### Department of Pesticide Regulation Environmental Monitoring Branch 1001 I Street, P.O. Box 4015 Sacramento, California 95812
Study 249. Statewide Urban Pesticide Use and Water Quality Monitoring Li-Ming (Lee) He
March 2008

1 INTRODUCTION

Urban pesticide use includes stru ctural pest control, landscape ma intenance, rights-of-way pest control, public health protecti on, and residential applications. The average annual non-residential reported pesticide use in California urban areas from 1995-2005 is ~14 million pounds of active ingredients (a.i.) (CDPR, 2006). The non-residential urban use of pesticides in 2006 in California amounted to ~500,000 lbs a.i. for permethrin, ~446,000 lbs a.i. for diuron, and ~220,000 lbs a.i. for oryzalin. The use of fipronil, which is ex clusively used in urba n areas in California (Gunasekara et al., 2007), has increased drama tically from 650 lbs in 2000 to ~100,000 lbs in 2006 (Ensminger, 2007). While residential use of pes ticides is not reporte d, total annual urban use may be approximately estimated for many pes ticides using pesticide sales data and reported use data. For example, the mean estimated annua l urban use of pesticid es during 2004 – 2005 in California was ~700,000 lbs a.i. for malathion, 200,000 lbs a.i. for carbaryl, and 740,000 lbs a.i. for pyrethroids. Based on comparison of pesticide use and sales data, pesticide applications in urban areas account for approximately 70% of pe sticide sales in California in 2005 (Spurlock, 2007). Higher urban pesticide use is anticipated in condense urba nized areas such as the San Francisco Bay, Sacramento, Los Angeles, and San Diego areas.

When urban use pesticide residues transport to storm drains or urban waterways by stormwater runoff (Guo et al., 2007) or urban baseflow, they may cause toxicity to sensitive aquatic species (Gunasekara et al., 2007; He et al., 2007). For example, stormwater samples collected from Chollas Creek, a highly urbanize d watershed in San Diego, Calif ornia exhibited toxicity to Strongylocentrotus and Ceriodaphnia . Toxicity identification ev aluations suggested that organophosphate pesticides, most likely diazinon and chlorpyrifos, were responsible for the toxicity observed in Ceriodaphnia (Schiff et al., 2002). Anothe r urban runoff study conducted in

### the great Los Angeles area indicated that commer cial and high-density residential land uses showed the highest diazinon concentrations as opposed to other urban land uses (Schiff and Sutula, 2004). The widespread urban use of orga nophosphate pesticides in California resulted in several urban waterbodies being placed in the Clean Water Act Section 303(d) list (SWRCB, 2007).

As urban uses of both diazinon and chlorpyrifos we re suspended in recent years, pyrethroid use has increased sharply. Recent monitoring of urban watersheds has identified potential pyrethroid impacts (Bondarenko et al., 2007; He et al., 2007; Xu et al., 2007; Yang et al., 2007). Nearly all creek sediments collected in Roseville, Califor nia - a typical suburban development in the Sacramento area caused toxicity to the amphipod Hyalella azteca , and about half the samples caused nearly complete mortality. The pyrethroi d bifenthrin was the primary cause of the toxicity, with additional contri butions from the pyrethroids cyfluthrin and cypermethrin. The dominant sources of these pyrethroids are stru ctural pest control by professional applicators and/or homeowner use of insecticides, particul arly lawn care products (Weston et al., 2005). The
authors concluded that the suburbs of Rosevill e are probably not unique, and similar sediment quality degradation is likely in other suburban ar eas, particularly in dry regions where landscape irrigation can dominate seasonal flow.

Pyrethroids are just one of the pe sticide groups that are widely used in urban areas in California. A recent retail store survey indicated that more than 320 pesticide products were on sale at three
stores in the San Francisco Ba y area, and these products contai ned 99 different a.i.’s (Moran, 2005). Another survey of 14 stores located in Sacramento County and the San Francisco Bay area revealed 542 different produc ts on sale, which contained 112 different a.i.’s (Flint, 2003), representing a wide spectrum of urban insecticides and herbicides. Data concerning how and to what degree the urban use of th ese pesticides impacts urban watersheds is lacking. Urban monitoring data are therefore needed in order to assess the potential imp acts of urban pesticide use on aquatic systems. A statewide consistent monitoring program will provide useful data on the environmental fate of urban use pesticides and for use in the deve lopment of management measures. This one-year project represents the Phase I of a multi-year monitoring program that includes urban pesticide use screen ing monitoring of water quality and focused investigations on potential source(s) and mitigati on measures for source reduction.

2

### 2 OBJECTIVES
This project attempts to address the following:

• Which pesticides (if any) are present in Califor nia urban surface waters at levels that have the potential to impact the bene ficial uses of those waters?

• 

### What are the potential sources of pesticides in urban runoff and their relative contribution to the receiving water problem?

The overall goal of the multiyear project is to assess urban pesticide use and water quality in urban drainage and receiving water from stormw ater runoff and baseflow in California’s major urbanized areas. The objectives of the first-year study include:

• Determining which pesticides are present in urban runoff,

• Evaluating the magnitude of measured concen trations relative to water quality or aquatic toxicity benchmarks, and

• Assessing the effect of waterbody type (stormwater drain vs. urban creek) and season (stormwater vs. non-stormwater ) on pesticide concentration and/or loading.
The proposed study will also measure other wa ter quality constituents, including dissolved oxygen, pH, electrolytic conductivity , and turbidity, to provide essential background information and an overall picture of wa ter quality as it relates to aquatic life criteria.

3 PERSONNEL
The study will be conducted by staff from the E nvironmental Monitoring Branch, Surface Water Protection Program, under the general direction of Dr. Kean S. Goh, Environmental Program Manager. Key personnel are listed below:
Project Leader: Li-Ming (Lee) He, P h.D. and Michael Ensminger, Ph.D.
Field Coordinator: Kevin Kelley and Matthew Goehring Senior Scientist: Frank Spurlock, Ph.D. Laboratory Liaison: Carissa Ganapathy

3

### Analytical Chemists: California Department of Food and Agriculture, Center for Analytical Chemistry. Staff Chemists

Questions concerning this monitori ng project should be directed to Li-Ming (Lee) He at (916) 327-7479 or by email at lhe@cdpr.ca.gov or Michael Ensminger at (916) 324-4186 or by email

at mensminger@cdpr.ca.gov

.

4 STUDY PLAN
4.1 Sampling

Monitoring will be conducted in four large urba n areas in northern and southern California, including the greater Sacramento area, the gr eater San Francisco Bay area, the greater Los Angeles area, and the greater San Diego area. This project will be coordina ted or leveraged with existing DPR-funded investigations including th ose monitoring efforts already underway through UC Riverside (Gan et al., 2007; Greenberg, 2007), UC Davis (Gan et al., 2007), and UC Cooperative Extension, or established relationships with Regional Water Quality Control Boards, Southern California Coastal Water Research Project, and California stormwater management agencies/organizations.

All monitoring sites will be established in each area by cooperating with local water quality agencies using currently available informa tion including land use data, catchment area, representativeness, historical wate r quality data, safety and accessi bility, and site reconnaissance.

There will be four or seven monitoring sites in each area (Appendices 1 and 2). The monitoring sites are categorized to stormdrain discharges a nd receiving waters. Stormdrain discharges refer to stormdrain outfalls, which represent effluent s that may contain pesticides. Such samples would represent worst-case conditions (i.e., high est possible pesticide co ncentrations). If the compounds are not detected in the discharges th emselves, it is unlikely that toxicity would
remain after release to and dilution within a receiving water. Receiving waters refer to any waterbody that receives runoff discharges. Samp ling at stormdrains and receiving waters is intended to identify potential pesticides cont ributed by each category of discharges, their concentration at the poin t of discharge, and differences be tween dry- and wet-flow conditions.

4

### Sampling will take place in both dry flow (basef low) and wet flow (rainstorm) conditions during the year of monitoring. Three dry- and three wet-flow samplings will be conducted at each sampling site in each area. The dry-flow sa mpling will be conducted during the dry weather season (May through September). The wet-flow sa mpling will include the time of the first flush of the first storm (2008-2009 water year) and the first flushes of two other rainstorm events (2007-2008 water year).

The composite sampling method will be used duri ng a storm event wherever feasible. Safety for equipment setup and/or limitation of appropriate field equipment availability may prevent the use of composite sampling. In this case, grab sa mpling will be used. Composite samples will be collected using polyethylene car boys and subsequently split in to amber glass bottles. Grab samples will be collected into 1-L amber glass bottles. Samples will be collected as close to center channel as possible. Excluding receiving water samples, all other discharges will be sampled just prior to the point of release to a receiving water to avoid the effect of dilution and mixing from other inputs upstream. Samples will be stored on ice (~4 o 

### C) and transported to the designated laboratory for chemical analysis.

Sediment samples (0 to 3 samples) will be colle cted into glass jars near the location of a stormdrain outfall during the dry-flow season. Effl uent quality is inherently variable, and it is possible that we could fail to obtain water samples from one or more of the discharges at times of significant pesticide input to a r eceiving water. Since sediments se rve as an integrator of longterm pesticide exposure, it is likely that a ny significant and persistent discharge would potentially produce elevated pesticide c oncentrations in nearby sediments.

4.2 Field Measurement

Physicochemical properties of water will be determined using a portable multi-parameter water quality monitoring system. Water parameters measured in situ at each site during each sampling event will include pH, temper ature, conductivity, turbidity, an d dissolved oxygen. Salinity and
total dissolved solids will be es timated from conductivity. These da ta will be used to supplement and help interpret other data including pesticides.

5

### To provide for interpretation of the monitoring data in the cont ext of the hydrological conditions present during monitoring events, rainfall amount a nd duration will be recorded from the nearest reliable rain gauge for each monitoring event. St ormdrain discharge or stream flow rates will be measured to characterize the flow regime in eff ect and to estimate the total loading of target pesticides. Flow will be measured using a deploy able flowmeter or a portable flow probe. Flow data may also be obtained from an existi ng stream gauge station where available.

All field measured data and other information will be recorded to a standardized field datasheet.

4.3 Laboratory Analysis
Pesticide analytes were determined based on cu rrent urban pesticide us e or sale information (Flint, 2003; Kreidich et al., 2005; Moran, 2007) , historical surface water monitoring data (CDPR, 2007), preliminary results from urban m onitoring in progress (G an et al., 2007), and aquatic toxicity (USEPA, 2007a). The current proposed list of analytes includes the following pesticide groups:

• Insecticides - Pyreth roids (in sediment only), carbama tes, organophosphates, and fipronil & metabolites;

• Herbicides - Dinitroanilines, photosynthetic inhibitors (e.g., tr iazines), and auxin transport inhibitors (e.g., phenoxys).

The full list of pesticides, including specific an alyte names, is available in Appendix 3. These pesticides will be analyzed using currently available analytical methods. All samples will be analyzed by the California Department of F ood and Agriculture’s Center for Analytical Chemistry, which is located in Sacramento, Ca lifornia. Analytical me thods, analytes, method detection limits, and reporting limits for this stu dy are also given in Appendix 3. Details of the chemical analysis methods and method detectio n/reporting limits for newly developed methods will be updated when available. The list of analyt es may be updated or modified at any time as
new information becomes available or due to changes in available resources.

6

### We will also measure total suspended solids (T SS) in water samples and total organic carbon (TOC) in both water and sediment samples using standard methods.

5 QUALITY ASSURANCE
Quality assurance and quality control (QA/QC) will be performed in acco rdance with Standard Operating Procedure QAQC001.00 (Segawa, 1995), whic h includes criteria for QC samples. Ten percent of the total number of samples will be submitted as field blanks, blind spikes, or field duplicates. In addition, QA/QC procedures developed by US EPA (1998) and for SWAMP by SWRCB (Puckett, 2002) will be consulted where applicable.

6 DATA MANAGEMENT

All data generated by this project will be ma intained in the DPR facility. DPR staff (its contractors if any) will be responsible for co llection of samples and field data. The project leaders will be responsible for managing all data including field information, field measurements, laboratory analytical data us ing an existing database or developing a new database for the project.

7 DATA ANALYSIS AND REPORTING

Water quality will be assessed based on comparison of analytical data with water quality objectives or benchmarks indica ting potential for biological eff ects. Water quality objectives established by US EPA or California will be used for comparison to measured concentrations whenever available. The benchmarks for pesticides developed by US EPA will be used when water quality standards are not av ailable (USEPA, 2007c). Other aquatic effects data may also be used for comparison to measured concentrations, including LC 50 

### or EC 50 

### (e.g., Table 1) (US EPA, 2007a). The content of pyrethroids in sedime nt will be compared with sediment toxicity data (Table 2) developed by Amweg et al. (200 5). Data collected from this project will be analyzed to determine summary statistics of concentrations and dete ction frequencies, and

7

### statistical analysis to de termine the effect of different factor s such as runoff type (e.g. stormwater vs. baseflow), season or geographic location ma y be conducted. Final project report(s) will be prepared by project leader(s ) in coordination with other project team members.

8

### Table 1. LC 50 

### or EC 50 

### of pesticides for select standa rd aquatic organisms (USEPA, 2007b)
derived from US EPA Pesticid e ECOTOX Database (2007a)

Insecticides LC 50 

### in μ g/L Herbicides EC 50 

### in μ g/L 3

Active Ingredients A. bahia 1 Daphnia 2 C. dubia 2 Active Ingredients Green Algae Beta-Cyfluthrin 0.00242 0.17 0.14 Atrazine 4.3
Bifenthrin 0.00397 0.32 0.07 Bromacil 6.8 Carbaryl 5.7 1.25 11.6 Dicamba 61 Chlorpyrifos 0.035 0.21 0.058 Dichlobenil 2700 Cyfluthrin 0.00242 0.17 0.14 Diuron 1.3 Cypermethrin 0.0047 0.36 0.889 Glyphosate 3530
Deltamethrin 0.0017 0.037 NA Linuron 38.8
Diazinon 4.2 0.65 0.21 Oryzalin 24
Esfenvalerate NA 0.27 0.28 Simazine 82 Fipronil 0.14 15.6 17.5 Imidacloprid 38 NA NA Lambda-Cyhalothrin 0.0041 1.04 0.3
Malathion 2.2 1.6 1.14
Permethrin 0.02 1.25 0.55
Tralomethrin NA 0.15 0.26

1 Americamysis bahia (Mysiopsis bahia) with the common name mysid shrimp. 96 h in marine water.

2 Daphnia and Ceriodaphnia dubia, 48 h in freshwater.

3 96-120 h.

NA - not available.

Table 2. Sediment toxicity of Hyalella azteca to pyrethroids (10-d LC50 in μ g/g sediment organic carbon) (Amweg et al., 2005)

Bifenthrin Cyfluthrin Deltamethrin Esfenvalerate Lambda-cyhalothrin Permethrin

0.18 1.08 0.79 0.89 0.45 4.88



### 9

### 8 PROJECT SCHEDULE

This one-year project represents the Phase I of a multi-year monitoring program that includes urban pesticide use screening monitoring of water quality and focused investigations on potential source(s) and mitigation measures for source reduction. The schedule of major activities associated with this project is shown in the follo wing table (Table 3). Some of the tasks listed in the table will be accomplished as scheduled, but they can be modified and improved as more information is obtained from ongoing monitorin g, for example, sampling protocol, chemical analysis, or data quality criteria may be modified as needed.

Table 3. Project Schedule

Tasks NOV DEC JAN FEB MAR APR MAY JUN JUL AUG SEP OCT NOV DEC JAN Identify sampling locations Develop field datasheet/contract Develop detailed sampling protocol Conduct sampling and
measurement Perform laboratory analysis Data Management Perform data analysis and interpretation Final Report



### 10

### 9 BUDGET
Provided below is the proposed budget for the project . Since the project will be carried out in the 2008 calendar year, the total cost has been proportioned in FY07-08 and FY08-09 as shown
below.

FY07-08 

### Sample Samples Price/Sample Cost
Stormdrain water 54 3715 200610 Receiving water 21 3715 78015
Sediment 14 800 11200 Field duplicate 8 3715 29720
Field Blank 4 3715 14860

Total 101 334,405* *See Appendix 1 for details.

The cost for continuing QC samples is not included.

FY08-09 

### Sample Samples Price/Sample Cost
Stormdrain water 54 3715 200610 Receiving water 21 3715 78015
Sediment 0 800 0 Field duplicate 4 3715 14860
Field Blank 0 3715 0

Total 79 293,485*

*See Appendix 2 for details. The cost for continuing QC samples is not included.



### 11

### 10 REFERENCES
Amweg, E.L., D.P. Weston, and N.M. Ureda. 2005. Us e and toxicity of pyret hroid pesticides in the Central Valley, California, USA. Environ Toxicol Chem 24:966-972. Bondarenko, S., F. Spurlock, and J. Gan. 2007. Analys is of pyrethroids in sediment pore water by solid-phase microextraction. Environ. Toxicol. Chem. 26:2587-2593. CDPR. 2006. Summary of pestic ide use report data 2005. 495 pp.
CDPR. 2007. Surface Water Database. http://www.cdpr.ca.gov/docs/emon/surfwtr/surfdata.htm

. Ensminger, M. 2007. Fipronil Use in California - 1999-2006. Flint, M.L. 2003. Residential pesticide use in Ca lifornia: A survey of the Sacramento, Stockton and San Francisco Bay Areas. 198 p. University of California. Gan, J., L. Oki, and D. Hover. 2007. Fipronil in urban runoff - A PowerPoint presentation. Greenberg, L. 2007. Measuring pesticide runo ff from individual homes - A PowerPoint presentation. Gunasekara, A., T. Truong, K.S. Goh, F. Spur lock, and R.S. Tjeerdema. 2007. Environmental fate and toxicology of fipronil. J. Pestic. Sci. 32:189-199. Guo, L., K. Kelley, and K.S. Goh. 2007. Evaluation of sources and loading of pesticides to the Sacramento River, California, USA, duri ng a storm event of winter 2005. Environ.
Contam. Toxicol. 26:2274-2281. He, L.-M., J. Troiano, A. Wang, and K. Goh. 200 7. Environmental chemistry, ecotoxicity, and fate of lambda-cyhalothrin. Reviews of Environmental Contamination and Toxicity In

press. Moran, K.D. 2005. San Francisco Bay Area pesticide retail store survey. 19 p. Moran, K.D. 2007. Pesticides in urban surface water- - Urban pesticides use trends annual report 2007. 45 p. Puckett, M. 2002. Quality Assurance Management Plan for the State of California's Surface Water Ambient Monitoring Program (SWAMP). California Department of Fish and Game, Monterey, CA. Prepared by the State Water Resources Control Board, Sacramento, CA. 145 pages plus appendices. Schiff, K., and M. Sutula. 2004. Organophosphorous pesticides in storm-water runoff from southern California (USA). Environ Toxicol Chem:1815-1821.

12

### Schiff, K., S. Bay, and C. Stransky. 2002. Charact erization of stormwater toxicants from an
urban watershed to freshwater and ma rine organisms. Urban Water 4:215-227. Segawa, R. 1995. Chemistry Laboratory Quality Control. Environmental Hazards Assessment Program QAQC001.00. Department of Pes ticide Regulation, Sacramento, CA. Spurlock, F. 2007. Urban pesticide use. SWRCB. 2007. 2006 Clean Water Act Section 303( d) list of water qua lity limited segments,
available on-line: http://www.swrcb.ca.gov/tmdl/303d_lists2006approved.html

. USEPA. 1998. Guidance for Quality Assuran ce Project Plans (QA/ G-5), EPA/600/R-98/018,
Office of Research and Development.
USEPA. 2007a. Pesticide ECOTOX database. http://cfpub.epa.gov/eco tox/quick_query.htm

. USEPA. 2007b. Guidelines establishi ng test procedures for the analys is of pollutants; Analytical methods for biological pollutant s in wastewater and sewage sludge: Final rule. Federal Register/Vol. 72, No. 57/Monday, March 26, 2007. USEPA. 2007c. Aquatic Life Benchmark Table. http://www.epa.gov/oppefed1/ecoris k_ders/aquatic_life_benchmark.htm

. Weston, D.P., R.W. Holmes, J. Y ou, and M.J. Lydy. 2005. Aquatic toxi city due to residential use of pyrethroid insecticides. E nviron. Sci. Technol. 39:9778-9784. Xu, Y., F. Spurlock, Z. Wang, and J. Gan. 2007. Comparison of five methods for measuring sediment toxicity of hydrophobic contaminan ts. Environ. Sci. Technol. Web Release
Date: 13-Nov-2007. Yang, W.C., W. Hunter, F. Spurlock, and J. Gan. 2007. Bioavailability of permethrin and cyfluthrin in surface waters with low levels of dissolved organic matter. . J. Environ. Qual. 36:1678-1685.

13Appendix 1. FY07-08 Monitoring sites, pesticides screening, and analyticalcost estimate for urban pesticides use and water quality

#Sampling Sites # Sampling EventsAnalytes

Sample Type S acramento A rea Bay Area LA Area San Diego Area Rainstorm Baseflow # Samples Fipronil (1) Pyrethroids(2) Carbamates(3) Organophosph ates (4) photosynthetic inhibitors (5) Dinitroanilines (6) Auxin transport inhibitors (7) TSS and TOC (8) Price/Sample CostStormdrain Discharges35551254$ 500$ -$ 800$ 320$ 720$ 800$ 575$ -$ 3,715$ 200,610Receiving Water12221221$ 500$ -$ 800$ 320$ 720$ 800$ 575$ -$ 3,715$ 78,015Sediment (same sites asstormdrain discharges)(9)24440114$ -$ 800$ -$ -$ -$ -$ -$ -$ 800$ 11,200Field Duplicate (wateronly)1111118$ 500$ -$ 800$ 320$ 720$ 800$ 575$ -$ 3,715$ 29,720Field Blank (water only)1111014$ 500$ -$ 800$ 320$ 720$ 800$ 575$ -$ 3,715$ 14,860Total4777101$ 15,660$ 334,405(1) Analytes include degradates.(2) Sediment sampling for 1 or 2 sites in each region.(3) Carbaryl included.(4) Malathion included. Only 2 sites in each region. 1/2 the price was used in estimating the cost.(5) Atrazine, simazine, diuron, bromacil included.(6) Oryzalin and prodiamine included.(7) The phenoxy screen includes dicamba.(8) To be analyzed in house or using a contract lab.(9) Sediment sampling and analysis are limited to pyrethroids only.Appendix 2. FY08-09 Monitoring sites, pesticides screening, and analyticalcost estimate for urban pesticides use and water quality

#Sampling Sites # Sampling EventsAnalytes

Sample Type S acramento A rea Bay Area LA Area S an Diego Area Rainstorm Baseflow # Samples Fipronil (1) Pyrethroids(2) Carbamates(3) Organophosph ates (4) photosynthetic inhibitors (5) Dinitroanilines (6) Auxin transport inhibitors (7) TSS and TOC (8) Price/Sample CostStormdrain Discharges35552154$ 500$ -$ 800$ 400$ 720$ 800$ 575$ -$ 3,795$ 200,610Receiving Water12222121$ 500$ -$ 800$ 400$ 720$ 800$ 575$ -$ 3,795$ 78,015Sediment (same sites asstormdrain discharges) (9)0000000$ -$ 800$ -$ -$ -$ -$ -$ -$ 800$ -Field Duplicate (water only)1111104$ 500$ -$ 800$ 400$ 720$ 800$ 575$ -$ 3,795$ 14,860Field Blank (water only)1111000$ 500$ -$ 800$ 400$ 720$ 800$ 575$ -$ 3,795$ -Total477779$ 15,980$ 293,485(1) Analytes include degradates.(2) Sediment sampling for 1 or 2 sites in each region.(3) Carbaryl included.(4) Malathion included. Only 2 sites in each region. 1/2 the price was used in estimating the cost.(5) Atrazine, simazine, diuron, bromacil included.(6) Oryzalin and prodiamine included.(7) The phenoxy screen includes dicamba.(8) To be analyzed in house or using a contract lab.(9) Sediment sampling and analysis are limited to pyrethroids only.15

### Appendix 3. Analytes, method detection limit, and reporting limit ǂ

Matrix: Water Analyte Group: Carbamates (CB)
Method: HPLC

Method Detection Limit Reporting Limit Compound ( μ g/L) ( μ g/L)
Aldicarb Sulfoxide 0.011 0.05
Aldicarb Sulfone 0.02 0.05 Methomyl 0.01 0.05
3-OH Carbofuran 0.011 0.05
Aldicarb 0.01 0.05
Carbofuran 0.01 0.05 Carbaryl 0.011 0.05 Oxymyl 0.02 0.05
Methiocarb 0.016 0.05

ǂ Listed in these tables are analytes include d in the long screening list of pesticides, some of which may not be used in urban a reas. Some of the pesticides presented in the table may not be analyzed when a short screening list is us ed for chemical analysis due to higher c osts for analyzing a full list of pesticides.Matrix: Water Analyte Group: Dinitroanilines (DN)
Method: GC/TQMS

Method Detection Limit Reporting Limit Compound ( μ g/L) ( μ g/L)
Benfluralin 0.012 0.05
Ethalfluralin 0.015 0.05
Oryzalin (LCQ) 0.0048 0.05

Pendimethalin 0.012 0.05
Prodiamine 0.012 0.05

Trifluralin 0.014 0.05 Oxyfluorfen 0.01 0.05



### 17Matrix: Water Analyte Group: Fipronil & Metabolites (FP)
Method: GC/MSD in the SIM mode

Method Detection Limit Reporting Limit Compound ( μ g/L) ( μ g/L) Fipronil 0.004 0.05 Desulfinyl fipronil 0.003 0.05 Desulfinyl fipronil amide 0.005 0.05 Fipronil sulfide 0.003 0.05 Fipronil sulfone 0.005 0.05 Fipronil amide 0.005 0.05



### 18Matrix: Water Analyte Group: Organophosphates (OP)
Method: GC/FPD

Method Detection Limit Reporting Limit Compound ( μ g/L) ( μ g/L) Ethoprop 0.0098 0.05
Diazinon 0.011 0.04
Disulfoton 0.0093 0.04 Chlorpyrifos 0.0109 0.04
Malathion 0.0117 0.04
Methidathion 0.0111 0.05 Fenamiphos 0.0125 0.05 Azinphos methyl 0.0099 0.05
Dichlorvos 0.0098 0.05
Phorate 0.0083 0.05
Fonofos 0.0080 0.04
Dimethoate 0.0079 0.04 Methyl Parathion 0.0080 0.03
Tribufos 0.0142 0.05
Profenofos 0.0114 0.05

GC/MS ( μ g/L) ( μ g/L)
Diazinon 0.0012 0.01 Chlorpyrifos 0.0079 0.01
*in clean American River wate r



### 19Matrix: Water Analyte Group: Auxin transport inhibitors [Phenoxys (PX)]
Method: GC/MS

Method Detection Limit Reporting Limit Compound ( μ g/L) ( μ g/L)
Dicamba 0.064 0.1 2,4-D 0.064 0.1
MCPA 0.064 0.1 Triclopyr 0.064 0.1



### 20Matrix: Sediment Analyte Group: Pyrethroids (PY)
Method: GC/ECD

Method Detection Limit Reporting Limit Compound ( μ g/kg) ( μ g/kg)
Bifenthrin 0.108 1.0 Fenopropathrin 0.109 1.0 Lambda-cyhalothrin epimer 0.117 1.0 Lambda-cyhalothrin 0.115 1.0
Permethrin cis 0.116 1.0
Permethrin trans 0.135 1.0 Cyfluthrin 0.183 1.0 Cypermethrin 0.107 1.0
Fenvalerate/esfenvalerate 0.143 1.0
Deltamethrin 0.0661 1.0 Resmethrin (GC/MSD) 0.870 1.5



### 21Matrix: Water Analyte Group: Photosynthetic inhibitors [Triazines (TR)]
Method: LC/MS/MS

Method Detection Limit Reporting Limit Compound ( μ g/L) ( μ g/L)
Atrazine 0.020 0.05
Simazine 0.013 0.05
Diuron 0.022 0.05
Prometon 0.016 0.05
Bromacil 0.031 0.05 Prometryn 0.016 0.05
Hexazinone 0.040 0.05
Metribuzin 0.025 0.05
Norflurazon 0.019 0.05
DEA 0.01 0.05
ACET 0.03 0.05
DACT 0.016 0.05



### 22