Nitrite monitoring with an online analyzer

hun�ng an elusive quarry for 20 years

2016 NJ WEA Annual Conference

Online Monitoring for Process Opt mizaton

Bruce Stevens – Regional ManagerScott Kahle – VP Engg

Roy McKnight PhD – Lab ManagerBernard Beemster – President

Automated spectrometers provide reliable, accurate

multi-parameter and multiple sample stream analysis

Single sample line photometers can do one parameter

Got started in 1993 after 7 years of NASA R+D via Biotronics

“If You Want to Control Process Chemistry,Measure Constituents + Species DIrectly”

If a plant has nitrogen and/or phosphorus discharge limits ……… then why measure anything other than NO2, NO3 + NH3 or PO4 for process control ?

Surrogate parameters such as DO, ORP, MLSS or O.U.R do not provide anydirect information about nutrient levels. pH, conductivity, and turbidity do nottell you if nitrification is happening either ?

TN and TP analysers do not speciate, are cumbersome and difficult tomaintain, so use B.A.T. for accurate, repetitive results ….

1980s was the Initial Research duringLunar Colonization Preparations

EPCOT begin a new era in WWTFs

Reedy Creek Improvement District (RCID)

Manages water, waste water and reclaimed water for the Disney resorts

ChemScan demo in 1993 for effluent monitoring to RIBs

Lab spectrometer

Automation is Applied Sample delivery and preparation is Simplified

ChemScan system with a proud operator

happily showing off their

20 yr old NO3 analyzer

inside a climate controlled enclosure

Internal Peristaltic

Pump

FlowCell

Zeroing and Cleaning Solution

Containers

Reagent Injectors

Reagents

Flow Cell

Reagent Injection

Two-Component Mixture

Example of a two-component mixture with little spectral overlap

Differential Spectrometry to isolate the chemical specie nuances at low levels

Example of a two-component mixture with significant spectral overlap

Pattern Recognition Software

An Online Lab Grade Spectrometer

Capable of handling both reagent assisted and directly read samples

Calibration / Validation Port for grab sample analysis and site specific optimization

Capable of field modification and correlation with lab results to build confidence

Self Zeroing, self cleaning and future options or enhancements in time as needed

Heater-Fan

Instrument Contol Circuit Spectrograph and Network Communication

Power Input

Flash Lamp

Fiber Optic Cable

A tool for effluent monitoring or BNR process decision making

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Fairfax County , VA demo test Fall 2012

•Nitrospira•Nitrobacter

•Nitrococcus•Nitrospina•Anammox

All species convert NO2 to N2 gas and can enable denitrification

Nitrite is a spurious compound in a biological treatment system that acts as an intermediary product and promulgator of reactions varying in concentration

Nitrospira

How important is NH3 + NO2 removal to costs ?

What about N2O …. Does this GHG play a role in BNR ?

BOD removal ~~~ 2# O2 / # BOD NH3 removal ~~~ 4.57# O2 / # NH3

NO2 Lock = 5 lbs CL2 per lb of NO2 in effluent

Half of the energy in the facility

The Iron Bridge Bardenpho System ... A Great Process Made Better!

Roy A. Pelletier, David S. Sloan, and Thomas L. Lothrop

T3P3-Phase 3 East-End of Reaer ation Basin

N02-N - N03-N - NH3-N - P04-P I

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01120 10 01125 10 01130 10 02..04 10 02..09 10

Flow Thru Cyclic Design

Separation of NO2 + NO3 is not easy Natural Absorbances from 210-230 nM and overlapping curves due to

ratios of NO3 to NO2 Sharon process ranges can be 200-300 mg/l NO2 Demon / Anita Mox can be 20-50 ppm NO2 with very low NO3

which is reverse of current nite - denite ratio data we have worked with…but there is promise

Most operating data shows relatively good NO3 to NO2 ratios < 10/1

Higher ratios make it difficult to detect the low level analyte thru thenoise of the primary component in the mixture

ChemScan’s original nitrate spectra

City of Tampa – Hookers Point WWTF Denitrification filter testing 1993-95

Excess iron salt use removed all the PO4 and no heterotrophs would not grow in the filters

Nitrate R+D leads to Nitrite Analysis

Spectral Signatures for NO2 using NED320nm to 420 nm

Concentrations [mg/L NO2-N]:Black – 0.30; Gray – 0.25; Blue – 0.20; Green – 0.15; Lt Blue – 0.10; Red – 0.05; Mauve – 0.00

ChemScan’s Original Low Level NO2 data

NO3 vs NOx

LOTT – Olympia, WA WWTF.

Shelters are beneficial for long term operations + maintenance effectiveness

L.O.T.T. - At-Tank Analysis SystemOlympia, WA Side by Side trials

Monitoring Post Anoxic Denitrification + MeOH

ChemScanNitrite

Detection optimized

Carbon Feedand

Monitored Nitrite Lock

R+D with spikes in distilled water

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Nitrite Spectra in Distilled Water

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16 mg/L

R+D with spikes in a waste water matrix

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Nitrite Spectra in Wastewater

0.1 mg/L

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14.2 mg/L

East Greenwich, RI WWTF Full Scale COLOX NO2 Shunt demonstration

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ChemScan Nitrite Calibration

ChemScan Value

Actual

Field generated spectra for WWTFs

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Higher range spikes add to pattern recognition

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Old bugs are back in style after millions of years

Heat Traced Sample Lines for Cold Weather Operations in Harrisburg, PA

Highspire PA analyzer shed

Neither wind, not rain, nor heat , nor driving snow or dark of nightshall deter staff from getting the job done

PWCSA - HL Mooney WWTF 10 old + 14 new = 24 Denite Filters

Spectral Comparisons - Ammonia

Spectral Comparisons - Nitrite

Spectral Comparisons - Nitrate

Hampton Roads Sanitation DistrictYork River Treatment Plant

• Located in York County, VA• 15 mgd rated design capacity

• VA DEQ implemented TN and TP WLAstarting in 2011

• 2006 performance• Effluent TN ~ 16.5 mg/l (~1,700 ppd)• Effluent TP ~ 1.40 mg/l (~140 ppd)

Parameter 2011

TN Waste Load Allocation

6.0 mg/l273,969 lb/year

TP Waste Load Allocation

0.7 mg/l31,963 lb/year

Unstable Nitrification

Temp > 15°C : After Day 75

HRSD - York River WWTP – TN Removal2011 Start-Up Performance

HRSD York River WWTP – Out of “NO2-N Lock”Deep Bed Denitrification Filter Start-Up

N2O sensor - Option III Combining the latest real time sensor technology from

Europe with our UV-4100 spectrometer

Up to 2 Sample Locations per controller Low Maintenance ( 1 Hour / month) Over 5 years of Proven Reliability 25 units installed for Anammox and other BNR process Appears to correlate very well with NO2 data

Green House Gas emissions drove the development of the technology in Europe

A unique silicone membrane with a special tip shape to focus gas for analysis

IF N2O ~~~ to NO2, then you can reduce GHG and optimize aeration energy as well as carbon feed

More Information is Available at:

ChemScan.com