater catchpits. Ammonia is generated from the biodegradation of organic matter containing nitrogen, such as plant debris. Within stormwater catchpits, this can occur from the biodegradation of nitrogen compounds found wit

2002), and this can be may be the cause of some of the elevated measurements.

The elevated pH values coinciding with the elevated ammoniacal-N concentrations suggest a discharge of ammonia solution, rather than the degradation of organic matter containing nitrogen. In addition, the data obtained during the period of sonde deployment suggests strongly that at least some of the contamination of the stream is unrelated to



Figure 47 Ammoniacal-N conceat this plot scale).

ntrations in Ha nt (note ations a R and H clearly ytons Stream catchme : low concentr t PAS-CA ER-UHD can not be seen


6.0

6.5

7.0

7.5

8.0

8.5

9.0

9.5

Dry

Wet Dr

Wet

3 J

Wet

3 J

Wet

3 J

Dry

Wet

24

J

Wet

24

J

Wet

24

J

Dry

Wet Dr

Wet

3 J

Wet

3 J

Wet

3 J

Dry

Wet

24

J

Wet

24

J

Wet

24

J

Dry

Wet Dr

Dry 2

0 M

29

A

y 4

Ju

ul #

1

ul #

2

ul #

3

22

J

ul #

1

ul #

2

ul #

3

20

M

29

A

y 4

Ju

ul #

1

ul #

2

ul #

3

22

Jul

ul #

1

ul #

2

ul #

3

20

Mar

29

Apr

y 4

Jun

22

Jular pr n ul ar pr n

HAS-GCP HAS-HTR HAS-SYR

pH

0

120

140

Am

mon

iaca

l-N (g

m -3

)

Ammoniacal-N

20

40

60

80

100

pH

Figure 48

4

Fertiliser works in Hornby is a possible source of this since fertiliser production involves the

a continuous discharge, such as from a vehicle wash, as well as from stormwater. Whilst release from sediments in the stormwater system is also a plausible

Relationship of pH and ammoniacal-N at sites in Haytons Stream.

.3.2 DRP

Comparison of DRP concentrations between sites indicates substantially higher concentrations at HAS-SYR than at HAS-GCP (Fig. 49). The Ravensdown

processing and storage of phosphate rock. The phosphate rock is stored inside under normal conditions, but excess rock may be stored outside when required (Cowie, 2003). Furthermore, dust containing phosphate can be released during processing and from vehicle movements through the site. These processes could all contribute to elevated concentrations of phosphorus in stormwater discharges from the site.

DRP concentrations were elevated during both dry and wet weather sampling, suggesting

source, there was no sediment at HAS-SYR and it is unlikely that sediment accumulates upstream within the piped stormwater system.


Figure 49 DRP concentrations in Haytons Stream catchment.

4.3.3 NOx-N

NOx-N concentrations in spring-fed rivers in Christchurch typically contain elevated NOx-N, due to its elevated concentration in shallow groundwater. NOx-N concentrations at most sites were within the range observed in the Heathcote and Avon Rivers or lower, with concentrations more elevated at HAS-SYR and HAS-HTR (Fig. 50). Two potential sources of the additional NOx-N are oxidation of ammoniacal-N in the stream, or a nitrogen-containing discharge into the stream upstream of this site. The former seems less likely, as NOx-N concentrations were elevated at all times at this site, while elevated ammoniacal-N concentrations were intermittent. The elevated concentrations during dry weather suggest a continuous discharge. During wet weather, NOx-N was typically lower, suggesting dilution from stormwater. Discharges from industries, such as the production of nitrogen-containing fertilisers, are a possible source of the additional NOx-N downstream of Symes Road.

4

Fluoride was at background concentrations upstream and in Paparua Stream but was elevated in stormwater samples collected at HAS-SYR and downstream. A potential source of fluoride is the Ravensdown Fertiliser works in Hornby. The site processes phosphate rock, as described above and this process releases fluoride. Sampling of stormwater from the Ravensdown Site (CCC 2001, unpublished data) showed elevated fluoride in the stormwater. In addition, fluoride can be released into the atmosphere during processing. This could enter the stormwater system directly through dissolution into rainwater (wet deposition), or indirectly through depositing onto impervious surfaces (dry deposition) and then dissolving into runoff passing over this surface.

4.3.5 Metals

The residential land use in the upper Paparua Stream appears to contribute to concentrations of copper, lead and zinc during storm events, as may be expected fromroad runoff. However, as there was only a single sample collected upstream of the residential area it is difficult to compare. Metal concentrations were highest

downstream of major roads, including Blenheim Road and Main South Road, which are likely to contribute to copper and zinc concentrations, through wear of brake pads (copper) and tyres (zinc). Road runoff typically generates zinc and copper at a ratio of between 2:1 and 6:1 (zinc:copper; Moores et al. 2009; Timperley et al. 2005).

.3.4 Fluoride

downstream of the industrial land use indicating industrial land use is the major source of metals into Haytons Stream (see Fig. 51 for total zinc). These sites are also



Figure 50 NOx-N concentrations in Hayt catchment. ons Stream


Figure 51 Total zinc concentrations in Hay catchtons Stream ment.


the zinc to copper ratios were generally between 10:1 and 70:1, well road runoff alone and suggesting additional sources of zinc

rce is likely to be roofing. Timperley et al (2005) reported that 82% of zinc in an industrial catchment was from roof runoff, with the j of Haytons Stream catchment shows large areas of roofing within the industrial areas, and mo roofing as a major source is supported by the high proportion of zinc that was in the diss veof the toand 81% for galvanised iron (Kingett Mitchell, Diffuse Sources 2003).

during dry weather may be discharges from metal treatment industries, dissolution of

ent, and the most likely source of copper is road runoff.

4.3.6 TSS

ue at HAS-GCP was associated with the pollution incident on 22 July and thought to be due to washing of

Effectiveness of Wigram Retention Basin

On the two occasions (one dry, one wet) when sampling was conducted both immediately upstream and downstream of the retention pond, there was a reduction in TSS, total metals and ammoniacal-N concentrations. There was a slight reduction in

In this study,above those expected frominto the catchment. The major additional sou

ma ority of that from unpainted galvanised iron roofing. An aerial photograph

Zinc concentrations were also elevated during dry weather sampling. Potential sources

zinc from contaminated sediment, or dissolution of zinc from galvanised iron structures in the stream or stormwater system. These have not been further identified at this stage.

Copper concentrations were elevated and frequently exceeded the PNRRP standard for urban streams in Haytons Stream catchment. Comparison of concentrations between sites did not suggest any point sources of copper within the catchm

Other metals and metalloids (arsenic, cadmium, chromium, lead and nickel) were generally below guidelines to protect aquatic ecosystems and were not elevated above that expected for urban streams and stormwater.

TSS was elevated at several sites within the catchment, predominantly during wet weather. This is expected due to the wash-off of diffuse sources of dust and debris into the stormwater system. There were high values during dry weather sampling on separate occasions at HAS-GCP and HAS-SYR. The elevated val

paint into the stormwater system. There was no obvious source for the elevated TSS at HAS-SYR.

ol d, rather than particulate, form. In Haytons Stream samples, a median of 75% tal zinc was in dissolved form. This compares with around 40% for roading

unpainted

st of these roofs appear to be unpainted galvanised iron. Galvanised iron

cBOD5 (both dates) and in DRP (20th March only). Conversely, NOx-N concentrations were higher in the output from the pond than in the input.

Further sampling during Stage 2 wet weather events indicate that the Wigram Retention Basin is effective in reducing peak concentrations of TSS and contaminants associated with solids (i.e., particulate metals). Total suspended solids, total copper, lead and zinc concentrations were all lower downstream of the retention basin than at upstream sites on Haytons Stream and Paparua Stream. The results also suggest that the basin may reduce total cadmium, chromium and nickel; however the data for these parameters is limited.

Dissolved metals, particularly copper and lead, showed little decrease in concentration downstream of the retention pond. The results do suggest some removal of dissolved zinc in the retention pond, possibly due to sorption onto sediments, which are then removed through deposition.

Some parameters that were at very high concentration in Haytons Stream (e.g., ammoniacal-N and DRP) were much lower in Paparua Stream. The flow from Paparua Stream would have decreased the overall concentration entering the retention basin, but without flow data to calculate loads, the extent of dilution cannot be assessed, making it difficult to assess whether the pond is reducing the concentrations.

Importantly, the retention basin appears to export higher concentrations of NOx-N than enter it. It is likely that this is due to the microbiologically mediated oxidation of ammoniacal-N to nitrite-N and nitrate-N, as there appears to be a decrease in ammoniacal-N. However some of the decrease in ammoniacal-N could be due to uptake by plants and algae in the pond, or due to volatilisation. It is possible that there is a source of NOx-N within the pond, or its immediate catchment, including the rural land surrounding it.

4.4 Effects on Heathcote/Opawaho River

Poor water quality in Haytons Stream may affect the Heathcote River downstream of the confluence. The water quality at the most downstream site on Haytons Stream (HAS-DWB), and in the Heathcote River upstream and downstream of the confluence are compared in Figs. 52 to 55. These figures suggest that Haytons Stream increases the concentrations of ammoniacal-N, DRP, cBOD5, total lead, total zinc and total nickel with regularly higher concentrations of these parameters downstream of the confluence. On some occasions, total copper (Fig. 54), total arsenic and total chromium (Fig. 55) were also higher downstream. In contrast, NOx-N concentrations were lower downstream than upstream in six out of ten samples. This is not unexpected, as the upper reaches of the Heathcote River is spring-fed and nitrate-N


concentrations are known to be elevated in the groundwater of the area (CCC 1999; Hanson 2002).

The effect of Haytons Stream on the Heathcote River was also assessed by comparing upstream and downstream water quality using a paired t-test on log-transformed data. This was undertaken for all parameters that were analysed at least three times and included data from both wet and dry weather sampling. The results for dissolved

The most apparent effect on the Heathcote River is for ammoniacal-N (Fig. 52).

ct from the Heathcote River. Dilution was most effective during the dry weather sampling (4 June, 22 July) when ammoniacal-N concentrations decreased from 0.90-0.93 at the outlet to 0.19 g m-3 downstream. This is probably due

lume of water discharged from Haytons Stream at that time.

arsenic, cadmium, chromium, nickel and total cadmium could not be compared statistically due to the large number of results that were below the detection limits. The comparison (Table 14) showed significantly higher concentrations of TSS, ammoniacal-N, DRP, cBOD5, dissolved and total zinc, and total nickel and lead, downstream of Haytons Stream confluence.

Concentrations of ammoniacal-N in the outlet from Wigram Retention Basin were substantially higher than those upstream in the Heathcote River, on all but one occasion (dry weather sampling, 20 March). The mean upstream concentration was 0.032 g m-3, compared to 0.82 g m-3 downstream. Downstream concentrations (mean 0.41 g m-3) were generally slightly lower than Haytons Stream concentrations, indicating a diluting effe

to the lower vo

DRP concentrations were consistently higher downstream of the confluence with Haytons Stream than upstream, with the exception of dry weather sampling on the 20 March (Fig. 52). During dry weather, DRP concentrations were much lower in the Heathcote River than in Haytons Stream, indicating dilution from upstream river water. During wet weather there was little difference in concentrations between HAS-DWB and HER-DHD suggesting that the flow from Haytons Stream contributes a much more significant proportion of the total flow in the Heathcote River during wet weather.

Both cBOD5 and zinc concentrations showed a similar trend to both ammoniacal-N and DRP, being higher downstream of Haytons Stream confluence than upstream. Total nickel concentrations demonstrated the same trend, and though there was limited data from the Wigram Retention Basin outlet, this suggested the same trend as the other parameters described above.


0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

Dry: 20 Mar

Dry:4 Jun

Dry:22 Jul

Wet: 29 Apr

Wet:3 Jul #1

Wet:3 Jul #2

Wet:3 Jul #3

Wet:24 Jul #1

Wet:24 Jul #2

Wet:24 Jul #3

Amm

onia

cal-N

(g m

-3 )

HAS-DWBHER-UHDHER-DHD

0.0

1.0

2.0

3.0

4.0

5.0

6.0

Dry: 20 Mar

Dry:4 Jun

Dry:22 Jul

Wet: 29 Apr

Wet:3 Jul #1

Wet:3 Jul #2

Wet:3 Jul #3

Wet:24 Jul #1

Wet:24 Jul #2

Wet:24 Jul #3

NO

x-N

(g m

-3 )


0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

Dry: 20 Mar

Dry:4 Jun

Dry:22 Jul

Wet: 29 Apr

Wet:3 Jul #1

Wet:3 Jul #2

Wet:3 Jul #3

Wet:24 Jul #1

Wet:24 Jul #2

Wet:24 Jul #3

DR

P (g

m-3

)


Figure 52 Total ammoniacal-N, NOx-N and DRP concentrations at the outlet of the Wigram Retention Basin (HAS-DWB), and in the Heathcote River upstream (HER-UHD) and downstream (HER-DHD) of Haytons Stream confluence.


0

10

20

30

40

50

60

70

80

90

Dry: Dry: Dry: Wet: Wet: Wet: Wet: Wet: Wet: Wet:

TSS

(g m

-3 )

20 Mar 4 Jun 22 Jul 29 Apr 3 Jul #1 3 Jul #2 3 Jul #3 24 Jul #1 24 Jul #2 24 Jul #3


0

1

2

3

4

5

6

7

8

cBO

D5 (

g m

-3 )


Dry: 20 Mar

Dry:4 Jun

Dry:22 Jul

Wet: 29 Apr

Wet:3 Jul #1

Wet:3 Jul #2

Wet:3 Jul #3

Wet:24 Jul #1

Wet:24 Jul #2

Wet:24 Jul #3

1

10

100

1000

10000

100000

Dry: Mar

Dry:4 Jun

Dry:22 Jul

Wet: 29 Apr

Wet: Wet: Wet: Wet: Wet: Wet:

20 3 Jul #1 3 Jul #2 3 Jul #3 24 Jul #1 24 Jul #2 24 Jul #3

E. c

oli (

cfu

100

mL-1

)


Figure 53 TSS, cBOD5 and E. coli concentrations at the outlet of the Wigram Retention Basin (HAS-DWB), and in the Heathcote River upstream (HER-UHD) and downstream (HER-DHD) of Haytons Stream confluence.


0

0.001

0.002

Tot

0.003

0.005

al c

opp

-3 )

0.004er

(g m

0.006

0.007

Dry: 20 Mar

Dry:4 Jun

Dry:22 Jul

Wet: 29 Apr

Wet:3 Jul #1

Wet:3 Jul #2

Wet:3 Jul #3

Wet:24 Jul #1

Wet:24 Jul #2

Wet:24 Jul #3


0.000

0.002

Dry: 20 Mar

0.004

tal l

e

0.006

0.010

Dry:4 Jun

Dry:22 Jul

Wet: 29 Apr

Wet:3 Jul #1

Wet:3 Jul #2

Wet:3 Jul #3

Wet:24 Jul #1

Wet:24 Jul #2

Wet:24 Jul #3

Toad

(g m

-3 ) 0.008

0.012HAS-DWBHER-UHDHER-DHD

0.00

0.05

0.10

0.15

(g m

-3

0.20

Dry: 20 Mar

Dry:4 Jun

Dry:22 Jul

Wet: 29 Apr

Wet:3 Jul #1

Wet:3 Jul #2

Wet:3 Jul #3

Wet:24 Jul #1

Wet:24 Jul #2

Wet:24 Jul #3

Tota

l zin

c )

0.25

0.30HAS-DWB

HER-UHD

HER-DHD

Figure 54 To(H hcote River upstream (HER-UHD) and downstream (H confluence.

tal copper, lead and zinc concentrations at the outlet of the Wigram Retention Basin AS-DWB), and in the HeatER-DHD) of Haytons Stream


0.0000

0.0005

0.0010

0.0025

Dry: 20 Mar

Wet: 29 Apr

Wet:3 Jul #1

Wet:3 Jul #2

Wet:3 Jul #3

Wet:24 Jul #1

Wet:24 Jul #2

Wet:24 Jul #3

Tota

l ars

enic

-3 )

0.0015

0.0020 (g m

0.0030


0.0000

0.0005

0.0010

0.0015ium

(g 0.0020

Dry: 20 Mar

Wet: 29 Apr

Wet:3 Jul #1

Wet:3 Jul #2

Wet:3 Jul #3

Wet:24 Jul #1

Wet:24 Jul #2

Wet:24 Jul #3

Tota

l chr

omm

-3 )

0.0025


0.0000

0.0004

0.0008

0.0012

0.0016

0.0020

Dry: 20 Mar

Wet: 29 Apr

Wet:3 Jul #1

Wet:3 Jul #2

Wet:3 Jul #3

Wet:24 Jul #1

Wet:24 Jul #2

Wet:24 Jul #3

Tota

l nic

kel (

g m

-3 )

HAS-DWBHER-UHD

HER-DHD

Figure 55 Total arsenic, chromium and nickel concentrations at the outlet of the Wigram Retention Basin (HAS-DWB), and in the Heathcote River upstream (HER-UHD) and downstream (HER-DHD) of Haytons Stream confluence.


Table 14 Comparison of water quality in the Heathcote River upstream and downstream of the

meter Mean Upstream a

Mean Downstream

Mean Difference b

P-value c

confluence with Haytons Stream.

Para

TSS 12 11 0 0.020

Ammoniacal-N 0.032 0.41 0.38 0.0002

NOx-N (nitrate-N + nitrite-N)

2.7 2.5 -0.2 0.273

DRP 0.057 0.166 0.110 0.020

cBOD5 1.6 2.6 1.0 0.047

Faecal coliforms 1600 2300 570 0.228

dCu 0.0013 0.0015 0.0002 0.071

dPb 0.00024 0.00022 -0.00002 0.461

dZn 0.033 0.090 0.057 0.0007

tCu 0.0023 0.0023 0.000003 0.385

tPb 0.0019 0.0023 0.0004 0.007

0.079 0.003

Total arsenic 0.0011 0.0016 0.0004 0.015

Total chromium 0.0008 0.0009 0.0001 0.099

Total nickel 0.0005 0.0008 0.0003 0.004

tZn 0.032 0.110

Notes a Including dry and wet event data. b Mean of individual differences for each (downstream minus upstream). A negative value indicates

higher values upstream. c One-tailed paired t-test on log-transformed data, null hypothesis downstream > upstream.

vel of 0.05 (95% confidence).

d Bold value indicates statistical significance at alpha le


5. Conclusions

The aims of the project were to investigate:

• the extent of contamination of the water and sediments of Haytons Stream;

• the location of primary contaminant sources during dry and wet weather; and

• the effects on the water and sediment quality of the Heathcote/Opawaho River.

Fig. 56 provides an overview of the key findings of the study in relation to these aims.

The results of sampling indicate that water quality in Haytons Stream is generally etter in the upper Paparua Stream than in reaches downstream of residential and

lly poorest at sites on Haytons Stream located at Gerald Connolly Place (HAS-GCP) and Symes Road (HAS-SYR), both of

hich lie downstream of areas of industrial activity in the central part of the catchment. Sampling at these sites showed extremely elevated ammoniacal-N on some

mpling.

hile the data suggests there may be more than one source of ammoniacal-N within e catchment, on a number of occasions the contamination of the stream coincided

with a regular daily cycle of rising and falling stream water levels that was unrelated to rainfall. This cycle appears to cease at weekends, indicating a probable link to a routine discharge to the stream. DRP concentrations were also elevated at the Symes Road sampling site, and this may relate to the production of fertiliser upstream of this site.

On one occasion, sampling at HAS-GCP coincided with the presence of an unidentified white substance in the stream, providing clear evidence of the occurrence of a dry weather discharge to the stream.

However, concentrations of several contaminants were higher during wet weather than dry weather sampling, confirming that the discharge of stormwater is another mechanism by which contamination of the stream occurs. These contaminants included TSS, total metals (which includes particulate forms) and indicator bacteria.

bindustrial land use. Water quality was genera

w

occasions (up to 100 g m-3), including during dry weather sa

Wth



Figure 56 Map of Haytons Stream catchment summarising key features of stream water quality characteristics

Least impacted water quality: low conc

Poore ater quality: for ins e conce tions of ammoniacal-N well in excess of water quality guidelineshigh concentrations of cBOD and presence of PAHs.

entration contaminants.

s of

st wntra

tanc

,

Elevat oncentrations of zinc, in ing in stream sedime The extensive areas o lvanised iron roofs i mid- and lower catchm are likely to be the pre inant sources.

ed ccludnts.f ga

n theentdom

Elevated concentrations of DRP (well in excess of water quality guidelines), downstream of fertiliser plant Wigram retention basin:

reduces concentrations of some contaminants; e.g. TSS, total metals, ammoniacal-N BUT concentrations of NOx-N increase

Paparua Stream

Haytons Stream

Improved water quality due to dilution by ‘cleaner’Paparua Stream water: e.g. lower concentrations of ammoniacal-N and DRP than in upper reaches of Haytons Stream

S pling detected a pol n i ent 22/7/09: the str c ned a white subst e with

ted concentrations SS, a oniacal-N & cBOD

lutioeamanc of T.

Impacts on Heathcote River: increased concentrations of ammoniacal-N, DRP, BOD and some metals downstream of Haytons Stream confluence

Industry

Industry

Reside l

Residential

ntia

amncidontai

elevamm

Zinc concentrations increased from upstream to downstream through the catchment and were elevated during both dry and wet weather sampling. Zinc concentrations in sediment were higher in Haytons Stream catchment than in other locations around Christchurch. The high proportion of dissolved zinc compared to particulate zinc suggests that the primary source of zinc in the catchment is runoff from zinc-coated roofs.

For some parameters (ammoniacal-N, DRP, TSS and total metals), there was an improvement in water quality downstream of the confluence with Paparua Stream and downstream of the Wigram Retention Basin. However, the Wigram retention basin exported higher concentrations of NOx-N than entered it. It is likely that this is due to the microbiologically mediated oxidation of ammoniacal-N to nitrite-N and nitrate-N, as there appeared to be a corresponding decrease in ammoniacal-N.

Despite dilution by Paparua Stream and the removal of contaminants by th Wigram Retention Basin, concentrations of ammoniacal-N, DRP, BOD and some metals

oncern ith respect to toxicity in aquatic biota. During dry weather, dilution in the Heathcote iver reduces the likelihood of potential effects, however during wet weather, dilution tes appear to be lower.

6. Recommendations

he presence of dry weather discharges into Haytons Stream from the Ravensdown ertiliser Works should be investigated. If discharges are identified, these should be

stopped, or treatment incorporated to reduce the impact on DRP, NOx-N and ammoniacal-N concentrations in downstream waterways. The apparent daily discharge to Haytons Stream and potential sources of ammoniacal-N upstream of Gerald Connolly Place should be further investigated; however, as these sources appear to be intermittent, they may be difficult to isolate, and education of occupants within the industrial area may provide a better long-term solution.

Further investigation of the zinc source should be undertaken as zinc concentrations in water and sediment were higher than other locations in Christchurch. Such an investigation could include an assessment of the area and proportion of zinc-coated roofing within the catchment and then a prediction of zinc from roof runoff, for comparison to other locations (e.g., industrial catchments in Auckland).

7. Acknowledgements

The authors would like to thank staff from Environment Canterbury and Christchurch City Council for their input into site selection. Paul Dickson of Christchurch City

e

remained elevated at the outlet of Haytons Stream catchment and at levels of cwRra

TF


Council is gratefully acknowledged forWigram Retention Basin. L

supplying and operating the autosampler at the andcare Research provided two of the Mannings

autosamplers, which were made available by Christchurch City Council.


8. References

& ARMCANZ. (2000). Australian and New Zealand Guidelines for Fresh and Marine Water Quality, Volume 1, The Guidelines. Canberra: Australian and

land Environ lture and Resource uncil

Co ciation sis. In Trace Ele y,

G. ed.), pp. 1–24. CRC Press Inc. Florida.

Blakely, T.; Harding, J. (2005). Longitudinal patterns in benthic communities in an tream under r hwater

earch 39: 17-28.

, S., Mason, P. an the Wigram Retention Ba C60510, prepared for

Co

quality data 1995-97, water quality trends 1986-97. Christchurch City Council Waste Management Unit Laboratory, Christchurch. April 1999.

Cowie, B. (2003). Decision of the Hearing Commissioners on Application CRC080001 by Ravensdown Fertiliser Cooperative Limited to discharge contaminants to air from a fertiliser works on Main South Road, Hornby, Christchurch. Environment Canterbury Regional Council.

Environment Canterbury, (2004). Variation 1, Proposed Natural Resources Regional Plan - Chapter 4: Water quality. Environment Canterbury Report No. R04/15/4. Environment Canterbury Regional Council, Christchurch.

Environment Canterbury, (2008). Consultants Brief: Investigation on Water and Sediment Contamination of Haytons Stream and Effects on Heathcote River.

Golder Kingett Mitchell (2007). Water quality assessment. South-West Christchurch Integrated Catchment Management Plan Technical Series Report No. 5. December 2007. 94 p + appendices.

ANZECC

New Zea ment and Conservation Council & AgricuManagement Co of Australia and New Zealand.

Batley, G. (1989). analy

llection, preparation and storage of samples for spement Speciation: Analytical Methods and Problems (Batle

urban s estoration. New Zealand Journal of Marine and FresRes

Brown d Snelder, T. (1996). Runoff quality in the catchment of sin. NIWA Consultancy Report No. CC

Christchurch City uncil.

Christchurch City Council, (1999). Christchurch City surface water



Hanson, C. (2002). Nitrate concentrations in Canter groundwater – a review of existing data. Report No. R02/17. Environment C bury, Christchurch. August 2002.

Kingett Mitchell (2005a). Pilot Study Stage One. South-West Christchurch Integrated Catchment Management Plan Technical Series Report No. 1. Jul 005. 127 p.

Kingett Mitchell (2005b). Sediment quality rv Sout t C urch Integrated Catch t Management Plan Tech al S es Re 2 2005. 86 p.

Kingett Mitchell, Diffuse Sources (2003). A stud f r runof ty in Auckland, Zealand: implications for stormwater management. Auckland Regional ncil Technical Publication No. 213. November 2003.

Liess, M. and Schulz, R. ( ) m n eth in r t Iater Analysis (Nollet, N. ed.), pp 1-24. CRC Press Inc: New York.

M , F.A; But . (2002) I odelling lly pots. Water Research 36(5): 1351-1359.

Meredith, A.; Hay S. ew of the water quality of th s and ms of the nterbury Region. Report No. R02/05. Environment Canterbury, stchurch.

Moores, J. (2009). Sampling road runoff to estimate loads of copper and zinc. WA 6th So Pacific NZWWA Stormwater Conference Auckland, April 29 ay 2009.

MfE / MoH, (2003). Microbiological water quality guidelines for marine and hwater Recr o e i for the i rlth, Wellingto 0 p.

NIWA, (2008) Investigation of water and sediment contami o f ream. ing information – with additions. C fide l p o d m ed to ironment Canterbury Decem .

NIWA, (2009). Stormw d w r quality i n e and ank S W e Re t L fro r. Octo

bury anter

y 2

est No.

uali

sunic

y o

ey. eri

oof

h-Wpor

f q

hri. Ju

stchly men

NewCou

of W

emonin gu

streaChri

NZW- 1 M

FresHea

PricEnv

MeaMet

2000 . Sa pli g M ods Su face Wa ers. n Handbook

ler, D dentification and m of dry weather processes

ward, Ca

(2002). An overvi e river

uth

eatin. 15

nal Ar

as. Min stry Env ronment and Minist y of

natisal

n oocu

Hayent

tonssub

Stmitton

2008ntia rop

18 ber

aterm. 200

anNI

9.

streA

am Cli

atent

monAK

tori200

g: B9-05

owd2 p

n Rrepa

oadred

d or owb

watetreaber

por


Pattle Delamore Partners Ltd (PDP), (2007). Avon/Otakaro and Heathcote/OpawahoRiv nalysis of water qualit 1 pr a for Environment Canterbury.

Robb, J. (1988). Heavy metals in r and estuaries of oli Chris and outlying areas. report prepared f aLaborator

Richardson, J. (1997). Acute ammonia toxicity for eight New Zealand indigenous freshwater species. New Zealand Journal of Marine and Freshwater Re28(2): 3 07.

Timperley .; Bailey G.; Pattinson P.; Kuschel G. (2003). Zinc, copper and lead in roa ff. Stormwater flow and quality monitoring: Central Business District (Aotea Square), Onehung 417 p.

Timperley loads of metals in urban stormw er. Auckland Regional Council Technical Publication No. ARC04104, Auckland, June 2005. 64 p + appendices.

d runo

ers: A

99-4

M

, M.; Williamson, B.; Mills, G.;

y Division, Chris A

a, Mission Bay. NIWA Client Report No AK02060

tchurch. March 1988.

the rive metrop

y data from 992-2006. Report U07/42 ep red

tan ge Board by

tchu

search

rch the or the Christchurch Drain

Horne, B.; Hasan, M. (2005). Sources andat

.

Haytons Stream Catch

Appendix 1 - Photographs of Sampling Locations

ment Water Quality Investigation 96

Figure A2 e men Rd (PA

Figure A1 Paparua Stream at Buchanans Rd (PAS-BUR)

Paparua Str am at Car S-CAR)

Haytons Stream Catch

Figure A3

ment Water Quality Investigation 97

Paparua Str

Figure A4 Paparua Stream at Hayton Rd (PAS-HTR)

eam at Racecourse Rd (PAS-RAR)


Figure A5 Haytons Stream

at Gerald Connolly Place (HAS-GCP)

Figure A6 Manhole cover indicating location of tributary of Haytons Stream at Symes Rd (HAS-SYR)


Figure A7 Haytons Stream at Hayton Rd (HAS-HTR)

Figure A8 upstream of Wigram Retention Basin (HAS-UWB) Haytons Stream

Haytons Stream

Figure A9

Catchment Water Quality Investigation 100

Haytons Stream downstream of Wigram Retention Basin (HAS-DWB)

luence (HER-UHD) Figure A10 Heathcote River upstream of Haytons Stream conf

Haytons Strea

Figure A11

m Catchment Water Quality Investigation 101

Heathcote River downstream of Haytons Stream confluence (HER-DHD)

Haytons Strea

Appendix 2 – Analytical Methods


Water Samples

Analysis Method

Total digestion Boiling nitric acid digestion. APHA 3030 E 21st ed. 2005.

TSS Filtration (GF/C, 1.2 µm), Gravimetric. APHA 254 D 21st ed. 2005.

Total ammoniacal nitrogen (NH4-N)

Filtered sample. Pheno/hypochlorite colorimetry. Discrete Analyser. (NH4-N = NH4-N + NH3-N). APHA 4500-NH3 F (modified from manual analysis) 21st ed. 2005.

Nitrate-nitrite nitrogen (NOx-N)

Total oxidised nitrogen. Automated cadmium reduction, flow injection analyser. APHA 4500-NO3- I (Proposed) 21st ed. 2005.

Dissolved reactive phosphorus (DRP)

Filtered sample. Molybdenum blue colorimetry. Discrete Analyser. APHA 4500-P E (modified from manual analysis) 21st ed. 2005.

Carbonaceous Biochemical oxygen demand (cBOD5)

Incubation 5 days, DO meter, nitrification inhibitor added, dilutions, seeded. APHA 5210 B 21st ed. 2005.

E.Coli Membrane filtration, Count on mFC agar, Incubated at 44.5oC for 22 hours. APHA 9222 D, 21st ed. 2005.

Faecal colliforms Membrane filtration, Count on mFC agar, Incubated at 44.5oC for 22 hours. APHA 9222 D, 21st ed. 2005.

Dissolved Zn, Cu, Pb, Cd, Ni, As, Cr

0.45 µm filtration, ICP-MS.

Total Zn, Cu, Pb, Cd, Ni, As, Cr

Nitric acid digestion, ICP-MS.

PAHs Solid phase extraction, SPE (if required) GC-MS SIM analysis. US EPA 8270C.

TPHs Solvent extraction, GC-FID analysis. US EPA 8015B/MfE Petroleum Industry Guidelines.

pH APHA 4500-Hill Laboratories+ B

Chloride Filtered sample. Ferric thiocyanate colorimetry. Discrete Analyser. APHA 4500-Cl- E (modified from continuous flow analysis)

Fluoride Ion selective electrode. APHA 4500-F- C (modified from manual analysis) 21st ed. 2005.

Total cyanide Distillation, colorimetry. APHA 4500-CN- C & E 21st ed. 2005.

Source: Hill Laboratories Environmental Catalogue, Version 6.0, July 2009.

Haytons Strea


Sediment Samples

Analysis Method

Preparation Air dried at 35oC and sieved, < 2mm fraction.

Ammonium (NH4-N) Potassium chloride extraction, Phenol/hypochorite colorimetry. Discrete Analyser. APHA 4500-NH3 G 21st ed. 2005.

Nitrate-nitrite nitrogen (NOx-N)

Automated cadmium reduction, FIA determination of es 2M potassium chloride extraction. APHA 4500-NO3

- I (proposed) 21st ed. 2005.

Total Recoverable phosphorus (TRP)

US EPA 200.2 digestion ICP-MS.

Zn, Cu, Pb Nitric / hydrochloric acid digestion, ICP-MS. US EPA 200.2.

PAHs Sonication extraction, SPE cleanup, GC-MS SIM analysis. US EPA 8270C.

TPHs Sonication extraction, Silica cleanup, GC-FID analysis. US EPA 8015B/MfE Petroleum Industry Guidelines.

Total Organic Carbon Acid pretreatment to remove carbonates if present, Elementar Combustion Analyser.

Source: Hill Laboratories Environmental Catalogue, Version 6.0, July 2009.

Appendix 3 – Field Observations and in situ physico-chemical measurements

Stage 1

Site Date Time Weather pH Conductivity

(uS/cm) Temp (oC)

DO (%) Water Colour Clarity (cm) Odour

Presence of Foam/Sheen Comment

Dry weather

PAS-BUR 20/03/2009 10:05 Dry - 79.6 14 71.4 Clear 92 None None Pool; Substrate - fines dominant

PAS-CAR 20/03/2009 11:20 Dry - 78.3 14.8 97.6 Clear 79 None None Stream; Substrate - Pebbles, Gravels and fines

PAS-RAR 20/03/2009 13:15 Dry - 88.8 14.7 73.7 Cloudy - grey 37 None Oily sheen (two small patches only)

Pool; Substrate - small cobbles, gravels, silt, plant debris

PAS-HTR 20/03/2009 9:00 Dry - 81.3 16.3 75.6 Clear 57 None None Pool & riffle - Substrate - large and small cobbles, gravel & fines

HAS-GCP 20/03/2009 12:30 Dry - 255 15.6 57.6 Turbid - grey/green 33 None Oily sheen, no foam

Stream; Substrate - Large and small cobbles, pebbles, gravels and fines. Oily sheen worse when substrate disturbed

HAS-SYR 20/03/2009 7:30 Dry - 143.8 14.4 48.6 Clear & colourless Not assessed,

insufficient water None None seen from road level Stream; patchy gravels and concrete.

HAS-HTR 20/03/2009 9:30 Dry - 193 13.4 52.3 Clear 83 None None Pool; Substrate - Large and small cobbles, pebbles, gravels and fines.

HAS-UWB 20/03/2009 14:40 Dry - 146.6 18.1 22.3 Turbid - grey/green 8 None None Pool; Substrate - small cobbles, gravels, silt

HAS-DWB 20/03/2009 15:45 Dry - 134.3 16.9 63 Clear (with suspended particulate

sediment) 72 None None Pool; Substrate - Large and small cobbles, pebbles, gravels and fines.

HER-UHD 20/03/2009 16:30 Dry - 321 14.4 39.6 Slightly cloudy - green/yellow 87 None None Substrate - fine, silty sediment; ~0.5m deep.

HER-DHD 20/03/2009 16:00 Dry - 257 15.4 44.9 Slightly cloudy - green yellow 87 None None Substrate - silt & plant debris; ~0.5m deep

Wet weather

PAS-BUR 29/04/2009 18:41 Wet 8.19 66.3 11.9 84.9 Very Cloudy - yellow/grey Too dark to

assess None Too dark to see

PAS-CAR 29/04/2009 18:30 Wet 7.99 44.1 12.1 92.3 Cloudy - yellow/grey Too dark to


PAS-RAR 29/04/2009 18:15 Wet 6.47 39.1 12.2 85.6 Slightly cloudy - yellow/grey Too dark to


PAS-HTR 29/04/2009 16.28 Wet 7.01 35.9 11.1 106.2 Moderately cloudy - pale grey 11.5 None None

HAS-GCP 29/04/2009 18:00 Wet 7.99 50.4 12.6 88.2 Slightly cloudy - pale grey Too dark to see Strong petro-chemical smell Too dark to see Oily film obvious 30/04/09 09:30 hrs

HAS-SYR 29/04/2009 16:00 Wet 6.75 138.5 12.1 94.7 Slightly cloudy - pale grey 22.5 None None

HAS-HTR 29/04/2009 16.35 Wet 6.61 80.2 10.6 87.1 Mod. cloudy - pale grey 8 None None

HAS-UWB 29/04/2009 16:55 Wet 6.43 70.1 12.5 80.4 Slightly cloudy - grey/yellow/green

tinge 25 None None

HAS-DWB 29/04/2009 17:28 Wet 8.01 119.1 14.3 95.5 Clear & colourless 84 None None

HER-UHD 29/04/2009 17:43 Wet 5.96 168.6 12.4 52.2 Clear & colourless 63 None None

HER-DHD 29/04/2009 17:30 Wet 7.7 123.8 13.7 77.1 Clear & colourless 68 None None



Stage 2

Site Date Time Weather Run pH Conductivity

(uS/cm) Temp (oC) DO (%) Water Colour

Clarity (cm) Odour

Presence of Foam/Sheen Comment

Dry weather

PAS-BUR 4/06/2009 12:58 Dry_STG 2 Sediment

samples only

PAS-CAR 4/06/2009 13:12 Dry_STG 2 7.5 101.5 6.2 121.6 Slightly cloudy 43 None None Adjacent road-works almost completed

PAS-RAR 4/06/2009 12:30 Dry_STG 2 Sediment

samples only

PAS-HTR 4/06/2009 9:30 Dry_STG 2 7.18 238 4.1 106.9 Slightly cloudy 48 None None

HAS-GCP 4/06/2009 11:30 Dry_STG 2 7.48 146.4 4.5 96.3 Slight/moderate cloudy 29 None Oily patches on water surface. Oily sheen worse when substrate disturbed

HAS-SYR 4/06/2009 8:40 Dry_STG 2 7.41 134.4 4.3 109.8 Clear & colourless n/a None None

HAS-HTR 4/06/2009 9:15 Dry_STG 2 6.62 110.5 5.3 109.9 Slightly cloudy 23 None None

HAS-UWB 4/06/2009 14:00 Dry_STG 2 Sediment

samples only

HAS-DWB 4/06/2009 14:36 Dry_STG 2 6.92 150.9 10.1 105.8 Clear 52 None* None * Slight sulphur smell when taking sediment sample

HER-UHD 4/06/2009 15:40 Dry_STG 2 6.46 288 9.9 85.3 Clear & colourless 92 None None

HER-DHD 4/06/2009 15:06 Dry_STG 2 6.73 255 10.6 106.5 Clear & colourless 92 None None

Dry weather

PAS-CAR 22/07/2009 11:00 Dry_STG 2 6.48 104.5 5.6 65 Clear & colourless 65 None None No flow. Water levels began falling 2 days ago

PAS-HTR 22/07/2009 12:20 Dry_STG 2 7.35 111.2 6.2 69 Slightly cloudy 22 None Nil foam; sheen - small patches Low water level - slow flow.

HAS-GCP 22/07/2009 11:30 Dry_STG 2 7.91 277 5.9 32 Opaque - white, cloudy 2 None Nil foam; sheen - small patches

Also surface patches of white particulate material. Hotline called. Photo taken.

HAS-SYR 22/07/2009 10:40 Dry_STG 2 7.2 248 6.1 64 Clear & colourless n/a None None Low water level - difficult to obtain sample

HAS-HTR 22/07/2009 12:40 Dry_STG 2 8.24 893 5.9 52 Slightly cloudy

(white/grey) 24 None None

No sign of white plume from upstream. Conductivity measurement re-checked upstream.

HAS-DWB 22/07/2009 14:10 Dry_STG 2 7.22 178.8 8.7 60 Clear & colourless 22 None None

HER-UHD 22/07/2009 13:20 Dry_STG 2 6.78 285 12.9 38 Clear & colourless 100 None None

HER-DHD 22/07/2009 13:45 Dry_STG 2 6.77 259 11.7 56 Clear & colourless 64 None None

Cloudy plume through centre of river, with 1 m clear swathe of water at bank margin. Samples taken from plume area.

Additional visits:

HAS-GCP 22/07/2009 14:40 7.1 133.4 9.7 53 Cloudy 18 None Plume clearing

HAS-HTR 23/07/2009 16:00 Opaque - white, cloudy ?From yesterdays plume moving downstream?


Appendix 4 – Analytical Results

Water Sampling

Stage 1 Dry weather samples

Sample Name:

PAS-BUR 20-Mar-2009

PAS-CAR 20-Mar-2009

PAS-RAR 20-Mar-2009

PAS-HTR 20-Mar-2009

HAS-GCP 20-Mar-2009

HAS-SYR 20-Mar-2009

HAS-HTR 20-Mar-2009

HAS-UWB 20-Mar-2009

HAS-DWB 20-Mar-2009

HER-UHD 20-Mar-2009

HER-DHD 20-Mar-2009

Water Blank - unfiltered

20-Mar-2009

Water Blank - filtered

20-Mar-2009

Lab

Number: 685162.1 685162.2 685210.2 685162.3 685210.1 685162.5 685162.4 685270.4 685270.2 685270.1 685270.3 685270.5 685270.6

pH pH Units 7 7.5 7.9 7.3 8.6 7.1 7.1 6.9 7.3 6.9 6.7 - - Total Suspended Solids g m P

-3P < 3.0 < 3.0 13 4 25 40 < 3.0 48 6.2 3.2 11 - -

Total Cyanide g m P

-3P < 0.0010 < 0.0010 0.0012 < 0.0010 < 0.0010 < 0.0010 < 0.0010 < 0.0010 < 0.0010 < 0.0010 < 0.0010 - -

Chloride g m P

-3P 1.2 1.2 2.3 1.5 5 4.5 7.6 6.5 12 13 16 - -

Fluoride g m P

-3P 0.054 0.07 0.053 0.066 0.085 2.1 2.5 0.75 0.6 0.38 < 0.050 - -

Total Ammoniacal-N g m P

-3P < 0.010 0.012 0.033 0.066 33 0.46 2.6 0.91 0.039 0.034 0.011 - -

Nitrate-N + Nitrite-N g mP

-3P < 0.0020 0.018 0.058 0.12 0.77 3.1 1.6 0.19 0.64 2.2 4.7 - -

Dissolved Reactive Phosphorus g m P

-3P 0.0049 0.016 0.015 0.043 0.34 1.1 0.55 0.34 0.62 0.34 0.0048 - -

Carbonaceous Biochemical Oxygen Demand g.O2/m3 < 1.0 < 1.0 1.3 1.2 27 < 1.0 1.4 1.8 1.2 1.4 < 1.0 - - Faecal Coliforms and E. coli profile - -

Faecal Coliforms cfu /

100mL 180 800 #3 6,000 #3 1,600 #3 1,100 #3 500 #3 55 > 60,000 #4 1,100 #3 900 #3 > 6,000 #4 - -

Escherichia coli cfu /

100mL 180 800 #3 6,000 #3 1,600 #3 1,100 #3 500 #3 55 > 60,000 #4 1,100 #3 900 #3 > 6,000 #4 - - Heavy metals, dissolved Dissolved Arsenic g m P

-3P < 0.0010 < 0.0010 < 0.0010 < 0.0010 < 0.0010 < 0.0010 0.0031 0.0019 0.0025 < 0.0010 < 0.0010 - < 0.0010

Dissolved Cadmium g m P

-3P < 0.000050 < 0.000050 < 0.000050 < 0.000050 0.000059 0.00015 0.000061 < 0.000050 < 0.000050 < 0.000050 < 0.000050 - < 0.000050

Dissolved Chromium g m P

-3P < 0.00050 < 0.00050 < 0.00050 < 0.00050 < 0.00050 0.00088 < 0.00050 < 0.00050 < 0.00050 < 0.00050 < 0.00050 - < 0.00050

Dissolved Copper g m P

-3P < 0.00050 < 0.00050 0.00054 0.00076 0.0023 0.00089 0.002 0.0024 0.0050 #2 0.0037 #2 0.0011 #2 - < 0.00050

Dissolved Lead g m P

-3P < 0.00010 0.00013 0.00038 0.00073 0.001 < 0.00010 0.00083 0.0011 0.00078 0.00017 < 0.00010 - < 0.00010

Dissolved Nickel g m P

-3P < 0.00050 < 0.00050 < 0.00050 < 0.00050 < 0.00050 0.00079 0.0012 0.0021 #2 0.00063 < 0.00050 < 0.00050 - < 0.00050

Dissolved Zinc g m P

-3P 0.031 #1 0.014 #1 0.017 0.019 0.13 0.15 #2 0.20 #2 0.015 0.061 0.025 #1 0.019 #1 - 0.018

Heavy metals, totals Total Arsenic g m P

-3P < 0.0011 < 0.0011 < 0.0011 0.0013 < 0.0011 < 0.0011 0.0032 0.003 0.0031 < 0.0011 < 0.0011 < 0.0011 -

Total Cadmium g m P

-3P < 0.000053 < 0.000053 < 0.000053 < 0.000053 0.0001 0.00018 0.000069 0.00012 < 0.000053 < 0.000053 < 0.000053 < 0.000053 -

Total Chromium g m P

-3P < 0.00053 < 0.00053 < 0.00053 < 0.00053 0.0007 0.0013 < 0.00053 0.0024 0.00065 < 0.00053 < 0.00053 < 0.00053 -

Total Copper g m P

-3P < 0.00053 < 0.00053 0.0013 0.0011 0.0033 0.0048 0.0023 0.0046 0.0025 #2 0.0020 #2 < 0.00053 #2 < 0.00053 -

Total Lead g m P

-3P 0.00017 0.00041 0.0024 0.0018 0.0024 0.00069 0.0017 0.01 0.0018 0.00084 0.00087 < 0.00011 -

Total Nickel g m P

-3P < 0.00053 < 0.00053 < 0.00053 < 0.00053 0.00055 0.00085 0.0012 0.0015 #2 0.0011 < 0.00053 < 0.00053 < 0.00053 -

Total Zinc g m P

-3P < 0.0011 #1 0.0022 #1 0.015 0.02 0.18 0.14 #2 0.15 #2 0.13 0.064 0.015 #1 0.0041 #1 < 0.0011 -

Analyst's comments:

#1 It has been noted that the results for the dissolved fraction were greater than those for the total fraction, and outside the analytical variation of the method. These have been confirmed by re-analysis indicating that the samples may have been contaminated during field filtering.

#2 It has been noted that the results for the dissolved fraction were greater than those for the total fraction, but within analytical variation of the method.

#3 Statistically estimated count based on the theoretical countable range for the stated method.

#4 Statistically estimated count based on the theoretical countable range for the stated method. This sample was unable to be re-set up to obtain a count.


Stage 1 Dry weather samples (cont.) Sample Name:

PAS-BUR 20-Mar-2009

PAS-CAR 20-Mar-2009

PAS-RAR 20-Mar-2009

PAS-HTR 20-Mar-2009

HAS-GCP 20-Mar-2009

HAS-SYR 20-Mar-2009

HAS-HTR 20-Mar-2009

HAS-UWB 20-Mar-2009

HAS-DWB 20-Mar-2009

HER-UHD 20-Mar-2009

HER-DHD 20-Mar-2009

Lab Number: 685162.1 685162.2 685210.2 685162.3 685210.1 685162.5 685162.4 685270.4 685270.2 685270.1 685270.3 Polycyclic Aromatic Hydrocarbons Acenaphthene g m P

-3P < 0.000008 < 0.000008 < 0.000020 < 0.000008 < 0.000020 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008

Acenaphthylene g m P

-3P < 0.000008 < 0.000008 < 0.000020 < 0.000008 < 0.000020 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008

Anthracene g m P

-3P < 0.000008 < 0.000008 < 0.000020 < 0.000008 < 0.000020 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008

Benzo[a]anthracene g m P

-3P < 0.000008 < 0.000008 < 0.000020 < 0.000008 < 0.000020 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008

Benzo[a]pyrene (BAP) g mP

-3P < 0.000008 < 0.000008 < 0.000020 < 0.000008 < 0.000020 < 0.000008 < 0.000008 0.000014 < 0.000008 < 0.000008 < 0.000008

Benzo[b]fluoranthene + Benzo[j]fluoranthene g m P

-3P < 0.000008 < 0.000008 < 0.000020 < 0.000008 < 0.000020 < 0.000008 < 0.000008 0.000016 < 0.000008 < 0.000008 < 0.000008

Benzo[g,h,i]perylene g m P

-3P < 0.000008 < 0.000008 < 0.000020 < 0.000008 < 0.000020 < 0.000008 < 0.000008 0.000015 < 0.000008 < 0.000008 < 0.000008

Benzo[k]fluoranthene g m P

-3P < 0.000008 < 0.000008 < 0.000020 < 0.000008 < 0.000020 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008

Chrysene g m P

-3P < 0.000008 < 0.000008 < 0.000020 < 0.000008 < 0.000020 < 0.000008 < 0.000008 0.000009 < 0.000008 < 0.000008 < 0.000008

Dibenzo[a,h]anthracene g m P

-3P < 0.000008 < 0.000008 < 0.000020 < 0.000008 < 0.000020 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008

Fluoranthene g m P

-3P < 0.000008 < 0.000008 < 0.000020 < 0.000008 < 0.000020 < 0.000008 < 0.000008 0.000024 < 0.000008 < 0.000008 < 0.000008

Fluorene g m P

-3P < 0.000008 < 0.000008 < 0.000020 < 0.000008 < 0.000020 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008

Indeno(1,2,3-c,d)pyrene g m P

-3P < 0.000008 < 0.000008 < 0.000020 < 0.000008 < 0.000020 < 0.000008 < 0.000008 0.000011 < 0.000008 < 0.000008 < 0.000008

Naphthalene g m P

-3P 0.00004 < 0.000040 0.0001 < 0.000040 0.0001 < 0.000040 < 0.000040 < 0.000040 < 0.000040 < 0.000040 < 0.000040

Phenanthrene g m P

-3P < 0.000008 < 0.000008 < 0.000020 < 0.000008 < 0.000020 < 0.000008 < 0.000008 0.000011 < 0.000008 < 0.000008 < 0.000008

Pyrene g m P

-3P 0.000008 < 0.000008 0.00002 < 0.000008 0.00002 < 0.000008 < 0.000020 0.000019 < 0.000008 < 0.000008 < 0.000008

Total Petroleum Hydrocarbons C7 - C9 g mP

-3P < 0.10 < 0.10 < 0.10 < 0.10 < 0.10 < 0.10 < 0.10 < 0.10 < 0.10 < 0.10 < 0.10

C10 - C14 g m P

-3P < 0.20 < 0.20 < 0.20 < 0.20 < 0.20 < 0.20 < 0.20 < 0.20 < 0.20 < 0.20 < 0.20

C15 - C36 g m P

-3P < 0.40 < 0.40 < 0.40 < 0.40 < 0.40 < 0.40 < 0.40 < 0.40 < 0.40 < 0.40 < 0.40

Total hydrocarbons (C7 - C36) g mP

-3P < 0.70 < 0.70 < 0.70 < 0.70 < 0.70 < 0.70 < 0.70 < 0.70 < 0.70 < 0.70 < 0.70

BTEX Benzene g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

Toluene g m P

-3P < 0.010 < 0.010 < 0.010 < 0.010 < 0.010 < 0.010 < 0.010 < 0.010 < 0.010 < 0.010 < 0.010

Ethylbenzene g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

m&p-Xylene g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

o-Xylene g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

Halogenated Aliphatics Bromomethane g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

Carbon tetrachloride g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

Chloroethane g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

Chloromethane g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

1,2-DibromoP

-3P-chloropropane g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

1,2-Dibromoethane (ethylene dibromide) g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

Dibromomethane g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

Dichlorodifluoromethane g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

1,1-Dichloroethane g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

1,2-Dichloroethane g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

1,1-Dichloroethene g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

cis-1,2-Dichloroethene g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

trans-1,2-Dichloroethene g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

Dichloromethane (methylene chloride) g m P

-3P < 0.10 < 0.10 < 0.10 < 0.10 < 0.10 < 0.10 < 0.10 < 0.10 < 0.10 < 0.10 < 0.10

1,2-Dichloropropane g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050


-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050


-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

1,1-Dichloropropene g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050


Stage 1 Dry weather samples (cont.) Sample Name:

PAS-BUR 20-Mar-2009

PAS-CAR 20-Mar-2009

PAS-RAR 20-Mar-2009

PAS-HTR 20-Mar-2009

HAS-GCP 20-Mar-2009

HAS-SYR 20-Mar-2009

HAS-HTR 20-Mar-2009

HAS-UWB 20-Mar-2009

HAS-DWB 20-Mar-2009

HER-UHD 20-Mar-2009

HER-DHD 20-Mar-2009

Lab Number: 685162.1 685162.2 685210.2 685162.3 685210.1 685162.5 685162.4 685270.4 685270.2 685270.1 685270.3 Halogenated Aliphatics contd. cis-1,3-Dichloropropene g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

trans-1,3-Dichloropropene g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

Hexachlorobutadiene g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

1,1,1,2-Tetrachloroethane g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

1,1,2,2-Tetrachloroethane g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

Tetrachloroethene (tetrachloroethylene) g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

1,1,1-Trichloroethane g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

1,1,2-Trichloroethane g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

Trichloroethene (trichloroethylene) g mP

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

Trichlorofluoromethane g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

1,2,3-Trichloropropane g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

1,1,2-Trichlorotrifluoroethane (Freon 113) g m P

-3P < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050

Vinyl chloride g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

Haloaromatics Bromobenzene g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

Chlorobenzene (monochlorobenzene) g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

2-Chlorotoluene g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

4-Chlorotoluene g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

1,2-Dichlorobenzene g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050


-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050


-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

1,2,3-Trichlorobenzene g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

1,2,4-Trichlorobenzene g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

Monoaromatic Hydrocarbons n-Butylbenzene g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

tert-Butylbenzene g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

Isopropylbenzene (Cumene) g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

4-Isopropyltoluene (p-Cymene) g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

n-Propylbenzene g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

sec-Butylbenzene g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

Styrene g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

1,2,4-Trimethylbenzene g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

1,3,5-Trimethylbenzene g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

Ketones Acetone g m P

-3P < 0.50 < 0.50 < 0.50 < 0.50 < 0.50 < 0.50 < 0.50 < 0.50 < 0.50 < 0.50 < 0.50

2-Butanone (MEK) g m P

-3P < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050

Methyl tert-butylether (MTBE) g mP

-3P < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050

4-Methylpentan-2-one (MIBK) g m P

-3P < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050

Trihalomethanes Bromodichloromethane g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

Bromoform (tribromomethane) g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

Chloroform (trichloromethane) g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

Dibromochloromethane g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050

Other VOCs Carbon disulphide g m P

-3P < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050 < 0.050

Naphthalene g m P

-3P < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050


Stage 1 Wet weather samples

Sample Name:

PAS-BUR 29-Apr-2009

6:41 pm

PAS-CAR 29-Apr-2009

6:30 pm

PAS-RAR 29-Apr-2009

6:15 pm

PAS-HTR 29-Apr-2009

4:28 pm

HAS-GCP 29-Apr-2009

6:00 pm

HAS-SYR 29-Apr-2009

4:00 pm

HAS-HTR 29-Apr-2009

4:35 pm

HAS-UWB 29-Apr-2009

4:55 pm

HAS-DWB 29-Apr-2009

5:28 pm

HER-UHD 29-Apr-2009

5:43 pm

HER-DHD 29-Apr-2009

5:30 pm Blank

29-Apr-2009 Lab Number: 691943.1 691943.2 691943.3 691943.4 691943.5 691943.6 691943.7 691943.8 691943.9 691943.1 691943.11 691943.12 pH pH Units 7 7 6.9 7 7.2 6.6 7 6.9 6.4 6.9 7 - Total Suspended Solids g m P

-3P 100 16 26 37 36 21 63 28 4.4 3.6 < 6.6 -


-3P < 0.010 0.024 0.052 0.15 0.17 5.7 1.7 0.74 0.19 < 0.010 0.1 -


-3P 0.18 0.16 0.19 0.25 0.42 0.68 0.55 0.72 0.96 2.2 1.1 -


-3P 0.027 0.036 0.07 0.12 0.11 8.8 2.5 0.84 0.62 0.081 0.47 -

Carbonaceous Biochemical Oxygen Demand g.O2/m3 1.7 2.4 2.4 3.8 3 2.5 3.8 2.4 < 1.0 3.3 1.6 - Faecal Coliforms and E. coli profile Faecal Coliforms cfu / 100mL 2,400 12,000 #1 10,000 #1 19,000 #1 10,000 #1 20,000 17,000 < 1,000 #1 2,100 10,000 #1 12,000 #1 - Escherichia coli cfu / 100mL 2,400 12,000 #1 10,000 #1 19,000 #1 10,000 #1 20,000 5,000 < 1,000 #1 2,100 10,000 #1 12,000 #1 - Heavy metals, dissolved Dissolved Arsenic g m P

-3P < 0.0010 0.0016 0.0015 0.0018 0.002 0.0049 0.0028 0.0023 0.0021 0.001 0.0019 < 0.0010


-3P < 0.000050 < 0.000050 < 0.000050 < 0.000050 < 0.000050 0.0004 0.00014 0.000057 < 0.000050 < 0.000050 < 0.000050 < 0.000050


-3P < 0.00050 0.00076 0.001 0.0011 0.0025 0.0021 0.0023 0.0014 < 0.00050 < 0.00050 < 0.00050 < 0.00050


-3P 0.0013 0.0025 0.0037 0.0045 0.0045 0.0057 0.0046 0.0049 0.0018 0.002 0.002 < 0.00050


-3P 0.00024 0.0005 0.00059 0.00058 0.00044 0.00037 0.00029 0.00049 0.0004 0.00031 0.0004 < 0.00010


-3P < 0.00050 < 0.00050 < 0.00050 < 0.00050 0.0006 0.0033 0.0013 0.001 0.00069 < 0.00050 0.00064 < 0.00050


-3P 0.0048 0.081 0.1 0.17 0.26 0.24 0.34 0.36 0.063 0.054 0.065 0.0038


-3P 0.002 0.002 0.0021 0.0024 0.0026 0.0058 0.0041 0.0029 0.0021 0.0012 0.0021 < 0.0011

Total Cadmium g m P

-3P < 0.000053 < 0.000053 < 0.000053 0.000076 0.000091 0.001 0.00039 0.00014 < 0.000053 < 0.000053 < 0.000053 < 0.000053


-3P 0.003 0.0012 0.002 0.0026 0.0044 0.0052 0.0063 0.0027 < 0.00053 < 0.00053 < 0.00053 < 0.00053

Total Copper g m P

-3P 0.0046 0.0039 0.0064 0.0099 0.0097 0.012 0.013 0.0084 0.0024 0.0052 0.0027 < 0.00053

Total Lead g m P

-3P 0.0056 0.0033 0.0056 0.011 0.0068 0.0058 0.01 0.0073 0.0013 0.00089 0.0012 < 0.00011

Total Nickel g m P

-3P 0.003 0.00087 0.00095 0.0012 0.0018 0.0041 0.0034 0.0016 0.00074 < 0.00053 0.0007 < 0.00053

Total Zinc g m P

-3P 0.02 0.088 0.12 0.24 0.38 0.3 0.52 0.39 0.068 0.049 0.064 0.0017

Polycyclic Aromatic Hydrocarbons Acenaphthene g m P

-3P < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000014 < 0.000008 < 0.000008 < 0.000008 < 0.000008 -


-3P < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000014 < 0.000008 < 0.000008 < 0.000008 < 0.000008 -

Anthracene g m P

-3P < 0.000008 < 0.000008 < 0.000008 < 0.000008 0.000013 < 0.000008 < 0.000014 < 0.000008 < 0.000008 < 0.000008 < 0.000008 -


-3P < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000014 < 0.000008 < 0.000008 < 0.000008 < 0.000008 -


-3P < 0.000008 < 0.000008 < 0.000008 < 0.000008 0.000008 < 0.000008 < 0.000014 < 0.000008 < 0.000008 < 0.000008 < 0.000008 -


-3P < 0.000008 0.000011 < 0.000008 < 0.000008 0.000013 0.000008 < 0.000014 < 0.000008 < 0.000008 < 0.000008 < 0.000008 -


-3P < 0.000008 0.00001 < 0.000008 < 0.000008 0.000013 < 0.000008 < 0.000014 < 0.000008 < 0.000008 < 0.000008 < 0.000008 -


-3P < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000014 < 0.000008 < 0.000008 < 0.000008 < 0.000008 -

Chrysene g m P

-3P < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000014 < 0.000008 < 0.000008 < 0.000008 < 0.000008 -


-3P < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000014 < 0.000008 < 0.000008 < 0.000008 < 0.000008 -

Fluoranthene g m P

-3P < 0.000008 0.000013 < 0.000008 < 0.000008 0.00002 < 0.000008 < 0.000014 < 0.000008 < 0.000008 < 0.000008 < 0.000008 -

Fluorene g m P

-3P < 0.000008 < 0.000008 < 0.000008 < 0.000008 0.00014 < 0.000008 < 0.000014 < 0.000008 < 0.000008 < 0.000008 < 0.000008 -


-3P < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000008 < 0.000014 < 0.000008 < 0.000008 < 0.000008 < 0.000008 -

Naphthalene g m P

-3P < 0.000040 < 0.000040 < 0.000040 < 0.000040 0.0004 < 0.000040 < 0.000067 < 0.000040 < 0.000040 < 0.000040 < 0.000040 -

Phenanthrene g m P

-3P < 0.000008 0.000013 < 0.000008 0.000011 0.00016 0.000021 < 0.000014 < 0.000008 < 0.000008 < 0.000008 < 0.000008 -

Pyrene g m P

-3P < 0.000008 0.000014 < 0.000008 0.000015 0.000083 0.000018 0.000019 < 0.000008 < 0.000008 < 0.000008 < 0.000008 -

Total Petroleum Hydrocarbons 0 0.000061 0 0.000026 0.00085 0.000047 0.000019 0 0 0 0 C7 - C9 g mP

-3P < 0.10 < 0.10 < 0.10 < 0.10 < 0.10 < 0.10 < 0.10 < 0.10 < 0.10 < 0.10 < 0.10 -

C10 - C14 g m P

-3P < 0.20 < 0.20 < 0.20 < 0.20 < 0.20 < 0.20 < 0.20 < 0.20 < 0.20 < 0.20 < 0.20 -

C15 - C36 g m P

-3P < 0.40 < 0.40 < 0.40 < 0.40 < 0.40 < 0.40 < 0.40 < 0.40 < 0.40 < 0.40 < 0.40 -

Total hydrocarbons (C7 - C36) g mP

-3P < 0.70 < 0.70 < 0.70 < 0.70 < 0.70 < 0.70 < 0.70 < 0.70 < 0.70 < 0.70 < 0.70 -

Analyst's comments:



Stage 2 Dry weather samples, sampling run 1

Sample Name:

PAS-CAR 04-Jun-

2009 1:12 pm

PAS-HTR 04-Jun-

2009 9:30 am

HAS-GCP 04-Jun-

2009 11:30 am

HAS-SYR 04-Jun-

2009 8:40 am

HAS-HTR04-Jun-

2009 9:15 am

HAS-DWB04-Jun-

2009 2:36 pm

HER-UHD04-Jun-

2009 3:40 pm

HER-DHD04-Jun-

2009 3:06 pm

Method Blank 04-Jun-2009 3:40 pm

Lab Number: 699908.11 699908.12 699908.13 699908.18 699908.14 699908.15 699908.16 699908.17 699908.19 pH pH Units 7.6 7.8 7.7 7.4 7.6 7.4 7.1 7.2 - Total Suspended Solids g mP

-3P 7.8 6.4 16 < 3.0 11 7.2 < 3.0 < 3.0 -

Dissolved Copper g mP

-3P < 0.00050 0.003 0.0026 - 0.0011 0.002 < 0.00050 0.0014 #2 -

Total Copper g mP

-3P 0.00059 0.0049 0.0087 - 0.002 0.003 0.0032 0.00075 #2 -

Dissolved Lead g mP

-3P 0.0024 #1 0.0014 0.00053 - 0.00025 0.00033 < 0.00010 0.00011 -

Total Lead g mP

-3P 0.00095 #1 0.004 0.0018 - 0.0023 0.0016 0.00023 0.00066 -

Dissolved Zinc g mP

-3P 0.0049 0.46 0.47 #2 - 0.047 0.23 0.0062 #2 0.052 -

Total Zinc g mP

-3P 0.0084 0.48 0.46 #2 - 0.062 0.24 0.0056 #2 0.057 -

Total Ammoniacal-N g mP

-3P < 0.010 14 2.5 < 0.010 0.16 0.93 < 0.010 0.19 -


-3P 0.018 0.68 0.61 3.3 0.73 1.3 4.8 4.1 -

Dissolved Reactive Phosphorus g mP

-3P 0.012 0.3 0.11 1.5 0.043 0.31 0.0064 0.062 -

Carbonaceous Biochemical Oxygen Demand g.O2/m3 4.6 4.1 5.6 5.5 4.6 4.4 3 3.4 - Faecal Coliforms and E. coli profile Faecal Coliforms cfu / 100mL 48 800 250 5 1,300 39 70 120 - Escherichia coli cfu / 100mL 48 800 250 5 1,300 39 70 120 - Heavy metals, dissolved Dissolved Arsenic g mP

-3P - - - < 0.0010 - - - - < 0.0010

Dissolved Cadmium g mP

-3P - - - 0.0001 - - - - < 0.000050

Dissolved Chromium g mP

-3P - - - < 0.00050 - - - - < 0.00050


-3P - - - < 0.00050 - - - - < 0.00050

Dissolved Lead g mP

-3P - - - < 0.00010 - - - - < 0.00010

Dissolved Nickel g mP

-3P - - - 0.00073 - - - - < 0.00050

Dissolved Zinc g mP

-3P - - - 0.066 - - - - 0.0017

Heavy metals, totals Total Arsenic g mP

-3P - - - 0.0017 - - - - < 0.0011

Total Cadmium g mP

-3P - - - 0.00033 - - - - < 0.000053

Total Chromium g mP

-3P - - - 0.00062 - - - - < 0.00053

Total Copper g mP

-3P - - - 0.0013 - - - - < 0.00053

Total Lead g mP

-3P - - - 0.00033 - - - - < 0.00011

Total Nickel g mP

-3P - - - 0.0016 - - - - < 0.00053

Total Zinc g mP

-3P - - - 0.13 - - - - 0.0017

Analyst's comments:

#1 It has been noted that the results for the dissolved fraction were greater than those for the total fraction, and outside the analytical variation of the method. These have been confirmed by re-analysis.

#2 It has been noted that the results for the dissolved fraction were greater than those for the total fraction, but within analytical variation of the method.


Stage 2 Dry weather samples, sampling run 2

Sample Name:

PAS-CAR 22-Jul-200911:00 am

PAS-HTR 22-Jul-2009 12:20 pm

HAS-GCP 22-Jul-2009 11:30 am

HAS-HTR 22-Jul-2009 12:40 pm

HAS-DWB22-Jul-2009

2:10 pm

HER-UHD 22-Jul-2009

1:20 pm

HER-DHD 22-Jul-2009

1:45 pm

HAS-SYR 22-Jul-2009 10:40 am

Method blank

Lab Number: 710744.1 710744.2 710744.3 710744.4 710744.5 710744.6 710744.7 710744.8 710744.9 pH pH Units 7.3 7.2 7.4 8.1 7.2 6.7 6.7 8.2 - Total Suspended Solids g mP

-3P < 3.0 9.6 470 23 16 < 3.0 3.6 5.4 -


-3P 0.0017 0.0028 0.007 0.0025 0.0011 < 0.00050 < 0.00050 - -

Total Copper g mP

-3P 0.0021 0.0052 0.014 0.0066 0.0027 < 0.00053 < 0.00053 - -

Dissolved Lead g mP

-3P 0.00038 0.00069 0.0016 0.00044 0.0003 < 0.00010 < 0.00010 - -

Total Lead g mP

-3P 0.0011 0.0029 0.0087 0.0097 0.0031 < 0.00011 0.00063 - -

Dissolved Zinc g mP

-3P 0.034 0.21 1.5 0.16 0.081 0.0036 0.02 - -

Total Zinc g mP

-3P 0.04 0.26 2 0.48 0.14 0.0043 0.029 - -


-3P 0.025 2.9 24 100 0.9 < 0.010 0.19 57 -

Nitrite-N g mP

-3P

Nitrate-N g mP

-3P


-3P 0.3 0.31 0.029 2.3 1.2 4.6 4 1.8 -


-3P 0.016 0.15 0.032 4.9 0.13 0.0047 0.028 5.2 -

Carbonaceous Biochemical Oxygen Demand g.O2/m3 2.4 9.1 450 7.2 7.2 < 1.0 2.3 12 - Faecal Coliforms and E. coli profile Faecal Coliforms cfu / 100mL 70 #1 130 #1 110 #1 350 270 26 55 40 #1 Escherichia coli cfu / 100mL 70 #1 130 #1 110 #1 350 270 26 55 40 #1 Heavy metals, dissolved Dissolved Arsenic g mP

-3P 0.0029 < 0.0010


-3P < 0.000050 < 0.000050


-3P < 0.00050 < 0.00050


-3P 0.0044 < 0.00050

Dissolved Lead g mP

-3P 0.00024 < 0.00010


-3P 0.0023 < 0.00050

Dissolved Zinc g mP

-3P 0.25 0.0014


-3P 0.0039 < 0.0011

Total Cadmium g mP

-3P 0.00023 < 0.000053

Total Chromium g mP

-3P 0.0012 < 0.00053

Total Copper g mP

-3P 0.007 < 0.00053

Total Lead g mP

-3P 0.0018 < 0.00011

Total Nickel g mP

-3P 0.0029 < 0.00053

Total Zinc g mP

-3P 0.44 < 0.0011

Analyst's comments:



Stage 2 Wet weather samples, sampling event 1

Sample Name:

PAS-CAR 02-Jul-2009

9:25 pm

PAS-CAR 02-Jul-2009 11:25 pm

PAS-CAR 03-Jul-2009

4:25 am

PAS-HTR 02-Jul-2009 10:20 pm

PAS-HTR 03-Jul-2009 12:20 am

PAS-HTR 03-Jul-200912:45 pm

HAS-GCP02-Jul-200910:25 pm

HAS-GCP02-Jul-200911:25 pm

HAS-GCP03-Jul-2009

7:05 am

HAS-HTR 02-Jul-200910:45 pm

HAS-HTR 03-Jul-200912:45 am

HAS-HTR 03-Jul-2009

4:45 am

HER-UHD 03-Jul-2009 12:25 am

HER-UHD 03-Jul-2009

5:25 am

HER-UHD 03-Jul-2009

9:25 am

HER-DHD03-Jul-200912:30 am

HER-DHD03-Jul-2009

6:30 am

HER-DHD03-Jul-2009

9:30 am

Method Blank

03-Jul-2009 Lab

N b706656.1 706656.2 706656.3 706656.4 706656.5 706656.6 706656.7 706656.8 706656.9 706656.10 706656.11 706656.12 706656.13 706656.14 706656.15 706656.16 706656.17 706656.18 706656.19

pH pH Units 7.1 6.8 6.9 7.3 7 7 6.7 6.9 6.8 6.6 6.7 6.7 7 6.8 6.8 7 7.1 7 -Total Suspended Solids g mP

-3P 13 95 23 140 150 27 210 190 19 230 110 27 < 3.0 82 16 7 34 16 -


-3P 0.00089 0.0015 0.00098 0.0033 0.0019 0.0019 0.004 0.0035 0.0028 - - - - - - - - - -

Total Copper g mP

-3P 0.0019 0.011 0.0026 0.025 0.017 0.0041 0.018 0.025 0.0054 - - - - - - - - - -

Dissolved Lead g mP

-3P < 0.00010 0.00019 0.00015 0.00045 0.00039 0.00026 0.0005 0.0014 0.00033 - - - - - - - - - -

Total Lead g mP

-3P 0.0014 0.022 0.0037 0.049 0.043 0.0057 0.028 0.038 0.0056 - - - - - - - - - -

Dissolved Zinc g mP

-3P 0.047 0.056 0.07 0.065 0.09 0.077 0.32 0.12 0.22 - - - - - - - - - -

Total Zinc g mP

-3P 0.071 0.2 0.092 0.64 0.34 0.11 0.62 0.71 0.27 - - - - - - - - - -


-3P 0.11 0.064 0.044 0.071 0.067 0.053 0.41 0.07 0.09 2 2.3 1.9 0.02 0.098 0.068 0.25 0.45 0.45 -

Nitrite-N g mP

-3P - - - - - - 0.02 0.014 0.011 - - - - - - - - - -

Nitrate-N g mP

-3P - - - - - - 0.35 0.27 0.14 - - - - - - - - - -


-3P 0.15 0.1 0.072 0.38 0.13 0.22 0.37 0.28 0.15 0.59 0.26 0.25 4.1 0.69 0.97 2.4 0.87 1 -


-3P 0.011 0.019 0.022 0.025 0.029 0.028 0.064 0.047 0.049 1.1 1.1 1.6 0.011 0.028 0.071 0.16 0.27 0.26 -

Carbonaceous Biochemical Oxygen Demand g.O2/m3 2.2 3.2 1.4 6.6 3.8 1.7 12 7.6 2.5 10 3.4 2.4 < 1.0 2.8 2.3 1.5 3 2.5 - Faecal Coliforms and E. coli profile Faecal Coliforms cfu / 100mL 80 #1 900 #1 340 900 #1 2,200 1,300 #1 1,000 #1 1,500 #1 200 #1 9,000 #1 500 #1 270 260 1,600 #1 1,500 #1 330 1,500 #1 370 Escherichia coli cfu / 100mL 80 #1 800 #1 260 900 #1 2,200 1,300 #1 1,000 #1 1,500 #1 200 #1 9,000 #1 500 #1 270 260 1,600 #1 1,500 #1 330 1,200 #1 290 Heavy metals, dissolved Dissolved Arsenic g mP

-3P - - - - - - - - - 0.0025 0.0023 0.0025 < 0.0010 0.0013 0.0021 0.0012 0.0018 0.0016 < 0.0010


-3P - - - - - - - - - < 0.000050 < 0.000050 0.00015 < 0.000050 < 0.000050 < 0.000050 < 0.000050 < 0.000050 < 0.000050 < 0.000050


-3P - - - - - - - - - 0.0021 0.0015 0.002 0.00060 #1 0.00072 0.0011 < 0.00050 0.00071 0.00058 < 0.00050


-3P - - - - - - - - - 0.0027 0.0019 0.0024 0.0007 0.002 0.0023 0.0012 0.0027 0.0026 < 0.00050

Dissolved Lead g mP

-3P - - - - - - - - - 0.00035 0.00037 0.0002 0.00011 0.00055 0.00064 0.00023 0.00042 0.00043 < 0.00010


-3P - - - - - - - - - 0.0011 0.00072 0.00076 < 0.00050 < 0.00050 < 0.00050 < 0.00050 0.00073 0.00079 < 0.00050

Dissolved Zinc g mP

-3P - - - - - - - - - 0.4 0.21 0.36 0.046 #2 0.054 0.053 0.11 0.17 0.19 0.079 #2


-3P - - - - - - - - - 0.0092 0.0044 0.0029 < 0.0011 0.0025 0.0026 0.0012 0.0024 0.002 < 0.0011

Total Cadmium g mP

-3P - - - - - - - - - 0.002 0.00057 0.00034 < 0.000053 0.000071 < 0.000053 < 0.000053 0.00011 < 0.000053 < 0.000053

Total Chromium g mP

-3P - - - - - - - - - 0.031 0.0098 0.0043 0.00057 #1 0.0024 0.0018 0.00056 0.0026 0.0012 < 0.00053

Total Copper g mP

-3P - - - - - - - - - 0.044 0.017 0.0071 0.00086 0.0056 0.0037 0.0019 0.0066 0.0043 < 0.00053

Total Lead g mP

-3P - - - - - - - - - 0.091 0.029 0.0064 0.00047 0.01 0.0045 0.0014 0.0086 0.0039 < 0.00011

Total Nickel g mP

-3P - - - - - - - - - 0.0083 0.0041 0.0017 < 0.00053 0.0013 0.00081 0.00073 0.0016 0.0011 < 0.00053

Total Zinc g mP

-3P - - - - - - - - - 3.1 0.6 0.44 0.015 0.078 0.062 0.13 0.25 0.21 < 0.0011

Polycyclic Aromatic Hydrocarbons

Acenaphthene g mP

-3P < 0.000005 < 0.000005 < 0.000008

Acenaphthylene g mP

-3P < 0.000005 < 0.000005 < 0.000008

Anthracene g mP

-3P < 0.000005 < 0.000005 < 0.000008

Benzo[a]anthracene g mP

-3P 0.00001 0.000015 < 0.000008


-3P 0.000009 0.000017 < 0.000008

Benzo[b]fluoranthene + Benzo[j]fluoranthene g mP

-3P 0.000024 0.000043 < 0.000008

Benzo[g,h,i]perylene g mP

-3P 0.000014 0.000022 < 0.000008

Benzo[k]fluoranthene g mP

-3P 0.000008 0.000012 < 0.000008

Chrysene g mP

-3P 0.00001 0.000015 < 0.000008

Dibenzo[a,h]anthracene g mP

-3P < 0.000005 < 0.000005 < 0.000008

Fluoranthene g mP

-3P 0.00003 0.000038 0.000016

Fluorene g mP

-3P 0.000018 0.000016 < 0.000008

Indeno(1,2,3-c,d)pyrene g mP

-3P 0.000007 0.000011 < 0.000008

Naphthalene g mP

-3P < 0.000020 0.000031 < 0.000040

Phenanthrene g mP

-3P 0.000024 0.000023 < 0.000008

Pyrene g mP

-3P 0.000044 0.000051 0.000028

Analyst's comments:



Stage 2 Wet weather samples, sampling event 2

Sample Name:

PAS-CAR 24-Jul-2009

2:50 am

PAS-CAR24-Jul-2009

3:50 am

PAS-CAR 24-Jul-2009

6:50 am

PAS-HTR 24-Jul-2009

3:15 am

PAS-HTR 24-Jul-2009

4:15 am

PAS-HTR24-Jul-2009

7:15 am

HAS-GCP 24-Jul-2009

2:40 am

HAS-GCP 24-Jul-2009

4:40 am

HAS-GCP 24-Jul-2009

5:40 am

HAS-HTR24-Jul-2009

3:25 am

HAS-HTR24-Jul-2009

4:25 am

HAS-HTR24-Jul-2009

7:25 am

HAS-DWB 24-Jul-2009

Composite of 6:45 am and 7:15

am samples

HAS-DWB24-Jul-2009


am samples

HAS-DWB 24-Jul-2009


am samples

HAS-DWB 24-Jul-2009


am samples

HAS-DWB 24-Jul-2009

Composite of 10:45 am and

11:15 am samples

HAS-DWB 24-Jul-2009

4:45 pm

HER-UHD24-Jul-2009

8:45 am

HER-UHD24-Jul-2009

8:45 am

HER-UHD24-Jul-2009

8:45 am

HER-DHD24-Jul-2009

8:45 am

HER-DHD24-Jul-2009

8:45 am

HER-DHD24-Jul-2009

8:45 am Lab Number: 711563.1 711563.2 711563.3 711563.4 711563.5 711563.6 711563.7 711563.8 711563.9 711563.10 711563.11 711563.12 711563.13 711563.14 711563.15 711563.22 711563.23 711563.24 711563.16 711563.17 711563.18 711563.19 711563.20 711563.21

pH pH Units 6.8 6.7 6.9 6.8 6.8 6.8 8.8 7 7 8.3 6.8 7 7.2 7.2 7.2 7.3 7.2 7.1 6.8 6.8 6.6 7 7 7 Total Suspended Solids g m P

-3P 130 92 13 80 120 39 180 33 30 190 100 31 13 15 14 9.4 14 16 5.6 < 3.0 < 3.0 12 11 14


-3P 0.0023 0.0019 0.0023 0.0063 0.0037 0.0028 0.0059 0.0057 0.0039 - - - 0.0014 0.0014 0.0014 0.0013 0.0015 0.0018 - - - - - -

Total Copper g m P

-3P 0.0077 0.0068 0.004 0.019 0.017 0.0068 0.029 0.015 0.0087 - - - 0.0028 0.0024 0.0024 0.0023 0.0023 0.004 - - - - - -


-3P 0.00025 0.00021 0.00024 0.0006 0.00037 0.00028 0.0013 0.00068 0.00046 - - - 0.00022 0.00024 0.00027 0.00024 0.00025 0.00032 - - - - - -

Total Lead g m P

-3P 0.013 0.012 0.0035 0.018 0.029 0.007 0.047 0.015 0.006 - - - 0.0027 0.0022 0.0021 0.0023 0.0022 0.0028 - - - - - -


-3P 0.13 0.11 0.12 0.42 0.2 0.17 0.43 0.35 0.28 - - - 0.1 0.1 0.1 0.1 0.1 0.15 - - - - - -

Total Zinc g m P

-3P 0.24 0.21 0.15 0.7 0.47 0.25 1 0.58 0.43 - - - 0.15 0.14 0.14 0.14 0.13 0.2 - - - - - -


-3P 0.26 0.17 0.27 0.73 0.49 0.26 33 0.29 0.46 54 8.2 3.6 0.86 0.9 0.9 0.86 0.9 1.7 0.018 0.016 0.053 0.63 0.63 1.2

Nitrite-N g m P

-3P

Nitrate-N g m P

-3P

Nitrate-N + Nitrite-N g m P

-3P 0.24 0.14 0.26 0.5 0.3 0.28 0.69 0.31 0.42 1.5 0.65 0.53 1.5 1.5 1.6 1.6 1.6 1.5 4.6 4.3 3.1 2.3 2.3 1.8


-3P 0.029 0.019 0.063 0.13 0.099 0.069 0.54 0.057 0.066 4.3 2.2 1.3 0.15 0.16 0.15 0.15 0.15 0.26 0.0048 0.0065 0.015 0.11 0.12 0.18

Carbonaceous Biochemical Oxygen Demand g.O2/m3 3.3 2.5 2 4.9 4.4 2 16 5.1 3.1 14 7.2 3 5.8 4 4.1 4 5.4 5.4 < 1.0 < 1.0 1.1 3.4 3.4 4.2 Faecal Coliforms and E. coli profile Faecal Coliforms cfu / 100mL 400 #1 210 600 #1 200 #1 400 600 #1 10 #1 2,200 3,000 180 9,300 #1 1,800 #1 140 #1 100 #1 90 #1 120 #1 50 #1 110 #1 60 #1 80 #1 170 #1 110 #1 170 #1 160 #1 Escherichia coli cfu / 100mL 400 #1 210 600 #1 200 #1 400 600 #1 10 #1 2,200 3,000 180 9,300 #1 1,800 #1 140 #1 100 #1 90 #1 120 #1 50 #1 110 #1 60 #1 80 #1 170 #1 110 #1 170 #1 160 #1 Heavy metals, dissolved Dissolved Arsenic g m P

-3P 0.0031 0.0024 0.0039 < 0.0010 < 0.0010 < 0.0010 < 0.0010 < 0.0010 0.0014


-3P 0.0001 0.00014 0.00014 < 0.000050 < 0.000050 < 0.000050 < 0.000050 < 0.000050 < 0.000050


-3P 0.0023 0.002 0.0062 < 0.00050 < 0.00050 < 0.00050 < 0.00050 < 0.00050 < 0.00050


-3P 0.0071 0.0062 0.0056 < 0.00050 < 0.00050 0.0014 0.001 0.00095 0.0017


-3P 0.00069 0.00064 0.00054 0.0001 0.00011 0.00029 < 0.00010 0.0002 0.00029


-3P 0.0032 0.0021 0.0013 < 0.00050 < 0.00050 0.00057 < 0.00050 < 0.00050 0.0007


-3P 0.73 0.8 0.51 0.015 0.011 0.064 0.073 0.084 0.12


-3P 0.0072 0.0047 0.0051 < 0.0011 < 0.0011 < 0.0011 0.0014 0.0013 0.0015

Total Cadmium g m P

-3P 0.0017 0.00077 0.00031 < 0.000053 < 0.000053 < 0.000053 < 0.000053 < 0.000053 < 0.000053


-3P 0.018 0.011 0.0096 < 0.00053 < 0.00053 0.00057 0.00057 0.00065 0.00091

Total Copper g m P

-3P 0.039 0.027 0.011 < 0.00053 < 0.00053 0.0019 0.0017 0.0018 0.003

Total Lead g m P

-3P 0.052 0.031 0.0087 0.00066 0.00028 0.001 0.0016 0.0017 0.0025

Total Nickel g m P

-3P 0.0088 0.0051 0.0025 < 0.00053 < 0.00053 0.00078 0.00064 0.00063 0.00092

Total Zinc g m P

-3P 2.5 1.3 0.66 0.016 0.011 0.063 0.1 0.11 0.15

Polycyclic Aromatic Hydrocarbons Acenaphthene g m P

-3P < 0.000008 < 0.000008 < 0.000008


-3P < 0.000008 < 0.000008 < 0.000008

Anthracene g m P

-3P < 0.000008 < 0.000008 < 0.000008


-3P 0.000009 < 0.000008 < 0.000008

Benzo[a]pyrene (BAP) g m P

-3P < 0.000008 < 0.000008 < 0.000008


-3P 0.000016 0.000011 0.000013


-3P < 0.000008 < 0.000008 < 0.000008


-3P < 0.000008 < 0.000008 < 0.000008

Chrysene g m P

-3P 0.000008 < 0.000008 < 0.000008


-3P < 0.000008 < 0.000008 < 0.000008

Fluoranthene g m P

-3P 0.000031 0.000021 0.00002

Fluorene g m P

-3P 0.000022 0.000018 0.000016


-3P < 0.000008 < 0.000008 < 0.000008

Naphthalene g m P

-3P 0.000047 0.000054 < 0.000040

Phenanthrene g m P

-3P 0.000034 0.000013 0.000011

Pyrene g m P

-3P 0.000041 0.000033 0.000031

Analyst's comments:



Sediment Samples

Sample Name:

PAS-BUR 04-Jun-2009

12:58 pm

PAS-CAR 04-Jun-2009

1:12 pm

PAS-RAR 04-Jun-2009

12:30 pm

PAS-HTR 04-Jun-2009

9:30 am

HAS-GCP 04-Jun-2009

11:30 am

HAS-HTR 04-Jun-2009

9:15 am

HAS-UWB 04-Jun-2009

2:00 pm

HAS-DWB 04-Jun-2009

2:36 pm

HER-UHD 04-Jun-2009

3:40 pm

HER-DHD 04-Jun-2009

3:06 pm Lab Number: 699908.1 699908.2 699908.3 699908.4 699908.5 699908.6 699908.7 699908.8 699908.9 699908.1 Dry Matter g/100g as rcvd 66 66 45 78 78 82 76 45 17 69 Total Recoverable Copper mg/kg dry wt 12 5.5 15 33 13 13 12 16 62 5.9 Total Recoverable Lead mg/kg dry wt 26 20 33 73 21 41 24 19 62 18 Total Recoverable Phosphorus mg/kg dry wt 700 310 600 3,100 710 880 580 900 800 440 Total Recoverable Zinc mg/kg dry wt 86 90 380 1,900 420 290 450 320 310 460 Ammonium-N mg/kg dry wt < 5.0 7 < 5.0 26 39 < 5.0 15 34 28 9.2 Nitrate-N + Nitrite-N mg/kg dry wt < 1.0 < 1.0 3.4 < 1.0 < 1.0 < 1.0 < 1.0 4.4 < 2.8 < 1.0 Total Organic Carbon g/100g dry wt 2.3 0.66 2.5 2 1.1 1.7 0.72 0.73 12 0.79 Polycyclic Aromatic Hydrocarbons Acenaphthene mg/kg dry wt < 0.0023 < 0.0023 0.005 0.0028 0.0037 < 0.0020 < 0.0027 < 0.0034 0.043 < 0.0022 Acenaphthylene mg/kg dry wt < 0.0023 0.0027 0.011 0.0066 0.0041 0.0053 < 0.0027 0.0042 0.022 0.0038 Anthracene mg/kg dry wt < 0.0023 0.0043 0.044 0.011 0.017 0.011 < 0.0027 0.0059 0.13 0.01 Benzo[a]anthracene mg/kg dry wt 0.0028 0.016 0.15 0.042 0.034 0.045 0.0068 0.021 0.48 0.051 Benzo[a]pyrene (BAP) mg/kg dry wt 0.0033 0.016 0.17 0.047 0.037 0.058 0.0085 0.026 0.45 0.048 Benzo[b]fluoranthene + B [j]fl th

mg/kg dry wt 0.0045 0.026 0.27 0.073 0.07 0.081 0.015 0.041 0.61 0.063 Benzo[g,h,i]perylene mg/kg dry wt 0.0035 0.016 0.17 0.044 0.059 0.048 0.012 0.027 0.32 0.031 Benzo[k]fluoranthene mg/kg dry wt < 0.0023 0.0099 0.097 0.028 0.021 0.03 0.0058 0.016 0.24 0.026 Chrysene mg/kg dry wt 0.003 0.018 0.15 0.048 0.041 0.041 0.0098 0.023 0.43 0.043 Dibenzo[a,h]anthracene mg/kg dry wt < 0.0023 0.0033 0.034 0.0091 0.009 0.012 < 0.0027 0.0056 0.074 0.0077 Fluoranthene mg/kg dry wt 0.0063 0.04 0.36 0.12 0.092 0.096 0.019 0.047 1.1 0.078 Fluorene mg/kg dry wt < 0.0023 0.0043 0.011 0.0071 0.027 0.0043 < 0.0027 0.0059 0.1 0.0042 Indeno(1,2,3-c,d)pyrene mg/kg dry wt < 0.0023 0.0098 0.12 0.031 0.026 0.037 0.0066 0.019 0.25 0.024 Naphthalene mg/kg dry wt < 0.012 < 0.012 < 0.017 < 0.010 0.19 < 0.010 < 0.014 < 0.017 < 0.044 < 0.011 Phenanthrene mg/kg dry wt 0.0029 0.034 0.16 0.087 0.077 0.052 0.0082 0.03 0.79 0.031 Pyrene mg/kg dry wt 0.0072 0.04 0.38 0.13 0.18 0.1 0.025 0.056 1 0.082 Total Petroleum Hydrocarbons C7 - C9 mg/kg dry wt < 11 < 11 < 16 < 9.2 < 17 < 16 < 17 < 30 < 77 < 19 C10 - C14 mg/kg dry wt < 20 < 20 < 23 < 20 < 23 < 22 < 24 < 42 < 110 < 27 C15 - C36 mg/kg dry wt < 30 < 30 94 < 30 100 < 31 < 34 91 380 < 38 Total hydrocarbons (C7 - C36) mg/kg dry wt < 60 < 60 95 < 60 100 < 60 < 60 94 410 < 60

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