U.S. Department of the Interior

U.S. Geological Survey

Prepared in cooperation with

Idaho Soil Conservation Commission

Soil Analyses for 1,3-Dichloropropene (1,3-DCP), So

N-Methyldithiocarbamate (Metam-Sodium), and The

Degradation Products Near Fort Hall, Idaho, Septem

1999 Through March 2000

Water-Resources Investigations Report 01–4052
Cover photo: Soil sample collection, October 1999; personnel from the Natural Resources Conserv

Service (NRCS) and Idaho Soil Conservation Commission
Soil Analyses for 1,3-Dichloropropene (1,3-DCP), So

N-Methyldithiocarbamate (Metam-Sodium), and The

Degradation Products Near Fort Hall, Idaho, Septem

1999 Through March 2000

By D.J. Parliman

Water-Resources Investigations Report 01–4052

Prepared in cooperation with

Idaho Soil Conservation Commission

Boise, Idaho

2001
U.S. DEPARTMENT OF THE INTERIOR

GALE A. NORTON, Secretary

U.S. GEOLOGICAL SURVEY

Charles G. Groat, Director 

Any use of firm, trade, and brand names in this report is for

identification purposes only and does not constitute 

endorsement by the U.S. Government.

Additional information can be obtained from:

District Chief

U.S. Geological Survey

230 Collins Road

Boise, ID 83702-4520

http://idaho.usgs.gov

This report is available online in PDF for

http://idaho.usgs.gov/public/reports.html

and can be viewed using Adobe Acrobat 

Reader. The URL is:
Con

Contents

Abstract .............................................................................................................................................................................

Introduction .......................................................................................................................................................................

Purpose and scope......................................................................................................................................................

Description of study area ...........................................................................................................................................

Soil fumigants ............................................................................................................................................................

Detection of soil fumigant compounds in ground water............................................................................................

Acknowledgments......................................................................................................................................................

Study approaches...............................................................................................................................................................

Sampling procedures and methods....................................................................................................................................

Sampling preparations................................................................................................................................................

Soil sample collection ................................................................................................................................................

Sample processing .....................................................................................................................................................

Results of soil analyses .....................................................................................................................................................

General observations..................................................................................................................................................

Effects of water versus sodium bisulfate (NaHSO4) preservative on pesticide detections .......................................

Cis- and trans-1,3-dichloropropene (1,3-DCP) .........................................................................................................

1,2,3-trichloropropane (1,2,3-TCP); 1,3-dichloropropane (1,3-DCP); 

1,2,2-trichloropropane (1,2,2-TCP); and 1,1,2-trichloroethane (1,1,2-TCE) .....................................................

Carbon disulfide (CS2) ..............................................................................................................................................

Methyl isothiocyanate (MITC) ..................................................................................................................................

1,2-dibromoethane (EDB)..........................................................................................................................................

Summary and suggestions for further investigations ........................................................................................................

Selected references............................................................................................................................................................

Appendix A. Excerpts from U.S. Environmental Protection Agency Method 5035 ........................................................

Appendix B. U.S. Geological Survey Laboratory memorandum, description of custom method....................................

FIGURES

1. Map showing location of Fort Hall, Idaho, and soil sample trenches...................................................................

2– 4. Photographs showing:

2. Backhoe constructing a soil sampling trench, October 1999, Fort Hall, Idaho..............................................

3. A set of soil sampling supplies.......................................................................................................................

4. Backhoe blade being cleaned with a hot-water, high-pressure sprayer, October 1999, Fort Hall, Idaho ......

5. Generalized diagram of a soil sampling trench.....................................................................................................

TABLES

1. Selected precipitation records for Fort Hall, Idaho ...............................................................................................

2. Generalized characteristics of soils near sampling trenches, Fort Hall, Idaho .....................................................

3. Selected information on 1,3-dichloropropene (1,3-DCP) and sodium n-methyldithiocarbamate 

(metam-sodium) ....................................................................................................................................................

4. Laboratory analyses of soil samples from Fort Hall, Idaho, September 1999 through March 2000 ....................
iv Soil Analyses for 1,3-DCP, Metam-Sodium, and Their Degradation Products Near Fort Hall, Idaho

CONVERSION FACTORS, VERTICAL DATUM, AND OTHER ABBREVIATED UNITS

Multiply By To obtain

 foot (ft) 0.3048 meter

inch (in.) 2.54 centimeter

mile (mi) 1.609 kilometer

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

°F=(1.8) (°C)+32

Sea level: In this report, “sea level” refers to the National Geodetic Vertical Datum of 1929—a geodetic datum derived from a gen

adjustment of the first-order level nets of the United States and Canada, formerly called Sea Level Datum of 1929. 

Other abbreviated units:

cc cubic centimeter, multiply by 0.06102 to obtain cubic inch

g gram, multiply by 0.0353 to obtain ounce

μg/L microgram per liter, equal to parts per billion

mg/L milligram per liter, equal to parts per million

mL milliliter
Ab

 ABSTRACT 

 Abstract 

Between September 1999 and March 2000, 

soil samples from the Fort Hall, Idaho, area were 

analyzed for two soil fumigants, 1,3-dichloropropene (1,3-DCP) and sodium n-methyldithiocarbamate (metam-sodium), and their degradation 

products. Ground water is the only source of 

drinking water at Fort Hall, and the purpose of the 

investigation was to determine potential risk of 

ground-water contamination from persistence and 

movement of these pesticides in cropland soils. 

1,3-DCP, metam-sodium, or their degradation 

products were detected in 42 of 104 soil samples. 

The samples were collected from 1-, 2-, and 3-foot 

depths in multiple backhoe trenches during four 

sampling events—before pesticide application in 

September; after application in October; before 

soil freeze in December; and after soil thaw in 

March. In most cases, concentrations of the pesticide compounds were at or near their laboratory 

minimum reporting limits.

U.S. Environmental Protection Agency 

Method 5035 was used as the guideline for soil 

sample preparation and analyses, and either 

sodium bisulfate (NaHSO4), an acidic preservative, or pesticide-free water was added to samples 

prior to analyses. Addition of NaHSO4 to the samples resulted in a greater number of compound 

detections, but pesticide-free water was added to 

most samples to avoid the strong reactions of soil 

carbonate minerals with the NaHSO4. As a result, 

nondetection of compounds in samples containing 

pesticide-free water did not necessarily indicate 

that the compounds were absent. 

Detections of these compounds were in

sistent among trenches with similar soil cha

istics and histories of soil fumigant use. Co

pounds were detected at different depths an

ferent trench locations during each samplin

event.

Overall results of this study showed tha

original compounds or their degradation pro

can persist in soil 6 months or more after th

application and are present to at least 3 feet 

land surface in some areas.

A few of the soil analyses results were 

pected. Degradation products of metam-sod

were detected in samples from croplands w

history of 1,3-DCP applications only, and w

not detected in samples from croplands with 

history of metam-sodium applications. Alth

1,2-dibromoethane (EDB) has not been used 

area for many years, EDB was detected in a 

soil samples. The presence of EDB in soil c

be caused by irrigation of croplands with E

contaminated ground water.

Analyses of these soil samples resulted 

many unanswered questions, and further stu

are needed. One potential study to determin

cal extent of pesticide compound migration 

iments, for example, would include analysis 

or more columns of soil and sediments (lan

face to ground water, about 35 to 50 feet be

land surface) in areas with known soil conta

tion. Another study would expand the scope 

contamination to include broader types of c

land conditions and compound analyses.

Soil Analyses for 1,3-Dichloropropene (1,3-DCP), 

Sodium N-Methyldithiocarbamate (Metam-Sodium

and Their Degradation Products Near Fort Hall, Ida

September 1999 Through March 2000

By D.J. Parliman
Figure 1. Location of Fort Hall, Idaho, and soil sample trenches.

0

0

1

1

2

2

3 MILES

3 KILOMETERS

Base from U.S. geological Survey

1:100,000 quadrangles

Gibson

Drain

Gibson

Canal

North

Canal

Fort

Fort

Hall

Main

Canal

Hall

Main

Canal

Fort Hall Indian Reservation Boundary

Fort

Hall

Indian

Reservation

Boundary

Fort Hall

Indian

Reservation

Boundary

FORT

HALL

BOTTOMS

91

15

91

15

112° 30'

112° 37' 30"

43° 30'

43° 07' 30"

IDAHO

Snake River

Study

area

Location and number of

T2 soil sample trench

Fort

Hall

BINGHAM COUNTY

BANNOCK COUNTY

Snake

River

American Falls

Reservoir

Blackfoot

River

Jimmy

Creek

Big

Spring

Creek

Clear

Creek

Ross

Fork

R. 32 E.

R. 33 E.

R. 34 E.

R. 35 E.

T.

3

S.

T.

4

S.

T.

5

S.

1 6

36 31

1 6

36 31

1 6

36 31

6

31

T5

T6

T7

T1

T2

T3

T4

T8
Introd

Table 1. Selected precipitation records for Fort Hall, Idaho

Precipitation (inches) September October November December January February 

Average total monthly, 

9/1/1948 to 3/31/2000

0.79 0.91 0.96 0.88 0.93 0.83 

Total monthly,

9/1/1999 to 3/31/2000

0.02 0.39 0.11 0.27 1.45 1.50 

INTRODUCTION

Introduction

In 1999, the U.S. Geological Survey (USGS), in 

cooperation with the Idaho Soil Conservation Commission (representing the Shoshone-Bannock Tribes), 

began a study to monitor movement of two soil fumigants—1,3-dichloropropene (1,3-DCP) and sodium nmethyldithiocarbamate (metam-sodium)—through the 

soil profile (root zone) in areas near Fort Hall, Idaho 

(fig. 1). Ground water is the only source of drinking 

water in this area. Ground-water contaminants1 in this 

area include concentrations of nitrate and 1,2-dibromoethane (ethylene dibromide or EDB) that exceed the 

U.S. Environmental Protection Agency (EPA) public 

drinking-water limits of 10 mg/L (as nitrogen) and 

5 μg/L, respectively (U.S. Environmental Protection 

Agency, 2000). Relatively small concentrations of several other volatile organic compounds (VOCs) and pesticides also are present in ground water in the area (Parliman and Young, 1993; USGS Idaho District waterquality data base; L. DeJongh, Shoshone-Bannock 

Tribes, written commun., 1995). Soil fumigants have 

been used extensively on Fort Hall area croplands, and 

personnel with agricultural agencies and the ShoshoneBannock Tribes have been increasingly concerned 

about potential movement of additional contaminants, 

including soil fumigation compounds, to ground-water 

zones.

1Contaminants are components that can limit water suitability for use or can represent degradation of water quality.

Purpose and Scope

The purpose of this report is to describe approaches, methods, and results of a study to determine 

potential risk of ground-water contamination from use 

of 1,3-DCP and metam-sodium (soil fumigants) in 

areas near Fort Hall, Idaho. Existing soil-sampling procedures were used or adapted to collect sample

sentative of 1- to 3-ft soil depths. Samples perio

were collected from several cropland locations t

mine persistence and migration of fumigant com

pounds moving through the soil zone. Suggesti

were proposed for further study of the vertical e

and transport mechanisms of these compounds 

determine their potential movement to ground-w

zones.

Description of Study Area

Soil sample areas were located in irrigated 

lands near Fort Hall in southeastern Idaho (fig. 

land surface is gently undulating, and land surfa

vation is about 4,430 ft above sea level. Econom

the area is strongly influenced by irrigated agric

Major crops include potatoes, grains, and alfalfa

are irrigated from about mid-April through Sep

Irrigation water is provided by surface-water div

(canals and ditches) and numerous, large-capac

wells.

The climate is semiarid, characterized by c

wet winters and hot, dry summers. Mean annua

cipitation from August 1948 through July 2000 

11.33 in. (National Weather Service, accessed O

25, 2000, online); precipitation generally is gre

during winter and spring and least during late s

Average total monthly precipitation (September 

through March 2000) and total monthly precipi

for September 1999 through March 2000 are sh

table 1.

Weather conditions in the study area were 

ally dry in late 1999 and unusually wet during e

2000. Total cumulative precipitation during Sep

October, November, and December 1999 (0.79 i

about 22 percent of normal (3.54 in.), and groun

water irrigation of fields continued into late Oct
4 Soil Analyses for 1,3-DCP, Metam-Sodium, and Their Degradation Products Near Fort Hall, Idaho

several weeks longer than usual (J. Helsel, ShoshoneBannock Tribes, oral commun., October 2000). Total 

cumulative precipitation during January, February, 

and March (3.76 in.) was about 137 percent of normal 

(2.74 in.). Soil freeze occurred after the December 

1999 sampling event, and soil thaw occurred in about 

mid-February 2000. 

Principal rock units in the study area are recent, 

unconsolidated stream and windblown deposits; older 

stream, glacial, windblown, lake, and playa deposits; 

and basalt and associated interbeds. Unconsolidated 

gravel, sand, silt, and clay are the predominant deposits 

and overlie the basalt (Parliman and Young, 1993, p. 4). 

Generalized soil characteristics for areas near sampling 

trenches are shown in table 2.

Soil Fumigants

Soil fumigants are chemicals (pesticides) that 

form gases that diffuse through soil. Fumigants such as 

1,3-DCP and metam-sodium are volatile liquids, existing as liquids under normal temperatures and pressures 

but vaporizing after injection into soil. Effectiveness of 

soil fumigation depends on environmental factors (soil

moisture, temperature, texture, amount of organ

ter, and compaction, for example) that change p

space characteristics in soil or solubility of fum

in soil and water. 

 1,3-DCP and metam-sodium commonly a

in the Fort Hall area for preplanting soil treatme

These chemicals are general soil biocides (fung

herbicide, and nematocide) and often are applied 

cropland by injection into soil to about 18 in. (1,

or through irrigation systems (metam-sodium). 

published, unpublished, and Internet-accessible 

ments are available on the general topic of soil 

gants, and inconsistencies in information exist, 

ing levels of toxicity to humans and environmen

and effects of parent compounds and degradatio

ucts. General information on 1,3-DCP and meta

sodium presented in table 3 is compiled from so

listed in the Selected References section.

Data on degradation rates, solubility, leach

rank, and risks of human exposure are not inclu

table 3 because these factors are strongly influen

changing environmental factors in the soil or be

wide range of reported study results are availab

general, parent products are reported to degrade 

ately rapidly (several weeks) to rapidly (hours), 

degradation products can be of more concern th

parent product to human health. For example, m

sodium is a minimal human health hazard, but t

radation products methyl isothiocyanate (MITC

hydrogen sulfide are moderately to strongly poi

Formulations of these pesticide products h

changed over time and vary among manufactur

but commercial formulations of 1,3-DCP curren

(2000) contain an approximately 50:50 mixture 

cis- and trans- isomers (compounds that have th

molecular formula but different molecular struc

Isomers of 1,3-DCP degradation products also 

listed in table 3.

Detection of Soil Fumigant Compoun

Ground Water

Ground water from the Fort Hall area has b

analyzed for VOCs, including 1,3-DCP degrada

compounds and commercial product contamina

more than 10 years as part of a statewide groun

quality monitoring program and by the Shoshon

Table 2. Generalized characteristics of soils near sampling 

trenches, Fort Hall, Idaho

[T, trench number; locations shown in figure 1]

T1, T2, 

T3, and 

T4

Sheepskin-Magallon Variant-Bartonflat 

Variant complex and Kukvey loamy sand,

0 to 3 percent slope:

Mixed coarse and gravelly or sandy alluvium, including gravelly loamy sand; sandy 

loam; and calcareous sand.

T5 and T6 Paniogue Variant-Tickason complex, 0 to 2 

percent slope:

Mixed loamy alluvium overlying sands and 

gravel, including loam; silty, calcareous, 

or cobbly loam; sand; and gravelly sand.

T7 Bahem silt loam, 0 to 2 percent slope:

Mixed silty alluvium overlying sand and 

gravel, including silt loam, gravelly loamy 

sand, and sand.

T8 Tickason sandy loam, 0 to 2 percent slope:

Mixed alluvium including loam and sandy, 

silty, gravelly, or calcareous loam.
Introd

Table 3. Selected information on 1,3-dichloropropene (1,3-DCP) and sodium 

n-methyldithiocarbamate (metam-sodium)

[CAS RN, Chemical Abstract Service Registry Number; URL, Uniform Resource Locater, a protocol 

for specifying addresses on the Internet; MSDS, Material Safety Data Sheet]

Chemical Name: 1,3-dichloropropene (CAS RN 542-75-6) 

Synonym: 1,3-DCP or 1,3-D

Chemical formula: C3H4Cl2

Isomers: cis- and trans-1,3-dichloropropene

Degradates include: cis- and trans-3-chloroallyl alcohol (CAAL)

cis- and trans-3-chloroacrylic acid (CAAC)

carbon dioxide (CO2)

Application 

practices:

generally injected into soil

URL for MSDS : http://www.horizononline.com/MSDS_Sheets/992.txt

Other ingredients 

or contaminants 

included in current 

or previous commercial products:

 1,3,3-trichloropropene (1,3,3-TCP)

 1,2-dichloropropane (1,2-DCP)

 1,3-dichloropropane (1,3-DCP)

 1,2,3-trichloropropane (1,2,3-TCP)

 1,2,2-trichloropropane (1,2,2-TCP)

 1,1,2-trichloroethane (1,1,2-TCE)

 epichlorohydrin (EPI)

Chemical Name: sodium n-methyldithiocarbamate (CAS RN 137-42-8)

Synonym: metam-sodium or metham-sodium

Chemical formula: C2H4NNaS2

Isomers: none

Degradates include: methyl isothiocyanate (MITC)

n,n-dimethyl thiuram disulfide 

carbon disulfide (CS2)

hydrogen sulfide (H2S)

monomethylamine

nitrogen oxides

sulfur (at pH 9.5)

Application 

practices:

injected into soil or applied through irrigation system

URL for MSDS: http://www.barc.usda.gov/fmod/sohes/msds_lab.htm

Other ingredients 

or contaminants 

included in current 

or previous commercial products

 information not available
6 Soil Analyses for 1,3-DCP, Metam-Sodium, and Their Degradation Products Near Fort Hall, Idaho

Bannock Tribes. To date, these compounds have not 

been detected in water analyses for the two programs. 

A trace amount of 3-chloroacrylic acid, a degradation product of 1,3-DCP, is reported to have been 

detected in ground water from a well near Fort Hall as 

part of an ongoing, nationwide tapwater study related 

to re-registration of a commercial brand of soil fumigant (I. VanWesenbeeck, Dow Agrosciences, written 

commun., December 2000). The tapwater study currently is not complete and results have not been published. There is no EPA public drinking-water limit for 

3-chloroacrylic acid (U.S. Environmental Protection 

Agency, 2000).

Acknowledgments

Successful completion of all phases of this project 

required the experience, expertise, and cooperation of 

many people from numerous agencies and groups. Special thanks are given to Jim Wood, Idaho Soil Conservation Commission (Boise); Wayne Duffy, Natural 

Resources Conservation Service (NRCS-Boise); John 

Helsel, Shoshone-Bannock Tribes (Fort Hall); 

LaGrande Coby, Shoshone-Bannock Tribes (Fort Hall); 

Michael Hepworth, Idaho Department of Agriculture 

(Idaho Falls); Steve Riedy, Idaho Department of Agriculture (Pocatello); Brad Duncan (NRCS-Idaho Falls); 

Jim Baker, Idaho Department of Agriculture (Boise); 

John Taberna, Western Agricultural Research (Blackfoot); and landowners near Fort Hall for access to their 

fields. Thanks also are extended to Ian VanWesenbeeck, Dow Agrosciences (Indianapolis) for information on DowElanco studies of the fate of 1,3-DCP in 

soils (Knuetson and others, 1997; Douglas and others, 

1998; Kennard and Buehrer, 1998) and for providing 

the USGS National Water Quality Laboratory (NWQL) 

with standards for selected compounds.

STUDY APPROACHES

From July to September 1999, study approaches 

were developed, including consideration of questions 

about collection and analyses of whole soil versus soil 

gas samples, potential cross contamination of soil 

zones by hole construction methods and sample container placement/retrieval, and concerns for hea

safety during soil sampling. Passive soil gas sam

(described by Vroblesky and others, 1996, p. 22

and Vroblesky and Robertson, 1996, p. 198-199

active soil gas sampling (by probe and onsite ga

matograph analysis) were considered but not us

this study, whole soil samples were collected to 

increase possibilities of detecting small amount

pesticide compounds and to avoid some disadva

in soil gas sampling. Disadvantages for passive 

pling were the increased labor and time require

place and retrieve soil gas equipment; compress

disturbance of soil to place and retrieve equipm

might affect compound detection; and potential 

hazards to personnel when placing and retrievin

equipment. Disadvantages for active soil gas sa

primarily were increased costs for labor and eq

ment and concern for potential onsite health haz

personnel.

A truck-mounted auger was tested for poss

use in soil sample collection, but auger drilling 

impeded by cobble zones in the soil. The most 

effective, labor- and time-efficient method with 

least number of soil-compaction, soil-disturban

and health-hazard problems for personnel was u

of a backhoe to dig shallow sampling trenches. 

backhoe and backhoe operator were supplied by 

Shoshone-Bannock Tribes (fig. 2).

In September 1999, personnel from the Sh

Bannock Tribes Agricultural Resources office a

NRCS (Idaho Falls) chose locations for soil sam

collection. Choices for locations were based pri

on history of pesticide and cropland uses, variet

soil types, accessibility during fall and winter m

and landowner permission. Initially, four areas 

Figure 2. Backhoe constructing a soil sampling tren

October 1999, Fort Hall, Idaho. 
Sampling Procedures and Me

chosen for soil sample collection—three areas with 

greater than 5 years of 1,3-DCP use only and one area 

with metam-sodium use only. Soil samples were collected from seven backhoe trenches in the four areas—

five trenches (T1, T2, T5, T6, and T7) in 1,3-DCP-only 

areas and two trenches (T3 and T4) in the metamsodium-only area (fig. 1). In each trench, soil samples 

were collected from 1-, 2-, and 3-ft depths below land 

surface.

Soil samples were collected four times between 

September 1999 and March 2000. The sampling dates 

were chosen to represent soil conditions prior to application of pesticides (September), immediately after 

pesticide application (early October), before soil freeze 

and after fall rain events (December), and after soil 

thaw (March). The first sampling event was September 

8, 1999. The second sampling event was October 19, 

1999, at least 2 weeks after fumigants were applied. In 

October, metam-sodium was applied to previously 1,3-

DCP-only areas (T5, T6, and T7), and T5 was replaced 

with T8, located in an area with at least 5 years of 1,3-

DCP-only use (fig. 1).

The third sampling was completed on December 7, 

1999, at least 6 weeks after the irrigation wells were 

shut down and irrigation ditches were dry. The fourth 

and final sampling was March 23, 2000, approximately 

1 month after soil thaw in the area but before spring 

irrigation or cropland preparation. 

SAMPLING PROCEDURES AND 

METHODS

Sampling Procedures and Methods

EPA Method 5035 (U.S. Environmental Protection Agency, 1996) was used as the basis for onsite procedures and methods. Excerpts from EPA Method 

5035, including Section 6—Sample collection, preservation, and handling—are provided in appendix A. Soil 

and quality assurance samples were analyzed at the 

NWQL in Denver, Colorado, and a USGS memorandum describing the custom method developed for analyses of the whole soil samples is provided in appendix 

B.

Some existing sampling methods were adapted or 

new methods developed to address concerns for minimizing soil disturbance; potential sample contamination from onsite techniques; cross contamination of soil 

sampling sites within each trench and from one trench 

to another; consistency of procedures among sampling 

sites, trenches, and dates; reactivity of soil to sodium 

bisulfate (NaHSO4) preservative; personnel saf

during sampling; and cost factors. Onsite proce

and methods can be separated into three parts—

sampling preparations, soil sample collection, a

sample processing.

Sampling Preparations

USGS personnel completed all sampling p

tions. Tare weights, to 0.01 g, were recorded fo

40-mL glass sample bottle (including magnetic 

5 mL NaHSO4 preservative or 5 mL pesticide-f

water, label, septum cap, and dust cap). Bottles 

taining NaHSO4 were prepared commercially. 

containing pesticide-free water were prepared a

USGS Idaho District laboratory in Boise, Idaho

Sets of supplies were prepackaged (ziplock 

for each sample site. Each package included tw

mL, tare-weight sample bottles and one 40-mL 

bottle; stainless steel sampling scoop; and one 1

safety syringe with end plug removed and safet

covered with aluminum foil (fig. 3). Extra sets o

tles were included for replicate samples.

Soil Sample Collection

A team of personnel from the USGS, Idah

Conservation Commission, NRCS, Shoshone-B

nock Tribes, Idaho Department of Agriculture, 

Western Agricultural Research collected the soi

ples. The backhoe blade was cleaned with a hot

Figure 3. A set of soil sampling supplies.
8 Soil Analyses for 1,3-DCP, Metam-Sodium, and Their Degradation Products Near Fort Hall, Idaho







 



Approximately 18

inches of tilled soil

Figure 5. Generalized diagram of a soil sampling trench.

 

 

Layers of loam, sand, and gravel interspersed

with lenses of the same materials

Front edge of

backhoe trenc

Trench approximately

3.5 to 4.0 feet deep

1 foot

3 foot

2 foot

Soil sample locations:

at 1, 2, and 3 feet below

land surface, approximately

1 inch of soil scraped off

face of trench to collect an 

undisturbed soil sample  





high-pressure sprayer before each trench was d

(fig. 4). Trenches were dug to a depth of about 

4 ft; the face at the front edge of the trench was 

tively vertical (fig. 5). Global Positioning Syste

(GPS) measurements were made at trench sites 

document locations of the trenches. Trenches w

constructed in approximately the same areas as 

earlier sampling events (but not the same locati

an effort to duplicate soil conditions while avoid

of previously disturbed soil. 

A pocket tape was used to measure 1-, 2-, a

depths from land surface. Sampling began at th

depth and successively proceeded to 2-ft and 1-

depths to prevent cross contamination of soil sa

within the trench. At each depth, a stainless stee

Figure 4. Backhoe blade being cleaned with a hot-water, was used to scrape approximately 1 in. of soil a

high-pressure sprayer, October 1999, Fort Hall, Idaho 
Sampling Procedures and Me

from the trench face and expose uncompressed soil that 

had not come in contact with the backhoe blade. Personnel collected soil samples in the shield section of a 

safety syringe by pushing the shield into the freshly 

exposed soil or by scooping soil into the shield with 

a stainless steel scoop when the soil zone was cobbly 

or densely packed (usually from silt or clay content). 

When the syringe shield was full, aluminum foil was 

placed over the top and the covered sample was placed 

into the syringe casing (fig. 3). An empty, 40-mL bottle 

also was filled with soil sample for laboratory soil 

moisture analyses. 

After the soil sample was collected, sampling 

syringes, soil moisture bottle, and sample scoop were 

placed in a ziplock bag labeled with sampling site location, and the ziplock bag was placed in an ice chest. 

The stainless steel trowel was scrubbed with a detergent solution and rinsed with deionized water before 

2-ft and 1-ft zones within each trench were sampled. 

Latex or nitrile gloves were worn by all personnel 

collecting or handling soil samples at each site. During 

the October sampling, personnel in the trench collecting soil samples and an observer at land surface were 

required to have enclosed-space, hazardous materials 

training and to wear appropriate respiratory equipment 

and protective clothing (cover photo). Although samples were collected several weeks after soil fumigant 

application and at least a week beyond required areaentry restrictions, there was a possibility that toxic or 

hazardous fumes may have persisted in some soil zones 

in the trench. During December and March sampling, 

protective clothing continued to be worn in the trench 

to keep potentially contaminated soil from contacting 

clothing or skin.

Sample Processing

Collection of samples from all trenches on each 

sampling date required about 2 hours, and when sampling was complete, each sample set was prepared for 

shipment and laboratory analyses. Samples were prepared at or near a sampling location by USGS personnel.

Soil samples were prepared in order from earliest 

to latest collection time. Tare-weight bottles containing 

5 mL of NaHSO4 or pesticide-free water were placed 

on a portable electronic scale, and the weight was 

zeroed. The aluminum cover on the syringe shield was 

removed, about 1/4 to 1/2 in. of soil was pushed up 

from the shield and discarded, and about 5 g (±0

the remaining soil was extruded or scooped out 

transferred to the prepared sample bottle. The b

was recapped with the septum cap and dust cov

site, sampling information, and total sample we

were written on the bottle label. 

After two sample bottles and one soil mois

bottle were prepared for each sampling site, bot

were put in a foam shipping container, which w

placed in a large ziplock bag, and the bag was pl

an ice chest. Ice was double-bagged in ziplock 

ensure that ice water did not come in contact w

ple bottles. Sample sets were shipped to the NW

within about 24 hours of sample collection. Sam

arrived at the laboratory within about 48 hours 

ple collection.

Weighing paper was used during onsite sam

weighing to keep the scale pan clean and avoid 

contamination of sample bottle sets. Powder-fre

gloves were worn at all times, and the sample p

tion area was cleaned between sample sets. Use

posable equipment and supplies were sealed in 

bags and put in solid waste collection bins. Exc

was left at the sample processing site.

Sodium bisulfate is an acidic preservative a

soil samples except “when samples are known o

pected to contain high levels of carbonates” (U.

ronmental Protection Agency, 1996). Before the 

ples collected in September 1999 were transferr

bottles containing NaHSO4, dilute hydrochloric 

was added to small amounts of the soil sample t

for carbonate content. Many soil samples strong

effervesced and most samples moderately efferv

when the acid was added. Pesticide-free water, 

native approach for sample preparation describe

Method 5035, was not available during soil sam

preparation in September, and soil samples with 

strongest reaction to acid were sent to the labor

bottles containing only stir bars. Samples with s

moderate reaction to acid were sent with NaHS

servative added. At the laboratory, 5 mL of pest

free water was added to dry samples. 

Pesticide-free water was added to most soi

ple sets collected in October and December 199

March 2000 to establish sample preparation con

between sampling events and to reduce possibil

strong chemical reactions in sample bottles. A f

licate samples with NaHSO4 preservative adde

sent to the laboratory along with the October an

March sample sets for analyses comparisons. Se
10 Soil Analyses for 1,3-DCP, Metam-Sodium, and Their Degradation Products Near Fort Hall, Idaho

of sampling sites for addition of NaHSO4 to replicates 

was based, in part, on previous detections of pesticide 

compounds with NaHSO4 preservative and history of 

reactivity of soil to the preservative. After September, 

all samples were sent to the laboratory either with 

water or NaHSO4 solutions.

About three replicate sets of soil samples were 

collected on each sampling date for quality control/quality assurance. Pesticide-free water only was 

added to most replicate samples, but at some locations, 

both water and NaHSO4 were added to replicates. 

Most locations for replicate collection were randomly 

selected. A few replicates were collected at sites where 

historically large degradation compound concentrations were documented. Baked, pesticide-free sand 

(provided by the NWQL) was added to sample bottles 

containing NaHSO4 or pesticide-free water, and bottles 

containing only 5 mL pesticide-free water or NaHSO4 

were included with sample sets for each sampling 

event. A sample of 1,3-DCP from a bulk distribution 

tank at Fort Hall was included in the October sampling. 

Water from the hot-water, high-pressure sprayer tank 

was included in the December sampling (water in the 

sprayer tank was not from the Fort Hall area).

Stainless steel scoops and stir bars were cleaned 

for reuse after each sampling event. Scoops, cleaned at 

the USGS Idaho District laboratory, were washed in a 

detergent solution, rinsed with deionized water, rinsed 

with methanol, rinsed with deionized water, air dried, 

and stored between sampling dates in ziplock bags. Stir 

bars were cleaned at the NWQL and returned to the 

Idaho District after each event.

RESULTS OF SOIL ANALYSES

Results of Soil Analyses

One hundred and fourteen analyses were completed for this study (table 4, back of report), of which 

104 were soil samples and 10 were samples of 1,3-

DCP from bulk tank storage, commercially prepared 

pesticide-free water, commercially prepared NaHSO4, 

pesticide-free baked sand, and equipment rinsewater. 

Degradation products of 1,3-DCP or metam-sodium 

were detected in 42 of the 104 soil samples (detections 

are shown in red in table 4). Twenty-one of the 104 soil 

samples were prepared with NaHSO4 preservative 

(shown in blue in table 4). Twenty of the 104 soil samples were replicates, consisting of water-only or water 

versus NaHSO4 samples. 

General Observations

Degradation products of 1,3-DCP and met

sodium were detected in soil samples from Sep

1999. These results were somewhat unexpected 

because soil fumigants had not been applied to t

for at least 12 months prior to the September sam

Although 1,2-dibromoethane (EDB) has not be

in the Fort Hall area for many years, it was une

edly detected in September, October, and March 

samples.

Effects of unusually dry weather condition

an extended irrigation season during late summ

fall 1999 on pesticide detections are unknown. 

moisture content in many March soil samples w

greater than in September samples, and March s

generally effervesced less strongly when NaHS

added than did September samples. Potential ef

greater soil moisture content on pesticide detect

unknown.

Diversity of 1,3-DCP degradation products 

greatest and the concentrations were largest in s

samples from T8. The pesticide application hist

this field has been documented by the Shoshone

nock Tribes since about 1995, but before this da

records are available. No explanation currently 

able for the diversity and concentrations of pest

compounds detected in soil from this area.

Effects of Water Versus Sodium Bisu

(NaHSO4) Preservative on Pesticide 

Detections

One or more of 9 pesticide degradation co

pounds were detected in samples from all trenc

and in 19 of 24 soil zones overall (table 4). One 

most important factors in detection of degradati

compounds in soil was addition of NaHSO4 to 

samples—compounds were detected in 95 perc

the samples (20 of 21) with NaHSO4 preservati

added, either onsite or at the laboratory. Compo

were detected in only 27 percent of the samples 

83) with water added. 

Nine sets of paired water versus NaHSO4 

cate samples were collected. Degradation comp

were detected only in the NaHSO4-preserved s

in four of nine sets. Compounds were detected 

water and NaHSO4-preserved samples in four o
Results of Soil Anal

sets. In these latter four sets, concentrations generally 

were larger in samples with NaHSO4 than in samples 

with water, but concentrations in water-only replicate 

samples were similar. Compounds were detected in the 

water-only samples, but not in the NaHSO4 samples, in 

only one of the nine replicate sets (T6, 1-ft depth, September). NaHSO4 was not added to December 1999 

samples, and degradation compounds were detected in 

samples from 2- and 3-ft depths at T7 and from all 

depths at T8.

The main objective of adding NaHSO4 to soil 

samples was to “reduce or eliminate the majority of the 

biological activity of the sample, thereby preventing 

biodegradation of the volatile target analytes” (U.S. 

Environmental Protection Agency, 1996, section 

6.1.1.3). The effect of using water rather than NaHSO4 

on biological activity (and potentially, on degradation 

or presence of pesticide compounds) of the samples is 

unknown. Original levels of biological activity in the 

soils are unknown, but biological activity in soil treated 

for years with fumigants may already be low or absent 

(J. Taberna, Sr., University of Idaho, Southwest Idaho 

Agricultural Research Center, Parma, Idaho, oral commun., 2000).

The greater number of compound detections in 

samples with NaHSO4 added may not be related to pH 

of the preservative or suppression of bacterial activity 

in the soil sample but may be caused by salts in the 

solution (sodium and sulfate) that strip pesticides from 

the soil particle surfaces (D. Rose, U.S. Geological 

Survey National Water Quality Laboratory, oral commun., October 2000). 

The preceding observations are important 

because, even though pesticide-free water was added to 

most soil samples owing to strong reactions of soil carbonate minerals with the acidic preservative NaHSO4, 

compounds were most often detected in samples with 

NaHSO4 added. Nondetection of compounds in samples with water added does not necessarily indicate that 

the compounds were absent. 

Because nondetection of degradation compounds 

in samples with water added is questionable and unreliable, no attempt was made to use the data for comparative trend analyses. Despite problems with comparability of analyses, the following generalizations can be 

made about the detected compounds.

Cis- and trans-dichloropropene (1,3-

Cis- and trans-1,3-DCP were the most com

detected degradation compounds in soil sample

are the major components of commercial 1,3-D

fumigant formulations. No EPA public drinking

limits have been established for 1,3-DCP or its 

dation products. These compounds have not bee

detected in ground water in the Fort Hall area.

• Most concentrations were less than the 

oratory minimum reporting limit (mrl) 

0.07 and 0.13 μg/L for cis- and trans-is

mers, respectively (concentrations belo

the mrl are indicated in table 4 by an ‘e

preceding the value or by the word ‘tra

• 1,3-DCP compounds were detected in s

with either water or NaHSO4 added to 

ples, but compounds were most consistently detected when NaHSO4 was use

• Concentrations of cis- and trans-DCP w

largest in replicate samples with NaHS

added, collected from 2- and 3-ft depth

T8, March 2000.

• Detections of cis- and trans-DCP in the 

September laboratory replicate, water-o

sample, from T6 (1-ft depth) are anoma

lous. Except for the September replicat

sample, no degradation compounds we

detected in soil from T6 during any oth

sampling event.

1,2,3-trichloropropane (1,2,3-TCP), 

1,3-dichloropropane (1,3-DCP), 

1,2,2-trichloropropane (1,2,2-TCP), an

1,1,2-trichloroethane (1,1,2-TCE)

These compounds were detected primarily 

samples and are suspected to be contaminants f

earlier commercial formulations of 1,3-DCP (D

U.S. Geological Survey National Water Quality 

ratory, oral commun., October 2000). EPA publ

drinking-water limits have been established onl

1,1,2-trichloroethane (5 μg/L). These compoun

not been detected in ground water in the Fort H

• All compounds except 1,1,2-TCE were 

detected in T8 samples from all depths 

most sampling events. 
12 Soil Analyses for 1,3-DCP, Metam-Sodium, and Their Degradation Products Near Fort Hall, Idaho

• Compounds were detected in T8 soil samples with either water or NaHSO4 solutions 

added.

• Concentrations of 1,2,3-TCP and 1,3-DCP 

generally were less than their mrls of 0.14 

and 0.07 μg/L, respectively.

• 1,2,2-TCP and 1,1,2-TCE were detected 

primarily in samples from T8. Causes for 

detection of these compounds at T8 and not 

in other areas with histories of 1,3-DCP 

application are unknown.

• 1,2,2-TCP detected in T7 samples (3-ft 

depth in December and 2-ft depth in 

March) are anomalous. No other degradation products were detected in soil from T7.

Carbon Disulfide (CS2)

CS2 detected in most samples is suspected to be 

the result of, or to include, contamination from the 

NaHSO4 preservative rather than the degradation products of metam-sodium (D. Rose, U.S. Geological Survey National Water Quality Laboratory, oral commun., 

October 2000). No EPA public drinking-water limit has 

been established for CS2, and the compound has not 

been detected in ground water at Fort Hall.

• CS2 was detected in at least one soil sample 

from all trenches except T7.

• CS2 was detected in all samples with 

NaHSO4 added except for two—T1, 3-ft 

depth in October, and T6, 1 ft-depth in September.

Methyl Isothiocyanate (MITC)

MITC is a degradation product of metam-sodium. 

No EPA public drinking-water limit has been established for MITC, and the compound has not been 

detected in ground water at Fort Hall.

• MITC was detected in a few soil samples 

from T1 and T2, located in areas where historically, only 1,3-DCP has been applied. 

Causes for the consistent detection of 

MITC in soil samples from T1 and T2 are 

unknown.

• MITC was not detected in samples from T3 

and T4, located in areas where historically, 

only metam-sodium has been applied.

• The largest concentration of MITC, 11 

μg/L, was from T2 (1-ft sampling depth

October 1999 (about 2 weeks after app

tion of metam-sodium to nearby fields)

other concentrations were lower than th

mrl of 1.8 μg/L. 

• During March 2000 sampling, MITC w

detected in soil from 1-ft depths at both 

and T2 (NaHSO4 replicate samples), w

indicates that this compound may persi

soil for extended periods of time.

1,2-Dibromoethane (EDB)

EDB historically has been a soil fumigant 

the Fort Hall area. An EPA public drinking-wat

of 0.05 μg/L has been established for EDB, and 

compound has been detected in Fort Hall groun

in concentrations exceeding the EPA limit (Idah

trict, USGS QWDATA data base).

• Detection of EDB in soil samples from 

and T2 was unexpected because this co

pound has not been applied to cropland

since the early 1990’s. 

• EDB was detected only in samples with 

NaHSO4 preservative added. 

• Sources of the compound are unknown 

may be caused by cropland irrigation w

EDB-contaminated ground water.

SUMMARY AND SUGGESTIONS FOR 

FURTHER INVESTIGATIONS

Summary and Suggestions for Further Investigations

The goal of the study was to determine pot

risk of ground-water contamination from use of 

DCP and metam-sodium on croplands near For

Results of this study show that parent compoun

their degradation products can persist in soil 6 m

or more after their application and are present t

least 3 ft below land surface in some areas.

• One hundred and four soil samples wer

analyzed for this study. Degradation pr

ucts of 1,3-DCP or metam-sodium wer

detected in 42 of the 104 soil samples. 

• In most cases, concentrations were at o

near the laboratory minimum reporting 

limit for each compound. Detections of 
Selected Refere

pesticide degradation compounds in soil 

were not always consistent with reported 

histories of soil fumigant use or between 

croplands with similar soil characteristics.

• Compounds were detected more frequently 

in NaHSO4-preserved replicate samples—

from all trench sites and sampling events—

than in water-only replicate samples.

• Concentrations of these compounds were 

largest in soil samples from the T8 area, 

which has little historical documentation of 

pesticide use prior to 1995. Degradation 

products of 1,3-DCP or contaminants from 

earlier formulations of 1,3-DCP were 

present in soil to at least 3 ft below land 

surface at T8 and persisted through March 

2000 sampling, at least 6 months after fall 

1999 pesticide applications. It is unclear at 

this time whether the compounds detected 

in March were the result of the migration of 

pesticides applied in fall 1999 or whether 

the compounds have persisted from previous applications. 

• MITC, a degradation product of metamsodium, was detected in a few soil samples 

from T1 and T2, located in areas where historically, only 1,3-DCP has been applied. 

Causes for the persistence of MITC in soil 

samples from T1 and T2 areas are 

unknown. 

Results of this study have produced a number of 

unanswered questions. The most significant questions 

relate to importance of compound detections from deep 

(3-ft) soil zones in some areas and mechanism(s) of 

compound transport. If compounds are consistently 

detected at 3-ft soil zones, are they migrating to underlying ground-water zones? If water is not an effective 

solvent for these compounds, how are they being transported through soil and unconsolidated sediments 

below the root zone? What other contaminants are 

present in soil and sediments and are potentially 

migrating to ground-water zones in the Fort Hall area? 

Additional studies of pesticide occurrence and persistence in soil and rock near Fort Hall may provide data 

to answer these questions.

One suggestion for further study is to analyze a 

column of soil (root zone) and sediments (rock underlying soil) for pesticides in an area where compounds 

have been consistently detected, such as at T8. The column would extend from land surface to the first waterbearing zone (35 to 50 ft below land surface), a

ples would be collected for compound analyses 

intervals throughout the column. Additional test

be developed to address questions about soil ch

and soil/sediment characteristics related to poss

downward movement of compounds in unsatur

materials. The study could be limited to selecte

ses of a single column at a single site or could b

expanded to include several columns in areas re

senting a variety of compounds, soil, sediment, 

hydrogeologic conditions. 

Additional studies could define migration 

cides in soils representing broader types of crop

conditions and applications of pesticide compou

Samples from many trenches could be analyzed 

short periods of time, probably in late winter or 

spring when soil moisture is high, before cropla

gation has begun, and before crops are planted. 

mation on topics such as quality of irrigation w

water application practices, history of pesticide 

and farming practices for each site could be com

and these data could be compared with soil samp

for trend analyses.

Soil column or trench sampling could be c

nated with other soil research, such as the effec

ticides on suppression of soil bacteria populatio

overall benefits of additional soil analyses studi

would include acquisition of additional tools to 

understand current pesticide migration problem

dict movement and effects of compounds, and m

ground-water resources in the area. 

SELECTED REFERENCES

Selected References

Benedict, P., 1995, Soil investigation of Fort Ha

Indian Reservation, Idaho, zone 1 of Fort 

River Basin study: Boise, Natural Resourc

Conservation Service, 143 p.

Clark, D.W., 1990, Pesticides in soils and groun

in selected irrigated agricultural areas near 

Ronan, and Huntley, Montana: U.S. Geolo

Survey Water-Resources Investigations R

90–4023, 34 p.

Douglas, B., Pottinger, M., Alexanader, S., Zab

and Dolder, S., 1998, Environmental fate 

dichloropropene in a cold climate, progres

#6: Indianapolis, Ind., Dow AgroSciences 

Study ID ENV95002.06, unpublished rep

140 p., 1 app.
14 Soil Analyses for 1,3-DCP, Metam-Sodium, and Their Degradation Products Near Fort Hall, Idaho

Dow AgroSciences LLC, 2000, Material Safety Data 

Sheet—Telone*II soil fumigant: accessed October 25, 2000, at URL http://www.dowagro.com/

label_system/label_files/us/msds/2422.pdf

DowElanco, 1996, 1,3-Dichloropropene, a profile: 

Indianapolis, Ind., unpublished report, 25 p.

Horizon, 2000, MSDS sheets: accessed October 25, 

2000, at URL http://www.horizononline.com/

MSDS_Sheets/992.txt

Kennard, L.M., and Buehrer, T.J., 1998, Aerobic soil 

metabolism of 1,3-dichloropropene on two soil 

horizons at three temperatures: Indianapolis, Ind., 

Dow AgroSciences LLC, Study ID ENV97008, 

87 p., 8 apps.

Knuteson, J.A., Dolder, S.C., Carver, L.S., Yoder, R.N., 

and Brink, D.L., 1997, Air, surface water, and 

ground water field study of 1,3-dichloropropene 

in a south Florida vegetable production system—

final report: Indianapolis, Ind., DowElanco Study 

ID ENV94004.05, unpublished report, 99 p., 

13 apps.

Mansfield, G.R., 1920, Geography, geology, and mineral resources of the Fort Hall Indian Reservation, Idaho: U.S. Geological Survey Bulletin 713, 

152 p.

Metam-Sodium Task Force Product Stewardship Committee, 2000, Metam-sodium information sheet, 

March 2000: accessed October 25, 2000, at URL 

http://www.metampsc.com/info.pdf

National Toxicology Program, 2000, Eighth Report on 

Carcinogens—1,2-dichloropropene (technical 

grade): accessed October 25, 2000, at URL 

http://ntp-server.niehs.nih.gov/roc/ninth/

rahc/1_3dichloropropene.pdf

National Weather Service, 2000, Idaho climate summaries—Fort Hall Indian Agency, Idaho (102297): 

accessed October 25, 2000, at URL 

http://www.wrcc.dri.edu/cgi-bin/cliMAIN/

pl?idfort

Parliman, D.J., and Young, H.W., 1993, Water levels 

in selected wells and directions of ground-water 

movement near Fort Hall, Fort Hall Indian Reservation, southeastern Idaho: U.S. Geological 

Survey Water-Resources Investigations R

92–4014, 13 p.

Syracuse Research Corporation, 2000, Environm

fate data base: accessed October 27, 2000

URL http://esc.syrres.com/efdb.htm

U.S. Department of Agriculture, Beltsville Agri

Research Center, 2000, Pesticide labels/m

safety data sheets (MSDS): accessed Octo

2000, at URL http://www.barc.usda.gov/fm

sohes/msds_lab.htm

U.S. Environmental Protection Agency, 1996, M

5035—Closed-system purge-and-trap and 

tion for volatile organics in soil and waste 

ples: accessed March 13, 2001, at URL 

http://www.epa.gov/epaoswer/hazwaste/te

5035.pdf

U.S. Environmental Protection Agency, 2000, D

water standards and health advisories: U.S

ronmental Protection Agency, Office of W

822–B–00–001, 18 p.

University of Nebraska-Lincoln, 2000, Soil fum

for the commercial/noncommercial pestic

applicator: accessed October 25, 2000, at 

http://ianrwww.unl.edu/ianr/pat/catmans/s

soil.htm

Vroblesky, D.A., Rhodes, L.C., Robertson, J.F.

Harrigan, J.A., 1996, Locating VOC conta

tion in a fractured-rock aquifer at the grou

water/surface-water interface using passiv

collectors: Ground Water, v. 34, no. 2, p. 2

Vroblesky, D.A., and Robertson, J.F., 1996, Tem

changes in VOC discharge to surface wate

a fractured rock aquifer during well instal

and operation, Greenville, South Carolina

Ground Water Monitoring and Remediatio

v. 16, no. 3, p. 196–201.
Table 4. Laboratory analyses of soil samples from Fort Hall, Idaho

September 1999 through March 2000
Blank page 8
lution added cis -1,3-dichloro- trans -1,3-dichloro- 1,2,3-trichloro- 1,3-dichloro- 1,2,2-trichloro- 1,1,2-trichloro- Carbon Methyl isothio- 1,2-dibromo- Soil Soil 

to sample propene propene propane propane propane ethane disulfide cyanate ethane sample, sample,

(cis -1,3-DCP) (trans -1,3-DCP) (1,2,3-TCP) (1,3-DCP) (1,2,2-TCP) (1,1,2-TCE) (CS2) (MITC) (EDB) weight (g) % moisture

 NaHSO4 e0.18 0.23 <0.14 --- --- --- e0.22 < 1.8 e0.08 5.00 8.52

 water <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.40 8.59

 water <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.30 8.17 water <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.30 7.48

 water <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.50 7.48

 NaHSO4 0.30 0.30 <0.14 <0.07 --- --- e0.1242 e1.101 e0.0706 5.90 7.48

 NaHSO4 e0.15 e0.21 <0.14 --- --- --- e0.14 < 1.8 e0.05 4.40 7.46

 water e0.12 e0.09 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.20 8.15

 water <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.00 9.03 water <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 4.90 8.50

 NaHSO4 e0.1252 e0.1845 <0.14 <0.07 --- --- e0.0874 < 1.8 e0.0502 5.40 8.50

 NaHSO4 e0.13 e0.13 <0.14 --- --- --- 0.28 < 1.8 e0.04 4.80 1.63

 water e0.07 e0.06 <0.14 <0.07 --- --- e0.03 e0.20 <0.09 5.00 6.12

 water <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.10 5.92 water <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.40 5.18

 water <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.40 5.18

 NaHSO4 0.29 0.32 <0.14 --- --- --- e0.19 < 1.8 e0.15 5.10 7.99

 water <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.40 8.19

aHSO4 e0.16 e0.19 <0.14 <0.07 --- --- 0.31 11.00 e0.04 5.20 8.19

 water <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.30 8.53

 water <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.20 8.53

 water <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.30 8.56

 NaHSO4 0.25 0.29 <0.14 <0.07 --- --- e0.0532 e0.4738 <0.09 5.10 8.56

 NaHSO4 e0.12 e0.10 <0.14 --- --- --- e0.13 < 1.8 e0.08 5.70 6.80

 water e0.05 e0.05 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.20 6.89

 water e0.06 e0.04 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.70 6.89

 water <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.00 6.35 water <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.50 9.39

ater <0.07 <0.13 <0.14 --- --- --- <0.08 < 1.8 <0.09 5.60 5.42

 water e0.14 e0.01 <0.14 <0.07 --- --- <0.08 e0.51 <0.09 5.10 8.94

aHSO4 e0.06 e0.07 <0.14 <0.07 --- --- e0.21 < 1.8 <0.09 5.10 8.94

 water <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.20 5.64 water <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.50 5.48

mples from Fort Hall, Idaho, September 1999 through March 2000

per liter (μg/L), equivalent to parts per billion; onsite, added at the time of sampling; lab, added at the U.S. Geological Survey National Water Quality Laboratory in Denver, Colorado; rep, 

ction of contaminant; NaHSO4, sodium bisulfate added to samples; <, less than; e or trace, less than laboratory minimum reporting limit; %, percent; n/a, not applicable; ---, compound not 

nth of a gram]
ion added cis -1,3-dichloro- trans -1,3-dichloro- 1,2,3-trichloro- 1,3-dichloro- 1,2,2-trichloro- 1,1,2-trichloro- Carbon Methyl isothio- 1,2-dibromo- Soil Soil 

sample propene propene propane propane propane ethane disulfide cyanate ethane sample, sample,

(cis -1,3-DCP) (trans -1,3-DCP) (1,2,3-TCP) (1,3-DCP) (1,2,2-TCP) (1,1,2-TCE) (CS2) (MITC) (EDB) weight (g) % moisture

aHSO4 <0.07 e0.05 <0.14 --- --- --- e0.12 < 1.8 <0.09 5.10 7.32

ater <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.20 7.05

ater <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.20 8.71

ater <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.20 8.72

aHSO4 <0.07 e0.07 <0.14 --- --- --- e0.15 < 1.8 <0.09 4.70 7.03

ater <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.20 9.00

ater <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.20 7.49

ater <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.10 6.41

aHSO4 e0.06 e0.08 <0.14 --- --- --- 0.33 < 1.8 <0.09 5.10 7.78

ater <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.00 7.29

ater <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.60 6.85

ater <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.30 5.69

aHSO4 e0.09 e0.11 <0.14 --- --- --- e0.16 < 1.8 <0.09 5.60 7.40

ater <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 4.80 6.79

ater <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.80 5.78

ater <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.20 5.98

aHSO4 <0.07 <0.13 <0.14 --- --- --- e0.14 < 1.8 <0.09 5.30 7.59

ater <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.10 4.36

ater <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.70 5.98

ater <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.70 5.16

aHSO4 <0.07 <0.13 <0.14 --- --- --- 0.29 < 1.8 <0.09 4.80 6.57

ater e0.03 trace <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.20 5.64

ater trace trace <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 4.90 5.64

SO4 e0.02 e0.04 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 4.90 5.64

ater <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.20 6.01

ater <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.40 6.01

ater <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 4.90 6.04

er <0.07 <0.13 <0.14 --- --- --- <0.08 < 1.8 <0.09 5.50 9.63

er <0.07 <0.13 <0.14 --- --- --- <0.08 < 1.8 <0.09 5.00 9.96

aHSO4 e0.04 e0.05 <0.14 --- --- --- e0.16 < 1.8 <0.09 5.60 4.85

mples from Fort Hall, Idaho, September 1999 through March 2000---Continued
n added cis -1,3-dichloro- trans -1,3-dichloro- 1,2,3-trichloro- 1,3-dichloro- 1,2,2-trichloro- 1,1,2-trichloro- Carbon Methyl isothio- 1,2-dibromo- Soil Soil 

mple propene propene propane propane propane ethane disulfide cyanate ethane sample, sample,

(cis -1,3-DCP) (trans -1,3-DCP) (1,2,3-TCP) (1,3-DCP) (1,2,2-TCP) (1,1,2-TCE) (CS2) (MITC) (EDB) weight (g) % moisture

HSO4 <0.07 <0.13 <0.14 --- --- --- <0.08 < 1.8 <0.09 5.30 13.10

e0.14 e0.16 <0.14 --- --- --- 0.68 < 1.8 <0.09 5.40 13.10

er <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.40 8.25

er <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.50 7.92

er <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.00 17.61

<0.07 <0.13 <0.14 --- --- --- <0.08 < 1.8 <0.09 5.30 13.56

er <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.20 8.13

er <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.50 5.30er <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.50 5.30

er <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.20 18.31

<0.07 <0.13 <0.14 --- --- --- <0.08 < 1.8 <0.09 5.20 10.33

er <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.30 4.45

er <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.20 3.70

er <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.10 10.54

<0.07 <0.13 <0.14 --- --- --- <0.08 < 1.8 <0.09 5.30 17.39

er <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 4.90 19.73er <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 4.90 19.73

er <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.20 15.65

er <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.40 16.14

<0.07 <0.13 <0.14 --- --- --- <0.08 < 1.8 <0.09 5.10 15.56

er <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.10 18.30

er <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 4.80 17.43

er <0.07 <0.13 <0.14 <0.07 e0.004 --- <0.08 < 1.8 <0.09 5.30 15.51

<0.07 <0.13 <0.14 --- --- --- <0.08 < 1.8 <0.09 5.20 11.48

er <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 4.60 15.10

er <0.07 <0.13 <0.14 <0.07 e0.007 --- <0.08 < 1.8 <0.09 5.20 15.11

er <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.00 6.91

es from Fort Hall, Idaho, September 1999 through March 2000---Continued
ion added cis -1,3-dichloro- trans -1,3-dichloro- 1,2,3-trichloro- 1,3-dichloro- 1,2,2-trichloro- 1,1,2-trichloro- Carbon Methyl isothio- 1,2-dibromo- Soil Soil 

sample propene propene propane propane propane ethane disulfide cyanate ethane sample, sample,

(cis -1,3-DCP) (trans -1,3-DCP) (1,2,3-TCP) (1,3-DCP) (1,2,2-TCP) (1,1,2-TCE) (CS2) (MITC) (EDB) weight (g) % moisture

ater e0.09 e0.15 e0.20 e0.17 0.52 --- <0.08 < 1.8 <0.09 5.00 9.30

ater <0.07 <0.13 e0.05 e0.09 e0.01 --- <0.08 < 1.8 <0.09 5.40 8.75

ater <0.07 <0.13 <0.14 <0.07 e0.0125 --- <0.08 < 1.8 <0.09 5.80 11.08

ater e0.0447 e0.0710 <0.14 <0.07 e0.0192 --- <0.08 < 1.8 <0.09 5.20 11.08

ater e0.06 e0.15 e0.07 e0.15 e0.13 --- <0.08 < 1.8 <0.09 4.90 8.15

ater <0.07 <0.13 <0.14 e0.06 e0.01 --- <0.08 < 1.8 <0.09 5.60 8.75ater <0.07 <0.13 <0.14 e0.09 e0.01 --- <0.08 < 1.8 <0.09 5.50 9.05

ater e0.0767 e0.1805 <0.14 e0.0658 e0.0185 --- <0.08 < 1.8 <0.09 4.90 11.04

aHSO4 2.54 3.52 e0.2333 e0.1559 e0.0361 --- 0.52 < 1.8 <0.09 4.80 11.04

ater e0.07 0.27 e0.05 0.23 e0.21 --- <0.08 <1.8 <0.09 4.90 8.03

ater <0.07 <0.13 <0.14 0.23 e0.03 e0.03 e0.08 <1.8 <0.09 5.10 9.91

ater e0.0947 0.44 <0.14 e.0837 e0.0182 --- <0.08 < 1.8 <0.09 5.50 11.23

ater e0.1070 0.37 <0.14 e0.0970 e0.0218 --- <0.08 < 1.8 <0.09 5.30 11.23

aHSO4 2.06 2.79 <0.14 e0.1390 e0.0332 --- 0.65 < 1.8 <0.09 5.50 11.23

P only 5.37 5.09 --- --- --- --- --- --- --- --- ---

(nanograms) (nanograms)

nly <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 n/a n/a

nly <0.07 <0.13 <0.14 <0.07 --- --- e0.04 < 1.8 <0.09 n/a n/a

nly <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 n/a n/a

4 only <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 n/a n/a

aHSO4 <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.00 1.58ater <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.10 1.58

ater <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.50 1.58

ater <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 5.30 1.58

ter only <0.07 <0.13 <0.14 <0.07 --- --- <0.08 < 1.8 <0.09 n/a n/a

mples from Fort Hall, Idaho, September 1999 through March 2000---Continued
Appendix A. Excerpts from U.S. Environmental Protection Agency Method 503

http://www.epa.gov/epaoswer/hazwaste/test/5035.pdf

Appendix A

Abbreviations and Conversions:

°C, degrees Celsius [°F=(1.8)(°C)+32]

cm, centimeter (multiply by 0.3937 to obtain inch)

μg/kg, microgram per kilogram

Revisi

December 

Appendix A 

METHOD 5035

CLOSED-SYSTEM PURGE-AND-TRAP AND EXTRACTION FOR 

VOLATILE ORGANICS IN SOIL AND WASTE SAMPLES

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

Refer to the introductory material in this chapter, Organic Analytes, Sec. 4.1, for general sample c

lection information. The low concentration portion of this method employs sample vials that are filled a

weighed in the field and never opened during the analytical process. As a result, sampling personnel 

should be equipped with a portable balance capable of weighing to 0.01 g.

6.1 Preparation of sample vials

The specific preparation procedures for sample vials depend on the expected concentration 

range of the sample, with separate preparation procedures for low concentration soil samples and 

high concentration soil and solid waste samples. Sample vials should be prepared in a fixed labor

tory or other controlled environment, sealed, and shipped to the field location. Gloves should be 

worn during the preparation steps.

6.1.1 Low concentration soil samples

The following steps apply to the preparation of vials used in the collection of low co

centration soil samples to be analyzed by the closed-system purge-and-trap equipment 

described in Method 5035.

6.1.1.1 Add a clean magnetic stirring bar to each clean vial. If the purge-and-trap 

device (Sec. 4.2) employs a means of stirring the sample other than a magnetic stirrer (e.g., 

sonication or other mechanical means), then the stir bar is omitted.

6.1.1.2 Add preservative to each vial. The preservative is added to each vial prior t

shipping the vial to the field. Add approximately 1 g of sodium bisulfate to each vial. If sam

ples markedly smaller or larger than 5 g are to be collected, adjust the amount of preservativ

added to correspond to approximately 0.2 g of preservative for each 1 g of sample. Enough 

sodium bisulfate should be present to ensure a sample pH of ≤2.

6.1.1.3 Add 5 mL of organic-free reagent water to each vial. The water and the pre

vative will form an acid solution that will reduce or eliminate the majority of the biological 

activity in the sample, thereby preventing biodegradation of the volatile target analytes.

6.1.1.4 Seal the vial with the screw-cap and septum seal. If the double-ended, fritte

vials are used, seal both ends as recommended by the manufacturer.

6.1.1.5 Affix a label to each vial. This eliminates the need to label the vials in the fi

and assures that the tare weight of the vial includes the label. (The weight of any markings 

added to the label in the field is negligible).

6.1.1.6 Weigh the prepared vial to the nearest 0.01 g, record the tare weight, and w

it on the label.

6.1.1.7 Because volatile organics will partition into the headspace of the vial from 

aqueous solution and will be lost when the vial is opened, surrogates, matrix spikes, and inte

nal standards (if applicable) should only be added to the vials after the sample has been add

to the vial. These standards should be introduced back in the laboratory, either manually by 
Revisi

December 

24 Soil Analyses for 1,3-DCP, Metam-Sodium, and Their Degradation Products Near Fort Hall, Idaho

puncturing the septum with a small-gauge needle or automatically by the sample introductio

system, just prior to analysis.

6.1.2 High concentration soil samples collected without a preservative

When high concentration samples are collected without a preservative, a variety of 

sample containers may be employed, including 60-mL glass vials with septum seals (see 

Sec. 4.4).

6.1.3 High concentration soil samples collected and preserved in the field

The following steps apply to the preparation of vials used in the collection of high co

centration soil samples to be preserved in the field with methanol and analyzed by the aqueo

purge-and-trap equipment described in Method 5030.

6.1.3.1 Add 10 mL of methanol to each vial.

6.1.3.2 Seal the vial with the screw-cap and septum seal.

6.1.3.3 Affix a label to each vial. This eliminates the need to label the vials in the fi

and assures that the tare weight of the vial includes the label. (The weight of any markings 

added to the label in the field is negligible).

6.1.3.4 Weigh the prepared vial to the nearest 0.01 g, record the tare weight, and w

it on the label.

NOTE: Vials containing methanol should be weighed a second time on the day that they ar

to be used. Vials found to have lost methanol (reduction in weight of >0.01 g) shou

not be used for sample collection.

6.1.3.5 Surrogates, internal standards and matrix spikes (if applicable) should be 

added to the sample after it is returned to the laboratory and prior to analysis.

6.1.4 Oily waste samples

When oily waste samples are known to be soluble in methanol or PEG, sample vials 

may be prepared as described in Sec. 6.1.3, using the appropriate solvent. However, when th

solubility of the waste is unknown, the sample should be collected without the use of a prese

vative, in a vial such as that described in Sec. 6.1.2.

6.2 Sample collection

Collect the sample according to the procedures outlined in the sampling plan. As with any s

pling procedure for volatiles, care must be taken to minimize the disturbance of the sample in ord

to minimize the loss of the volatile components. Several techniques may be used to transfer a sam

ple to the relatively narrow opening of the low concentration soil vial.

These include devices such as the EnCoreTM sampler, the Purge-and-Trap Soil SamplerTM, a

a cut plastic syringe. Always wear gloves whenever handling the tared sample vials. 

6.2.1 Low concentration soil samples

6.2.1.1 Using an appropriate sample collection device, collect approximately 5 g of 

sample as soon as possible after the surface of the soil or other solid material has been expo
Revisi

December 

Appendix A 

to the atmosphere: generally within a few minutes at most. Carefully wipe the exterior of th

sample collection device with a clean cloth or towel.

6.2.1.2 Using the sample collection device, add about 5 g (2 - 3 cm) of soil to the s

ple vial containing the preservative solution. Quickly brush any soil off the vial threads and 

immediately seal the vial with the septum and screw-cap. Store samples on ice at 4°C.

NOTE: Soil samples that contain carbonate minerals (either from natural sources or applied 

an amendment) may effervesce upon contact with the acidic preservative solution 

the low concentration sample vial. If the amount of gas generated is very small (i.e

several mL), any loss of volatiles as a result of such effervescence may be minima

the vial is sealed quickly. However, if larger amounts of gas are generated, not onl

may the sample lose a significant amount of analyte, but the gas pressure may shat

the vial if the sample vial is sealed. Therefore, when samples are known or suspect

to contain high levels of carbonates, a test sample should be collected, added to a v

and checked for effervescence. If a rapid or vigorous reaction occurs, discard the 

sample and collect low concentration samples in vials that do not contain the 

preservative solution.

6.2.1.3 When practical, use a portable balance to weigh the sealed vial containing t

sample to ensure that 5.0 ± 0.5 g of sample were added. The balance should be calibrated in 

field using an appropriate weight for the sample containers employed (Sec. 4.5.5). Record th

weight of the sealed vial containing the sample to the nearest 0.01 g.

6.2.1.4 Alternatively, collect several trial samples with plastic syringes. Weigh eac

trial sample and note the length of the soil column in the syringe. Use these data to determin

the length of soil in the syringe that corresponds to 5.0 ± 0.5 g. Discard each trial sample.

6.2.1.5 As with the collection of aqueous samples for volatiles, collect at least two 

replicate samples. This will allow the laboratory an additional sample for reanalysis. The se

ond sample should be taken from the same soil stratum or the same section of the solid wast

being sampled, and within close proximity to the location from which the original sample w

collected.

6.2.1.6 In addition, since the soil vial cannot be opened without compromising the 

integrity of the sample, at least one additional aliquot of sample must be collected for screen

ing, dry weight determination, and high concentration analysis (if necessary). This third aliquot may be collected in a 60-mL glass vial or a third 40-mL soil sample vial. However, thi

third vial must not contain the sample preservative solution, as an aliquot will be used to det

mine dry weight. If high concentration samples are collected in vials containing methanol, th

two additional aliquots should be collected, one for high concentration analysis collected in 

vial containing methanol, and another for the dry weight determination in a vial without eith

methanol or the low concentration aqueous preservative solution.

6.2.1.7 If samples are known or expected to contain target analytes over a wide ran

of concentrations, thereby requiring the analyses of multiple sample aliquots, it may be advi

able and practical to take an additional sample aliquot in a low concentration soil vial contai

ing the preservative, but collecting only 1-2 g instead of the 5 g collected in Sec. 6.2.1.1. Th

aliquot may be used for those analytes that exceed the instrument calibration range in the 5-

analysis.

6.2.1.8 The EnCoreTM sampler has not been thoroughly evaluated by EPA as a sam

ple storage device. While preliminary results indicate that storage in the EnCoreTM device m
Revisi

December 

26 Soil Analyses for 1,3-DCP, Metam-Sodium, and Their Degradation Products Near Fort Hall, Idaho

be appropriate for up to 48 hours, samples collected in this device should be transferred to th

soil sample vials as soon as possible, or analyzed within 48 hours.

6.2.1.9 The collection of low concentration soil samples in vials that contain metha

nol is not appropriate for samples analyzed with the closed-system purge-and-trap equipmen

described in this method (see Sec. 6.2.2).

6.2.2 High concentration soil samples preserved in the field

The collection of soil samples in vials that contain methanol has been suggested by 

some as a combined preservation and extraction procedure. However, this procedure is not

appropriate for use with the low concentration soil procedure described in this method. 

NOTE: The use of methanol preservation has not been formally evaluated by EPA and 

analysts must be aware of two potential problems. First, the use of methanol as a 

preservative and extraction solvent introduces a significant dilution factor that will 

raise the method quantitation limit beyond the operating range of the low 

concentration direct purge-and-trap procedure (0.5-200 μg/kg). The exact dilution 

factor will depend on the masses of solvent and sample, but generally exceeds 100

and may make it difficult to demonstrate compliance with regulatory limits or actio

levels for some analytes. Because the analytes of interest are volatile, the methanol 

extract cannot be concentrated to overcome the dilution problem. Thus, for sample

unknown composition, it may still be necessary to collect an aliquot for analysis by 

this closed-system procedure and another aliquot preserved in methanol and analyz

by other procedures. The second problem is that the addition of methanol to the 

sample is likely to cause the sample to fail the ignitability characteristic, thereby 

making the unused sample volume a hazardous waste.

6.2.2.1 When samples are known to contain volatiles at concentrations high enough 

that the dilution factor will not preclude obtaining results within the calibration range of the 

appropriate determinative method, a sample may be collected and immediately placed in a 

sample vial containing purge-and-trap grade methanol.

6.2.2.2 Using an appropriate sample collection device, collect approximately 5 g of 

sample as soon as possible after the surface of the soil or other solid material has been expo

to the atmosphere: generally within a few minutes at most. Carefully wipe the exterior of th

sample collection device with a clean cloth or towel.

6.2.2.3 Using the sample collection device, add about 5 g (2 - 3 cm) of soil to the v

containing 10 mL of methanol. Quickly brush any soil off the vial threads and immediately 

seal the vial with the septum and screw-cap. Store samples on ice at 4°C.

6.2.2.4 When practical, use a portable balance to weigh the sealed vial containing t

sample to ensure that 5.0 ± 0.5 g of sample were added. The balance should be calibrated in 

field using an appropriate weight for the sample containers employed (Sec. 4.5.5). Record th

weight of the sealed vial containing the sample to the nearest 0.01 g.

6.2.2.5 Alternatively, collect several trial samples with plastic syringes. Weigh eac

trial sample and note the length of the soil column in the syringe. Use these data to determin

the length of soil in the syringe that corresponds to 5.0 ± 0.5 g. Discard each trial sample.

6.2.2.6 Other sample weights and volumes of methanol may be employed, provide

that the analyst can demonstrate that the sensitivity of the overall analytical procedure is app

priate for the intended application.
Revisi

December 

Appendix A 

6.2.2.7 The collection of at least one additional sample aliquot is required for the 

determination of the dry weight, as described in Sec. 6.2.1.6. Samples collected in methanol 

should be shipped as described in Sec. 6.3, and must be clearly labeled as containing methanol, so that the samples are not analyzed using the closed-system purge-and-trap equipment 

described in this procedure.

6.2.3 High concentration soil samples not preserved in the field

The collection of high concentration soil samples that are not preserved in the field g

erally follows similar procedures as for the other types of samples described in Secs. 6.2.1 a

6.2.2, with the obvious exception that the sample vials contain neither the aqueous preserva

tive solution nor methanol. However, when field preservation is not employed, it is better to 

collect a larger volume sample, filling the sample container as full as practical in order to m

mize the headspace. Such collection procedures generally do not require the collection of a 

separate aliquot for dry weight determination, but it may be advisable to collect a second sam

ple aliquot for screening purposes, in order to minimize the loss of volatiles in either aliquot

6.2.4 Oily waste samples

The collection procedures for oily samples depend on knowledge of the waste and it

solubility in methanol or other solvents.

6.2.4.1 When an oily waste is known to be soluble in methanol or PEG, the sample 

may be collected in a vial containing such a solvent (see Sec. 6.1.4), using procedures simila

to those described in Sec. 6.2.2.

6.2.4.2 When the solubility of the oily waste is not known, the sample should either 

collected in a vial without a preservative, as described in Sec. 6.2.3, or the solubility of a tri

sample should be tested in the field, using a vial containing solvent. If the trial sample is sol

ble in the solvent, then collect the oily waste sample as described in Sec. 6.2.2. Otherwise, c

lect an unpreserved sample as described in Sec. 6.2.3.

6.3 Sample handling and shipment

All samples for volatiles analysis should be cooled to approximately 4°C, packed in appropr

ate containers, and shipped to the laboratory on ice, as described in the sampling plan.

6.4 Sample storage

6.4.1 Once in the laboratory, store samples at 4°C until analysis. The sample storage area 

should be free of organic solvent vapors.

6.4.2 All samples should be analyzed as soon as practical, and within the designated holdin

time from collection. Samples not analyzed within the designated holding time must be noted and 

the data are considered minimum values.

6.4.3 When the low concentration samples are strongly alkaline or highly calcareous in 

nature, the sodium bisulfate preservative solution may not be strong enough to reduce the pH of t

soil/water solution to below 2. Therefore, when low concentration soils to be sampled are known 

suspected to be strongly alkaline or highly calcareous, additional steps may be required to preserv

the samples. Such steps include: addition of larger amounts of the sodium bisulfate preservative t

non-calcareous samples, storage of low concentration samples at -10°C (taking care not to fill the 

vials so full that the expansion of the water in the vial breaks the vial), or significantly reducing th
Revisi

December 

28 Soil Analyses for 1,3-DCP, Metam-Sodium, and Their Degradation Products Near Fort Hall, Idaho

maximum holding time for low concentration soil samples. Whichever steps are employed, they 

should be clearly described in the sampling and QA project plans and distributed to both the field 

and laboratory personnel. See Sec. 6.2.1.2 for additional information.
Appendix B. U.S. Geological Survey Laboratory Memorandum,

Description of Custom Method

Appendix B

Abbreviations and Conversions:

°C, degrees Celsius [°F=(1.8)(°C)+32]

centimeter (multiply by 0.3937 to obtain inch)

meter (multiply by 3.281 to obtain foot)

mm (millimeter, multiply by 0.03937 to obtain inch)

μm, micrometer

ug/kg, microgram per kilogram

App

 Date: 11/29/99 Memorandum

To: Deb Parliman

Cc: Ralph White

From: Donna Rose

RE: Proposal CL99II- Analysis of MITC and other VOCs in soils from Idaho by purge and trap GC/MS

DESCRIPTION OF CUSTOM METHOD FOR LAB CODE 8133:

Soil samples received from the Idaho district were analyzed according to U. S. Environmental Protection Agency (U

Method 5035 (December 1996, Revision 0). Five grams of soil were added in the field to a vial containing five millilit

of water, 1 gram of sodium bisulfate as a preservative, and a magnetic stir bar. The sodium bisulfate preservative w

for those samples that contained high amounts of carbonate minerals per method 5035 (Section 6.2.1.2). The vial 

and sent to the laboratory in a cooler. Samples were stored at 4°C until analysis. Percent moisture was determined 

infra-red balance. Instrument operating conditions are listed in Table 1. Compound identifications and quantitatio

determined according to Connor and others, 1998. The quantitation ions, qualification ions, and calibration ranges a

Table 2.

Table 1: Instrument Operating Conditions for LC 8133

Autosampler Varian Archon Autosampler, chilled to 4°C, Soil mode 

operation

Sample Preheat Temp 40  ̊C

Preheat Time 3 minutes

Purge & Trap Concentrator Tekmar Liquid Sample Concentrator, Model 3000 

Trap Supelco Vocarb 3000

Purge 11 minutes

Dry Purge 3 minutes

Desorb Preheat 245  ̊C

Desorb 3 minutes at 250  ̊C

 Bake 17 minutes at 260  ̊C

Gas Chromatograph Hewlett Packard 5890 Gas Chromatograph, split/splitless 

mode

Column 60 meter, 0.25 mm inner diameter, 1.4 μm film thickness, 

RTX 624 

Initial Temperature 35  ̊C for 8 minutes

Temperature ramp 8.0  ̊C/minute to 200 ̊C

Final temperature/time 200 ̊C for 12 minutes

Mass Spectrometer Hewlett Packard 5971 Mass selective detector, electron 

impact mode

Scan range 41 atomic mass units (amu) to 310 amu 
32 Soil Analyses for 1,3-DCP, Metam-Sodium, and Their Degradation Products Near Fort Hall, Idaho

Table 2: Quantitation Ions, Identification Ions, and Calibration Ranges for LC 8133

{n/a, not applicable}

Short-Term Method Detection Level, and Laboratory Report Level (LRL)

The short-term method detection levels (MDL’s) were calculated for each compound according to the proced

in CFR § 136 Appendix B. The MDL samples were prepared by adding 5.0 grams of Ottawa sand, previous

burned, to a vendor prepared (Eagle Picher) soil VOC vial containing 5.0 mLs of water, 1.0 gram of sodium 

bisulfate preservative, and a magnetic stir bar. One microliter of the calibration standard was spiked into the 

water, with the needle of the syringe placed about two centimeters below the surface of the water. The vial w

capped, and placed in the autosampler for analysis. A total of nine MDL samples were prepared and analyz

on three separate days (3 samples per day). 

The laboratory report level (LRL) for all compounds is calculated as two times the short-term MDL for this c

tom lab code. As the method progresses, and long-term data are available, the LRL may be re-evaluated 

using the long-term MDL. Refer to U. S. Geological Survey Open-File Report 99-193 for information on dete

mining long-term MDLs, and LRLs (Childress, et al, 1999). Refer to Table 3 for short-term MDLs, and LRLs 

LC 8133. 

Compound Quantitation Ion 

(mass/charge)

Qualifying Ions

(mass/charge)

Calibration 

Range 

(nanograms)

Carbon disulfide 76 78 1 to 200

cis 1,3-Dichloropropene 110 75,49 1 to 200

trans 1,3-Dichloropropene 110 75,49 1 to 200

1,3-Dichloropropane 76 78,63 1 to 200

1,2-Dibromoethane 107 109 1 to 200

1,2,3-Trichloropropane 110 112,99 1 to 200

Methyl isothiocyanate (MITC) 73 72,45 3.1 to 620

1,2-Dichloroethane d4, surrogate 65 67, 102 n/a

Toluene d8, surrogate 98 100, 70 n/a

1,4-Bromofluorobenzene, surrogate 95 174,176 n/a

Fluorobenzene, internal standard 96 70, 50 n/a
Appendix B 

Custom Lab Code 8133- Analysis of VOCs in Soil 

Table 3: Short-Term Method Detection Levels, and Laboratory Report Levels

Quality Control:

Several types of quality control samples are analyzed along with the samples to ensure high quality data. Quality c

ples consist of continuing calibration verification standards (CCVs), set blanks, set spikes, matrix spikes, and laborato

level (LRL) check standards.

Continuing Calibration Verification Standards (CCVs) - reported in percent recovery

CCVs are analyzed throughout the run, or at least every 12th injection.

Set blanks- reported in ug/Kg

Sample results are not blank-subtracted. Sample results, that are not significantly different from the bracketing set 

be censored. Set blanks are analyzed throughout the run, or at least after every CCV.

Set Spike- reported in percent recovery

The set spike is prepared from a different source than the calibration standards. Sample results are not corrected fo

spike recoveries.

Matrix Spike- reported in percent recovery.

Samples chosen at random were spiked at the same level as the CCVs, and analyzed. Sample results are not cor

poor matrix spike recoveries. A poor recovery will provide information on how the particular compound reacts in the 

matrix.

Laboratory Reporting Level (LRL) check standard- reported percent recovery

LRLs are spiked at the level of the lowest calibration standard, and analyzed at the beginning of the run, and the en

to verify the compound can be detected at this low level, and to verify the quantitation at this low level.

Bias and Variability Data:

Several types of bias and variability data are reported in Tables 4, 5, 6, 7, 8, and 9. Data for Ottawa sand spiked at two 

analyzed over several days is reported in Tables 4 and 5. Bias and variability data is also reported for the CCVs in T

Compound

MDL for 9

Replicates

ug/kg

Laboratory 

Report 

Level

(LRL)

ug/kg

Standard 

Deviation 

ug/kg

Amount 

Spiked 

ug/kg

Carbon disulfide 0.04 <0.08 0.0129 0.2

cis 1,3-Dichloropropene 0.04 <0.07 0.0123 0.2

trans 1,3-Dichloropropene 0.07 <0.13 0.0228 0.2

1,3-Dichloropropane 0.04 <0.07 0.0122 0.2

1,2-Dibromoethane 0.04 <0.09 0.0151 0.2

1,2,3-Trichloropropane 0.07 <0.14 0.0248 0.2

Methyl isothiocyanate (MITC) 0.9 <1.8 0.3126 0.62
34 Soil Analyses for 1,3-DCP, Metam-Sodium, and Their Degradation Products Near Fort Hall, Idaho

for the LRLs is reported in Table 7. Data for the set spikes are reported in Table 8. Data for soils chosen 

random, and spiked at the laboratory are reported in Table 9. 

Custom Lab Code 8133- Analysis of VOCs in Soil

Table 4: Bias and Variability for Replicate Spikes in Ottawa Sand 

Spiked from 2.0 to 6.2 ug/kg

Analyzed from September 9, 1999 through October 25, 1999

 Compound

Amount 

Spiked

ug/kg

Average

Percent 

Recovery

Std

Dev

Percent

Rel Std 

Deviation

Percent

Number 

of 

spikes

Carbon disulfide 2.0 105 6 5 11

cis 1,3-Dichloropropene 2.0 106 7 6 11

trans 1,3-Dichloropropene 2.0 104 6 5 11

1,3-Dichloropropane 2.0 108 4 4 11

1,2-Dibromoethane 2.0 110 5 4 11

1,2,3-Trichloropropane 2.0 108 6 5 11

Methyl isothiocyanate (MITC) 6.2 117 11 10 11
Appendix B 

Custom Lab Code 8133- Analysis of VOCs in Soil

Table 5: Bias and Variability for Low Level Ottawa Sand Spikes

Spiked from 0.2 to 0.62 ug/kg

Analyzed from September 9, 1999 through October 25, 1999

1 An interfering column bleed peak elutes slightly to the right of MITC, resulting in higher recoveries and standard deviation at this low l

Custom Lab Code 8133- Analysis of VOCs in Soil 

Table 6: Bias and Variability for Continuing Calibration Verification Standards

Spiked from 2.0 to 6.2 ug/kg

Analyzed from September 9, 1999 through October 25, 1999

 Compound

Amount 

Spiked

ug/kg

Average

Percent 

Recovery

Std

Dev

Percent

Rel Std 

Deviation

Percent

Number 

of 

spikes

Carbon disulfide 0.2 109 13 12 11

cis 1,3-Dichloropropene 0.2 119 11 9 11

trans 1,3-Dichloropropene 0.2 115 13 11 11

1,3-Dichloropropane 0.2 117 6 5 11

1,2-Dibromoethane 0.2 113 8 7 11

1,2,3-Trichloropropane 0.2 123 14 12 11

Methyl isothiocyanate (MITC) 0.62 1591 53 34 11

 Compound

Amount 

Spiked

ug/kg

Average

Percent 

Recovery

Std 

Dev

Percent

Rel Std 

Deviation

Percent

Number 

of 

CCVs

Carbon disulfide 2.0 94 5 5 19

cis 1,3-Dichloropropene 2.0 95 8 8 19

trans 1,3-Dichloropropene 2.0 93 6 7 19

1,3-Dichloropropane 2.0 96 7 7 19

1,2-Dibromoethane 2.0 97 8 8 19

1,2,3-Trichloropropane 2.0 95 8 9 19

Methyl isothiocyanate (MITC) 6.2 95 9 10 19
36 Soil Analyses for 1,3-DCP, Metam-Sodium, and Their Degradation Products Near Fort Hall, Idaho

Custom Lab Code 8133- Analysis of VOCs in Soil 

Table 7: Bias and Variability for Laboratory Report Level Check Standards

Spiked from 0.2 to 0.62 ug/kg

Analyzed from September 9, 1999 through October 25, 1999

Custom Lab Code 8133- Analysis of VOCs in Soil

Table 8: Bias and Variability for Set Spikes

Spiked from 1.0 to 4.0 ug/kg

Analyzed from September 9, 1999 through October 25, 1999

 Compound

Amount 

Spiked

ug/kg

Average

Percent 

Recovery

Std 

Dev

Percent

Rel Std 

Deviation

Percent

Number 

of

LRLs

Carbon disulfide 0.2 95 11 11 5

cis 1,3-Dichloropropene 0.2 103 8 8 5

trans 1,3-Dichloropropene 0.2 95 11 12 5

1,3-Dichloropropane 0.2 99 10 10 5

1,2-Dibromoethane 0.2 96 10 10 5

1,2,3-Trichloropropane 0.2 105 10 9 5

Methyl isothiocyanate (MITC) 0.62 129 24 19 5

 Compound

Amount 

Spiked

ug/kg

Average

Percent 

Recovery

Std 

Dev

Percent

Rel Std 

Deviation

Percent

Number 

of set 

spikes

Carbon disulfide 1.6 97 15 15 7

cis 1,3-Dichloropropene 1.8 92 8 8 7

trans 1,3-Dichloropropene 2.6 83 8 9 7

1,3-Dichloropropane 2.4 94 7 8 7

1,2-Dibromoethane 1.0 90 7 8 7

1,2,3-Trichloropropane 4.0 78 9 12 7

Methyl isothiocyanate (MITC) not 

spiked

n/a n/a n/a 0
Appendix B 

Custom Lab Code 8133- Analysis of VOCs in Soil

Table 9: Bias and Variability for Soils from Ft. Hall Project

Soil Samples Chosen at Random, Spiked in the laboratory at 2.0 to 6.2 ug/kg

Analyzed from September 14, 1999 through October 21, 1999

1One of the four samples had only 3% recovery, with the other samples recovering at 101%, 63%, and 63%.

Analyst’s Notes

A small amount of mass 73, due to an interfering column bleed peak, was present in the retention time wind

for MITC. The amount was quantitated, and treated as a “blank” contaminant. 

Carbon disulfide was also detected in small amounts in some of the set blanks. The presence of carbon dis

fide may be a byproduct from the sodium bisulfate preservative. Blanks without the preservative were analyz

and did not contain carbon disulfide.

REPORTS:

Individual reports for each sample are being provided electronically in an Excel workbook, via email.

REFERENCES:

Childress, C. J., Foreman, W. T., Connor, B. F., and Maloney, T. J., 1999, “New Reporting Procedures Based 

Long-Term Method Detection Levels and Some Considerations for Interpretations of Water-Quality Da

Provided by the U. S. Geological Survey National Water Quality Laboratory”, 19 pages.

Connor, B.F., Rose, Donna L., Noriega, Mary C., Murtagh, Lucinda K., and Abney, Sonja R., 1998, “Method

Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of 86 Volat

Organic Compounds in Water by Gas Chromatography/Mass Spectrometry, Including Detections Less 

Than Reporting Limits”, 78 pages.

U. S. Environmental Protection Agency, 1992, Guidelines establishing test procedures for the analysis of po

ants (Part 136, Appendix B. Definition and Procedure for the Determination of the Method Detection 

LimitRevision 1.11): U. S. code of Federal Regulations, Title 40, revised as of July 1, 1992, p. 565-5

U. S. Environmental Protection Agency, 1996, Method 5035Closed-System Purge-and-Trap and Extracti

for Volatile Organics in Soil and Waste Samples: CD-ROM Revision 0, December 1996, 24 pages.

 Compound

Amount 

Spiked

ug/kg

Average

Percent 

Recovery

Std 

Dev

Percent

Rel Std 

Deviation

Percent

Count

Carbon disulfide 2.0 90 11 12 4

cis 1,3-Dichloropropene 2.0 74 19 25 4

trans 1,3-Dichloropropene 2.0 75 15 20 4

1,3-Dichloropropane 2.0 82 12 15 4

1,2-Dibromoethane 2.0 79 11 14 4

1,2,3-Trichloropropane 2.0 75 14 18 4

Methyl isothiocyanate1 (MITC) 6.2 58 41 70 4

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