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, 4 th Floor, Albany, NY

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 CARP C ONTAMINANT A SSESSMENT and R EDUCTION P ROJECT  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 use manufacturing plants, and urban areas Carrier – lake/river bed sediment, aquatic life, whole/filtered water, plants, wind, herbivores, and sewage Trend (1960s-1990s) – OC studies decreasing in sediments and water Solubility (log K ow ) – S OC < S OP in water; log K ow,OC > log K ow,OP Concentrations – detected less than conventional est. detection limits of current validated methods

NYSDEC HRMS-2 Analytical Method for Detecetion of Organochlorine Pesticides: NYSDEC HRMS-2 HRGC  High  Resolution  Gas  Chromatography HRMS  High  Resolution  Mass  Spectrometry NYSDEC HRMS-2 is a performance based method.

27 ANALYTES of INTEREST FRACTION 1: Hexachlorobenzene (HCB) (alpha-, beta-, gamma-) Hexachlorocyclohexane (HCH) Heptachlor Aldrin (oxy-, cis-, trans-) Chlordane (cis-, trans-) Nonachlor Mirex (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 Method (1 L aq. samples) Analytes Number of Pests of Interest to NYS Est. Detection Range (  g/L) U.S. EPA 608 Aro/OC’s U.S.G.S SH2010 Pests/degr U.S.G.S LC9060 Pests/degr U.S. EPA 8081 OC’s U.S.G.S. NWQL Pests/degr NYSDEC HRMS-2 OC’s

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. 13 C 12 -Aldrin and 13 C 9 -  -Endosulphan). 2.Adding recovery standards to the sample just prior to analysis (e.g. 13 C 12 -PCB52, 13 C 12 -PCB138, and 13 C 12 -PCB153). 3.Concentrating the sample extract to a final volume (SDS Extraction with hexane to  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 ( 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 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, DDT HCH 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 ALAB QLAB W Samples Analyzed Possible Results Results > 5*DL Results > 1*DL

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-EBs mean result > 5*DL XAD SAs mean factor > 5*DL 4,4’DDD5.0 ± ,4’-DDE2.1 ± ,4’-DDD2.0 ± 1012 Methoxychlor1.2 ± Hexachlorobenzene1.1 ± exception …

Highest resultLowest resultExceed 90 th 90 th %tile FBs-EBs10 th %tile SAs%tile Blanks HCB %  -HCH % 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 (90 th percentile) only exceeded 10 th 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 = 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-nonachlor 92%  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 K ow Mean Frequency of Detection (%) (>5*DL) Log Kow (Table 3.7 L.H. Nowell et al., 1999) HCB Dieldrin Mirex DDDs DDEs DDTs Chlordanes Nonachlors HCHs Endosulfans

Arthur Kill OPR: Frequency of Detection versus Half-Life HCB Dieldrin Mean Frequency of Detection (%) (>5*DL) Days (Table 3.7 L.H. Nowell et al., 1999) Mirex Endrin DDDs DDEs DDTs Heptachlors Lindane Endosulfan 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-chlordane 89%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 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. Mean Results (  g/kg wet weight) (>5*DL) MBs: – 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

Comparison of Concentrations of CARP Pesticides of Interest plasma sludge bed sediment XAD

Comparison of Mean Pesticide Frequency and Log K ow by Sample Media Mean Frequency of Detection (%) (>5*DL) Log Kow (Table 3.7 L.H. Nowell et al., 1999)

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/mi 2 ). High detections/concentrations = pesticide manufacturing company and urban (20,000+ persons/mi 2 ).

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 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

 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 ???