Prepared in cooperation with the U.S. Environmental Protection Agency

Collection of Pyrethroids in Water and Sediment Matrices: 

Development and Validation of a Standard Operating 

Procedure

U.S. Department of the Interior

U.S. Geological Survey

Scientific Investigations Report 2009–5012
 1

Cover: Demonstrating the use of a churn sampler, 2005. (Photograph taken by Mark Sandstrom, U.S. Geological survey.)
Collection of Pyrethroids in Water and 

Sediment Matrices: Development and 

Validation of a Standard Operating 

Procedure

By Michelle L. Hladik, James L. Orlando, and Kathryn M. Kuivila

Prepared in cooperation with U.S. Environmental Protection Agency

Sciencific Investigations Report 2009–5012

U.S. Department of the Interior

U.S. Geological Survey
U.S. Department of the Interior

KEN SALAZAR, Secretary

U.S. Geological Survey

Suzette M. Kimball, Acting Director

U.S. Geological Survey, Reston, Virginia: 2009

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Suggested citation:

Hladik, M.L., Orlando J.L., and Kuivila, K.M., 2009, Collection of pyrethroids in water and sediment matrices: 

development and validation of a standard operating procedure: U.S. Geological Survey Scientific Investigations 

Report 2009–5012, 22 p. Available at http://pubs.usgs.gov/sir/2009/5012/
iii

Acknowledgments

We would like to thank Debra Denton, Patti Tenbrook, John Zimmerman and 

Brian Schumacher of the U.S. Environmental Protection Agency (USEPA) for their 

technical guidance. Dave Crane, California Department of Fish and Game, and 

Li-Ming He, California Department of Pesticide regulation, provided assistance in 

reviewing the report.
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v

Contents

Abstract...........................................................................................................................................................1

Introduction.....................................................................................................................................................1

Prior Research on Pyrethroid Losses ...............................................................................................2

Sample Containers ......................................................................................................................2

Sample Holding ............................................................................................................................3

Purpose and Scope ..............................................................................................................................3

Experimental Design and Methodology.....................................................................................................3

Sample-Collection Design...................................................................................................................3

Sampling Devices .................................................................................................................................3

Water Matrices ............................................................................................................................3

Sediment Matrices ......................................................................................................................4

Pyrethroid Analysis...............................................................................................................................5

Quality Control ......................................................................................................................................5

Results .............................................................................................................................................................5

Sample Devices for Water Matrices .................................................................................................5

One–Liter Containers ..................................................................................................................5

Glass ..................................................................................................................................5

Teflon ..................................................................................................................................8

Large-Volume Containers...........................................................................................................8

Low-density polyethylene 4- and 19-liter Cubitainers® ................................................8

Nineteen-Liter Stainless-Steel Soda Kegs ..................................................................10

Collection and Processing Equipment for Water Matrices .........................................................10

Filtration Apparatus ..................................................................................................................10

Teflon Churn................................................................................................................................10

US D-96 Isokenetic Depth-Integrating Sampler...................................................................12

ISCO Autosampler .....................................................................................................................12

Sample Containers for Sediment Matrices ...................................................................................12

Summary........................................................................................................................................................13

References Cited..........................................................................................................................................13

Appendix: Standard Operating Procedure for Sampling Pyrethroid Insecticides in 

Water and Sediment......................................................................................................................15

Procedures...........................................................................................................................................16

1.0 Purpose and Applicability...............................................................................................16

2.0 Summary of the Method.................................................................................................16

3.0 Definitions..........................................................................................................................17

4.0 Health and Safety Warnings...........................................................................................17

5.0 Cautions .............................................................................................................................17

6.0 Interferences ....................................................................................................................17

7.0 Personnel Qualifications.................................................................................................17

8.0 Equipment And Supplies .................................................................................................17

9.0 Sample Collection—Overview.......................................................................................18

10.0 Sample Collection—Method Options............................................................................20
vi

10.1 Water................................................................................................................................20

10.1.1 Grab Sample........................................................................................................20

10.1.2 Isokinetic Depth-Integrated Sample...............................................................20

10.1.3 Large-Volume Sample .......................................................................................20

10.1.4 Autosampler........................................................................................................21

10.2 Sediment Sample ...........................................................................................................21

11.0 Sample Handling and Preservation......................................................................................21

11.1 Sample Holding...............................................................................................................21

11.2 Sample Handling ............................................................................................................21

12.0 Quality Assurance and Quality Control................................................................................22

Figures

Figure 1. Fraction of pyrethroids associated with 1-liter glass bottle walls.....................................7

Figure 2. Fraction of pyrethroids associated with 1-liter glass bottles at 

 two different concentrations...................................................................................................7

Figure 3. Fraction of pyrethroids associated with 1-liter glass bottles with varying DOC .............8

Figure 4. Fraction of pyrethroids associated with 1-liter glass and Teflon bottles..........................9

Figure 5. Fraction of pyrethroids associated with 1-liter Teflon bottles............................................9

Figure 6. Fraction of pyrethroids left in the filtration pump ...............................................................11

Figure 7. Fraction of pyrethroids associated with the churn walls..................................................11

Tables

Table 1. Summary of devices tested for pyrethroid losses for water samples ...............................4

Table 2. Comparison of the project quality-assurance/quality control (QA/QC) plan 

 with the Surface Water Ambient Monitoring Program (SWAMP) quality-control 

 requirements for organic constituents (pesticides) in water and sediment .....................6

Table 3. Loss of pyrethroids to 4-liter and 19-liter Cubitainers®, and to 19-liter 

 stainless-steel soda kegs ........................................................................................................10

Table 4. Losses of pyrethroids to 3-liter Teflon bags .........................................................................12

Table 5. Losses of pyrethroids from sediment to 500-millliliter glass jars ......................................12

Appendix Table A1. Range of percent of 14 pyrethroid compounds spiked in 

 environmental samples and exposed to various sampling equipment/container 

 materials......................................................................................................................................19
vii

Abbreviations and Acronyms

(Additional information or clarification given in parentheses)

Brij-35, polyoxyethyleneglycol dodecyl ether

DCM, dichloromethane

DOC, dissolved organic carbon

EPA, U.S. Environmental Protection Agency

FEP, fluorinated ethylene polypropylene 

GC/MS, gas chromatography-mass spectrometry 

HDPE, high-density polyethylene

i.d., inner diameter 

LDPE, low-density polyethylene

nd, not detected

PEG, polyethylene glycol

PTFE, polytetrafluoroethylene

PVC, polyvinylchloride

rpm, revolutions per minute

SD, standard deviation

SOP, standard operating procedure

SPE, solid-phase extraction 

SRM, standard reference material

SSC, suspended-solids concentration

SWAMP, Surface Water Ambient Monitoring Program (California)

USGS, U.S. Geological Survey

Units of Measurement

cm, centimeter

g, gram

L, liter

L/min, liter per minute

lb, pound

m, meter

μg/L, micrograms per liter

μL, microliter

mg, milligram

mg/L, milligram per liter

mL, milliliter

mL/cm2

, milliliters per square centimeter

mL/min, milliliter per minute

mm, millimeter

mM, millimolar

ng, nanogram

ng/g, nanogram per gram

ng/L, nanogram per liter

ng/μL, nanogram per microliter

Notes

Temperature in degrees Celsius (°C) may be converted to degrees Fahrenheit (°F) as follows:

°F = (1.8 × °C) + 32

Chemical concentrations in water are reported in units of nanograms per liter (ng/L). Chemical 

concentrations in sediment are reported in units of nanograms per gram of dry weight sediment (ng/g).

Use of liter (L) as a special name for cubic decimeter (dm3) is restricted to the measurement of liquids and 

gases. 
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Introduction 1

Abstract

Loss of pyrethroid insecticides onto surfaces during 

sample collection can confound the interpretation of analytical 

and toxicity test results. Sample collection devices, container 

materials, and water matrix composition have a significant 

influence on the association of pyrethroids to container walls, 

which can be as high as 50 percent. Any sample collection 

method involving transfer through multiple containers or 

pieces of equipment increases the potential for pyrethroid loss. 

This loose “surface-association” with container walls can be 

reversed through agitation. When sampling water matrices 

with pumps or autosamplers, no pyrethroids were lost as long 

as the water was moving continuously through the system. 

When collecting water matrices in containers, the material 

with the least amount of pyrethroid sorption is as follows: 

glass less than (<) plastic less than (<) Teflon. Additionally, 

pyrethroids were easier to re-suspend from the glass container 

walls. Since the amount of surface-association is proportional 

to the ratio of volume-to-contact-area of the sample, taking 

larger-volume field samples (greater than 3 liters) reduced 

pyrethroid losses to less than 10 percent. The amount of 

surface-association cannot be predicted easily because of the 

dependence on water matrix composition; samples with higher 

dissolved organic carbon or suspended-sediment concentrations were observed to have lower percent loss. Sediment 

samples were not affected by glass-container sorption (the 

only containers tested). Standardized sample-collection protocols are critical to yield accurate pyrethroid concentrations for 

assessment of potential effects, and have been summarized in 

an accompanying standard operating procedure.

Introduction

Pyrethroids have replaced diazinon and chlorpyrifos as 

the most common insecticides in agricultural areas and the 

urban marketplace (California Department of Pesticide Regulation, 2005; TDC Environmental, 2005). Because pyrethroids 

are highly toxic to aquatic organisms, and because researchers have detected pyrethroids in surface waters and (more 

frequently) in sediments, they must be able to be accurately 

measured in the environment (TDC Environmental, 2008). 

Pyrethroids are known from previous research to “associate” with container surfaces, but the extent of their association 

has not been tested with respect to field sampling devices. The 

loss of pyrethroids to surfaces is labeled as an “association” 

because the process is reversible and the compounds do not 

chemically “bind” to the surfaces. Sample-collection devices, 

sample-collection and laboratory-container material, container 

size, holding conditions, and sample-handling procedures have 

been found by researchers to have significant influences on the 

losses of pesticides onto container walls (see section called 

“Sample Containers” of this report). Determining the optimum 

sample-collection procedures for minimizing association of 

pyrethroids to container and sampling-equipment surfaces, and 

disseminating a validated standard operating procedure (SOP), 

helps ensure that consistent and technically sound methods are 

available for sample collection and handling.

Collection of Pyrethroids in Water and Sediment Matrices: 

Development and Validation of a Standard Operating 

Procedure

By Michelle L. Hladik, James L. Orlando, and Kathryn M. Kuivila
2 Collection of Pyrethroids: Development and Validation of a Standard Operating Procedure

Prior Research on Pyrethroid Losses 

The following summarizes prior published literature 

about the association of aqueous pyrethroids. This includes 

pyrethroid association to sample containers, and the effects of 

hold time.

Sample Containers

For many years, researchers have observed that a significant fraction of pyrethroids can associate to sample containers, and thereby complicate analysis. Sharom and Solomon 

(1981) noted that when trying to perform bioassays with glass 

or plastic containers, permethrin showed a significant amount 

of loss. Glass scintillation vials containing 5, 10, and 20 mL 

of water, with volume-to-contact-area ratios of 0.32, 0.38, and 

0.44 mL/cm2, had permethrin losses of 70, 63, and 42 percent 

(after 48 hours), respectively. The data showed that an increase 

in the volume-to-contact-area ratio was associated with a 

decrease in pyrethroid loss. Other researchers have noted similar behavior of pyrethroids. In studies using 30-mL glass centrifuge tubes, approximately 60 percent of λ-cyhalothrin and 

tefluthrin in water was associated to the container (Zhou and 

others, 1995; 1997). Lee and others (2002) found a 36-percent 

loss of permethrin to a 1-L glass bottle, (volume-to-contactarea ratio of 0.62 mL/cm2

, converted from 1.6 cm2/mL in 

the original paper), agreeing well with Sharom and Solomon 

(1981). Association losses similar to permethrin were found 

for bifenthrin and deltamethrin, with all three pyrethroids 

tested reaching equilibrium within 24 hours (Lee and others, 

2002). Wheelock and others (2005), using 1-L glass bottles, 

found that approximately 20 percent of λ-cyhalothrin in water 

remained on the container walls after 24 hours. Pyrethroid 

association was less than that observed by Lee and others 

(2002), but the time to reach equilibrium was the same (24 

hours).

Plastic containers also have been tested for pyrethroid 

losses. Polyethylene, polyvinylchloride (PVC), and Teflon showed 60, 50, and 25 percent loss, respectively, after 

120 hours (15 mL of water in a 20-mL scintillation vial) 

(Sharom and Solomon, 1981). Another study, using sample 

containers made of Teflon, high-density polyethylene (HDPE), 

and glass, found that values of aqueous pyrethroids associated to the walls of the 20-mL beakers were ranked highest to 

lowest as Teflon greater than (>) HDPE greater than (>) glass 

(Wheelock and others, 2005). Furthermore, this study also 

explored 400-mL polycarbonate and 400-mL glass beakers. 

Initially the polycarbonate had less loss of λ-cyhalothrin to the 

container walls compared to glass, but after 24 hours, more 

was lost to the polycarbonate surface than to the glass. Polytetrafluoroethylene (PTFE) bottles (100 mL) retained more pyrethroids than did glass bottles of the same size; for cypermethrin, fenvalerate, and permethrin, the amount retained on the 

bottle walls was 90–95 percent for PTFE and 70–95 percent 

for glass after 66 hours (House and Ou, 1992).

The loss of aqueous pyrethroids to sample containers is 

sometimes reversible, suggesting that the loss from solution 

may not be caused by chemisorption. Sharom and Salomon 

(1981) demonstrated that permethrin could be re-suspended 

in solution from glass and Teflon, but not from polyethylene 

and PVC. Lee and others (2002) noted that vigorous shaking 

of bottles prior to analysis did not result in complete resuspension of pyrethroids; however, shaking resulted in less pyrethroid loss to container walls than in comparable samples that 

were unshaken. Wheelock and others (2005) found that vortexing scintillation vials returned 100 percent of λ-cyhalothrin 

to solution. House and Ou (1992) rinsed the sample bottle 

with dichloromethane after the removal of the sample water 

and were able to reclaim the pyrethroids associated with the 

surface, although there was not a complete mass balance. 

The amount of suspended sediment or dissolved organic 

carbon (DOC) in a water sample also affects the association 

of pyrethroids-to-container surfaces. Researchers found that 

when adding 2 g of sediment to a water matrix, association 

to the container for tefluthrin decreased from approximately 

60 percent to less than 3 percent after 25 hours (Zhou and others, 1997). Lee and others (2002) found pyrethroid association 

to 1-L glass bottles to be 30 to 40 percent for deionized water, 

but this loss decreased to 20 to 30 percent for stormwater 

runoff containing 25 mg/L of suspended solids. While pyrethroids sorb to both DOC and suspended sediments, it appears 

that they prefer suspended sediments to DOC (Liu and others, 

2004).

Filtering is another source of loss of pyrethroids during 

sample handling. House and Ou (1992) tested several filters, 

including cellulose nitrate, anopore, nuclepore, and glass fiber, 

and found that the lowest pyrethroid losses occurred with the 

glass fiber filter (5–20 percent). 

Mitigation of the pyrethroid losses has been attempted 

for analytical purposes. A solvent such as methanol can be 

added to increase pyrethroid recovery. In one case, 30 percent 

methanol was added to the water sample prior to solid-phase 

extraction (SPE) (van der Hoff and others, 1996). The amount 

of solvent added must be monitored to minimize SPE column 

breakthrough. This study used C18 SPE cartridges and found 

that 30 percent was the maximum level before breakthrough. 

Brouwer and others (1994) were trying to analyze pyrethroids 

and found their solubility in water could be enhanced by adding Brij-35 (polyoxyethyleneglycol dodecyl ether), a neutral 

surfactant. Other modifications have been attempted but were 

not successful at reducing pyrethroid sorption; these include 

aeration, silylating, using polyethylene glycol (PEG) to coat 

active sites on the glass surface (Wheelock and others, 2005), 

and addition of 10 mM carbonate buffer (House and Ou, 

1992). 
Experimental Design and Methodology 3

Sample Holding

It is important to determine how long samples can be 

held before pyrethroid association to the container becomes 

irreversible or degradation begins. In water, the pyrethroids 

appear to be relatively unstable to degradation when stored 

in a refrigerator (4oC). Data from the U.S. Geological Survey 

(USGS) National Water Quality Laboratory list holding times 

for λ-cyhalothrin as 3 days, while the other pyrethroids tested 

(bifenthrin, cyfluthrin, cypermethrin, and tefluthrin) have 

holding times of 15 days to greater than 28 days (Sandstrom 

and others, 2001). One caveat for these holding-time tests is 

that the method used lists the recovery of these compounds as 

low and variable (Sandstrom and others, 2001); losses may 

come from container association rather than from degradation. 

Another study also found that λ-cyhalothrin showed significant degradation losses (20 to 30 percent) after only a few 

days in water (Bennett and others, 2000). Additional studies 

conducted as part of a pyrethroid method development project 

by the USGS, California Department of Food and Agriculture, 

and California Department of Fish and Game showed that the 

acceptable holding time for water samples is around 4 days, 

but that with the addition of a keeper solvent (hexane), the 

holding time can be extended to 28 days (Hladik, 2007). 

Pyrethroids in sediment appear to be much more stable 

to degradation when stored in a freezer (–20oC). Data from 

the pyrethroid method development project demonstrated that 

pyrethroid sediment samples that are frozen can be stable for 

at least 6 months (Hladik, 2007).

Purpose and Scope

This report summarizes the findings when various 

sampling devices were tested for pyrethroid losses and this 

information lead the development of the validated SOP 

(appendix A). Following the SOP will help ensure minimal 

losses of pyrethroids on sampling equipment and container 

surfaces. The main objective of this project is to test field sampling devices to support the development and validation of a 

standard operating procedure for the collection of pyrethroids 

in water and sediment matrices. This report is intended to 

supplement other documents that describe how to collect water 

and sediment samples: for example the USGS National Field 

Manual for the Collection of Water-Quality Data or comparable methods. 

Experimental Design and Methodology

Loss of pyrethroids to sampling containers were conducted using laboratory and natural waters spiked with 

pyrethroids. Sampling devices tested are those commonly used 

by researchers who collect water and sediment samples for 

pyrethroid analysis. 

Sample-Collection Design

Some of the most commonly used sample-collection 

devices were tested for loss of pyrethroids. As it is hard to find 

environmental samples that have consistent concentrations 

of pyrethroids, samples used for this study were laboratoryspiked water and sediment matrices collected from sites that 

had no known sources of pyrethroid contamination. Deionized 

water was used only for 1-L grab samples to represent the 

maximum pyrethroid loss in water matrices, since losses were 

expected to be somewhat mitigated in the environmental samples due to naturally occurring particulate matter. The rest of 

the tests were run using natural waters to better simulate field 

conditions. Water used for the majority of the experiments 

was collected from the American River near California State 

University, Sacramento, in 19-L stainless-steel soda kegs, and 

was subsequently filtered through a 0.7-mm glass-fiber filter 

into another soda keg and stored at 4oC. A sufficient volume 

of American River water could not be collected all at once for 

testing of all techniques, but changes in water composition 

were minimal over the duration of the testing (suspended sediment concentrations [SSC] 15–20 mg/L; DOC 1–2 mg/L; pH 

6.5–7.5). The American River water had relatively low SSC 

and DOC, thus minimizing potential sorption competition. In 

addition, a high-DOC water was mixed with American River 

water to test the effects of varying the DOC; this water matrix 

was from Georgia, and was collected in a baked 4-L amber 

glass bottle; the water was filtered through a 0.7-mm glass 

fiber filter, and DOC was measured (40 mg/L). Bed sediment 

was collected as a depositional grab sample using a stainlesssteel spoon, using methods described by Radtke (2005). Sediment was sieved (stainless mesh) to remove particles larger 

than 4 mm in diameter and homogenized with a stainless-steel 

spoon to ensure consistent composition. Sediment moisture 

and percent organic carbon were measured (50 and 1 percent, 

respectively; Hladik and Orlando, 2008). Sediment was stored 

in a clean, baked, glass container at –20oC. All water and sediment matrices were tested for any pyrethroids prior to use in 

spiking experiments, and none were detected.

Sampling Devices

Water Matrices

Devices for sampling waters included grab, composite, 

integrated, and auto-samplers. Each of these devices was 

tested according to standard practices (Ward and Harr, 1990; 

Lane and others, 2003; U.S. Geological Survey, 2006). If 

appreciable pyrethroid sorption (greater than 10 percent) was 

found to occur, then the methods were adjusted to try to lessen 

pyrethroid losses. The adjustments included agitating the 

samples between transfers, and changing the sample device 

composition where possible. Table 1 summarizes the devices 

used to test pyrethroid losses from water to equipment and 

container surfaces. 
4 Collection of Pyrethroids: Development and Validation of a Standard Operating Procedure

Sampling device description Water Concentration 

of pyrethroids Hold time Agitation

Solvent and 

volume for 

rinsing

Grab sample—1-liter glass or Teflon Deionized or 

American River 

water

200 and 

400 ng/L

24 hours Shaking for 

1 minute, 

pouring, 

pumping at 

10 mL/min

12 mL DCM

Georgia water 

(DOC 40 mg/L) 

diluted with 

American River 

water

200 ng/L 3 days None

Grab sample or US D-95 isokinetic depthintegrating sampler—1-liter Teflon with 

nozzle

Deionized water 400 ng/L 1 hour; 24 hours Shaking for 

1 minute

12 mL methanol

Large Volume—Cubitainers® (LDPE; 4 and 

19-L) and 19 L stainless steel soda kegs

American River 

water

400 ng/L 7 days (Cubitainers): 

24 hours 

(soda kegs) 

Shaking for 

1 minute

100 mL (4 L) 

and 200 mL 

(19 L) 

methanol

Filtration—1-liter sample (diaphragm pump 

with Teflon lined pumphead, 1 m of 9.5-mm 

i.d. Teflon tubing, 150-mm glass fiber filter, 

flow rate of 0.5 L/min)

American River 

water

400 ng/L None None 150 mL methanol

Composite samples—14-liter Teflon churn American River 

water

400 ng/L 1 hour Churned for 

1 minute

100 mL methanol

US D-96 isokinetic depth-integrating 

sampler—3-liter Teflon bag with nozzle

American River 

water

400 ng/L 1 hour Shaking for 

1 minute

50 mL methanol

ISCO autosampler peristaltic pump, 15 m 

of 9.5 mm i.d. Teflon tubing, flow rate of 

1 L/min. Pyrethroid-spiked water stored in 

tubing for 1 hour prior to flushing with three 

volumes of deionized water.

American River 

water

400 ng/L 0 hours and 3 

hours

None 300 mL methanol

Table 1. Summary of devices tested for pyrethroid losses for water samples. 

[Devices were held at 4 degrees Celsius. DCM, dichloromethane; DOC, dissolved organic carbon; i.d., inner diameter; LDPE, low-density polyethylene; L/min, 

liter per minute; m, meter; mg/L, milligram per liter; mL, milliliter; mL/min, milliliter per minute; min, minute; mm, millimeter; ng/L, nanogram per liter]

Sediment Matrices

Sediments sampled for pyrethroid toxicity or chemical analysis are most commonly collected as “grab samples” 

using a stainless-steel spoon to take the top 2 cm of depositional sediment. While other sediment-collection methods (for 

example, Eckman, Ponar, cores; Radtke, 2005) may collect a 

larger volume of sample than the grab-sample, these generally are not employed for the pyrethroids. Diagnostic sediment samples simulating grab samples were tested by taking 

sediment (100 g) from a central California agricultural drain 

into a 500-mL glass container. This sediment is expected to 

be representative of most sediments sampled; it is from an 

agricultural area with 1-percent organic carbon content. The 

sediment was spiked with pyrethroids at a final concentration 

of 100 ng/g. The sediment sample was equilibrated at room 

temperature for 24 hours and then put in the freezer (–20°C) 

for an additional 6 days (sediment samples can be stored for 

up to 6 months in a freezer; Hladik, 2007). After thawing, the 

sediment was scooped out with a stainless-steel spoon. The 

spoon and the jar were each rinsed with 10 mL of dichloromethane. The lid to the jar was not rinsed as the sediment did 

not come into contact with the Teflon-lined plastic lid.
Results 5

Pyrethroid Analysis

Water and sediment samples were spiked with up to 14 

pyrethroids (allethrin, bifenthrin, cyfluthrin, λ-cyhalothrin, 

cypermethrin, deltamethrin, esfenvalerate, fenpropathrin, 

τ-fluvalinate, permethrin, resmethrin, sumithrin, tefluthrin, and 

tetramethrin) using a methanol carrier solvent. Water samples 

were spiked to achieve an expected concentration of 400 ng/L, 

and sediment samples were spiked to achieve an expected 

concentration of 100 ng/g. Sample containers and sampling 

apparatus parts were rinsed with methanol or dichloromethane 

(DCM) after the matrix water was removed, to capture and 

measure the portion of the pyrethroids that were retained on 

the surfaces (pyrethroids were not measured in the aqueous 

solution). 

The DCM was effective at removing the pyrethroids 

associated with the container surface. In previous studies 

(Hladik, 2007), a mass balance was completed for 1-L water 

samples in an amber glass bottle; total recoveries ranged from 

88 to 95 percent. In separate tests, methanol was found to be 

as effective as DCM in removing surface-associated pyrethroids. Teflon bottles were rinsed with methanol and then 

DCM, and no additional levels of pyrethroids were detected in 

the dichloromethane fraction.

The solvent was blown down under a gentle stream of 

nitrogen to 0.5 mL, exchanged into ethyl acetate (0.2 mL), and 

deuterated internal standards were added. All sample extracts 

were analyzed by gas chromatography-mass spectrometry 

(GC/MS). Instrument detection limits were 0.01 to 0.025 ng/

mL, which translates to 2 to 5 ng/L in a water sample (well 

below the spiking concentrations). Complete details of the 

GC/MS analysis are described elsewhere (Hladik and others, 

2008). 

Because only the containers were tested for pyrethroids, 

the SPE water extraction technique was not used in this study. 

However, this is a common technique for measuring pyrethroids in water, and the possible losses from this method are 

explored in this report.

Quality Control 

A number of quality-control checks were implemented 

to assess whether data quality requirements are being met 

(table 2). All quality-control checks met or exceeded California Surface Water Ambient Monitoring Program (SWAMP) 

requirements (California State Water Resources Control 

Board, 2002). Many samples collected in California are 

required to meet SWAMP criteria; therefore these standards 

are used. Because this study involved only laboratory-spiked 

water- and sediment matrices to test sampling devices, no field 

blanks or field replicates were needed.

Results

The results are presented according to matrix (water or 

sediment) and sample device tested. Quality control for each 

device is presented within each section. 

Sample Devices for Water Matrices

Results are presented for two types of 1-L containers (glass 

and Teflon) and three types of large-volume containers (4-L 

and 19-L LDPE Cubitainers® and 19-L stainless-steel soda 

kegs).

One–Liter Containers

Glass

One-liter glass containers were tested using deionized 

water and natural water matrices. For tests using deionized 

water, the deionized water was removed from the glass bottles 

in one of three ways: by a pump at 10 mL/min to simulate 

SPE; poured out of the bottle; or, shaken vigorously for 1 minute before the water was poured out of the bottle. Pumping the 

water at 10 mL/min to simulate SPE conditions gave the most 

sorption (fig. 1); in deionized water, the surface-association 

was near 30 percent for most compounds (fig. 1). Pouring out 

the water or shaking the bottle vigorously for 1 minute before 

pouring out the water reduced losses caused by association 

to the container walls to below 5 percent (fig. 1). Testing two 

different concentrations of aqueous pyrethroids (200 and 

400 ng/L) and removing the water by pumping showed no 

significant difference in the amount of loss at the two different 

concentrations (fig. 2). 

The amount of loss to glass containers also depended on 

the composition of the water. To test how pyrethroid sorption to dissolved compounds in a natural water can affect the 

pyrethroid association to the container walls, samples that had 

varying concentrations of DOC (1, 4, and 8 mg/L that were 

made as a blend of American River water and a 40-mg/LDOC water from Georgia) were spiked with pyrethroids. The 

water for each bottle was removed by pumping at 10 mL/min. 

The results showed that the higher the DOC concentration 

the lower the loss to the bottle walls (fig. 3). The pyrethroids 

prefer to associate with the dissolved compounds rather than 

the container walls (in this case only glass was tested).
6 Collection of Pyrethroids: Development and Validation of a Standard Operating Procedure

QC Sample Type SWAMP Requirements Project QA/QC Acceptance Criteria

External/internal calibration Follow manufacturer's or procedures in specific analytical protocols. A minimum three- point 

calibration at each setup, major 

disruption, and when routine 

calibration check exceeds specific control limits.

Five- to eight-point calibration curve 

ranging from 0.025 to 5 nanograms 

per microliter at each instrument 

setup, major disruption, and when 

routine calibration check exceeds 

specific control limits.

Linear regression, r > 0.995.

Calibration verification After initial calibration or recalibration. Every 10 samples.After initial calibration or recalibration. Every 6 samples. Percent recovery equals 80 to 

120 percent

Laboratory blanks One method blank per 20 samples 

or one per batch, whichever is 

more frequent. At least one bottle blank per batch. One reagent 

blank prior to use of a new batch 

of reagent and whenever method 

blank exceeds control limits.

One method blank per 10 samples or 

one per batch, whichever is more 

frequent. Laboratory blanks should 

comprise 10 percent of all samples 

per sampling event. 

Blanks < MDL for target 

analyte.

CRM (reference material) Method validation: As many as 

required to assess accuracy and 

precision of method before routine analysis of samples. Routine 

accuracy assessment: one (preferably blind) per 20 samples or 

one batch.

Water—National Water Quality Laboratory Schedule 2003/2033 

(1 microgram per milliliter) spiked 

into a 1-L water sample. 

Measured value 70 to 130 percent of 95-percent confidence 

intervals, if certified. Otherwise, percent recovery equals 

50–150 percent

Sediment—standard reference 

material (SRM 1941b) organics in 

marine sediment. Note, this sample 

does not contain pyrethroids, but 

can be used to assess the method 

(no SRM exists for pyrethroids). 

Routine accuracy assessment every 

20 samples.

Matrix spikes One per 20 samples or one per 

batch, whichever is more frequent.

One per 10 samples or one per batch, 

whichever is more frequent. Matrix 

spikes will comprise 10 percent of 

all samples per sampling event

Percent recovery equals 70 to 

130 percent or control limits 

on the basis of three times 

the standard deviation of 

laboratory's actual method 

recoveries.

Matrix spike replicate One duplicate per 20 samples or 

one per batch, whichever is more 

frequent.

One duplicate per 20 samples per 

sampling event

RPD <25 percent for duplicates.

Surrogate spikes (for non-spiked 

samples only)

In every calibration standard, 

sample, and blank analyzed for 

organics by GC or isotope dilution GC/MS; added to samples 

prior to extraction.

Isotopically labeled compounds 

added to every sample and blank 

analyzed for organics by GC/MS; 

added to samples prior to extraction. Representative pyrethroid is 

cis-permethrin

Percent recovery equals 70 to 

130 percent

Table 2. Comparison of the project quality-assurance/quality-control (QA/QC) plan with the Surface Water Ambient Monitoring Program 

(SWAMP) quality-control requirements for organic constituents (pesticides) in water and sediment.

[SWAMP QC plan information from California State Water Resources Control Board, 2002. Acceptance criteria meets both SWAMP and project QA/QC plan criteria. GC, gas chromatography ; GC/MS, gas chromatography/mass spectrometry; L, liter; MDL, method detection limit; QA/QC, quality assurance/quality control; 

RPD, relative percent difference; SRM, standard referece material; <, less than; >, greater than]
Results 7

10

0

15

5

20

Bifenthrin

Cyfluthrin

Cyhalothrin

Cypermethrin

Deltamethrin

Esfenvalerate

Fenpropathrin

Fluvalinate

Permethrin

Resmethrin

Sumithrin

PERCENT ON BOTTLE WALL

Shaken

Poured

Pumped

PYRETHROIDS

20

25

30

35

40

0

5

10

15

PERCENT ON BOTTLE WALL

PYRETHROIDS

400 ng/L

200 ng/L

Allethrin

Bifenthrin

Cyfluthrin

Cyhalothrin

Cypermethrin

Deltamethrin

Esfenvalerate

Fenpropathrin

Fluvalinate

Permethrin

Resmethrin

Sumithrin

Tetramethrin

Figure 1. Fraction of pyrethroids associated with 1-liter glass bottle walls. Pyrethroids were spiked at 400 nanograms per liter into 

deionized water. Spiked bottles were allowed to sit for 24 hours prior to having the water removed by pumping at 10 milliliters per minute, 

pouring the water out of the bottle or shaking the bottle for 1 minute and then pouring the water out of the bottle.

Figure 2. Fraction of pyrethroids associated with 1-liter glass bottles at two different concentrations. Pyrethroids were spiked at 400 or 

200 nanograms per liter (ng/L) into deionized water. Spiked bottles were allowed to sit for 24 hours prior to having the water removed by 

pumping at 10 milliliters per minute.
8 Collection of Pyrethroids: Development and Validation of a Standard Operating Procedure

Teflon

Teflon bottles can be used to obtain a grab sample or as 

part of a US D-95 isokinetic depth-integrating sampler. The 

Teflon bottle is connected to a Teflon nozzle and encased 

in the sampler housing. The water sample only contacts the 

Teflon bottle and nozzle, so these were tested for pyrethroid 

losses. The losses caused by association to the Teflon bottle 

are presented below. There were no losses to the Teflon nozzle 

(water was poured through but did not come into contact with 

the nozzle for extended periods of time).

Teflon bottles had greater losses of pyrethroids than did 

glass containers under similar conditions (fig. 4). The glass 

bottles had pyrethroid losses in the range of 20 to 30 percent 

while losses for the Teflon bottles were 30 to 40 percent (for 

most compounds). When the Teflon bottles were shaken for 

1 minute before the contents were poured out, the amount of 

loss decreased to 10 to 20 percent (fig. 5). Shaking did not 

decrease the pyrethroid loss for the Teflon bottles as much as it 

did for the glass bottles. A test of shaking for longer amounts 

of time also did not decrease the pyrethroid loss to the Teflon 

bottle, indicating the some of the pyrethroids might be associating more strongly to the Teflon bottle. 

Another set of Teflon bottles was spiked and allowed to 

sit for only 1 hour (more representative of an integrated field 

sample) rather than for 24 hours. The pyrethroid losses were 

less than 10 percent for all compounds if the bottles were 

shaken before the water was poured out (fig. 5). These data 

suggest that glass bottles should be used whenever possible, 

and that if Teflon must be used (such as for an integrated 

sample), then it is optimal to transfer the sample to a glass 

bottle as soon as possible to minimize losses of pyrethroids.

Large-Volume Containers

Low-density polyethylene 4- and 19-liter Cubitainers®

Association of pyrethroids to the walls of the LDPE 

Cubitainers® was low. LDPE containers were tested because 

they commonly are used by toxicologists working with 

pyrethroid solutions. The 4-L containers had zero to 7 percent 

of pyrethroids remaining on the walls after the water was 

removed, whereas the 19-L containers had zero to 4 percent 

remaining on the walls (table 3). The loss was lower for the 

larger container because the volume-to-contact-area ratio of 

the water to the container surface is greater; 4.5 and 2.6 mL/

cm2 for the 19- and 4-L containers, respectively. Water samples were held for 1 week to simulate sample collection procedures used by other researchers for toxicity tests. Pyrethroid 

degradation may have occurred, as shown by other researchers 

(Sandstrom and others, 2001), and it is not recommended that 

water samples be kept this long before analysis.

Figure 3. Fraction of pyrethroids associated with 1-liter glass bottles with varying DOC. Pyrethroids were spiked at 400 nanograms per 

liter into a blend of filtered natural waters. Spiked bottles were allowed to sit for 3 days prior to having the water removed by pumping at 

10 milliliters per minute. PERCENT ON BOTTLE WALL

Bifenthrin

Cyfluthrin

Cyhalothrin

Cypermethrin

Deltamethrin

Esfenvalerate

Fenpropathrin

Fluvalinate

Permethrin

Sumithrin

PYRETHROIDS

1 mg/L DOC

4 mg/L DOC

8 mg/L DOC

10

0

15

5

20

25

30

35
Results 9

PERCENT ON BOTTLE WALL

PYRETHROIDS

Glass

Teflon

50

40

30

20

10

0

Allethrin

Bifenthrin

Cyfluthrin

Cyhalothrin

Cypermethrin

Deltamethrin

Esfenvalerate

Fenpropathrin

Fluvalinate

Permethrin

Resmethrin

Sumithrin

Tetramethrin

PERCENT ON BOTTLE WALL

Teflon 24 hours

Teflon 1 hour

0

5

10

15

20

25

PYRETHROIDS

Allethrin

Bifenthrin

Cyfluthrin

Cyhalothrin

Cypermethrin

Deltamethrin

Esfenvalerate

Fenpropathrin

Fluvalinate

Permethrin

Resmethrin

Sumithrin

Tetramethrin

Figure 4. Fraction of pyrethroids associated with 1-liter glass and Teflon bottles. Pyrethroids were spiked at 400 nanograms per liter 

into deionized water. Spiked bottles were allowed to sit for 24 hours prior to having the water removed by pumping at 10 milliliters per 

minute. 

Figure 5. Fraction of pyrethroids associated with 1-liter Teflon bottles. Pyrethroids were spiked at 400 nanograms per liter into a 

natural water (dissolved organic carbon = 2 milligrams per liter). Spiked bottles were allowed to sit for 1or 24 hours prior to having the 

water removed by shaking for 1 minute and then pouring the water out of the bottle. 
10 Collection of Pyrethroids: Development and Validation of a Standard Operating Procedure

Nineteen-Liter Stainless-Steel Soda Kegs 

Nineteen-L soda kegs were filled with water from the 

American River and spiked with pyrethroids. The samples 

were allowed to sit for 24 hours. The water was then agitated for 1 minute and poured out of the soda keg. Loss of 

pyrethroids to the inner stainless-steel surfaces of the soda 

kegs was minimal (table 3); the amount of pyrethroids that 

remained associated to the walls was less than 4 percent for all 

compounds.

Collection and Processing Equipment for Water 

Matrices

Collection and sample-processing equipment tested for 

this study included filtration apparatus, Teflon churns used for 

compositing samples, the US D-96 Isokenetic Depth-Integrating Sampler, and an ISCO autosampler (Teledyne Isco, Inc., 

Lincoln, Nebraska).

Filtration Apparatus 

About 10 percent of the pyrethroids spiked into the 1-L 

water samples and then run through the pump (500 mL/min) 

for filtration were retained in the pump filter (see table 1 for 

more details) and housing (fig. 6); however, not all of this 

mass is from pyrethroids associating to the surfaces of the 

apparatus. The pump housing holds about 50 to 75 mL of 

water that we infer would account for 5 to 7 percent of the 

loss; the loss to the housing is a loss that would be encountered in any filtration, and is not unique to the pyrethroids. The 

pump-housing loss does not affect the concentration in the 

water, just the total volume of water after filtration. Additional 

deionized water was not filtered through the pump after the 

sample because some of the pyrethroids associating to the 

surfaces of the apparatus might have become re-suspended. 

Taking into account the amount of water left in the housing, 

the loss of pyrethroids to the surfaces themselves was inferred 

to be minimal and no further tests were undertaken. An additional indication that the mass left in the pump housing is from 

residual water (and not surface-associated pyrethroids) is the 

amount of allethrin and tetramethrin measured. Allethrin and 

tetramethrin vary in their ring structure (they do not contain 

benzene rings) from the other pyrethroids and they do not 

associate to containers to the same degree as the other pyrethroids (figs. 2 and 4), indicating these compounds remain in 

the aqueous phase.

Teflon Churn

The Teflon churn consists of a thick-walled, cylindrical vessel and agitator and a “push-pull” type spigot that is 

supplied to draw off sub-samples from the splitter. The churn 

used for this study has a volume of 14 L. For a 3-L volume 

of samples water in the, pyrethroid losses ranged from 8 to 

16 percent (fig. 7). As with the pump (tested previously), 

there were about 50 mL of water that could not be removed 

from the churn prior to rinsing, accounting for approximately 

2 percent of the mass of pyrethroids that was lost. The 3 L 

of water in the churn represents the worst-case scenario, as 

this is the smallest amount of water that would be placed in 

the churn, having the smallest volume-to-contact-area ratio. 

To further test losses to the churn, 8 L of water was tested. 

Pyrethroid losses were less than 7 percent (fig. 7), because of 

the increased volume-to-contact-area ratio. To minimize losses 

of pyrethroids to the churn, a larger volume of water (>3 L), or 

a smaller churn, should be used.

Table 3. Loss of pyrethroids to 4-liter and 19-liter Cubitainers®, and to 19-liter stainless-steel soda kegs. 

[Pyrethroid concentration in the water was 400 nanograms per liter; samples sat for 1 week (Cubitainers) or 24 hours (soda kegs) before being shaken for 1 

minute and the water removed; n = 3; L, liter. Values are given in percent. Value in parentheses is the standard deviation, in percent]

Compound 4-liter Cubitainer® 

percent loss 

19-liter Cubitainer® 

percent loss 

19-liter stainless-steel soda keg 

percent loss

Allethrin 0 (0) 0 (0) 1 (0)

Bifenthrin 6 (1) 3 (0) 4 (0)

Cyfluthrin 7 (1) 3 (0) 3 (1)

λ-Cyhalothrin 5 (1) 3 (1) 2 (0)

Cypermethrin 6 (1) 3 (0) 2 (1)

Deltamethrin 4 (1) 3 (1) 3 (0)

Esfenvalerate 6 (1) 4 (1) 3 (0)

Fenpropathrin 5 (1) 3 (1) 2 (0)

τ-Fluvalinate 5 (1) 3 (0) 3 (1)

Permethrin 6 (1) 3 (0) 4 (0)

Resmethrin 5 (0) 3 (0) 1 (0)

Sumithrin 4 (1) 3 (0) 4 (0)

Tetramethrin 0 (0) 0 (0) 2 (1)
Results 11

0

5

10

15

PYRETHROIDS

Allethrin

Bifenthrin

Cyfluthrin

Cyhalothrin

Cypermethrin

Deltamethrin

Esfenvalerate

Fenpropathrin

Fluvalinate

Permethrin

Resmethrin

Sumithrin

Tetramethrin

PERCENT REMAINING IN APPARATUS

3 L

8 L

PERCENT ON CHURN WALL

0

5

10

15

20

PYRETHROIDS

Allethrin

Bifenthrin

Cyfluthrin

Cyhalothrin

Cypermethrin

Deltamethrin

Esfenvalerate

Fenpropathrin

Fluvalinate

Permethrin

Resmethrin

Sumithrin

Tetramethrin

Figure 6. Fraction of pyrethroids left in the filtration pump. Pyrethroids were spiked at 400 nanograms per liter into a natural water 

(dissolved organic carbon = 2 milligrams per liter) in 1-liter Teflon bottles. Water from the pyrethroid spiked bottles were run through the 

pump at 500 milliliters per minute. 

Figure 7. Fraction of pyrethroids associated with the churn walls. Pyrethroids were spiked at 400 nanograms per liter into 3 or 8 liters 

of a natural water (dissolved organic carbon = 2 milligrams per liter) in a 14-liter Teflon churn. The pyrethroid spiked water was allowed 

to sit in the churn for 1 hour prior to having the water removed. 
12 Collection of Pyrethroids: Development and Validation of a Standard Operating Procedure

US D-96 Isokenetic Depth-Integrating Sampler

The US D-96 sampler holds a 3-L Teflon bag that is connected to a Teflon nozzle and encased in the sampler housing. 

The water sample only contacts the Teflon bag and nozzle, 

so these were tested for pyrethroid losses. The losses to the 

Teflon bag are presented below. There were no losses to the 

Teflon nozzle (water was poured through but did not come into 

contact with the nozzle for extended periods of time).

Pyrethroid losses to the 3-L Teflon bag used with the 

D-96 was between approximately 2 and 10 percent (table 4); 

as seen with other bottles, Teflon is not the best material to 

minimize pyrethroid association to the container wall. Shaking 

the bags did not disassociate the pyrethroids from the inner 

surfaces of the bag (as observed by no measurable change in 

pyrethroid losses).

ISCO Autosampler

The autosampler is set to pump water through tubing into 

sample containers at pre-determined time points. The water 

that contacts tubing goes up to and through the autosampler 

before entering the end sample container. Once each sample 

container is full, the autosampler can be purged with sample 

water to an outlet before filling the next sample container.

Sorption to the autosampler was tested under two conditions: the first scenario had pyrethroid-spiked water pumped 

through the system, the system was drained (to simulate 

sample collection), and purged with deionized water and then 

solvent-rinsed; the second scenario differed from the first in 

that the pyrethroid-spiked water was allowed to sit for 3 hours 

in the autosampler prior to purging with deionized water. The 

purpose of the second test was to simulate the sampling of 

matrix water having a high concentration of pyrethroids, and 

to determine if this would contaminate subsequent samples. 

The glass sample containers that typically are used in the 

ISCO autosampler were not tested for pyrethroid losses, these 

are the final sample containers and the pyrethroids associating 

to the containers can be resuspended easily and losses should 

be no more than 5 percent (similar to 1-L glass bottles). 

When the autosampler was rinsed with organic solvent to 

remove any associated pyrethroids, the extracts had no detectable losses of pyrethroids in either of the cases tested. The lack 

of associated pyrethroids in the rinsate indicates that purging 

the autosampler with deionized water is enough to resuspend 

any pyrethroids that associated to the apparatus while the 

water was stagnant (even if the water contained high levels of 

pyrethroids).

Sample Containers for Sediment Matrices 

Pyrethroid losses from sediment samples to the inside 

surfaces of glass jars used for sample collection were less than 

2 percent (table 5), indicating that sediment-bound pyrethroids are less likely to associate to glass containers than to 

aqueous pyrethroids. Negligible amounts (0 to 0.1 percent) 

of pyrethroids were found on the spoon used to transfer the 

sediments. These tests cover the most commonly used method 

for the collection of pyrethroids associated with sediments, 

although other methods are available (see Sampling Devices 

section of this report.)

Table 4. Losses of pyrethroids to 3-liter Teflon bags. 

[Pyrethroid concentration in the water was 400 nanograms per liter; samples 

sat for 1 hour before being shaken for 1 minute and the water removed; n = 3. 

Values are given in percent]

Compound Percent 

loss

Standard

deviation

Allethrin 3 1

Bifenthrin 8 1

Cyfluthrin 10 2

λ-Cyhalothrin 9 2

Cypermethrin 9 1

Deltamethrin 9 1

Esfenvalerate 9 1

Fenpropathrin 9 2

τ-Fluvalinate 10 2

Permethrin 4 1

Resmethrin 7 3

Sumithrin 8 2

Tetramethrin 2 0

Table 5. Losses of pyrethroids from sediment to 500-millliliter 

glass jars. 

[Pyrethroid concentration in the sediment was 100 nanograms per gram; sediment was removed with a stainless-steel spoon; n = 3. Values given in percent]

Compound Percent

loss

Standard 

deviation

Allethrin 1 0

Bifenthrin 1 0

Cyfluthrin 1 0

λ-Cyhalothrin 1 0

Cypermethrin 1 0

Deltamethrin 1 0

Esfenvalerate 1 0

Fenpropathrin 1 0

τ-Fluvalinate 1 0

Permethrin 2 0

Resmethrin 1 0

Sumithrin 1 0

Tetramethrin 0 0
References Cited 13

Summary

Techniques and information to minimize pyrethroid association to the surfaces of sampling equipment and containers 

are listed below:

• Container composition affects the extent of aqueous 

pyrethroid loss; pyrethroids associate less to glass 

containers than to plastic (HDPE or LDPE), and Teflon 

has the greatest pyrethroid loss caused by association 

to the container surface.

• Containers should be agitated vigorously for at least 1 

minute immediately before transfer to another sample 

container.

• Maximize the volume-to-contact-area ratio.

• When using a filtration apparatus or autosampler, 

pump speeds should be at 500 mL/min when pumping 

aqueous pyrethroids.

• Composition of the water matrix affects the extent of 

pyrethroid association. Higher amounts of DOC or 

suspended sediments lessen the amount of pyrethroids 

associated to the container surfaces.

• Appreciable losses of pyrethroids were not found for 

sediment samples collected in glass containers.

• When possible, water samples should be analyzed 

within 3 days of collection. Sediment samples can be 

frozen for up to 6 months (prior to extraction).

References Cited

Bennett, E.R., Moore, M.T., Cooper C.M., and Smith, S., 

2000, Method for the simultaneous extraction and analysis 

of two current use pesticides, atrazine and lambda-cyhalothrin, in sediment and aquatic plants: Bulletin of Environmental Contamination and Toxicology, v. 64, p. 825–833.

Brouwer, E.R., Struys, E.A., Vreuls, J.J., and Brinkman, 

U.A.T., 1994, Automated-determination of pyrethroid insecticides in surface-water by column liquid-chromatography 

with diode-array UV detection, using online micellemediated sample preparation: Fresenius Journal of Analytical Chemistry, v. 350, p. 487–495.

California Department of Pesticide Regulation, 2005, Pesticide 

use data for 2005 [digital data]: Sacramento, California, 

Department of Pesticide Regulation.

California State Water Resources Control Board, 2002, Quality assurance management plan for the State of California’s 

Surface Water Ambient Monitoring Program: “SWAMP”, 

144 p. http://www.swrcb.ca.gov/swamp/docs/swamp_qapp.

pdf.

Hladik, M.L., 2007, Methods development for the analysis of 

pyrethroid pesticides in environmental samples: Final report 

for CALFED Recipient Agreement No. ERP-02-P42, 98 p.

Hladik, M.L., and Orlando, J.L., 2008, Level 1 water-quality 

inventory of baseline levels of pesticides in urban creeks—

Golden Gate National Recreation Area and the Presidio of 

San Francisco, California: U.S. Geological Survey Data 

Series 338, 14 p.

Hladik, M.L., Smalling, K.L., and Kuivila, K.M., 2008, A 

multi-residue method for the analysis of pesticides and 

pesticide degradates in water using HLB solid-phase extraction and gas chromatography-ion trap mass spectrometry: 

Bulletin of Environmental Contamination and Toxicology, 

v, 80, p. 139–144.

House, W.A., and Ou, Z., 1992, Determination of pesticides 

on suspended solids and sediments: Investigation on the 

handling and separation: Chemosphere, v. 24, p. 819–832.

Lane, S.L., Flanagan, Sarah, and Wilde, F.D., March 2003, 

Selection of equipment for water sampling (ver. 2.0): U.S. 

Geological Survey Techniques of Water-Resources Investigations, book 9, chap. A2, accessed October 7, 1998, at 

http://pubs.water.usgs.gov/twri9A2/

Lee, S., Gan, J.Y., and Kabashima, J., 2002, Recovery of 

synthetic pyrethroids in water samples during storage and 

extraction: Journal of Agricultural and Food Chemistry, v. 

50, p. 7194–7198.

Liu, W.P., Gan, J.J., Lee, S., and Kabashima, J.N., 2004, Phase 

distribution of synthetic pyrethroids in runoff and stream 

water: Environmental Toxicology and Chemistry, v. 23, p. 

7–11.

Radtke, D.B., revised June 2005, Bottom-material samples: 

U.S. Geological Survey Techniques of Water-Resources 

Investigations, book 9, chapter A8: Bottom sample materials. Available at http://pubs.water.usgs.gov/twri9A.

Sandstrom, M.W., Stroppel, M.E., Foreman, W.T., and Schroeder, M.P., 2001, Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Moderate-Use Pesticides and Selected Degradates in 

Water by C-18 Solid-Phase Extraction and Gas Chromatography/Mass Spectrometry: U.S. Geological Survey WaterResources Investigation Report 01–4098, 70 p.

Sharom, M.S. and Solomon, K.R., 1981, Adsorption and 

desorption of permethrin and other pesticides on glass and 

plastic materials used in bioassay procedures: Canadian 

Journal of Fisheries and Aquatic Sciences, v. 38, p. 199–

204.

TDC Environmental, 2005, Pesticides in urban surface water: 

Urban pesticides use trends annual report 2005, 29 p. 
14 Collection of Pyrethroids: Development and Validation of a Standard Operating Procedure

TDC Environmental, 2008, Pesticides in urban surface water: 

Annual review of new scientific findings 2008, 32 p. 

van der Hoff, G.R., Pelusio, F., Brinkman, U.A.T., Baumann, 

R.A., and van Zoonen, P., 1996, Automated solid-phase 

extraction coupled to gas chromatography with electroncapture detection: A combination of extraction and clean-up 

of pyrethroids in the analysis of surface water: Journal of 

Chromatography A, v. 719, p. 59–67.

Ward, J.R., and Harr, C.A., eds., 1990, Methods for collection 

and processing of surface-water and bed-material samples 

for physical and chemical analyses: U.S. Geological Survey 

Open-File Report 90-140, 71 p.

Wheelock, C.E., Miller, J.L., Miller, M.J., Phillips, B.M., Gee, 

S.J., Tjeerdema, R.S., and Hammock, B.D., 2005, Influence 

of container adsorption upon observed pyrethroid toxicity to 

Ceriodaphnia dubia and Hyalella azteca: Aquatic Toxicology, v. 74, p. 47–52.

U.S. Geological Survey, 2006, Collection of water samples 

(ver. 2.0): U.S. Geological Survey Techniques of WaterResources Investigations, book 9, chap. A4, accessed October 7, 2008, at http://pubs.water.usgs.gov/twri9A4/

Zhou, J.L., Rowland, S., and Mantoura, R.F.C., 1995, Partition 

of synthetic pyrethroid insecticides between dissolved and 

particulate phases: Water Resources, v. 29, p. 1023–1031.

Zhou, J.L., Rowland, S.J., Mantoura, R.F.C., and Lane, 

M.C.G., 1997, Desorption of tefluthrin insecticide from 

soil in simulated rainfall runoff systems-kinetic studies and 

modeling: Water Resources, v. 31, p. 75–84.
Appendix 15

Appendix 

Standard Operating Procedure for Sampling Pyrethroid Insecticides in Water and Sediment

Prepared by: Michelle Hladik Date: August 6, 2008 

Reviewed by: Lisa Olsen Date: August 25, 2008 

Approved by: Keith Kirk Date: January 14, 2009 

UNITED STATES GEOLOGICAL SURVEY

CALIFORNIA WATER SCIENCE CENTER
16 Collection of Pyrethroids: Development and Validation of a Standard Operating Procedure

Table of Contents

1.0 Purpose and Applicability .................................................................................................. 16

2.0 Summary of the Method ......................................................................................................16

3.0 Definitions ..............................................................................................................................17

4.0 Health and Safety Warnings ...............................................................................................17

5.0 Cautions..................................................................................................................................17

6.0 Interferences.........................................................................................................................17

7.0 Personnel Qualifications .....................................................................................................17

8.0 Equipment and Supplies ......................................................................................................17

9.0 Sample Collection-Overview ..............................................................................................18

10.0 Sample Collection-Method Options.................................................................................20

11.0 Sample Handling and Preservation .................................................................................21

12.0 Quality Assurance and Quality Control ...........................................................................22

Procedures

1.0 Purpose and Applicability

The purpose of this Standard Operating Procedure (SOP) is establish guidelines for the collection and handling of water and 

sediment samples that will be analyzed for pyrethroid insecticides. The procedures outlined are designed to be used as a general 

guide for pyrethroid sample collection; pyrethroids are more hydrophobic than other current-use pesticides and require that 

specific steps be taken to ensure that representative results are obtained. This SOP is intended to supplement other documents 

that describe how to collect water and sediment samples: for example, the USGS National Field Manual for the Collection of 

Water-Quality Data, or comparable methods.

2.0 Summary of the Method

Due to their hydrophobicity, pyrethroid insecticides may adhere to sampling equipment, sample containers, as well as to 

laboratory analysis and testing equipment. Losses from environmental samples to these materials may be as high as 50 percent, 

biasing results. The tendency of pyrethroids to adhere to the surfaces of containers and equipment varies depending on the container material, the volume-to-contact-area ratio, and the water matrix composition (concentrations of dissolved organic carbon 

and suspended sediment). Minimizing the loss of pyrethroids during sampling, storage and processing is accomplished most 

effectively by using equipment and containers made out of glass, stainless steel, or plastic (low-density polyethylene [LDPE] 

or high-density polyethylene [HDPE]); Teflon can be used if the sample is kept flowing or sits for less than 1 hour. Shaking the 

sample vigorously immediately prior to transferring to a different container or for analysis or by maintaining a continuous flow 

of water through the sampling apparatus, and sub-sampling from equipment and containers that have a high sample volume-tocontact-area ratio, will also help to minimize the loss of pyrethroids. 

Sampling situations vary widely, but this SOP encompasses many procedures commonly used by field personnel. 

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3.0 Definitions

1. Pyrethroid: any of various synthetic compounds that are related to the pyrethrins and resemble them in insecticidal properties. 

4.0 Health and Safety Warnings

Persons who collect samples should treat all sources of sample water and sediment as though they contained chemical or biological agents that could cause illness or harm. The sampler should wear protective gloves, at a minimum, and additional safety 

gear as necessary. Personnel collecting samples should wear U.S. Coast Guard approved personal floatation devices when working on or near the water. Samples are often collected from bridges, and personnel should be aware of road traffic and exercise 

appropriate traffic control procedures.

5.0 Cautions

Organic solvents may be used during the processing of samples. Standard laboratory safety procedures, as well as specific safety 

information contained in the Material Safety Data Sheets for these chemicals, must be followed.

6.0 Interferences

The purpose of representative sampling is to characterize the true concentrations of constituents of concern (in this case pyrethroid insecticides) in environmental samples. Unintended sample contamination is a point of concern, and steps must be taken 

to limit it. Sampling equipment and sample containers must be cleaned thoroughly prior to sampling. For water samples, containers should be rinsed three times with site water prior to collecting the sample. Pyrethroid insecticides are a common ingredient in household pesticide products. Field personnel should be aware of this and limit their exposure to these products prior to 

sample collection. To further confirm that there is no unintended sample contamination, field blanks must be included. 

Because of the hydrophobicity of pyrethroids, particular attention should be given to materials used in sampling equipment, 

sample containers, and items that may come into contact with samples during laboratory analysis and testing. 

7.0 Personnel Qualifications

This SOP is written for a wide audience. Personnel should have proper training in field sample collection, sample handling and 

laboratory processing techniques, as mandated by their respective organizations. 

8.0 Equipment And Supplies

Equipment needed for the collection of pyrethroids in water samples may include:

• Glass, plastic (HDPE or LDPE), or Teflon bottles

• Sampling nozzles for US D-95 and US D-96 samplers

• US D-95 isokinetic depth-integrating sampler

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18 Collection of Pyrethroids: Development and Validation of a Standard Operating Procedure

• US D-96 isokinetic depth-integrating sampler

• Teflon bags for D-96 sampler

• Teflon churn

• Stainless-steel soda kegs

• Autosampler (ISCO)

• Pump capable of flow rates greater than 500 mL/min

• Pump tubing (Teflon or stainless steel)

• Ice

• Coolers (and packing equipment)

• Chain-of-custody forms, field data sheets, field notebook

• Cleaning reagents, including pesticide grade methanol

• Sample-container labels

• Approved QA project plan

• Approved field health and safety plan

Equipment needed for the collection of pyrethroids associated with sediments includes:

• Glass jars

• Stainless-steel scoop or spoon

• Ice

• Coolers (and packing equipment)

• Chain–of-custody forms, field data sheets, field notebook

• Cleaning reagents

• Sample container labels

• Approved QA project plan

• Approved field health and safety plan

9.0 Sample Collection—Overview

General sampling methods for the collection of water and sediment samples are beyond the scope of this document. It is recommended that personnel follow the standard sample-collection, quality-assurance/quality-control (QA/QC), and equipment-cleaning procedures required by their respective agencies. This document pertains solely to the collection of samples to be analyzed 

for pyrethroid pesticides, which require that certain equipment and sample containers be used and that additional sample handling guidelines be followed as outlined below. A summary of the loss of pyrethroids to sampling apparatuses tested is detailed 

in table A1.

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1. Sampling equipment components (housings, pump heads, tubing, etc.) that come into contact with the sample 

should be constructed of stainless steel, glass, plastic (LDPE or HDPE) or Teflon. 

 

2. When samples are collected using an automatic sampler or pump, input and output lines should be flushed a 

minimum of three times (flow rate greater than 500 mL/min) with sample water, equal to the total volume of the 

sampling lines, immediately prior to sample collection. This is in addition to any standard cleaning procedures 

conducted prior to the initial sampling. 

3. Sample containers should be constructed of stainless steel, glass, or plastic (HDPE or LDPE). Use containers that 

are the appropriate size for the volume of sample to be collected to minimize the amount of surface area to which 

the sample is exposed.

4. Do not store samples for longer than 1 hour in containers made of Teflon. 

5. Immediately prior to transferring sample water from equipment (sampler, churn, etc.) or a container, shake the 

sample water vigorously for a minimum of one minute. If the transfer takes longer than a few minutes, shake the 

sample continuously during the process. These procedures are not required for sediment samples.

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Table A1. Range of percent loss to containers of 14 pyrethroid compounds spiked in environmental samples and exposed to various 

sampling equipment/container materials.

[Agitated samples were shaken vigorously for 1 minute or run through a pump system immediately prior to water removal and testing. i.d., inner diameter; 

LDPE, low-density polyethylene. L, liter; hr, hour; mm, millimeter; L/min, liter per minute. Values given in percent]

Sampler/container description

Pyrethroids range of 

percent loss to containers 

(not agitated)

Pyrethroids range of 

percent loss to containers 

(agitated)

Glass 1-L bottle (stored 24 hrs) 4–31 2–4

Teflon 1-L bottle (stored 1 hr) Not tested 2–8

Teflon 1-L bottle (stored 24 hrs) 4–31 2–21

Teflon 3-L bag (stored 1 hr) Not tested 2–10

Teflon churn (3 L of water, stored 1 hr) Not tested 2–16

Teflon churn (8 L of water, stored 1 hr) Not tested 3–7

LDPE Cubitainer® 4 L (stored 7 days) Not tested 0–8

LDPE Cubitainer® 19 L (stored 7 days) Not tested 0–4

Stainless steel keg 20 L (stored 24 hrs) Not tested 1–4

Stainless steel filter housing1 Not tested 2–6

ISCO automatic sampler2 Not tested 0

Glass 500-milliliter sediment jars3 0–2 Not tested

1

 Diaphragm pump with Tefon-lined pumphead, 1 m of 9.5-mm i.d. Teflon tubing, 150-mm glass-fiber filter, flow rate of 0.5 L/min.

2

 Peristaltic pump, 15 m of 9.5-mm i.d. Teflon tubing, flow rate of 1 L/min. Pyrethroid spiked water stored in tubing for 1 hr prior to flushing with three 

volumes of deionized water.

3

 Jars contained 100 grams of sediment spiked with pyrethroids. Sample stored at room temperature for 24 hrs, then frozen for 6 days prior to testing.
20 Collection of Pyrethroids: Development and Validation of a Standard Operating Procedure

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10.0 Sample Collection—Method Options

10.1 Water

10.1.1 Grab Sample

A grab sample is appropriate in situations where the waters to be sampled are known to be well-mixed and where flow rates are 

nearly uniform both laterally and vertically.

1. Use a 1-L amber glass bottle that has been baked at 450°C for 4 hours, or a plastic (LDPE or HDPE) or Teflon container that has been solvent-rinsed with methanol.

2. Rinse the container three times with water to be sampled.

3. Fill the container to at least the shoulder of the bottle with the sampled water.

4. Cap the container and place on ice.

10.1.2 Isokinetic Depth-Integrated Sample

An integrated sample is appropriate in situations where the waters to be sampled are not well-mixed in terms of water-quality 

characteristics and/or flow.

1. Use an approved isokinetic, depth-integrating sampler such as a US D-95, or US D-96 (Lane and others, 2003).

2. The sample container should be solvent-cleaned with pesticide-grade methanol.

3. Rinse sampler and container three times with water to be sampled.

4. Collect the water sample using appropriate techniques.

5. Do not store the sample for longer than 1 hour in Teflon containers. After sampling, shake bottle vigorously for 1 minute and transfer to a glass container.

6. Cap the container and place on ice.

10.1.3 Large-Volume Sample

Large-volume water samples (> 4 L) are typically collected using a pump and tubing apparatus, commonly for the isolation of 

large amounts of suspended sediments or for toxicity testing.

1. Pump parts and tubing exposed to sample water should be constructed of Teflon or stainless steel, and cleaned with 

methanol prior to sampling. Sample water equal to three times the volume capacity of the pump and tubing should be 

rinsed through the equipment prior to collecting a sample, and water must be pumped at a flow rate of 500 mL/min.

2. Sample water should be pumped into containers constructed of stainless steel or plastic (LDPE and HDPE), which 

have been cleaned with methanol.
Procedures 21

10.1.4 Autosampler

An autosampler is useful for situations where multiple samples must be collected over a period of time (for example, a 

storm event), or in situations were sampling is initiated automatically by a change in stream stage.

1. Pump parts and tubing exposed to sample water should be constructed of Teflon or stainless steel, and cleaned 

with methanol prior to any collection of samples. The autosampler should be set to sample water equal to three 

times the volume capacity of the pump and tubing.Water must be pumped at a flow rate of 500 mL/min.

2. Sample water should be pumped into glass bottles in the autosampler that have been baked at 450°C for 4 hours.

10.2 Sediment Sample

Sediment samples generally are collected as multiple individual grab samples and later composited (Radtke, 2005). 

1. Sediments should be collected using equipment constructed of glass or stainless steel.

2. After collection, sediment samples should be transferred to glass containers that have been baked at 450°C for 4 

hours and then allowed to cool to room temperature.

3. Cap the container and place on ice.

11.0 Sample Handling and Preservation

11.1 Sample Holding

1. Water samples should be held in glass containers at 4°C until analysis. Samples should be analyzed within 3 days 

of collection.

2. Sediment samples should be held in glass containers at –20°C until analysis. Samples should be held for a maximum of 6 months prior to analysis. Leave adequate headspace for expansion during freezing.

11.2 Sample Handling

1. Water samples must be agitated vigorously by hand for 1 minute prior to transferring, filtering, or compositing.

2. For dissolved water samples, the water should be filtered through a diaphragm pump with a Teflon-lined pumphead, 1 m of 5-mm i.d. Teflon tubing, 150 mm of glass-fiber filter (pre-baked at 450°C for 4 hours), flow rate of 

0.5 L/min. Filtration should happen as soon as possible after sample collection (in the field, if possible).

3. If water samples are being composited, this should be done through a Teflon churn. Sample water should be agitated continuously during compositing, and sample water should not be stored in the churn for more than 1 hour 

prior to compositing. 

4. Sediment samples should be composited using stainless-steel equipment that has been cleaned with methanol.

 

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22 Collection of Pyrethroids: Development and Validation of a Standard Operating Procedure

12.0 Quality Assurance and Quality Control

Given the tendency of pyrethroid pesticides to adhere to equipment/container surfaces, QA/QC samples are an essential tool used 

to characterize sample contamination, pyrethroid carryover between samples, and the loss of pyrethroids to equipment/container 

surfaces. Field, equipment, and laboratory blank samples as well as field and laboratory replicate samples and matrix-spike samples 

should be collected in accordance with standard QA/QC guidelines. 

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Manuscript approved for publication, January 14, 2009

Prepared by the USGS Publishing Network,

Publishing Service Center, Sacramento, California

Susan Davis

 Yvonne Roque

 Carol Sanchez

For more information concerning the research in this report, contact the

California Water Science Center Director,

U.S. Geological Survey, 6000 J Street

Sacramento, California 95619

http://ca.water.usgs.gov
Hladik and others—Collection of Pyrethroids in Water and Sediment Matrices: Development and Validation of a Standard Operating Procedure—

Scientific Investigations Report 2009–5012

ISBN

Printed on recycled paper