PESTICIDES in the HUDSON RIVER BASIN

analyzed by HRGC/HRMS:

RESULTS, DATA QUALITY, and IMPLICATIONS

Victoria A. Pretti

New England Interstate Water Pollution Control Commission/New York State Division of Water

625 Broadway, 4th Floor, Albany, NY 12233-3502

Acknowledgements

AXYS Analytical Services, Ltd., Sidney, BC, Canada Dale Hoover, Coreen Hamilton, Steve Kennedy, and

Laurie Phillips New England Interstate Water Pollution

Control Commission, Lowell, MA Susan Sullivan

New York State Department of Environmental Conservation – Division of Water, Albany, NY Simon Litten, Larry Bailey, Jason Fagel, and Dawn

McReynolds

Outline

What is CARP? Why Pesticides in the Harbor? What Methods are currently used? How does the NYSDEC High Resolution

Chlorinated Pesticide Method Work? How does the Frequency and Quality of

the Chlorinated Pesticide Results Look in Various Media?

What Implications and Conclusions were drawn from the Results?

Is this CARP ???

New York - New Jersey CARPCONTAMINANT

ASSESSMENT and

REDUCTION

PROJECT

Part of U.S. EPA National Harbor Estuary Plan

Established in 1997 Focus on PAHs, PCBs,

Pesticides, and Metals

GOAL: ENVIRONMENTALLY SOUND DREDGING PLAN

Organochlorine Pesticides (i.e., OC’s)

Source – agriculture, forestry, residential usemanufacturing plants, and urban areas

Carrier – lake/river bed sediment, aquatic life, whole/filtered water, plants, wind, herbivores, and sewage

Trend (1960s-1990s) – OC studiesdecreasing in sediments and water

Solubility (log Kow) – SOC < SOP

in water; log Kow,OC > log Kow,OP

Concentrations – detected less than conventional est. detection limits of current validated methods

Analytical Method for Detecetion of Organochlorine Pesticides:

NYSDEC HRMS-2NYSDEC HRMS-2

HRGC High

Resolution

Gas

Chromatography

HRMS High

Resolution

Mass

SpectrometryNYSDEC HRMS-2 is a performance based method.

27 ANALYTES of INTEREST

FRACTION 1:Hexachlorobenzene (HCB)(alpha-, beta-, gamma-)

Hexachlorocyclohexane (HCH) HeptachlorAldrin(oxy-, cis-, trans-) Chlordane(cis-, trans-) NonachlorMirex(2,4’-, 4,4’-) DDD(2,4’-, 4,4’-) DDE(2,4’-, 4,4’-) DDT

FRACTION 2:Heptachlor epoxide

(alpha-, beta-) Endosulfan

Endosulphan sulfate

Dieldrin

Endrin

Endrin ketone

Endrin aldehyde

Organochlorine Pesticides of Primary Interest to CARP

The primary pests include:

total DDT (DDD + DDE + DDT)

total Dieldrin (dieldrin + aldrin)

total Chlordane (cis + trans + oxy)

total Nonachlor (cis + trans)

Of lesser importance are DDDs and DDEs.

Current Analytical Methods

MethodMethod

(1 L aq. samples)(1 L aq. samples)

AnalytesAnalytes Number of Pests Number of Pests of Interest to NYSof Interest to NYS

Est. Detection Est. Detection RangeRange ( (g/L)g/L)

U.S. EPA 608U.S. EPA 608 Aro/OC’s 14 0.003-0.240

U.S.G.S SH2010U.S.G.S SH2010 Pests/degr 5 0.001-0.18

U.S.G.S LC9060U.S.G.S LC9060 Pests/degr 0 0.001-0.18

U.S. EPA 8081U.S. EPA 8081 OC’s 22 0.6-1.8

U.S.G.S. NWQLU.S.G.S. NWQL Pests/degr 4 0.001-0.006

NYSDEC HRMS-2NYSDEC HRMS-2 OC’s 27 0.0001-0.005

NYSDEC HRMS-2 Sample Preparation, Extraction, Cleanup, and Analysis:

Vary depending on the Sample Matrix, BUT includes

1. Spiking the sample with 20 C-13 labeled surrogate standards (e.g. 13C12-Aldrin and 13C9--Endosulphan).

2. Adding recovery standards to the sample just prior to analysis (e.g. 13C12-PCB52, 13C12-PCB138, and 13C12-PCB153).

3. Concentrating the sample extract to a final volume (SDS Extraction with hexane to 20-500 L).

4. Performing column cleanup (Gel Permeation, Cu Cleanup, Florisil).

5. Analysis by a HRMS equipped with a HRGC (>8,000 mass resolution).

6. Initial calibration with 5-point series (10-4000 ng/ml) and calibration verification with mid-level standard (every 12 hrs).

7. Monitoring method performance (lab blanks, spiked reference material).

R E S U L T SR E S U L T S

PESTICIDES attached to XAD RESIN

Trace Organics Platform Sampler – processes large volumes of water through a series of filters (suspended fraction) and XAD resin columns (dissolved fraction) WHOLE WATER SAMPLES

COMPARISON of PESTICIDE DETECTION in 279 XAD SAMPLES and 29 Field BLANKS:

DDD, DDE, DDTHCH isomers

Aldrin Chlordanes

Dieldrin HCB

Endrins

Nonachlors

Pesticides Most Often Detected in 279 XAD Samples:

By Mean Frequency at 5*IDL:

Lindane (-HCH) (79%) and -HCH (62%) Dieldrin (74%)

2,4’-DDD (59%) and 4,4’-DDD (71%) HCB (54%)

Total HCH ~47% to the mean total mass.

~3%, ~6%, and ~8% from 2,4’-DDE, HCB, and 4,4’-DDE.

LAB A LAB Q LAB W

Samples Analyzed

244 21 14

Possible Results 6587 588 378

Results > 5*DL 3404 105 104

Results > 1*DL 4765 224 153

Pesticides Most Often Detected in 29 XAD Field and Equipment Blanks:

Potential Results = 783

Results 5*DL Criteria = ~92%

Results 1*DL Criteria = ~83%

Analytes with the Highest Mean Frequency of Detection in Blanks at 5*IDL:

HCB > Endosulfan sulfate > 4,4’-DDD

(79% ) (24%) (14%)

Do the Blank Results Impinge on the Sample Results ?

Analyte(ng/sample)

XAD FBs-EBsmean result > 5*DL

XAD SAsmean factor > 5*DL

4,4’DDD 5.0 ± 25 12

4,4’-DDE 2.1 ± 11 16

2,4’-DDD 2.0 ± 10 12

Methoxychlor 1.2 ± 4.6 15

Hexachlorobenzene 1.1 ± 0.95 11

exception …

Highest result Lowest result Exceed 90th

90th %tile FBs-EBs 10th %tile SAs %tile Blanks

HCB 2.9 2.5 15%

-HCH 1.2 14 3%

• Blank contamination attributed to carryover from samples taken from sites high in pesticides.

• Blank contamination attributed to lack of thorough cleaning/rinsing practices.

Occurred at > 1*IDL.

How Do The XAD Lab Blanks Fare at 1*IDL ?

• The highest method blank results (90th percentile) only exceeded 10th percentile sample (lowest) results for CB ~2%.

• Laboratory blanks for lindane never exceeded the XAD sample results at the analyte specific detection level.

Mean Total Pesticide Results (> 10*IDL) in Waters of the Hudson River Basin

WWTP and Wallkill R. contribute the largest total concentration of pesticides, followed by landfills.

13 SLUDGE SAMPLES from 8 WPCF Sites

Potential Results = 351 273 Results > 1*DL (78%)

208 Results > 5*DL (59%)

Mean value

Pesticides Most Often Detected in Sludge (> 5*idl):

100% 2,4’-DDD, 4,4’-DDD, 4,4’-DDE; cis- and trans-chlordane; dieldrin; and trans-nonachlor92% 2,4’-DDE

Mean total concentration contributed by each site = 300 ± 80 g/kg dw (Mean total result for Harbor = 4000 ± 200 g/kg dw)

+ -Chlordane + 4,4’-(DDE + DDD) ~69% of the mean total result for the Harbor (cis+ trans-Chlordane + 4,4’-DDE = 56 ± 4% from each site)

HCB contributed ~2% to the mean total Harbor result.

On-Going Precision and Recovery Arthur Kill BED Sediment Sample

Frequency range = 0-100%; 0 value 5*IDL or not detected.Potential results = 1053; n=29; % of results lost to 5*DL=~7%.

Pesticides Most Often Detected in BED SEDIMENT (> 5*IDL):

HCB (100%) 2,4’- and 4,4’-DDD, DDE (97-100%)

cis-and trans-chlordane (97%) 4,4’-DDT (93%)

Dieldrin and trans-nonachlor (88%)

Mean total analyte range ND to 260 g/kg dw

(endosulfan, endrin, and endrin ketone) to (4,4’-DDD)

Total DDT ~95% of the mean total mass for the Kill.Total chlordanes ~3% and HCB <1% of the mean total mass.

Arthur Kill OPR: Frequency of Detection versus Log Kow

0

20

40

60

80

100

0 1 2 3 4 5 6 7 8

LAB A LAB Q LAB W AVERAGEM

ean

Fre

qu

ency

of

Det

ecti

on (

%)

(>5*

DL

)

Log Kow (Table 3.7 L.H. Nowell et al., 1999)

HCB

Dieldrin

Mirex

DDDsDDEsDDTsChlordanesNonachlors

HCHsEndosulfans

Arthur Kill OPR: Frequency of Detection versus Half-Life

0

25

50

75

100

0 1000 2000 3000 4000 5000

LAB A LAB Q LAB W Average

HCB

Dieldrin

Mea

n F

req

uen

cy o

f D

etec

tion

(%

)(>

5*D

L)

Days (Table 3.7 L.H. Nowell et al., 1999)

Mirex

Endrin

DDDsDDEsDDTs

HeptachlorsLindaneEndosulfan sulfate

PESTICIDES in PLASMA from 3-week old CORMORANTS around Lake Erie

Potential Results = 972; 677 Results > 5*DL (70%); n=36

Pesticides Most Often Detected in Cormorant Plasma, Lake Erie:

100% 4,4’-DDE, dieldrin, endrin aldehyde, HCB, and mirex

97% Endrin ketone, heptachlor epoxide, and oxy-chlordane89% 2,4’-DDD and DDE, cis-nonachlor, and methoxychlor

Mean total range in plasma ND to 12 g/kg ww (endosulfan) to (4,4’-DDE)

4,4’-DDE ~63% to the mean total pesticide result.Total dieldrin ~6% to total pesticide mass.Total chlordane ~8% to total pesticide mass.HCB < 2%

How do the Lake Erie Results compare with NY Harbor Results (>1*IDL)?

• DDE occurred at the greatest concentrations of all pesticides.Mean range 1.1 to 42 g/kg (Lake Erie) vs. 1.07 to 89 g/kg ww (NY Harbor)

• Dieldrin had the second highest concentrations.Mean value 950 pg/g ww (Lake Erie) vs. 890 pg/g ww (NY Harbor)

• HCB levels were relatively low.Mean value 280 pg/g ww (Lake Erie) vs. 290 pg/g ww (NY Harbor)

• Pesticide levels in plasma were orders of magnitude lower than levels detected in cormorant eggs, but 4,4’-DDE still dominated the total DDT group (Parsons 2003).

• Levels in plasma attributed to pest plant (Parsons 2003).

Do the Plasma Method Blanks Impinge on the Cormorant Sample Results?

MB results do impinge on SA results, but only those analytes detected at or near 5*IDL.

Mea

n R

esu

lts

(g/

kg

wet

wei

ght)

(>5*

DL

)

0

2

4

6

8

10

12

14

2,4'-DD

D2,4'-D

DE

2,4'-DD

T4,4'-D

DD

4,4'-DD

E4,4'-D

DT

Aldrin

BH

C, alpha

BH

C, beta

BH

C, gam

ma

Chlordane,cis-

Chlordane, trans-

Chlordane,oxy-

Dieldrin

Endosulfan sulfate

Endosulfan, alpha

Endosulfan, beta

Endrin

Endrin aldehyde

Endrin k

etoneH

eptachlorH

eptachlor epoxideH

exachlorobenzeneM

ethoxychlorM

irexN

onachlor, cis-N

onachlor, trans-

samples method blanks

MBs: 0.0315 – 0.200

SAs: 5*DL – 12.4

Comparison of Whole Water XAD Samples (>10*idl) to NYS Water Quality Standards:

~68% of results < lowest USGS conventional est. DL of 1 ng/L.

Fewer detections/smaller concentrations “cleaner” waters.

Greater detections/larger concentrations urban areas or “orchard” valley.

TDDT and Tchlordane largest in Wallkill R. crop insecticides.

HCB low in all matrices, but WWTP synthetic fungicide.

Comparison of CARP Pesticides of Interest by Sample Medium

0

25

50

75

100

2,4'-DD

D2,4'-D

DE

2,4'-DD

T4,4'-D

DD

4,4'-DD

E4,4'-D

DT

Aldrin

BH

C, alpha

BH

C, beta

BH

C, gam

ma

Chlordane,alpha

Chlordane,gam

ma

Chlordane,oxy-

Dieldrin

Endosulfan sulfate

Endosulfan, alpha

Endosulfan, beta

Endrin

Endrin aldehyde

Endrin k

etoneH

eptachlorH

eptachlor epoxideH

exachlorobenzeneM

ethoxychlorM

irexN

onachlor, cis-N

onachlor, trans-Fr

eque

ncy

of C

ompo

unds

Det

ecte

d (>

5*D

L)

Plasma Sludge Bed Sediment XAD

Comparison of Concentrations of CARP Pesticides of Interest

plasmasludgebed sedimentXAD

Comparison of Mean Pesticide Frequency and Log Kow by Sample

MediaM

ean

Fre

qu

ency

of

Det

ecti

on (

%)

(>5*

DL

)

Log Kow (Table 3.7 L.H. Nowell et al., 1999)

0

25

50

75

100

2.5 3.5 4.5 5.5 6.5

sludge sediment bird plasma XAD

SUMMARY

NYSDEC HRMS-2 was capable of detecting chlorinated pesticides at sub-ppt levels in different media.

• The levels of pesticides in Hudson R. Basin waters were detected below conventional analytical method DLs (EPA method 608 and USGS NWQA method).

• NYS Water Quality Standards (WQS) are stringent and set below conventional analytical method DLs.

• NYS WQS between 1 (aldrin/dieldrin) and 40 ng/L (HCB) while EPA method 608 MDLs between 3 and 75 ng/L.

• About 88% of the ambient water data in the Harbor samples are < 3 ng/L (EPA 608).

Summary Continued Sample media influenced the detection of

pesticides. • aqueous medium “–” trend (low result w/ high S or high

Kow).• sludge, sediment, and plasma “+” trend (low result w/

low S or low Kow).

Frequency of detection and OC concentrations seen at sampling sites indicate the common land-use setting of that site.

• High detections/concentrations = OC application in agriculture valley and residential (3-711 persons/mi2).

• High detections/concentrations = pesticide manufacturing company and urban (20,000+ persons/mi2).

SUMMARY continued

The frequency of detection of OCs and their analytical results were dependent on sorption parameters, solubility in water and bioconcentration factors.

• BHCs contributed ~47% of the mean total mass in XAD samples (high S >1, low Kow <4).

• Total DDT contributed ~95% … in Arthur Kill bed sediment samples (low S <1 and high Kow >5).

• 4,4’-DDE contributed ~63% … in Lake Erie cormorant plasma samples and were very similar to NY Harbor results (high Koc) (Parsons for NYSDEC Fish and Wildlife 2003).

• 4,4’-DDD and DDE, -chlordane, and -chlordane contributed ~69% … in sludge samples (low S and high Kow).

Blanks impinge on the quality of the sample results.• But, the contribution is at relatively low (at 1*DL) levels.

• XAD sample handling methodologies in urban/residential field sites and the ubiquitous nature most likely contributed to the blank impingements at the IDL.

• Solution: Rinse extremely well between samples to eliminate carryover from sites known to be high in pesticides.

HCB was detected in all matrices at least 75% of the time.

• However, HCB contributed very little, < 6%, to the overall mean total pesticide concentration in any of the matrices.

SUMMARY continued

SUMMARY continued

NYS water quality standards were exceeded.• All sites exceeded NYSWQS for total chlordane.

• Wallkill R. and wastewater plants exceeded all WQS.

• Large tributaries and open water areas (NY Bight) exceeded the least number of WQS = “clean.”

The largest contributors of OCs to the Hudson R. Basin included …

• Wastewater treatment plants in an urban area (NY City).

• Wallkill R. at New Paltz in an agricultural valley.

• Landfills in an urban area (NY City).

Future Research

• Modeling the interactions between pesticides and trace, potentially toxic metals (Fe, Hg, Pb, Cd, …)– look at trend of HCB in the Basin since HCB infiltrates from metal

refineries and is synthetically produced and atmospherically transported to remote, open waters (Larsen et al., 1997).

• Obtaining studies of pesticide levels in cormorant plasma.– To our knowledge none exist, although there is information on

nestling carcasses and livers (Kury 1969, Kuiken et al. 1999, Custer et al. 2001).

• Extrapolating individual stream watershed interactions before applying it to a “regional” scale.

ANY QUESTIONS or COMMENTS ???