1 using integrative passive samplers to monitor current-use and legacy pesticides in san francisco...
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![Page 1: 1 Using Integrative Passive Samplers to Monitor Current-Use and Legacy Pesticides in San Francisco Bay, CA Kelly L. Smalling and Kathryn M. Kuivila USGS](https://reader035.vdocuments.site/reader035/viewer/2022070410/56649f045503460f94c17d96/html5/thumbnails/1.jpg)
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Using Integrative Passive Samplers to Monitor Current-Use and Legacy
Pesticides in San Francisco Bay, CA
Kelly L. Smalling and Kathryn M. Kuivila
USGS California Water Science CenterSacramento, CA
April 24, 2007
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Suisun Marsh
• Largest contiguous estuarine marsh on US west coast
• Major, but often ignored, component of the SF Estuary
• Covers 116,000 acres, including managed wetlands, upland grasses, tidal wetlands, channels and sloughs
• Intensely altered and managed for more than 100 years, mostly as a non-tidal freshwater wetland for waterfowl
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Importance of Suisun Marsh
• Recognized as valuable tidal brackish environment and important habitat for native fish
• Supports at least 43 plant and animal species of special concern
• Best place left in the estuary to restore large areas of tidal marsh
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Sampled 3 Sloughs with different contaminant inputs Summer 2005 and Winter 2006
Hill Slough
Peytonia Slough
Boynton Slough
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• Urban input: EPA 303d list for current-use insecticides• Travis AFB - legacy organochlorine pesticides and current-use pesticides• Inactive landfills - legacy organochlorine pesticides
Hill Slough
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• Urban input: EPA 303d list for current-use insecticides and likely other pesticides from home use
• Managed wetlands - duck ponds with high DOM
Peytonia Slough
Duck Clubs
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• WWTP: likely source of current-use pesticides from home use
Boynton Slough
WWTP
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Why Passive Samplers?
• Integrate over time
• Interested in a wide range of pesticides (log Kow = 1.5-7)
– Combined SPMDs and POCIS to cover the range of Kow
• Monitoring legacy organochlorines and pyrethroids
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Polar organic chemical integrative sampler (POCIS)
used to monitor hydrophilic contaminants in water
• Easy to extract and analyze
• Contaminants with log Kow <4
• Integrates over time
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SPMD/POCIS deployment/retrieval
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POCIS Extraction/Analysis• Rinsed HLB sorbent
into glass columns with MeOH
• Extracted w/ 1:1:8 MeOH:EtOAc:DCM
• Filtered particulates using GF/F.
• Removed matrix with carbon SPE cartridges
• Analyzed by GC/MS for ~ 50 pesticides
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Pesticide Concentrations in POCIS Samplers (ng/gPOCIS)
1
10
100
1000
10000
Boynton
SloughHill
SloughPeytonia Slough
BoyntonSlough
Hill Slough
CP
OC
IS (
ng
/g)
SIMAZINE
METOLACHLOR
TRIFLURALIN
PENDIMETHALIN
FIPRONIL
Summer Winter
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POCIS Field Validation
• Collected water samples at beginning and end of each deployment
• Current-use pesticides detected in both water samples at a site (pendimethalin, simazine)
• Other pesticides were only detected in one of the samples at a site (hexazinone, oxyfluorfen)
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TRIF
LURALI
N
SIMAZI
NE
METO
LACHLO
R
PENDIMETH
ALIN
FIPRO
NIL
0
1
1
0
PO
CIS
Wa
ter
Frequency of Detection
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Comparison of Water Analysis with POCIS
• If detected in water, results of POCIS agreed well (pendimethalin, simazine, trifluralin)
• Some pesticides detected at low concentrations in POCIS but at or below detection limit in water (metolachlor)
• Transient compounds do not show up in POCIS (hexazinone)
• Good indicator of water concentration over time • Eliminates the need to catch definitive pesticide ‘pulses’• Does not over estimate
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PROBLEMS ??
Biofouling and sediment build-up may hinder uptake in environments with high-suspended sediment loads
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Semi-permeable membrane devices (SPMDs)
used to monitor hydrophobic contaminants in water
• Samples only dissolved form
• Contaminants with log Kow >4
• Integrates over time
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SPMD Extraction/Analysis• Dialyzed 24 hrs in hexane
(EST)• Matrix/lipid removed by GPC
(98:2 DCM:MeOH)• Clean-up/fractionation
– 5 g Florisil (5% deactivated)– 5 g activated silica gel– Collected 2 fractions
• Analyzed by GC/MS (25 current-use) and GC/ECD (26 legacy OCs)
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0.2
0.6
1.0
1.4
1.8
-C
hlor
dane
Die
ldrin
4,4
DD
E
4,4
DD
D
4,4
DD
T
Re
lati
ve
Ab
un
dan
ce
C
hlor
dane
Boynton SloughHill SloughPeytonia Slough
0.2
0.6
1.0
1.4
1.8
Summer
Winter
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0
1
10
100
1000
10000
Boynton Slough
HillSlough
PeytoniaSlough
Boynton Slough
Hill Slough
Co
nce
ntr
atio
n (
ng
/SP
MD
) TRIFLURALIN
PCA
PCNB
CHLORPYRIFOS
PENDIMETHALIN
BIFENTHRIN
PERMETHRIN
Summer Winter
Current-use Pesticides in SPMDs
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0
1
2
3
4
5
6
7
8
9
10
Boynton Slough
Hill Slough
PeytoniaSlough
BoyntonSlough
Hill Slough
Nu
mb
er
of
de
tec
tsCurrent-useLegacy OCs
Summer Winter
• Constant source of legacy OCs to the estuary year around
• Occurrence of current-use pesticides dependent on use and run-off
• Greater number of detects in the winter compared to the summer
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POCIS
SPMD
decreasing solubility –increasing
hydrophobicity
Metolachlor
Fipronil
Simazine
Trifluralin
Pendimethalin
PCA
Chlorpyrifos
PCNB
Dieldrin
Bifenthrin
Chlordanes
4,4 DDD
Permethrin
4,4 DDE
4,4 DDT
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• Of interest due to increasing use and high toxicity to fish
• Should work since log Kow > 4
• But size and shape hinder their passing through the SPMD membrane
• Also more difficult to remove pyrethroids from SPMDs, resulting in high background of extracted samples
Pyrethroids in SPMDs
O
Cl
O
FF
F
ClO
O
O
Cl
O
O
NH
Cl
F
F
F
O N
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Using Passive Samplers for Pesticides
• Useful to combine POCIS (more polar/hydrophilic) with SPMDs (more hydrophobic/less water soluble)
• Good indicator for concentrations below typical MDLs
• Integrate over time – eliminate complexity due to episodic pulses
• ALWAYS TEST – potential problems with pyrethroids
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Future Directions
• Laboratory uptake studies to validate effectiveness of passive samplers for current-use pesticides
• Specifically focus on pyrethroids and uptake/extraction from SPMDs
• Future deployments of samplers in other areas where dissolved pesticides are of concern
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Acknowledgments
• Funded by USGS Priority Ecosystem Science Study
• James Orlando (USGS Sacramento, CA)• Cynthia Brown, Ed Moon and Francis Parcheso
(USGS, Menlo Park, CA)• Carl Orazio, David Alvarez, and Walter Crannor
(USGS, Columbia, MO)• Environmental Sampling Technologies (EST)