PESTICIDES in the HUDSON RIVER BASIN analyzed by HRGC/HRMS: RESULTS, DATA QUALITY, and IMPLICATIONS...
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Transcript of PESTICIDES in the HUDSON RIVER BASIN analyzed by HRGC/HRMS: RESULTS, DATA QUALITY, and IMPLICATIONS...
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 ???