Prepared by the U.S. Geological Survey Office of Water Quality, National Water Quality Laboratory 

Determination of Wastewater Compounds in Sediment and Soil 

by Pressurized Solvent Extraction, Solid-Phase Extraction, and 

Capillary-Column Gas Chromatography/Mass Spectrometry 

Chapter 2 

Section B, Methods of the National Water Quality Laboratory 

Book 5, Laboratory Analysis 

Techniques and Methods 5–B2 

U.S. Department of the Interior 

U.S. Geological Survey 
 

 

 

 

 

 

 

Determination of Wastewater Compounds 

in Sediment and Soil by Pressurized Solvent 

Extraction, Solid-Phase Extraction, and 

Capillary-Column Gas Chromatography/Mass 

Spectrometry 

By Mark R. Burkhardt, Steven D. Zaugg, Steven G. Smith, and Rhiannon C. ReVello 

Techniques and Methods 5–B2 

U.S. Department of the Interior 

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

P. Lynn Scarlett, Deputy Secretary and Acting Secretary 

U.S. Geological Survey 

P. Patrick Leahy, Acting Director 

U.S. Geological Survey, Reston, Virginia: 2006 

Revised: 2007 

For product and ordering information: 

World Wide Web: http://www.usgs.gov/pubprod 

Telephone: 1-888-ASK-USGS 

For more information about the USGS—the Federal source for science about the Earth, its natural and living 

resources, natural hazards, and the environment: 

World Wide Web: http://www.usgs.gov 

Telephone: 1-888-ASK-USGS 

Any use of trade, product, or firm names in this publication is for descriptive purposes only and does not imply 

endorsement by the U.S. Government. 

Although this report is in the public domain, permission must be secured from the individual copyright owners to 

reproduce any copyrighted materials contained within this report. 

Suggested citation: 

Burkhardt, M.R., Zaugg, S.D., Smith, S.G., and ReVello, R.C., 2006, Determination of wastewater compounds in 

sediment and soil by pressurized solvent extraction, solid-phase extraction, and capillary-column gas 

chromatography/mass spectrometry: U.S. Geological Survey Techniques and Methods, book 5, chap. B2, 40 p. 
 

 

 

 

 

 

 

 

 

 

 

 

iii 

Contents 

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

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

Purpose and Scope ..............................................................................................................................2
 

Analytical Method..........................................................................................................................................3
 

1. Scope and Application..................................................................................................................3
 

2. Method Summary...........................................................................................................................3
 

3. Safety Precautions and Waste Disposal ...................................................................................3
 

4. Interferences..................................................................................................................................3
 

5. Apparatus and Instrumentation ..................................................................................................6
 

6. Reagents and Consumable Materials ........................................................................................6
 

7. Standards........................................................................................................................................7
 

8. Sample Preparation.......................................................................................................................8
 

9. Sample Analysis Procedure.......................................................................................................10
 

10. Instrument Calibration.................................................................................................................10
 

11. Quality Assurance and Quality Control ....................................................................................11
 

12. Calculation of Results..................................................................................................................15
 

Results and Discussion of Method Validation ........................................................................................17
 

Summary and Conclusions.........................................................................................................................28
 

References Cited..........................................................................................................................................28
 

Glossary.........................................................................................................................................................33
 

Figures 

1. 	Manual integration of the extracted ion profile for the quantitation ion 


(mass-to-charge ratio 135) of para-nonylphenol from the 2 nanogram-


per-microliter calibration solution for the wastewater method ...............................................7
 

2. Analysis of 103 environmental sediment and soil samples ........................................................27
 
iv 

Tables 

1. 	Wastewater method compound names, endocrine-disrupting potential, 

parameter/method codes, and possible compound uses ..........................................................4 

2. 	Wastewater method compound retention time, quantitation ion, confirmation 

 ions, surrogate compounds, and internal standard reference compounds.........................12 

3. 	Gas chromatography/mass spectrometry analytical sequence suggested 

for use in determining wastewater compounds in sediment and soil ...................................15 

4. 	Wastewater method compounds detected in unfortified reagent-sand, 

river-sediment, and topsoil samples ............................................................................................18 

5. 	Wastewater method mean bias and precision of spike recovery data for 

seven or eight replicates with compounds spiked at two concentrations 

ranging from 4 to 720 micrograms per sample in reagent-sand (including 

calculated method detection limits), river-sediment, and topsoil samples...........................20 

6. 	Wastewater method compounds that failed method acceptance criteria and 

are not included in this method. Mean bias and precision of spike recovery 

data for seven or eight replicates with compounds fortified at two concentrations 

ranging from 4 to 720 micrograms per sample in reagent-sand, river-sediment, 

and topsoil samples ........................................................................................................................24 

7. 	Initial method detection limits for the wastewater method calculated from 

the precision data reported in table 5 using the eight replicate reagent-sand 

samples fortified with compound concentrations ranging from 4 to 72 micrograms..........25 
v 

Conversion Factors 

Multiply By To obtain 

Length 

centimeter (cm) 0.3937 inch (in.) 

micrometer (μm) 0.00003937 inch (in.) 

millimeter (mm) 0.03937 inch (in.) 

meter (m) 39.37 inch (in) 

Volume 

liter (L) 0.2642 gallon (gal) 

microliter (μL) 0.000000264 gallon (gal) 

milliliter (mL) 0.000264 gallon (gal) 

milliliter per minute (mL/min) 0.0338 ounce per minute 

Mass 

gram (g) 0.03527 ounce, avoirdupois (oz) 

kilogram (kg) 2.205 pound avoirdupois (lb) 

microgram (μg) 0.00000003527 ounce, avoirdupois (oz) 

milligram (mg) 0.00003527 ounce, avoirdupois (oz) 

Pressure 

kilopascal (kPa) 0.1450 pound-force per inch (lbf/in) 

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

as follows: 

°C = (°F-32)/1.8 

Abbreviated water-quality units used in this report: 

in. inch 

L/min liters per minute 

min minute 

mg/kg milligram per kilogram 

mg/mL milligram per milliliter 

μg/L microgram per liter 

ng/μL nanogram per microliter 

μg/kg microgram per kilogram 

Other abbreviations used in this report: 

AHTN acetyl-hexamethyl-tetrahydronaphthalene 

AP alkylphenol 

APEC alkylphenol ethoxycarboxylate 

APEO alkylphenol polyethoxylate 

ASE accelerated solvent extractor 

CAS Chemical Abstracts Service 

CCV continuing calibration verification solution 

CLLE continuous liquid–liquid extraction 

DCM dichloromethane 

DEE diethyl ether 
vi 

ETFE ethylenetetrafluoroethylene 

GC gas chromatograph or gas chromatography 

GCC glass bottle, amber 

GC/MS gas chromatography/mass spectrometry 

HHCB hexahydrohexamethyl-cyclopentabenzopyran 

IPA isopropyl alcohol 

IDL instrument detection level 

LT–MDL long-term method detection level 

MDL method detection limit 

min minute 

MRL minimum reporting level 

MS mass spectrograph or mass spectrometry 

m/z mass-to-charge ratio 

NP nonylphenol 

NPEO nonylphenol ethoxylate 

NWQL National Water Quality Laboratory 

N/A not applicable 

OPEO octylphenol ethoxylate 

PAH polycyclic aromatic hydrocarbon 

PCB polychlorinated biphenyl 

PLE pressurized liquid extraction 

PLEHW pressurized liquid extraction with subcritical heated water 

PSDVB polystyrene-divinylbenzene 

PTFE polytetrafluoroethylene 

QA/QC quality assurance and quality control 

RSD relative standard deviation 

SPE solid-phase extraction 

USEPA U.S. Environmental Protection Agency 

USGS U.S. Geological Survey 
 

 

 

 

Determination of Wastewater Compounds in Sediment 

and Soil by Pressurized Solvent Extraction, Solid-Phase 

Extraction, and Capillary-Column Gas Chromatography/ 

Mass Spectrometry 

By Mark R. Burkhardt, Steven D. Zaugg, Steven G. Smith, and Rhiannon C. ReVello 

Abstract 

A method for the determination of 61 compounds in 

environmental sediment and soil samples is described. The 

method was developed in response to increasing concern over 

the effects of endocrine-disrupting chemicals in wastewater 

and wastewater-impacted sediment on aquatic organisms. This 

method also may be used to evaluate the effects of combined 

sanitary and storm-sewer overflow on the water and sediment quality of urban streams. Method development focused 

on the determination of compounds that were chosen on the 

basis of their endocrine-disrupting potential or toxicity. These 

compounds include the alkylphenol ethoxylate nonionic 

surfactants and their degradates, food additives, fragrances, 

antioxidants, flame retardants, plasticizers, industrial solvents, 

disinfectants, fecal sterols, polycyclic aromatic hydrocarbons, 

and high-use domestic pesticides. 

Sediment and soil samples are extracted using a pressurized solvent extraction system. The compounds of interest 

are extracted from interfering matrix components by highpressure water/isopropyl alcohol extraction. The compounds 

were isolated using disposable solid-phase extraction (SPE) 

cartridges containing chemically modified polystyrene-divinylbenzene resin. The cartridges were dried with nitrogen 

gas, and then sorbed compounds were eluted with methylene chloride (80 percent)-diethyl ether (20 percent) through 

Florisil/sodium sulfate SPE cartridge, and then determined by 

capillary-column gas chromatography/mass spectrometry. 

Recoveries in reagent-sand samples fortified at 4 to 72 

micrograms averaged 76 percent ±13 percent relative standard 

deviation for all method compounds. Initial method reporting levels for single-component compounds ranged from 50 to 

500 micrograms per kilogram. The concentrations of 20 out 

of 61 compounds initially will be reported as estimated with 

the “E” remark code for one of three reasons: (1) unacceptably low-biased recovery (less than 60 percent) or highly 

variable method performance (greater than 25 percent relative 

standard deviation), (2) reference standards prepared from 

technical mixtures, or (3) potential blank contamination. 

Samples were preserved by freezing to –20 degrees 

Celsius. The U.S. Geological Survey National Water Quality 

Laboratory has established a 1-year sample-holding time limit 

(prior to sample extraction) from the date of sample collection 

(if the sample is kept at –20o

C) until a statistically accepted 

method can be used to determine the effectiveness of the 

sample-freezing procedure. 

Introduction 

Industrial and domestic wastes need to be managed 

effectively to meet the challenges of increasing population, 

regulatory requirements, and aging wastewater-treatment 

facilities in the United States. Specific analytical methods 

are available for use in monitoring selected chemical compounds in wastewater to meet these challenges. The U.S. 

Environmental Protection Agency (USEPA) regulates many 

compounds, and appropriate analytical methods generally are 

available (U.S. Environmental Protection Agency, 1995) to 

monitor them in industrial wastes or in discharge from wastewater-treatment facilities. However, because of the complexity of the sample matrices for soils, sediments, and suspended 

sediments, specific analytical methods are required to determine polar and nonpolar organic compounds that might affect 

water quality. Other compounds known to be toxic to aquatic 

life currently (2005) are unregulated even though some, such 

as nonylphenol ethoxylates (NPEOs), are on the USEPA 

Toxic Substance Control Act Priority Testing List (U.S. Environmental Protection Agency, 1996). To meet some of the 

challenges of assessing the effect of wastewater discharge on 

water quality, the U.S. Geological Survey (USGS) National 

Water Quality Laboratory (NWQL) has developed an 
 

 Determination of Wastewater Compounds in Sediment and Soil 

analytical method to determine representative compounds 

from various chemical classes that reflect possible contamination from wastewater in environmental sediment samples. 

Hydrophobic organic compounds, including the alkylphenol ethoxylate nonionic surfactants and their degradates 

(Geiger and others, 1984; Jobling and Sumpter, 1993; Blackburn and Waldock, 1995; Barber and others, 2000; Hale and 

others, 2000), food additives (Seiler and others, 1999), fragrances (Franke and others, 1999; Fromme and others, 1999; 

Simonich and others, 2000; Standley and others, 2000), flame 

retardants (de Boer and others, 1998; van Stee and others, 

1999; Kuosmanen and others, 2001), plasticizers (Yang and 

others, 1997), industrial solvents (Yang and others, 1997), 

disinfectants (McMurry and others, 1998; van Stee and others, 

1999), fecal sterols (Shigenaka and Price, 1988), polycyclic 

aromatic hydrocarbons (Hawthorne and others, 2000), and 

high-use domestic pesticides (Gan and others, 1999) may be 

associated with particulates or sediments, or both, in the environment (Yang and others, 1997; Field and Reed, 1999; Gan 

and others, 1999; Hawthorne and others, 2000; Wilkison and 

others, 2000; Kuosmanen and others, 2001; Dabrowski and 

others, 2002; Ying and others, 2002). Traditional methods for 

determining organic compounds in environmental sediment 

or soil samples generally are optimized for one or two classes 

of compounds and use liquid-solid extraction with an organic 

solvent followed by analysis with gas chromatography (GC) 

or gas chromatography/mass spectrometry (GC/MS) detection 

(Furlong and others, 1996; Jha and Wydoski, 2003). 

Pressurized liquid extraction (PLE) demonstrates advantages for automation, reduced extraction time, and requires 

less solvent than conventional Soxhlet extraction. Recently 

(2005), PLE with subcritical heated water (PLEHW) has 

been used for extracting polar to moderately polar organic 

compounds from sediments. At temperatures above 250oC, 

extraction of nonpolar high molecular weight compounds, 

such as polycyclic aromatic hydrocarbon compounds (PAHs) 

(Hawthorne and others, 2000) and polychlorinated biphenyl compounds (PCBs) (Field and Reed, 1999) have been 

reported. The pressure required for PLEHW must be high 

enough to maintain water in the liquid state, but otherwise 

has little effect on solubility (U.S. Environmental Protection 

Agency, 2000). The PLEHW of sediments provides more 

selectivity for analytes than conventional Soxhlet extraction 

using organic solvents as evidenced by a dramatic reduction in 

the extraction of the bulk organic nonpolar matrix (Anderson 

and others, 2000). Although it is still possible to gain some 

degree of selectivity using modified PLEHW by varying the 

modifier concentration, the use of organic cosolvents produces 

dirtier extracts that often require cleanup prior to analysis. In 

a production laboratory, where stable reproducible instrument 

response with minimum maintenance is desirable, extract 

quality (low matrix background, greater than 60-percent 

analyte recovery) is important. PLEHW field extraction of 

petroleum-contaminated sediment samples with simultaneous 

absorption onto solid-phase extraction (SPE) disks has been 

reported to produce clean extracts (Hawthorne and others, 

2000). However, in a laboratory setting, more options are possible for washing, adjusting the pH, and eluting SPE cartridges 

if the SPE is cleaned up offline. 

The ASETM 200 is a commercially available PLE instrument produced by Dionex (Sunnyvale, Calif., USA), and the 

process, which has been termed “accelerated solvent extraction” (ASE), generally uses conventional organic solvents at a 

temperature of about 100oC. The upper operating temperature 

limit of 200oC for the ASETM 200 is too low to effectively 

extract nonpolar high molecular weight organic compounds, 

such as PAHs (about molecular weight 202 or higher) using 

subcritical water, without the addition of a cosolvent. Thus, 

substantially increasing the solvating power of PLEHW 

requires the addition of a few percent of cosolvent. 

Environmental sediment samples require extensive extract 

clean-up procedures to provide the low matrix background 

extract that can be analyzed routinely in a production laboratory and yet retain most of the compounds of interest. Because 

most existing environmental sediment methods often use 

labor-intensive Soxhlet extraction and require extensive extract 

clean-up steps, it has become imperative to implement more 

efficient, environmental friendly methods. Analytical methods that use SPE as an alternative to liquid–liquid extraction 

have been implemented for the determination of pesticides in 

filtered water (Furlong and others, 2001; Sandstrom and others, 1992, 2001; Zaugg and others, 1995). These SPE methods 

are attractive because they are rapid, efficient, use much less 

solvent than liquid–liquid extraction, and, consequently, are 

more affordable and produce less toxic waste. Coupling SPE 

and PLE allows for extracting complex matrices, minimizing 

matrix interferences, and analyzing by full-scan GC/MS. 

Purpose and Scope 

This report describes a method (O-5433-05) for determining a broad range of wastewater compounds in environmental sediment and soil samples. It is rapid, efficient, and was 

developed potentially to replace Soxhlet sample-preparation 

techniques in use at the NWQL. The method supplements 

other methods of the USGS for the determination of organic 

substances in water that have been described previously by 

Wershaw and others (1987), Fishman (1993), and Zaugg and 

others (2002). Not all of the compounds in Schedule 1433 

(Zaugg and others, 2002) appear in this new method; some 

were excluded because of high or low recovery, relative standard deviations greater than 30 percent, or low probability of 

the compounds partitioning into soil or sediment. This new 

method was approved for use by the USGS and is scheduled to 

be implemented at the NWQL in June 2006. 

There are substantial advantages of using this method 

over previously used sediment methods. The pressurized solvent extraction, coupled with the solid-phase based clean-up 

step, provides a low matrix-background extract, which reduces 

chemical noise, resulting in low detection limits or use of fullscan ion monitoring, or both. The full-scan ion monitoring 
 

 

 

 

 

Analytical Method 

allows for more specific compound identification along with 

the potential to tentatively identify unknown compounds in the 

sample extracts. The method also allows different compound 

classes to be monitored at the same time for use as a screening 

method in water-quality studies with several compound classes 

being determined from the sample extract. 

This report provides a detailed description of all aspects 

of the method, including the apparatus and instrumentation, 

reagents, sample preparation and analysis (including pressurized solvent extraction characteristics and SPE procedure 

required for sample analysis), and instrument calibration. 

Method performance (bias and precision) and estimated 

method detection limits for 61 compounds are presented. 

The scope of the study includes determination of method 

performance in reagent-sand, in river-sediment samples collected from Cherry Creek near Garland Park, Denver, Colorado, and in topsoil from a commercially available mixture. 

Method performance was determined at two appropriate concentrations for each compound (4- and 40-μg spikes for most 

compounds) in each sediment type. Method detection limits 

(MDL) were determined according to an accepted statistical 

procedure (U.S. Environmental Protection Agency, 1997). 

Analytical Method 

Organic Compounds and Parameter Codes: 

Wastewater compounds, bottom sediment, soils, 

and solids, pressurized solvent extraction, solidphase extraction, gas chromatography/mass 

spectrometry, O-54-05, Lab Schedule 54 

(see table 1). 

1. Scope and Application 

This method is suitable for determining the compounds 

listed in table 1, in microgram-per-kilogram concentrations, 

in bed-sediment (stream and lake beds), aqueous suspendedsediment, and soil samples. The method includes many 

compounds that typically are associated with industrial and 

household wastewater (Paxéus and others, 1992), as well as 

some that are known or suspected endocrine-disrupting compounds. The method is applicable to compounds that are (1) 

efficiently extracted from sediment samples using high-pressure water/isopropyl alcohol, (2) partitioned from the resulting 

water/isopropyl alcohol extract onto polystyrene-divinylbenzene (PSDVB) in the organic phase, (3) volatile and thermally 

stable for gas chromatography (GC), and (4) sufficiently stable 

to chemical and thermal degradation to allow accurate quantification. Method compounds, endocrine-disrupting potential, 

Chemical Abstracts Service numbers, parameter and method 

codes, and possible compound uses or sources are listed in 

table 1. 

. Method Summary 

2.1 Collect soil or sediment samples in the field by using 

the method outlined by Radtke and others (1998a). 

2.2 Extract the sediment samples using water/isopropyl 

alcohol on a pressurized solvent extraction system. 

2.3 Isolate the selected compounds from these extracts 

using a disposable, polypropylene SPE cartridge, which contains a PSDVB phase. Dry the SPE cartridges for 5 minutes. 

The SPE cartridges are not dried exhaustively. 

2.4 Elute the compounds of interest with a mixture of 

dichloromethane (DCM) and diethyl ether (DEE) at an 80:20 

ratio, respectively. 

2.5 Also use the DCM–DEE to elute sorbed compounds 

from a Florisil/sodium sulfate SPE cartridge. 

2.6 Evaporate the extract in a hood by using a gentle 

stream of nitrogen to a final volume of 1 mL. 

2.7 Determine the compounds of interest in the concentrated extracts by capillary-column gas chromatography/mass 

spectrometry (GC/MS). 

. Safety Precautions and Waste Disposal 

3.1 Conduct all steps in the method that require the use 

of organic solvents, such as cartridge cleaning, bottle rinsing, cartridge elution, and extract concentration, in a fume 

hood. Wear eye protection, gloves, and protective clothing in 

the laboratory area, and when handling reagents, solvents, or 

any corrosive materials. Typical laboratory disposable nitrile 

gloves do not provide adequate protection from dichloromethane (DCM), so avoid contact with DCM. 

3.2 The liquid waste stream produced during sample 

preparation is about 95-percent water (pH 7 buffer), with 

the rest of the volume made up of organic solvents. These 

solvents include isopropyl alcohol, DEE, acetone, and DCM. 

Collect the waste stream in thick-walled carboys and dispose 

of according to local regulations for chlorinated waste streams. 

Dispose of solvents used to clean or rinse glassware, equipment, and cartridges in the appropriate waste containers. The 

solid-waste stream produced during sample analysis is composed of used SPE cartridges, extracted sediment or soil, and 

assorted glassware (sample vials and pipette tips). Dispose of 

the solid-waste stream according to local policy. 

4. Interferences 

Compounds that compete with or displace the compounds 

of interest from the SPE cartridge materials (PSDVB phase 

and Florisil) might cause interferences or low method recovery, or both. In addition, compound classes, such as humic 

and fulvic acids, might influence the extraction efficiency and 

because of the complex nature of sediment and soil samples, 

recoveries of compounds of interest might be reduced. 
4 Determination of Wastewater Compounds in Sediment and Soil 

Table 1. Wastewater method compound names, endocrine-disrupting potential, parameter/method codes, and possible compound 

uses. 

[EDP, endocrine-disrupting potential; S, suspected; K, known; CAS, Chemical Abstracts Service; F, fungicide; H, herbicide; I, insecticide; FR, flame retardant; 


GUP, general use pesticide; WW, wastewater; Manuf, manufacturing; >, greater than; CP, combustion product; PAH, polycyclic aromatic hydrocarbon; 


UV, ultraviolet; NA, not applicable; --, no data]
 

Parameter/ CAS Compound name EDP1 method Possible compound uses or sources 

number codes 

1,4-Dichlorobenzene4 S 106-46-7 63163 Moth repellent, fumigant, deodorant 

1-Methylnaphthalene -­ 90-12-0 63165 2-5 percent of gasoline, diesel fuel, or crude oil 

2,6-Dimethylnaphthalene4 -­ 581-42-0 63167 Present in diesel/kerosene (trace in gasoline) 

2-Methylnaphthalene -­ 91-57-6 63168 2-5 percent of gasoline, diesel fuel, or crude oil 

3,4-Dichlorophenyl isocyanate -­ 102-36-3 63169 Degradate of diuron, a noncrop herbicide 

3-beta-Coprostanol -­ 360-68-9 63170 Carnivore fecal indicator 

3-Methyl-1H-indole (skatol) -­ 83-34-1 63171 Fragrance, stench in feces and coal tar 

3-tert-Butyl-4-hydroxyanisole (BHA) K 25013-16-5 63172 Antioxidant, general preservative 

4-Cumylphenol K 599-64-4 63173 Nonionic detergent metabolite 

4-n-Octylphenol K 1806-26-4 63174 Nonionic detergent metabolite 

4-tert-Octylphenol K 140-66-9 63176 Nonionic detergent metabolite 

Acetophenone -­ 98-86-2 63178 Fragrance in detergent and tobacco, flavor in beverages 

Acetyl-hexamethyl-tetrahydro- -­ 21145-77-7 63179 Musk fragrance (widespread use) persistent in ground water 

naphthalene (AHTN) 

Anthracene4 -­ 120-12-7 63180 Wood preservative, component of tar, diesel, or crude oil, CP 

Anthraquinone4 -­ 84-65-1 63181 Manuf dye/textiles, seed treatment, bird repellent 

Atrazine -­ 1912-24-9 63182 Selective triazine herbicide 

Benzo[a]pyrene4 K 50-32-8 63183 Regulated PAH, used in cancer research, CP 

Benzophenone S 119-61-9 63184 Fixative for perfumes and soaps 

beta-Sitosterol -­ 83-46-5 63185 Plant sterol 

beta-Stigmastanol -­ 19466-47-8 63186 Plant sterol 

Bisphenol A K 80-05-7 63188 Manuf polycarbonate resins, antioxidant, FR 

Bromacil4 -­ 314-40-9 63189 H (GUP), >80 percent noncrop usage on grass/brush 

Camphor -­ 76-22-2 63192 Flavor, odorant, ointments 

Carbazole -­ 86-74-8 63194 I, Manuf dyes, explosives, and lubricants 

Chlorpyrifos4 K 2921-88-2 63195 I, domestic pest and termite control (domestic use restricted 

as of 2001) 

Cholesterol -­ 57-88-5 63196 Often a fecal indicator 

Diazinon4 K 333-41-5 63198 I, > 40 percent nonagricultural usage, ants, flies 

Diethyl phthalate -­ 84-66-2 63202 Plasticizer for polymers and resins 

Diethylhexyl phthalate -­ 117-81-7 63187 Plasticizer for polymers and resins, pesticides 

d-Limonene -­ 5989-27-5 63203 F, antimicrobial, antiviral, fragrance in aerosols 

Fluoranthene4 -­ 206-44-0 63208 Component of coal tar and asphalt (only traces in gasoline or 

diesel fuel), CP 

Hexahydrohexamethyl-cyclopenta­ -­ 1222-05-5 63209 Musk fragrance (widespread use) persistent in ground water 

benzopyran (HHCB) 

Indole -­ 120-72-9 63210 Pesticide inert ingredient, fragrance in coffee 

Isoborneol -­ 124-76-5 63211 Fragrance in perfumery, in disinfectants 

Isophorone4 -­ 78-59-1 63212 Solvent for lacquer, plastic, oil, silicon, resin 
Analytical Method 5 

Table 1. Wastewater method compound names, endocrine-disrupting potential, parameter/method codes, and possible compound 

uses.—Continued 

[EDP, endocrine-disrupting potential; S, suspected; K, known; CAS, Chemical Abstracts Service; F, fungicide; H, herbicide; I, insecticide; FR, flame retardant; 


GUP, general use pesticide; WW, wastewater; Manuf, manufacturing; >, greater than; CP, combustion product; PAH, polycyclic aromatic hydrocarbon; 


UV, ultraviolet; NA, not applicable; --, no data]
 

Parameter/ CAS Compound name EDP1 method Possible compound uses or sources 

number codes 

Isopropylbenzene (cumene) -­ 98-82-8 63213 Manuf phenol/acetone, fuels and paint thinner 

Isoquinoline4 -­ 119-65-3 63214 Flavors and fragrances 

Menthol -­ 89-78-1 63215 Cigarettes, cough drops, liniment, mouthwash 

Metalaxyl4 -­ 57837-19-1 63216 H, F (GUP), mildew, blight, pathogens, golf/turf 

Methyl salicylate -­ 119-36-8 63217 Liniment, food, beverage, UV-absorbing lotion 

Metolachlor4 -­ 51218-45-2 63218 H (GUP), indicator of agricultural drainage 

N,N-Diethyl-meta-toluamide (Deet) -­ 134-62-3 63219 I, urban uses, mosquito repellent 

Naphthalene4 -­ 91-20-3 63220 Fumigant, moth repellent, major component (about 10 

percent) of gasoline 

Nonylphenol, diethoxy- (total, K 26027-38-3 63200 Nonionic detergent metabolite 

NPEO2) 

Nonylphenol, monoethoxy- (total, -­ NA 63221 Nonionic detergent metabolite 

NPOE1) 

Octylphenol, diethoxy- (OPEO2) K 26636-32-8 63201 Nonionic detergent metabolite 

Octylphenol, monoethoxy- K 26636-32-8 63206 Nonionic detergent metabolite 

(OPEO1) 

para-Cresol4 S 106-44-5 63222 Wood preservative 

para-Nonylphenol (total) K 84852-15-3 63175 Nonionic detergent metabolite 

Pentachlorophenol4 S 87-86-5 63223 H, F, wood preservative, termite control 

Phenanthrene4 -­ 85-01-8 63224 Manuf explosives, component of tar, diesel fuel, or crude 

oil, CP 

Phenol4 -­ 108-95-2 63225 Disinfectant, manuf several products, leachate 

Prometon4 -­ 1610-18-0 63226 H (noncrop only), applied prior to blacktop 

Pyrene4 -­ 129-00-0 63227 Component of coal tar and asphalt (only traces in gasoline or diesel fuel), CP 

Tetrabromodiphenyl ether -­ 40088-47-9 63166 Fire retardant 

Tri(2-butoxyethyl) phosphate -­ 78-51-3 63229 Flame retardant 

Tri(2-chloroethyl) phosphate S 115-96-8 63230 Plasticizer, flame retardant 

Tri(dichloroisopropyl) phosphate S 13674-87-8 63235 Flame retardant 

Tributyl phosphate -­ 126-73-8 63231 Antifoaming agent, flame retardant 

Triclosan S 3380-34-5 63232 Disinfectant, antimicrobial (concern for acquired microbial resistance) 

Triphenyl phosphate -­ 115-86-6 63234 Plasticizer, resin, wax, finish, roofing paper, FR 

1

World Wildlife Fund Canada (1999).
 

2

Parameter codes define sample constituent variables linked to compound analytical results stored in the National Water Information System data base 


(U.S. Geological Survey, 2003). 

3

ChemFinder Webserver (2001); National Toxicology Program (2001); National Institute of Standards and Technology (2001); Spectrum Laboratories, Inc. 

(2001); HealthCentral.com (2001); EXtension TOXicology NETwork (2001). 

4

Compound determined by at least one other method at the National Water Quality Laboratory. 
 

 

6 Determination of Wastewater Compounds in Sediment and Soil 

Compounds that have gas-chromatographic retention times 

and characteristic ions with a mass-to-charge ratio identical 

to or similar to the compounds of interest might interfere, and 

again because of the complex nature of sediment and soil samples, often there are unknown compounds that might interfere. 

Phthalates, antioxidants, and preservatives in the SPE 

cartridge housing often contribute to low-concentration contamination. Samples, collection equipment, or SPE cartridges 

that are handled improperly also might become contaminated 

with soaps, caffeine, and fragrances. Precautions are necessary 

to avoid contamination during sample collection (see section 

11.1, Field Sampling) because some method compounds are 

contained in commonly used commercial consumer products. 

Sample-collection protocols and cleaning procedures for field 

equipment (Radtke and others, 1998a, p. 57; 1998b, p. 11–13) 

need to be followed to reduce interferences. 

5. Apparatus and Instrumentation 

5.1 Cleaning and elution module—For cleaning and 

preparation of SPE cartridges, Supelco, Inc., Visiprep SolidPhase Extraction Vacuum Manifold or equivalent. 

5.2 Pressurized extraction system—Dionex ASE 200 

Accelerated Solvent Extractor or equivalent. 

5.2.1 Operating conditions—Pressure 13,800 kPa 

(2,000 lb/in2), temperatures 120o and 200oC, preheat time 0, heat 

time 0, static time 10 minutes, flush volume 25 mL, purge time 

20 seconds, static cycles 3, solvent concentrations 50 percent 

water/50 percent isopropyl alcohol, solvent concentrations 20 

percent water/80 percent isopropyl alcohol. 

5.3 Vacuum tubing—1.27-cm (0.5-in.) outside diameter 

by about 3 m (118 in.) length, for vacuum pumping samples 

through SPE cartridges. 

5.4 Extraction cells—Dionex ASE 200 stainless steel 22­

mL extraction cells and end caps or equivalent. 

5.5 Carboy—NalgeneTM, thick-walled, capable of maintaining a vacuum of 200 kPa (29 in.) of mercury, 10-L volume, 

Van Waters & Rogers Scientific, Inc. (VWR) or equivalent. 

5.6 Bottle-top solvent dispensers—Adjustable from 2 to 

5 mL, 5 to 25 mL, and 10 to 100 mL; Brinkman Dispensette, 

VWR or equivalent. 

5.7 25-mL graduated Kuderna-Danish receivers 

(concentrator tubes)—Kontes part number 570081-2526 or 

equivalent. 

5.8 Solvent reservoirs—Amber glass, 1,000-mL. 

5.9 Vacuum pump—Any adjustable vacuum pump with 

sufficient capacity to maintain a vacuum of 200 kPa (29 in.) of 

mercury. 

5.10 Analytical balances—Balance for accurately weighing samples, 1,400 ± 1 g. Balance for standard preparation accurately weighs 10 ± 0.01 mg. 

5.11 Nitrogen evaporative concentrator—Organomation 

N-Evap or equivalent. 

5.12 Micropipettes—50-, 100-, and 200-μL fixed-volume and 

variable-volume micropipettes with disposable glass bores; VWR 

Scientific or equivalent. 

5.13 Glass and stepper syringes—10 to 500-μL volumes. 

5.14 Adapters and valves— Teflon, connects SPE cartridge 

barrels to male Luer fitting. 

5.15 Positive pressure nitrogen manifold or equivalent. 

5.16 Fused-silica capillary column—Any column that provides adequate resolution, capacity, accuracy, and precision. A 30-m 

by 0.25-mm inside diameter fused-silica capillary column coated 

with a 0.50-μm bonded film of 5-percent polyphenylmethylsilicone; 

Hewlett-Packard HP-trace analysis column or equivalent. 

5.17 GC/MS bench-top system—Agilent Technologies, Model 

5973 or equivalent. 

5.17.1 GC condition—Oven, 40°C (hold 3 minutes), then 

ramp at 4°C/min to 100°C, and 9°C/min to 320°C; injection port, 

290°C with electronic pressure control set for a constant flow of 

helium carrier gas of 0.9 mL/min; injection volume, 2 μL, splitless 

injection. 

5.17.2 MS conditions—Source, 200°C; analyzer, 100°C; 

interface, held at 250°C and programmed at 9°C/min to 290°C when 

the oven temperature surpasses 250°C; electron-impact ionization 

mode (70 electron volts). Full-scan mode from 45 to 450 atomic 

mass units in 0.5 second. 

6. Reagents and Consumable Materials 

6.1 Helium carrier gas (99.999 percent)—Gas chromatography carrier gas. 

6.2 Glass fiber thimble—Whatman glass fiber thimble-shaped 

filters, item number 2814199 or equivalent. 

6.3 Nitrogen gas—For evaporation, 99.999 percent pure. 

6.4 Collection vials—Dionex 60 mL, clear or amber 

collection vials or equivalent. 

6.5 Florisil SPE cartridges—6-mL barrel, packed with 1 g of 

Florisil, IST Inc., catalog number 712-0100-C or 

equivalent. 

6.6 Column reservoir—Polypropylene 150 mL, empty column, 

Macherey-Nagel GMBH and Co., KG, custom made or equivalent. 

6.7 Isolation SPE cartridges—20-mL barrel, packed with 1 g 

of PSDVB; OASIS PSDVB packing material, Waters Inc., catalog 

number 186000117 or equivalent. 

6.8 Glass bottles—Amber, 1,000 mL, wide mouth, baked at 

450°C for 2 hours, fitted with Teflon-lined screw caps or equivalent. 

6.9 Solvents—Dichloromethane (DCM), pentane, acetone, isopropyl alcohol (IPA), and diethyl ether (DEE); B&J Brand pesticide 

grade or equivalent. 

6.10 Organic free water—Prepared by Solution 2000 purification system or equivalent. 

6.11 Potassium phosphate buffer—pH 7.0 (dilute 10 g dipotassium hydrogen phosphate and 7 g potassium dihydrogen phosphate 

in 1-L reagent water). 
 7 

6.12 Dichloromethane:diethyl ether mixture—80:20 

volume per volume. 

6.13 Water/isopropyl alcohol mixtures—50:50 volume 

per volume, and 20:80 volume per volume. 

6.14 Sodium sulfate—Aldrich Chemical Co. reagent 

grade or equivalent, baked at 450oC for at least 1 hour. 

6.15 Reagent sand—Ottawa reagent sand or equivalent, 

Fisher Scientific, Inc., for samples, set spikes, and reagent 

blanks, heated to 450oC for 4 hours. 

7. Standards 

7.1 Stock standard solutions at 10,000 ng/μL—Obtain 

method compounds and surrogate compounds at greater than 

99-percent purity, if available, from commercial vendors. 

Prepare stock standard solutions of each individual compound 

at about 10,000 ng/μL (10 mg/mL) by accurately weighing, 

to the nearest 0.002 mg, 20 mg of the neat material in a 2-mL 

volumetric flask and dilute to volume with DCM. Three of the 

method compounds (para-nonylphenol, OPEO1, and OPEO2) 

are only available in technical mixtures. For the technical 

grade nonylphenol (NP) mixture (NPOE1 and NPOE2) and 

the OPEO1 and OPEO2 mixtures, the final concentration of 

each component in the stock standard solutions is calculated 

on the basis of the percentage contribution of each compound 

to the total ion chromatograms of the technical mixtures. 

These compounds are identified in the total ion chromatogram 

by referring to their characteristic ions and relative retention 

times (see table 2 in Section 10, Instrument Calibration). 

The total contribution of the para-nonylphenols (total) in 

the NP technical mixture is determined by manually integrating the sum of the peaks within the expected retention time 

window (fig. 1) for the quantitation ion (m/z 135, see table 2, 

Section 10). Also, the qualification ion profile patterns (m/z 

220 and 107) are compared to the m/z to verify the elution 

range of the ions used. The ortho-NPs elute prior to the 

para-NPs and are not determined in this method because their 

contribution to the total ion chromatogram is minimal (less 

than 7 percent). In general, it is desirable for the purposes of 

making dilutions of the mixed standard solution, to prepare a 

stock standard solution of the para-NP isomers (total), which 

is 16 times the concentration of the stock standard solutions of 

the single-component compounds in the method. To prepare 

this stock standard solution, calculate the necessary amount of 

the technical mixture needed (about 180 mg/mL). 

The Igepal 210 technical mixture is mainly composed of 

single components of OPEO1 and OPEO2 in a ratio of about 

10 to 1, respectively. A convenient concentration of a stock 

standard solution for OPEO1 is prepared at 4 times the concentration of the single-component compounds, or 40 mg/mL. 

This concentration also provides enough material for calibrating OPEO2 (about 4 mg/mL) from the same stock standard 

solution. The preparation of the OPEO1 and OPEO2 stock 

standard solution, thus, generally requires about 45 mg/mL (as 

calculated) of the Igepal 210 technical mixture. 

Analytical Method 

Figure 1. Manual integration of the extracted ion profile for the 

quantitation ion (mass-to-charge ratio 135) of para-nonylphenol 

from the 2 nanogram-per-microliter calibration solution for the 

wastewater method (from Zaugg and others, 2002, p. 10). 

During development of the custom wastewater method 

(Zaugg and others, 2002) that this method is based on, NPEO1 

and NPEO2 only were available in a technical mixture. 

Since 2002, a source of NPEO2 standard has been identified 

and evaluated for purity, so it was included in this method. 

Standards of the NPEO1 compounds also became available 

and currently (2005) are being evaluated for composition and 

purity for possible inclusion in the method. 

7.2 Intermediate method compound standard solution at 

100 ng/μL—Prepare a mixed stock standard solution that contains each method compound at 100 ng/μL. Use an adjustable 

100-μL dispenser and a 10-mL volumetric flask to prepare this 

intermediate method compound standard solution and dilute 

with DCM. 

7.3 Surrogate spiking solution at 80 ng/μL—Combine 

400 μL of stock standard solution at 10,000 ng/μL for each 

surrogate compound listed in table 2 (see Section 10, Instrument Calibration) in a 50-mL volumetric flask and dilute with 

isopropyl alcohol. 

Add 100 μL of the surrogate 80-ng/μL spiking solution 

to a 25-g environmental sample to obtain a surrogate spiking 

concentration of 400 μg/kg. A surrogate concentration of 8 

ng/μL is expected in a 1.0-mL extract if 100 percent of the surrogate is recovered through the sample preparation procedure. 

7.4 Method compound solution at 50 ng/μL—Add 5.0 

mL of the 100-ng/μL intermediate method compound standard 

solution (see section 7.2) to a 10-mL flask. Add 50 μL of each 

of the stock standard solutions at 10,000 ng/μL (see section 

7.1) and dilute with DCM. This mixture is used to prepare the 

calibration solutions (section 7.7). 
 

8 Determination of Wastewater Compounds in Sediment and Soil 

7.5 Spiking solution at 20 ng/μL—Dilute 2.0 mL of the 

intermediate method compound standard solution at 100 ng/μL 

in a 10-mL volumetric flask with isopropyl alcohol. Add 200 

μL to a 15-g sand sample to obtain a compound concentration 

of 267 μg/kg. A concentration of 4.0 ng/μL is expected in a 

1.0-mL extract if 100 percent of the spike is recovered. 

7.6 Polycyclic aromatic hydrocarbon (PAH) procedural internal standard solution at 100 ng/μL—The internal 

standards (see table 2, Section 10, Instrument Calibration) are 

obtained from Supelco in a mixture at 2,000 ng/μL. Add 2.5 

mL of this mixture to a 50-mL flask and dilute with DCM. 

Note that 20 μL of PAH procedural internal standard solution 

at 100 ng/μL in a 1.0-mL extract is equivalent to a concentration of 2 ng/μL. 

7.7 Calibration solutions—Prepare a series of calibration 

solutions in DCM that contain all of the method and surrogate 

compounds at concentrations for most compounds ranging 

from 0.05 to 40.0 ng/μL (0.05, 0.1, 0.2, 0.5, 1.0, 2.0, 5.0, 10, 

20, 40 ng/μL). The concentration of single-component solutions in the calibration mixture that responds poorly by GC/ 

MS (cholesterol, 3-beta-coprostanol, beta-stigmastanol, betasitosterol, OPEO1, and 5-methyl-1H-benzotriazole) needs to 

be 4 times that of the other single-component compounds. 

The concentration of the multicomponent compounds in the 

calibration solution, NP (total) and NPEO2 (total), needs to 

be 20 and 16 times, respectively, that of the single-component 

compounds in the calibration solution. The concentration of 

the PAH procedural internal standard compounds in the calibration solutions is kept constant at 5.0 ng/μL. Prepare these 

calibration solutions by adding the appropriate volumes of the 

mixed surrogate and method compound solution at 50 ng/μL 

and the PAH procedural internal standard solution at 

100 ng/μL into volumetric flasks and diluting to volume with 

DCM. 

8. Sample Preparation 

8.1 Collection, shipment, and storage of sediment 

samples—Collect bed-sediment (stream and lakebeds), aqueous suspended-sediment, and soil samples using sampling 

methods that accurately represent the organic contamination 

and concentrations at a given location. Use sampling equipment that is free of plastic tubing, gaskets, and other parts 

that might leach interferences, absorb compounds of interest, 

or potentially contaminate or degrade the sediment samples. 

Collect the sediment samples using the process described by 

Radtke and others (1998a). Field-sampling procedures need to 

follow those typically used to collect samples for trace organic 

compound analyses (Hardy and others, 1989; Ward and Harr, 

1990; Radtke and others, 1998a, 1998b). 

CAUTION: Some of the compounds that are determined 

by this method are found in commonly used products, such 

as coffee, tea, cola, soap, and insecticide repellent. Project 

personnel need to be careful to avoid potential contamination 

of samples from such sources by avoiding consumption or 

contact with these materials immediately prior to and during 

sampling procedures. Limit or avoid contact with any fragranced materials. The probability of sample contamination 

with compounds determined by this method is higher than for 

other NWQL methods. For this reason, sample duplicates or 

field blank samples, or both, need to be analyzed routinely to 

monitor for potential sample contamination. 

All sampling equipment needs to be cleaned according to 

procedures outlined by Wilde and others (1998) to remove all 

traces of possible contamination. The sampling equipment has 

to be cleaned before each sample is collected to prevent crosscontamination between samples. 

Ship all sediment samples on ice to the NWQL in 500- or 

1,000-mL wide-mouth glass jars with lids lined with polytetrafluoroethylene (PTFE) via overnight service as soon as 

possible after collection. The amount of water in the container 

should be minimized. Allow adequate space for the water 

present in the sample to expand during freezing. If adequate 

space is not allowed, the glass container will break and the 

sample is susceptible to contamination or loss. 

Sediment samples are stored at the NWQL after login 

at –20o

C or less until the sample is extracted. The NWQL 

has established a 1-year sample-holding time limit (Maloney, 

2005; U.S. Environmental Protection Agency, 1998, table 

8-2) from the date of sample collection to the date of sample 

extraction. This holding time will be used until an accepted 

statistical procedure determines its effectiveness. 

8.2 ASE extraction—Retrieve samples from sample 

freezer and allow to thaw completely. Thoroughly homogenize each sample with a clean spatula or scoopula. Place 

a glass fiber filter thimble into the 22-mL ASE extraction 

cells and weigh. Remove any excess glass fiber thimble with 

a razor blade. Fill the thimbles with sample. Typical wet 

sample weights used range from 0.5 g (high organic content 

samples) to 40 g (typical sandy river sediment). Place the 

extraction cells into the ASE system. Extract the samples 

twice using the conditions outlined in section 5.2. Two collection vessels are required for each sample; a collection vessel 

is required for the 120o

C and the 200oC extraction of each 

sample. Add 3 mL of pentane to the 200o

C collection vessel 

to reduce analyte loss. Extraction volumes range from 20 to 

50 mL. After extraction, weigh the extraction vessel with the 

thimble and sample. Remove the thimble and sample. The 

difference between the weight of the extraction vessel after 

extraction (includes thimble and sample) and the weight of 

the extraction vessel and thimble pre-extraction equals the dry 

weight of the sample processed. This measurement is required 

for calculating the final concentrations of the compounds of 

interest in a known amount of environmental sample. 

Prepare laboratory reagent-sand set blank and set spike 

samples with each set (10 environmental samples). Add 50 μL 

of the surrogate solution (80 ng/μL; see section 7.3) to each 

sample, set spike, and set blank by using a stepper syringe to 

make the 100-μL additions. Fortify the spike sample with 200 

μL of the spiking solution (20 ng/μL; see section 7.5) by using 

a micropipette dispenser and 200-μL disposable glass bore. 
 

Note: Allow the spike and surrogate solutions to come to 

room temperature, and then shake well before adding them to 

samples. 

8.3 SPE cartridge cleaning—Add 20 mL (the OASIS 

SPE barrel volume) of the elution solvent (DCM–DEE, 80:20 

volume per volume) to rinse the OASIS SPE cartridges and 

polypropylene reservoirs. Allow the solvent to drain by gravity until the phase is completely saturated before applying vacuum. Then open the Luer-Lok fittings on the vacuum manifold 

by turning them counterclockwise to allow the solvent to be 

removed from the cartridges by vacuum. Rinse the cartridges 

with an additional 10 mL of DCM–DEE and allow at least 10 

minutes for the vacuum to remove any residual solvent. Dispose of solvent following current local guidelines. 

Add 10 mL (the Florisil SPE barrel volume) of acetone to 

rinse the Florisil SPE cartridges. Allow the solvent to drain by 

gravity until the phase is completely saturated before applying 

vacuum. Then open the Luer-Lok fittings on the vacuum manifold by turning them counterclockwise to allow the solvent 

to be removed from the cartridges by vacuum. Rinse the cartridges with an additional 10 mL of acetone and allow at least 

10 minutes for the vacuum to remove any residual solvent. 

Dispose of solvent following current NWQL guidelines. 

Note: Unlike most other SPE phases, it is permissible for 

PSDVB to dry prior to sample extraction. 

8.4 Sample isolation—Immediately prior to using the 

SPE cartridges, visually inspect by rotating them to ensure that 

there is no substantial void-volume between the polyethylene 

frits and the PSDVB phase. Attach the SPE cartridges to the 

vacuum lines from the vacuum manifold assembly. 

CAUTION: Loosely packed PSDVB phase can cause 

uneven flow or channeling during the SPE process and result 

in reduced compound recoveries. Therefore, it is essential to 

ensure that the PSDVB phase is packed firmly before using 

SPE cartridges. If the PSDVB phase is loosely packed, dispose of the SPE cartridge and prepare another SPE cartridge 

for use. 

CAUTION: Ensure that the 10-L waste carboys have 

enough headspace (empty volume) remaining to accommodate 

the total water/isopropyl alcohol volume from all samples 

before a new sample set is extracted, otherwise it may be difficult to exchange carboys during the extraction. 

Attach a polypropylene 150-mL empty sample reservoir 

to each cleaned OASIS SPE cartridge using a Teflon valved 

Luer-Lok adapter in the closed position. Next, add the 200oC 

ASE extracts to each corresponding reservoir. Add 50 mL of 

the phosphate buffer solution to each ASE collection vial. Cap 

and shake collection vial for 10 seconds. Add this buffer solution to each corresponding reservoir. Repeat the phosphate 

buffer cleaning step one additional time. Open the Teflon 

valve between the OASIS cartridge and the reservoir to allow 

gravity to pull the ASE extract and buffer washes through 

the OASIS SPE cartridges. A small vacuum may have to be 

applied to start the extraction. Obtain the desired extraction 

flow-rate range (between 5 to 10 mL/min) by loosening the 

vacuum manifold system frits, which might need to be done 

Analytical Method  

once or twice during sample extraction. Repeat this entire 

process by extracting the 120o

C ASE extract into the same 

SPE cartridge used for the 200oC ASE extracts. 

Note: Reasonable extraction times range from 15 to 30 

minutes for 150-mL samples and correspond to flow rates 

between 5 and 10 mL/min. No adverse effects on compound 

recoveries have been observed when flow rates are maintained 

in this operating range. 

8.5 Cartridge drying—Dry the OASIS SPE cartridges at 

2 L/min of nitrogen for 15 minutes by using a positive pressure nitrogen manifold. 

Note: The color of the PSDVB phase becomes lighter as 

it dries, and the wet/dry boundary layer is noticeable if carefully observed. It is important to ensure that the cartridge does 

not completely dry. 

Note: Recoveries of compounds more volatile than 

naphthalene have been observed to decrease by about 10 to 

20 percent if cartridges are allowed to remain under vacuum 

beyond 15 minutes. 

8.6 Compound elution—Attach the corresponding 150­

mL polyethylene reservoir to the corresponding OASIS SPE 

cartridges with a Teflon adapter. Add ~2.5 g baked sodium 

sulfate to the top of each Florisil cartridge. Attach a Florisil/ 

sodium sulfate SPE cartridge to the bottom of the dried OASIS 

SPE cartridge. Place the end of these three stacked components (reservoir, OASIS SPE cartridge, and Florisil/sodium/ 

sulfate SPE cartridge) in 30-mL glass receivers. 

Note: Thoroughly rinsing the sample reservoirs is important because as much as 30 to 40 percent of some hydrophobic 

compounds (particularly PAHs, sterols, and organochlorine 

compounds) might adhere to the polypropylene walls. 

Add 10 mL of DCM–DEE to the 150-mL polyethylene 

reservoir to elute the OASIS SPE cartridge. The first 10 mL 

will only wet the OASIS and Florisil SPE beds. Add another 

10 mL of the DCM–DEE and allow gravity to pull the elution 

solvent into the 30-mL glass receivers. Allow the DCM–DEE 

level to merge with the top of the OASIS bed before adding 

the next aliquot. Repeat this process a third time, using a large 

syringe or small vacuum to force all residual DCM–DEE from 

the two stacked SPE cartridges. The addition of 30 mL of 

DCM–DEE to the two SPE cartridges will result in about 25 

mL of elution solvent to be collected. Five milliliters of the 

DCM–DEE will be retained on the SPE beds. 

Note: During the developmental stages of this method, 

it was observed that most problems with compound recovery 

were associated with difficulties in the elution step, usually 

related to complete removal of water from the SPE cartridges 

prior to elution. 

8.7 Sample concentration—Prepare the 24-position 

N-Evap nitrogen evaporator by attaching cleaned and baked 

stainless-steel needles in each position. Set the nitrogen flow 

rate to about 3.5 L/min and adjust this flow visually so that 

a slightly detectable ripple can be seen on the surface of the 

extracts. When the extract volume is between 2 and 5 mL, add 

20 μL of the internal standard solution (100 ng/μL) by using a 

1.0-mL stepper syringe. Remove each extract when the final 
 

 

10 Determination of Wastewater Compounds in Sediment and Soil 

volume is about 1 mL, but to maintain a more consistent flow 

rate for the remaining samples, leave the needles attached to 

the N-Evap with the flow of nitrogen remaining unaltered. 

Concentrate the DCM–DEE extract at ambient temperature 

and periodically check the extract; do not allow the extract 

to evaporate completely. Allow about 60 to 120 minutes for 

evaporation of nearly 25 mL of DCM–DEE to 1 mL. 

8.8 Vial sample extracts—Vortex the extract so that 

the solvent rinses the glass walls of the receiver. Then use a 

baked, disposable glass Pasteur pipette to transfer concentrated 

extracts to appropriately labeled GC vials. Store extracts in a 

freezer (–10oC) prior to GC/MS analysis. 

. Sample Analysis Procedure 

The performance of the analytical instrumentation is 

checked at least every 24 hours to ensure that it meets quality-control guidelines of sensitivity and accuracy necessary to 

obtain reproducible sample results. 

9.1 Gas Chromatograph (GC) Performance Evaluation 

9.1.1 GC performance normally is indicated by peak 

shape, compound resolution, and variation of selected-compound response factors relative to response factors obtained by 

using a new capillary column and freshly prepared calibration 

solutions. An example of the separation and peak shape for 

the complex mixture of nonylphenol compounds is shown in 

the selected ion chromatogram (fig. 1) of a 2.0-ng/μL calibration solution. Change the injection port liner or perform 

maintenance on the capillary column to bring the GC into 

compliance if peak shape and resolution deteriorate (indicated 

by a loss in the number of resolved NP isomers) or if compounds fail to meet the calibration criteria (see section 10, 

Instrument Calibration). About 0.6 m (one column loop) of 

the capillary-column inlet end often can be removed to restore 

GC performance. Specifically, a loss in response greater than 

30 percent for cholesterol indicates the need for replacement 

of the GC inlet liner or maintenance of the column, or both. 

Sediment samples generally require capillary column maintenance (including removing one column loop) after every set of 

12 environmental samples to maintain method performance. 

Instrument maintenance requires recalibrating the method 

compounds. 

9.2 Mass Spectrometer Performance Evaluation 

9.2.1 Check for air (m/z 28 and 32) and water (m/z 

18) leaks in the GC/MS prior to analysis. If air leaks are 

detected, as indicated by the presence of nitrogen (m/z 28) 

greater than 10 percent of the m/z 69 peak area of the perflurotributylamine (PFTBA) tuning compound, locate and fix 

the leaks. Also, check the instrument before every analytical 

set to ensure that MS performance is in accordance with the 

PFTBA tuning criteria outlined in section 9.2.2. In addition, 

initially adjust the MS response (also outlined in section 9.2.2) 

to ensure that the established minimum reporting level (MRL) 

for each selected compound can be achieved. 

9.2.2 Check the mass spectrometer tune before every 

analytical set. 

Note: The following guidance applies to the Agilent 

Technologies model 5973 GC/MS system. Other GC/MS 

systems might require different adjustments to achieve the 

method performance criteria. 

PFTBA is introduced into the MS vacuum manifold 

through a factory-set calibrated leak. Set mass axis and MS 

peak-width adjustment characteristics to give ±0.15-atomic 

mass unit accuracy at m/z 69, 219, and 502 in the spectrum 

of PFTBA. Adjust the electron multiplier voltage to achieve 

about 1,000,000 counts for the m/z 69. This setting generally 

provides sufficient signal to meet detection requirements for 

method compounds at method detection limit (MDL) concentrations in samples, provided that the GC is performing 

properly. Manually adjust the MS characteristics so that m/z 

ion 69 has 100-percent abundance, m/z 219 is 40 ±20 percent, 

and m/z 502 is 3 ±2 percent relative abundance. Check mass 

assignments to ensure accuracy to ±0.15 atomic mass unit. 

Adjust peak widths measured at half height for m/z 69, 219, 

and 502 so that they range from about 0.5 to 0.65 atomic mass 

unit. Adjustment of tune settings requires subsequent recalibration of the method compounds. 

10. Instrument Calibration 

10.1 Acquire initial calibration data by using a new 

capillary column and freshly prepared calibration solutions 

(section 7.7). Use these data in subsequent evaluation of the 

GC/MS performance. 

10.2 Prior to the analysis of each sample set and every 

10 samples thereafter during a series of analyses, analyze 

and evaluate a calibration check solution (or solutions) that 

contains all of the method compounds to ensure that GC/MS 

performance is in compliance. The observed concentration of 

method compounds in the continuing calibration verification 

solutions (CCVs), using the initial calibration curve, generally 

should be within ±20 percent of the expected concentration. 

Specific acceptance criteria for each compound may be established as subsequent data are acquired. 

10.3 Inject 2 μL of each calibration solution into the 

GC/MS and acquire data by using the previously described 

GC/MS conditions. Enter the compound names, mass spectral 

ions, approximate retention times (table 2), and calibration 

concentration levels into the data system. The GC/MS dataprocessing software then calculates the relative retention time 

and response factors for each compound and surrogate in 

relation to their designated internal standards in the calibration solution. The data-processing software also uses linear 

regression (or other) routines to calculate and plot calibration 

curves for each compound. Typical equations used to calculate 

calibration curves for this method are similar to other NWQL 

methods (Sandstrom and others, 2001). Compound quantitation ions and their respective PAH internal-standard reference 

compounds used for these calculations are listed in table 2. 
 

Analytical Method 11 

10.4 In the course of performing sample analyses, it is 

not necessary to perform a full calibration with each analytical 

batch, as long as performance criteria are met for CCVs and 

other QC samples (section 11). 

10.5 Calibration of multicomponent compounds—The 

para-NPs, NPEO1, and NPEO2 mixtures are each composed 

of 10 to 20 discernible isomers. They are calibrated manually by integrating the area of their respective quantitation ion 

peaks that are present in the expected range of the retention 

time window (table 2). This range is 1 to 1.5 minutes wide. 

This approach also was used for determining the concentration 

of compounds in the preparation of stock standard solutions 

(section 7.1) and also has been used in other studies (Blackburn and Waldock, 1995). 

10.6 Qualitative determination—A compound is identified based on retention time relative to the internal standard. 

It is also identified by comparing the background-subtracted 

mass spectrum with the confirmation ions (table 2) of a reference mass spectrum obtained from calibration standards. 

Three or four confirmation ions are defined as the ions that 

have the greatest relative intensity, or are desirable for their 

unique mass, in the reference spectrum. Compounds are 

identified as present when the following criteria are met (or as 

reason allows): 

10.6.1 Retention time—The intensities of the characteristic ions of a compound are at a maximum that coincides 

within ±0.05 minute of the selected compound’s relative 

retention time. For this schedule, the method is set (under 

Global to Compound ID) to choose the peak in a sample that 

is closest to the specified peak retention time derived from the 

calibration standards. In addition, the quantification ion and 

associated confirmation ions should have their maxima within 

0.01 minute of each other. However, matrix effects can have a 

substantial influence on GC retention times, and retention time 

reproducibility can be highly compound dependent. 

10.6.2 Spectra—The identity of each selected compound is verified by comparing the mass spectrum at the apex 

of the extracted ion profile of the quantitation ion with a reference spectrum obtained from the standard for that compound. 

In particular, the relative ratios of the extracted ion profiles 

need to be within 20 percent of the relative ratios obtained on 

injection of a calibration standard solution produced using the 

conditions of this method. It is difficult to define explicitly 

which features of a sample mass spectrum must be present 

to consider the identification to be positive. In general, the 

sample spectrum should have the same base peaks, major 

fragmentation ions, significant isotope clusters, and molecular 

ion (where appropriate) as a standard. The analyst determines 

if the ratios of Target® ion profiles are appropriate and have 

relative intensities that are consistent with the reference mass 

spectrum, or if differences are caused by interference ions, or 

are a result of contributions of Target® and interference ions. 

Experience and training are necessary for the analyst to recognize the salient features of individual mass spectra as well as 

potential interferences. 

11. Quality Assurance and Quality Control 

The NWQL has prepared a Quality Management System 

guidance document (Maloney, 2005) for Analytical Services 

that is followed for this wastewater sediment method to ensure 

that QC standards are correctly established and consistently 

met. The sample matrix, sample-preparation, and sampleanalysis steps are evaluated to determine data quality for each 

sample individually, and for all samples as part of a samplepreparation set and a sample-analysis set. 

Quality-control information needs to be evaluated in 

aggregate to determine whether analytical data are acceptable 

for reporting or if corrective actions are needed. Minimum 

quality-control requirements include the following: (1) determination of potential field-sampling errors; (2) determination 

of potential matrix effects; (3) analysis of third-party check 

solutions; (4) determination of potential blank contamination 

in the set blank; (5) determination of method performance by 

analysis of the set spike and CCV samples; (6) determination of the surrogate recovery for the individual sample; (7) 

determination of internal standard volume correction; and (8) 

corrections for instances of out-of-acceptance criteria. 

11.1 Field sampling—Accuracy of the sampling process 

and possible contamination from handling samples in the field 

(proper sample containers, proper sample storage) is monitored when the appropriate field blanks and field duplicates 

are submitted to the laboratory for analysis. Even then, only 

limited information can be inferred because each individual 

sample is handled separately. 

Before sample-hold time expiration, each environmental 

sample is prepared for analysis as part of a sample-preparation 

set that contains a laboratory reagent set spike and set blank 

to monitor method performance and contamination. There is 

no guarantee, however, that each unique sample matrix will 

perform similarly to the recoveries of compounds and surrogates obtained from the reagent set spike and set blank. Consequently, spiking of field duplicate samples at the laboratory 

is encouraged, as part of a project quality assurance/quality 

control (QA/QC) plan, to gain some indication of how method 

compounds perform in a particular sample matrix. Laboratory 

set spikes do not reflect matrix effects, either positively or negatively, because they are prepared in reagent sand, which usually is not indicative of the sample matrix. Furthermore, surrogate compounds added to monitor gross sample preparation 

might perform well in a given matrix, but this does not mean 

that all method compounds will perform equally well. Historically, statistical data for set spikes may be used to anticipate 

method compound recovery, but they are no substitute for field 

sample spikes to determine specific matrix effects. 

11.2 Sample matrix compatibility—The sample matrix 

needs to be consistent with the requirements of the method 

(bed sediment, suspended sediment, soil samples). Problematic sample matrices will affect the performance of the method 

during sample preparation and analysis. Extremely complex 

sample matrices, such as raw sewage, are discouraged for 

this method because they contaminate sample-preparation 
12 Determination of Wastewater Compounds in Sediment and Soil 

Table 2. Wastewater method compound retention time, quantitation ion, confirmation ions, surrogate compounds, and internal 

standard reference compounds. 

[Compounds are listed in order of retention time. min, minutes; m/z, mass-to-charge ratio; IS, internal standard; --, not used] 

Retention Quantitation Confirmation Confirmation Internal 

Compound name time ion ion ion standard 

(min) (m/z) (m/z) (m/z) reference 

Isopropylbenzene (cumene) 11.507 105 120 -­ IS1 

Phenol 13.651 94 66 65 IS1 

1,4-Dichlorobenzene 15.212 146 148 111 IS1 

d-Limonene 15.819 93 136 121 IS1 

Acetophenone 17.234 105 120 77 IS1 

para-Cresol 17.460 107 108 77 IS1 

Isophorone 19.298 82 138 -­ IS2 

Camphor 20.135 90 105 152 IS2 

Isoborneol 20.582 95 136 140 IS2 

Menthol 20.921 95 123 138 IS2 

Naphthalene 21.123 128 127 102 IS2 

Methyl salicylate 21.269 120 152 92 IS2 

Isoquinoline 22.834 129 102 -­ IS2 

Indole 23.418 117 89 -­ IS2 

Diethyl phthalate 23.500 149 177 -­ IS3 

2-Methylnaphthalene 23.568 142 141 115 IS3 

3,4-Dichlorophenyl isocyanate 23.639 187 189 124 IS3 

1-Methylnaphthalene 23.869 142 141 115 IS3 

3-Methyl-1H-indole (skatol) 25.120 130 131 -­ IS3 

2,6-Dimethylnaphthalene 25.519 156 141 -­ IS3 

Atrazine 26.550 200 215 202 IS3 

3-tert-Butyl-4-hydroxyanisole (BHA) 26.606 180 165 137 IS3 

N,N-Diethyl-meta-toluamide (Deet) 27.983 119 190 91 IS3 

4-tert-Octylphenol 28.320 135 206 107 IS3 

Nonylphenol, monoethoxy- (total, NPEO1) 28.5–29.5 179 193 207 IS4 

Benzophenone 28.806 182 105 77 IS3 

Tributyl phosphate 28.830 99 155 211 IS3 

para-Nonylphenol (total) 29.7–30.6 135 220 107 IS4 

Prometon 30.099 210 225 168 IS4 

Tri(2-chloroethyl) phosphate 30.311 249 251 205 IS4 

Pentachlorophenol 30.394 266 264 268 IS4 

4-n-Octylphenol 30.448 107 206 -­ IS4 

Diazinon 30.673 304 179 199 IS4 

Phenanthrene 30.903 178 176 89 IS4 

Octylphenol, monoethoxy-(OPEO1) 30.903 135 107 179 IS4 

Anthracene 31.044 178 176 89 IS4 

Acetyl-hexamethyl-tetrahydro­ 31.538 243 258 197 IS4 

naphthalene (AHTN) 
Analytical Method 13 

Table 2. Wastewater method compound retention time, quantitation ion, confirmation ions, surrogate compounds, and internal 

standard reference compounds.—Continued 

[Compounds are listed in order of retention time. min, minutes; m/z, mass-to-charge ratio; IS, internal standard; --, not used] 

Retention Quantitation Confirmation Confirmation Internal 

Compound name time ion ion ion standard 

(min) (m/z) (m/z) (m/z) reference 

Carbazole 31.524 167 139 166 IS4 

Hexahydrohexamethyl cyclopentabenzo- 31.468 243 258 213 IS4 

pyran (HHCB) 

4-Cumylphenol 31.576 197 212 -- IS4 

Metalaxyl 32.135 206 220 249 IS4 

Bromacil 32.587 205 207 -- IS4 

Metolachlor 32.850 162 138 240 IS4 

Chlorpyrifos 32.878 314 316 197 IS4 

Anthraquinone 33.095 208 180 152 IS4 

Fluoranthene 34.134 202 101 203 IS4 

Triclosan 34.378 288 290 218 IS4 

Diethylhexyl phthalate 34.700 149 167 279 IS5 

Pyrene 34.731 202 101 203 IS5 

Bisphenol A 34.994 213 228 119 IS5 

Octylphenol, diethoxy- (OPEO2) 35.168 223 135 294 IS5 

Nonylphenol, diethoxy- (total, NPEO2) 335.7–36.5 237 223 279 IS5 

Tetrabromodiphenyl ether 35.7 328 326 324 IS5 

Tri(dichloroisopropyl) phosphate 36.400 379 383 381 IS5 

Tri(2-butoxyethyl) phosphate 37.054 299 199 125 IS5 

Triphenyl phosphate 37.176 326 325 215 IS5 

Benzo[a]pyrene 41.431 252 250 126 IS6 

3-beta-Coprostanol 42.927 373 355 388 IS6 

Cholesterol 43.209 386 301 275 IS6 

beta-Sitosterol 45.038 414 396 381 IS6 

beta-Stigmastanol 45.193 416 401 233 IS6 

Surrogates 

Decafluorobiphenyl 18.786 334 265 -- IS2 

Fluoranthene-d10 34.087 212 106 -- IS4 

Bisphenol A-d3 34.947 216 234 -- IS4 

Internal Standards 

1,4-Dichlorobenzene-d4

 (IS1) 15.132 150 152 -- -­

Naphthalene-d8 (IS2) 21.048 136 -- -- -­

Acenapthene-d10 (IS3) 26.700 164 162 160 -­

Phenanthrene-d10 (IS4) 30.842 188 -- -- -­

Chrysene-d12 (IS5) 38.010 240 -- -- -­

Perylene-d12 (IS6) 41.558 264 132 -- -­
14 Determination of Wastewater Compounds in Sediment and Soil 

equipment and instrumentation, thus affecting the results of 

subsequent samples. In contrast, the reagent sand used for 

set spikes and blanks is not representative (lacking dissolved 

organic carbon) of an environmental sample matrix. Consequently, recoveries of surrogate and method compounds from 

reagent sand often are less than or greater than spike recoveries obtained from environmental sample matrices. This result 

demonstrates some of the limitations of comparing different 

sample matrices; however, laboratory spike recovery control 

limits need to be used as a basis to assess matrix spike recoveries. 

11.3 Third-party check—The third-party check is either a 

commercially available mixture of the compounds of interest or separate lot of a mixture. The third-party check is 

analyzed in each sequence after the calibration standards to 

independently verify the calibration curve. The third-party 

calculated check concentrations need to be within ±30 percent 

of the expected concentration. If the third-party check sample 

concentrations do not fall within the ±30-percent window, the 

source of the error needs to be determined before any environmental samples are analyzed. 

11.4 Set blank—Some compounds in the wastewater 

method are common in personal-care products and might be 

detected occasionally in laboratory or field blanks. If compounds are detected in more than 10 percent of the historical 

laboratory set blanks, they are treated as though they always 

are potentially present in sample background. If this is the 

case, use the 95th percentile of historical laboratory blank 

concentrations to establish a higher MRL for the specific 

compound than might otherwise be derived from the standard 

MDL calculation (U.S. Environmental Protection Agency, 

1995). 

Set blanks provide information regarding possible contamination introduced to the sample at the laboratory. Each 

time a set of samples is extracted, a set blank is extracted using 

a sand matrix. The set blank monitors all reagents, glassware, 

equipment, and the entire extraction process for potential 

contamination. If contamination interferes with the identification or quantification of the compounds of interest, the source 

of contamination needs to be identified and eliminated before 

additional environmental samples are processed. If the contamination cannot be eliminated, the data associated with the 

contamination are qualified with a remark code (per NWQL 

QA/QC policy; Maloney, 2005), or the minimum reporting 

level is adjusted to a higher concentration to reflect the level of 

contamination. 

11.5 Set spike and continuing calibration verifications— 

Set spikes provide information regarding method performance 

for each compound. Each time a set of samples is extracted, a 

set spike is extracted using a sand matrix. The set spike monitors the recovery of the compounds of interest through the 

entire process (includes reagents, glassware, sample extraction 

process, and sample analysis). If there appears to be a process 

error that interferes with the identification or quantification 

of the compounds of interest, the source of the error needs 

to be identified and corrected before additional environmental samples are processed. If the error cannot be corrected, 

the data associated with the error must be qualified with an 

appropriate remark code according to NWQL QA/QC policy 

(Maloney, 2005). 

Laboratory set spike data are acquired and statistically 

evaluated to develop acceptance criteria on an on-going 

basis. These control limit criteria are entered into the Target 

spike and CCV sublists. If a sample set contains a spike with 

unacceptable recovery results (as judged by the spike sublist), 

then surrogate recovery in the associated samples and blank 

need to be evaluated along with any observations recorded 

during sample preparation. If it is apparent that the unacceptable recovery is caused by laboratory process error, then the 

possibility of the error adversely affecting the other samples 

associated with that set needs to be considered. 

Concentrations determined by this method for compounds and surrogates in environmental samples are reported 

without correction for spike recoveries. 

11.6 Surrogate recovery—Surrogate compounds, which 

are chemically similar to method compounds, are added to 

each sample prior to preparation. Surrogate standard recoveries are used to measure gross sample-processing problems and 

matrix effects. Control limits for surrogates generally are set at 

the mean percent recovery ±3 standard deviations as compiled 

from laboratory set spike and blank samples. The recoveries 

of bisphenol A-d3 and fluoranthene-d10 may be used to monitor sample preparation and potential matrix effects for their 

respective nonisotopically labeled analogs, as well as other 

chemically similar (by functionality, reactivity, or volatility) 

compounds. Surrogate recoveries generally are used to evaluate specific sample-preparation steps and are of limited use for 

assessing compound recoveries. 

Concentrations reported by this method for compounds in 

environmental samples are not corrected for surrogate recoveries. 

11.7 Internal standard—Each environmental sediment 

sample and all method QC samples have internal standard 

compounds added, just prior to final extract vialing, to correct 

automatically for any differences (generally less than ±10 

percent) in extract volume, as well as automatically adjust for 

slight variations in instrumental performance. The internal 

standards are used to monitor instrument conditions, such as 

extract injection errors, GC retention time shifts, or instrument 

abnormalities caused by power interruptions or component 

malfunctions. 

11.8 Out-of-acceptance criteria—It is difficult to 

troubleshoot QA/QC problems that may represent a combination of a dirty sample matrix, sample preparation errors, 

or a marginally acceptable analysis. Certain process failures 

require sample preparation to be repeated if sufficient sample 

has been received. Other failures might be identified as 

“matrix-induced” and be impossible to correct, thus requiring 

associated data qualifiers for reporting results. In rare cases, 

certain failures, such as unacceptable surrogate recoveries, 

might indicate that sample results are unreliable and should 

not be reported. 
 

Analytical Method 15 

If the instrument performance does not meet acceptance 

criteria, then follow suggested procedures of cleaning and 

maintenance (see section 9.1) to bring the instrument back into 

compliance. It might be possible to reanalyze only that portion of the sequence corresponding to the instrumental failure 

between bracketing CCVs because samples are analyzed in a 

specific sequence. In some cases, identifying and removing 

problematic sample extracts from sequences, or reorganizing 

sequences, might be required to meet performance criteria for 

other sample results. 

11.9 Instrumental analysis quality control—A typical analytical sequence used for this method is listed in table 

3. Sample extract(s) are analyzed in an instrument batch or 

sequence to provide additional information for quality assurance and to facilitate corrective actions that might be required 

if performance criteria are not met. The analytical sequence 

includes continuing calibration verification solutions (CCVs) 

to check periodically at designated intervals (10 environmental samples or less) that the instrument is in compliance 

with initial calibration criteria. For those compounds that are 

quantitatively reported (not permanently assigned an estimated 

concentration) by using this method, a calculated concentration within ±20 percent of the expected CCV concentration 

is required. Finally, a low-concentration standard equivalent 

[instrument detection level (IDL)] to 1 μg per sample (or less) 

is analyzed in each sequence after the environmental samples 

to ensure that instrument sensitivity is maintained throughout 

the sample set. 

1. Calculation of Results 

Before quantitative results are reported, each compound 

first needs to meet qualitative criteria. 

12.1 Qualitative Identification—The retention time of 

the quantitation ion for the compound of interest should be 

within 0.1 minute (±6 seconds) of the expected retention time 

(as calculated from the relative retention time of calibration 

standards and the retention time of the internal standard in the 

sample) in the absence of any obvious matrix effects. Furthermore, the profiles of the two qualification and the quantification ion peaks must maximize within two scans of each other 

(in the absence of any obvious interference). Visually compare 

the sample compound spectra to the reference standard spectra 

and confirm a reasonable match. 

Note: Occasionally, ion(s) can appear to be missing or 

ion abundance ratios can appear to be distorted in the spectrum 

of a compound in a sample when compared to the reference 

spectrum, especially at concentrations near the MDL if there 

is interfering spectral contamination. A distorted sample spectrum often results from automatic data-processing routines 

that subtract the average of the two spectra before and after 

the spectrum at the apex of the peak. Subtracting the spectral 

background of a well-defined sample peak usually enhances 

the spectrum, whereas subtracting interfering ions with substantial ion abundances from a poorly defined sample peak 

Table . Gas chromatography/mass spectrometry analytical 

sequence suggested for use in determining wastewater 

compounds in sediment and soil. 

Analytical Sample type 

sequence 

1 Decafluorotriphenylphosphine mass spectrometer 

calibration solution 

2 Instrument blank (injection of pure solvent) 

3 Instrument detection level (IDL) solution 

4 Third-party check (if available, only during full 

calibration, section 11.3) 

5 Continuing calibration verification (CCV) solution 

6 Set A spike 

7 Set A blank 

8 Sample 1 Set A 

9 Sample 2 Set A 

10 Sample 3 Set A 

11 Sample 4 Set A 

12 Sample 5 Set A 

13 Sample 6 Set A 

14 Sample 7 Set A 

15 Sample 8 Set A 

16 CCV solution 

17 Sample 9 Set A 

18 Sample 10 Set A 

19 Set B spike 

20 Set B blank 

21 Sample 1 Set B 

22 Sample 2 Set B 

23 Sample 3 Set B 

24 Sample 4 Set B 

25 Sample 5 Set B 

26 Sample 6 Set B 

27 CCV solution 

28 IDL solution 

can result in a nonsensical spectrum. In this situation, the main 

consideration for positive identification of a compound is the 

requirement for the ion profiles to maximize within two scans 

of each other (after accounting for interfering ion profiles, if 

necessary). If the compound is present, an improved spectrum 

also needs to be obtained after manually subtracting appropriate background scan(s) that are free from the ions of the 

interfering peak. 
 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

16 Determination of Wastewater Compounds in Sediment and Soil 

12.2 Quantitation 

12.2.1 Determination of single-component 

compounds—The concentration of a compound is calculated 

according to the calibration curve used to establish the best fit 

between the calibration points after a compound has passed 

qualitative criteria. Curve-fitting routines provided by the 

instrument manufacturer, and summarized in similar NWQL 

method reports (Furlong and others, 1996; Jha and Wydoski, 

2003), are used to obtain a calibration curve for each compound. If the calculated concentration of a compound exceeds 

the highest concentration point of the calibration curve by 20 

percent or more, add higher concentration calibration standards to the curve or dilute the extract to bring the compound 

response within the range of the calibration curve. Concentration results need to be reported as estimated with the “E” 

qualifier code if compound response is less than the lowest 

point on the calibration curve or the minimum reporting level 

(MRL). If curve-fitting routines (quadratic curves and power 

curves) are used for calibration, verify that the sample compound response is not outside the working range of the calibration curve (or in a region of unexpected deviations in the 

calibration curve); or recalculate the concentration by using 

another type of calibration curve. 

12.2.2 Determination of multicomponent compounds—The para-NPs, NPEO1, and NPEO2 mixtures each 

consist of 10 to 20 discernable isomers. Manually integrate 

the isomeric peak areas of their respective quantitation ions 

present in the expected retention time window range (table 2), 

similar to the calibration process described earlier (section 10, 

Instrument Calibration) for these compounds. If interferences 

cause the ratios of the quantitation ions to the confirmation 

ions to be unreasonable, then integrate that portion of the ion 

chromatogram that is caused by the contamination or interference (peaks in the sample chromatogram that are not in the 

calibration standard chromatogram) and subtract the interference from the total. 

Note: This procedure seldom is necessary because the 

quantitation and confirmation ions for para-NP, NPEO1, 

and NPEO2 compounds normally are unique from coeluting 

interference. 

12.2.3 Calculations—The calculation of a final 

concentration of the compounds of interest in a sediment 

sample requires multiple calculations, as follows: 

12.2.3.1 Calculate the dry weight of sediment extracted, in grams (W ):

s

W = (W + W + W ) (1) s cell thimble w postextraction 

– (W + W ) cell thimble preextraction 

where 

W = dry weight of sediment, in grams; w 

Wcell = weight of ASE extraction cell, in grams; and 

W = weight of glass fiber thimble, in grams. thimble 

12.2.3.2 Calculate sample concentrations. 

If the compound of interest has met the qualitative identification criteria, calculate the compound concentration in the 

sample, as follows: 

C = C / W (2) o s 

where 

C = the concentration of the compound of interest in 

the sample, in micrograms per kilogram; 

C = raw amount of analyte calculated from the cali­ o 

bration curve, in micrograms; and 

W = the dry weight of sample extracted, in kilograms, s 

calculated above. 

12.2.3.3 Calculate the percent recovery of 

the surrogate compounds in each sample using 

R = [(C × V )/(C × V )] × 100 (3) a s f a a

where 

R = recovery of surrogate in sample, in percent; a 

C = concentration of surrogate in sample, in micro­ s 

grams per kilogram, calculated using equations 

3 and 4; 

Vf = final extract volume, in microliters; 

C = concentration of compound in the surrogate a 

solution added to the sample, in micrograms 

per kilogram; and 

V = volume of surrogate solution added to the a 

sample, in microliters. 

12.2.3.4 Calculate the percent recovery of 

compounds in set spike sample using 

R = [(C × V )/(C × V )] × 100 (4) b sp f b b

where 

Rb = recovery of fortified compound in the set spike 

sample, in percent; 

C

sp = concentration of compound in set spike sample, 

in micrograms per kilogram, calculated using 

equations 3 and 4; 

Vf = final extract volume, in microliters; 

Cb = concentration of compound in individual spike 

solution added to sample, in micrograms per 

kilogram; and 

Vb = volume of individual spike solution added to the 

sample, in microliters. 
 

Results and Discussion of Method Validation 17 

12.3 Reporting of Results—The wastewater method 

requires that results be transmitted to project investigators and 

data interpreters because it is used in calculating the presence, fate, and transport of compounds in the environment. 

Therefore, data are reported according to the latest laboratory 

quality-assurance information (Maloney, 2005; Childress and 

others, 1999). Alphanumeric data-qualifier codes are used to 

report information about the presence and concentration of 

a compound when concentrations are less certain because of 

matrix effects, interferences, and other unexpected circumstances. 

The wastewater sediment method is considered to be 

“information-rich” (Childress and others, 1999) because compound identifications are determined by mass spectrometry; 

consequently, results are not censored at the MRL. Compound 

concentrations, therefore, are reported as follows. 

If the concentration is equal to or greater than the MRL, 

the concentration is reported to three significant figures. If the 

concentration is less than either the MRL or the lowest calibration standard (usually equivalent to 8.0 μg/kg), results are 

reported by using the “E” code to indicate that it has been estimated. Other instances where it is appropriate to use the “E” 

code have been documented (Maloney, 2005; Childress and 

others, 1999). They include, for example, matrix interferences, 

method compounds that have been permanently assigned an 

“E” code, and those compounds that do not meet quality-control criteria, such as being out of calibration by more than ±20 

percent. If the result is greater than the highest concentration 

standard in the calibration curve, then the sample is diluted 

into the range of the calibration curve and reanalyzed. 

Note: MRL data are subject to annual change in conjunction with the NWQL long-term method detection level 

(LT–MDL) program (Childress and others, 1999). 

The attempt to report consistent data near the method 

detection limit (MDL) is difficult, especially with the intention to transmit as much information as possible in complex 

samples and also avoid data censoring. Reporting compound 

results as estimated because their concentrations are less than 

the MRL need not decrease confidence in qualitative identification. However, there is more uncertainty for concentrations 

reported near or less than the MDL. If compounds are barely 

discernible in mass spectra and responses are near or less than 

the MDL, then the potential for reporting false detections 

(false positives) or mistakenly reporting compounds as not 

present (false negatives) increases. In most of these instances, 

when there is considerable doubt about qualitative identification, reporting conservative results (less than the MRL, analyte 

undetected) is appropriate. 

12.4 Reporting Units—Report compound concentrations 

for field samples in microgram per kilogram dry sediment (μg/ 

kg) using three significant figures. Report surrogate data for 

each sample as percent recovery. Report data for the set spike 

as percent recovery. Compounds identified and quantified in 

the set blank are reported in microgram per kilogram, assuming a 25-g dry-weight sample. 

Results and Discussion of Method 

Validation 

Reagent-sand samples and surface-water sediment samples collected from Cherry Creek near Garland Park, Denver, 

Colo., and soil samples collected from a commercially available topsoil mix, were used to test method performance. One 

set of the subsamples was fortified at a lower concentration 

(4 to 72 μg) of each compound, and the other set was fortified 

at a higher concentration (40 to 720 μg) of each compound. 

In addition, the three sample matrices were extracted and 

analyzed (unfortified) to determine the ambient concentrations 

of any method compounds (table 4). The average concentration of selected compounds found in the reagent-sand blank 

samples processed with each sample set is listed in table 4. 

The presence of 16 compounds in the reagent-sand sample 

blank at or near detectable concentrations reemphasizes the 

ubiquitous presence of about half of the method compounds, 

as well as the importance of avoiding contamination throughout sample collection, preparation, and analysis. 

Fortified samples were extracted and analyzed on different days, so comparisons of different matrices and concentrations include day-to-day variation. Mean bias and precision 

data from the analyses are listed in table 5. Recovery was 

corrected for concentration of compounds found in the unfortified matrices. The matrix samples were fortified (after loading 

into ASE extraction cells) with a known concentration (in 

micrograms), and percent recoveries were calculated. Average 

recovery of all method compounds for short-term single-operator results in reagent-sand samples fortified at 4 to72 μg was 

76 ± 13 percent relative standard deviation. Initial method 

detection limits for single-component compounds ranged from 

12.5 to 852 μg/kg. Because environmental sediment and soil 

samples contained rock, twigs, plant and animal materials, 

even with sample mixing, exact matrix duplicates (by weight) 

were difficult to obtain. The sample concentrations were not 

converted to micrograms per kilogram because of the potential variability in loading these variable samples into the ASE 

extraction cells. 

The concentration of 20 compounds will be reported as 

estimated with the “E” remark code for one of three reasons: 

(1) unacceptably low-biased recovery (less than 60 percent) or 

highly variable method performance (greater than 25 percent RSD), (2) reference standards prepared from technical 

mixtures, or (3) potential blank contamination. Initial MDLs 

were calculated for compounds in reagent sand by using the 

corresponding spike concentration as listed in table 5. 

Table 6 lists the compounds (Zaugg and others, 2002) 

that were investigated in the development of this method but 

were excluded because of high (>120 percent) or low (<30 

percent) recovery, or relative standard deviations greater than 

30 percent. 
18 Determination of Wastewater Compounds in Sediment and Soil 

Table 4. Wastewater method compounds detected in unfortified reagent-sand, river-sediment, and topsoil samples. 

[μg/kg, micrograms per kilogram; < MRL, less than minimum reporting level; n, number of samples; *, detected but average less than 1.0 μg/kg] 

Average concentration (μg/kg) Compound name 

Sand n = 14 River sediment n =  Topsoil n =  

1,4-Dichlorobenzene < MRL < MRL < MRL 

1-Methylnaphthalene < MRL < MRL < MRL 

2,6-Dimethylnaphthalene <1* < MRL < MRL 

2-Methylnaphthalene < MRL < MRL < MRL 

3-beta-Coprostanol < MRL < MRL < MRL 

3-Methyl-1H-indole (skatol) < MRL 40.0 < MRL 

3-tert-Butyl-4-hydroxyanisole (BHA) < MRL < MRL < MRL 

3,4-Dichlorophenyl isocyanate < MRL < MRL < MRL 

4-Cumylphenol < MRL < MRL < MRL 

4-n-Octylphenol < MRL < MRL < MRL 

4-tert-Octylphenol < MRL < MRL < MRL 

Acetophenone < MRL 24.8 < MRL 

Acetyl-hexamethyl-tetrahydro-naphthalene (AHTN) < MRL < MRL < MRL 

Anthracene <1* < MRL < MRL 

Anthraquinone < MRL < MRL < MRL 

Atrazine < MRL < MRL < MRL 

Benzo[a]pyrene < MRL 31.7 < MRL 

Benzophenone 2.1 < MRL 100 

beta-Sitosterol < MRL 367 4,440 

beta-Stigmastanol < MRL 224 1,380 

Bisphenol A < MRL < MRL < MRL 

Bromacil < MRL < MRL < MRL 

Camphor < MRL < MRL < MRL 

Carbazole < MRL < MRL < MRL 

Chlorpyrifos < MRL < MRL < MRL 

Cholesterol 35 384 800 

Diazinon < MRL < MRL < MRL 

Diethyl phthalate 8.4 < MRL < MRL 

Diethylhexyl phthalate 160 102 410 

d-Limonene < MRL < MRL < MRL 

Fluoranthene <1* 122 < MRL 

Hexahydrohexamethyl cyclopentabenzopyran (HHCB) < MRL < MRL < MRL 

Indole <1* 35.2 < MRL 

Isoborneol < MRL < MRL < MRL 

Isophorone 1.7 < MRL < MRL 

Isopropylbenzene (cumene) < MRL < MRL < MRL 

Isoquinoline < MRL < MRL < MRL 

Menthol 1.4 < MRL < MRL 

Metalaxyl < MRL < MRL < MRL 
Results and Discussion of Method Validation 1 

Table 4. Wastewater method compounds detected in unfortified reagent-sand, river-sediment, and topsoil samples.—Continued 

[μg/kg, micrograms per kilogram; < MRL, less than minimum reporting level; n, number of samples; *, detected but average less than 1.0 μg/kg] 

Average concentration (μg/kg) Compound name Sand n = 14 River sediment n =  Topsoil n =  

Menthol 1.4 < MRL < MRL 

Metalaxyl < MRL < MRL < MRL 

Methyl salicylate < MRL < MRL < MRL 

Metolachlor < MRL < MRL < MRL 

N,N-Diethyl-meta-toluamide (Deet) < MRL < MRL < MRL 

Naphthalene <1* < MRL < MRL 

Nonylphenol, diethoxy- (total, NPEO2) < MRL 225 < MRL 

Nonylphenol, monoethoxy-(total, NPEO1) < MRL < MRL 200 

Octylphenol, diethoxy- (OPEO2) < MRL < MRL < MRL 

Octylphenol, monoethoxy- (OPEO1) 9.0 < MRL < MRL 

para-Cresol <1* 59.4 100 

para-Nonylphenol (total) < MRL < MRL < MRL 

Pentachlorophenol < MRL < MRL < MRL 

Phenanthrene <1* 74.7 < MRL 

Phenol 8.2 40.6 270 

Prometon < MRL < MRL < MRL 

Pyrene < MRL 76.6 < MRL 

Tetrabromodiphenyl ether < MRL < MRL < MRL 

Tri(2-butoxyethyl) phosphate < MRL < MRL < MRL 

Tri(2-chloroethyl) phosphate <1* < MRL < MRL 

Tri(dichloroisopropyl) phosphate < MRL < MRL < MRL 

Tributyl phosphate < MRL < MRL < MRL 

Triclosan < MRL < MRL < MRL 

Triphenyl phosphate < MRL < MRL < MRL 
 

20 Determination of Wastewater Compounds in Sediment and Soil 

Table 5. Wastewater method mean bias and precision of spike recovery data for seven or eight replicates with compounds spiked at 

two concentrations ranging from 4 to 720 micrograms per sample in reagent-sand (including calculated method detection limits), riversediment, and topsoil samples. 

[μg, micrograms; μg/kg, micrograms per kilogram; RSD, relative standard deviation; MDL, method detection limit] 

Compound name 

Spike 

amount 

(μg) 

Mean recovery (percent) 

Sand River 

sediment Topsoil Sand 

RSD (percent) 

River 

sediment Topsoil 

Initial 

MDL 

(μg/kg) 

1,4-Dichlorobenzene 4.0 

40 

70.1 

64.6 

45.4 

51.6 

67.2 

64.4 

7.02 

8.60 

14.0 

16.9 

4.97 

10.8 

27.6 

1-Methylnaphthalene 4.0 

40 

76.7 

78.5 

77.5 

78.1 

77.2 

82.6 

6.48 

5.18 

13.5 

8.26 

3.78 

1.04 

27.8 

2,6-Dimethylnaphthalene 4.0 

40 

75.7 

78.5 

77.0 

77.4 

75.6 

82.3 

5.86 

4.55 

12.1 

7.87 

4.82 

1.70 

24.8 

2-Methylnaphthalene 4.0 

40 

76.7 

78.5 

77.5 

78.1 

77.2 

82.6 

6.48 

5.18 

13.5 

8.26 

3.78 

1.04 

27.8 

3,4-Dichlorophenyl isocyanate1 4.0 

40 

43.3 

24.9 

36.3 

26.1 

36.4 

31.8 

24.9 

74.3 

18.0 

26.7 

28.0 

28.8 

60.4 

3 beta-Coprostanol 16 

160 

105.7 

92.6 

73.18 

77.3 

93.1 

70.2 

15.2 

14.6 

31.7 

12.8 

23.4 

8.27 

359.7 

3-Methyl-1H-indole (skatol) 4.0 

40 

83.1 

84.7 

99.9 

106.6 

78.9 

80.2 

6.65 

2.54 

11.9 

10.6 

8.41 

4.01 

30.9 

3-tert-Butyl-4-hydroxyanisole 

(BHA)1 

4.0 

40 

79.0 

66.0 

40.6 

38.1 

93.6 

80.5 

22.9 

17.7 

26.9 

45.5 

8.52 

9.54 

101 

4-Cumylphenol 4.0 

40 

85.9 

92.9 

79.6 

96.5 

84.0 

92.0 

7.01 

4.80 

10.6 

4.69 

4.80 

6.81 

33.7 

4-n-Octylphenol 4.0 

40 

82.3 

89.3 

77.1 

90.5 

82.5 

88.5 

7.97 

5.22 

10.1 

6.34 

5.24 

9.79 

36.8 

4-tert-Octylphenol 4.0 

40 

85.3 

87.4 

82.9 

88.5 

86.7 

89.0 

4.79 

3.06 

10.5 

4.73 

5.08 

2.59 

22.9 

Acetophenone1 4.0 

40 

45.0 

53.6 

26.7 

42.2 

28.9 

39.6 

40.0 

13.7 

49.5 

9.35 

67.5 

7.79 

101 

Acetyl-hexamethyl-tetrahydronaphthalene (AHTN) 4.0 

40 

76.8 

82.7 

76.6 

78.2 

78.4 

82.2 

3.84 

4.02 

14.2 

6.32 

6.30 

7.75 

16.5 

Anthracene 4.0 

40 

78.1 

84.2 

80.3 

83.1 

75.7 

79.4 

4.54 

2.88 

10.9 

5.16 

7.06 

2.18 

19.8 

Anthraquinone 4.0 

40 

84.3 

84.4 

87.0 

74.7 

84.3 

85.6 

5.15 

2.72 

6.22 

39.5 

4.73 

2.45 

24.3 

Atrazine 4.0 

40 

78.7 

99.7 

70.0 

92.1 

66.0 

86.6 

13.4 

4.97 

16.9 

7.10 

15.4 

6.93 

58.9 

Benzo[a]pyrene 4.0 

40 

77.8 

81.7 

84.7 

79.2 

75.8 

76.9 

5.64 

3.82 

22.2 

5.22 

7.05 

9.47 

24.6 

Benzophenone 4.0 

40 

88.8 

87.5 

87.9 

86.4 

96.1* 

95.8* 

6.4 

0.92 

7.75 

3.83 

5.51 

2.98 

31.8 
 

Results and Discussion of Method V alidation 21 

Table 5. Wastewater method mean bias and precision of spike recovery data for seven or eight replicates with compounds spiked at 

two concentrations ranging from 4 to 720 micrograms per sample in reagent-sand (including calculated method detection limits), riversediment, and topsoil samples.—Continued 

[μg , micrograms; μg/kg, micrograms per kilogram; RSD, relative standard deviation; MDL, method detection limit] 

Compound name 

Spike 

amount 

(μg) 

Mean recovery (percent) 

Sand River 

sediment Topsoil Sand 

RSD (percent) 

River 

sediment Topsoil 

Initial 

MDL 

(μg/kg) 

beta-Sitosterol 16.0 

160 

97.4 

82.1 

123 

66.8 

101* 

83.8 

16.7 

10.9 

25.7 

12.9 

28.6 

12.1 

363 

beta-Stigmastanol 16.0 

160 

96.1 

79.8 

73.2 

63.8 

92.8 

72.2 

17.1 

9.73 

27.2 

9.41 

31.4 

9.10 

367 

Bisphenol A1 4.0 

40 

64.5 

53.5 

53.2 

44.4 

58.0 

59.6 

8.75 

13.5 

18.1 

5.64 

15.6 

7.99 

31.6 

Bromacil1 14.0 

140 

62.8 

78.3 

43.9 

63.6 

48.9 

52.7 

20.7 

5.13 

36.0 

8.07 

39.8 

11.1 

254 

Camphor 4.0 

40 

79.1 

87.3 

70.6 

84.6 

67.6 

84.4 

6.09 

1.90 

12.8 

5.87 

17.1 

6.47 

27.0 

Carbazole 4.0 

40 

82.9 

93.2 

82.0 

91.5 

79.7 

91.4 

4.83 

1.34 

7.51 

4.02 

4.79 

4.12 

22.4 

Chlorpyrifos 4.0 

40 

60.4 

92.0 

62.2 

92.3 

68.3 

86.4 

9.92 

7.58 

29.1 

5.67 

18.9 

5.42 

33.6 

Cholesterol 16.0 

160 

99.3 

92.3 

125 

77.3 

92.4 

70.2 

7.57 

14.6 

19.2 

19.1 

16.9 

12.1 

168 

Diazinon 4.0 

40 

75.8 

76.9 

75.5 

70.8 

76.0 

80.2 

11.5 

5.02 

28.2 

10.4 

13.1 

4.47 

48.7 

Diethyl phthalate3 4.0 

40 

58.2 

70.3 

58.3 

74.8 

61.0 

82.6 

14.3 

5.58 

5.73 

9.13 

7.86 

9.8 

46.7 

Diethylhexyl phthalate3 4.0 

40 

153 

82.9 

147 

75.4 

129 

58.2 

16.1 

11.2 

25.2 

13.0 

20.6 

5.52 

138 

d-Limonene1 4.0 

40 

65.7 

65.1 

29.0 

48.0 

64.2 

64.8 

6.45 

10.5 

20.6 

21.3 

5.09 

12.1 

23.7 

Fluoranthene 4.0 

40 

81.0 

84.7 

102 

85.1 

82.0 

85.6 

5.11 

2.80 

38.0 

5.33 

4.23 

3.23 

23.2 

Hexahydrohexamethyl-cyclo­

 pentabenzopyran (HHCB) 

4.0 

40 

78.0 

83.7 

79.0 

77.4 

80.4 

83.6 

2.86 

3.85 

10.0 

6.11 

6.14 

5.3 

12.5 

Indole 4.0 

40 

82.0 

83.3 

89.4 

71.8 

74.6 

65.0 

11.7 

3.35 

18.0 

6.94 

19.5 

19.4 

Isoborneol 4.0 

40 

86.5 

86.9 

78.8 

76.2 

85.0 

87.6 

8.11 

5.14 

20.3 

8.80 

9.02 

2.74 

39.3 

Isophorone1 4.0 

40 

12.1 

46.3 

4.53 

33.0 

5.47 

32.8 

64.1 

12.3 

45.9 

11.9 

56.8 

20.2 

43.4 

Isopropylbenzene (cumene)1 4.0 

40 

54.4 

61.0 

15.1 

37.1 

52.8 

59.1 

28.4 

9.56 

41.0 

28.8 

10.5 

15.0 

86.6 
 

 Determination of Wastewater Compounds in Sediment and Soil 

Table 5. Wastewater method mean bias and precision of spike recovery data for seven or eight replicates with compounds spiked at 

two concentrations ranging from 4 to 720 micrograms per sample in reagent-sand (including calculated method detection limits), riversediment, and topsoil samples.—Continued 

[μg , micrograms; μg/kg, micrograms per kilogram; RSD, relative standard deviation; MDL, method detection limit] 

Spike Mean recovery (percent) RSD (percent) Initial 

Compound name amount River River MDL 

(μg) Sand Topsoil Sand Topsoil (μg/kg) sediment sediment 

Isoquinoline1 4.0 

40 

59.5 

65.6 

46.3 

49.7 

37.3 

42.8 

25.0 

11.2 

31.8 

15.1 

50.0 

4.59 

83.1 

Menthol 4.0 

40 

88.4 

86.9 

84.2 

70.8 

82.9 

94.2 

8.50 

16.3 

12.8 

9.83 

18.0 

12.9 

42.0 

Metalaxyl 4.0 

40 

57.7 

79.7 

37.6 

53.2 

41.3 

53.6 

20.7 

5.85 

43.4 

24.0 

61.8 

16.1 

53.4 

Methyl salicylate1 4.0 

40 

13.4 

22.7 

12.3 

14.4 

35.4 

46.4 

47.7 

42.7 

156 

51.9 

77.9 

36.9 

35.8 

Metolachlor 4.0 

40 

83.9 

92.0 

85.7 

92.3 

81.2 

86.4 

7.91 

7.58 

10.5 

5.67 

4.84 

5.42 

37.2 

N,N-Diethyl-meta-toluamide

 (Deet)1 

4.0 

40 

76.3 

75.5 

58.7 

62.4 

56.7 

58.0 

13.2 

10.2 

27.5 

14.1 

35.8 

7.54 

56.2 

Naphthalene 4.0 

40 

75.7 

78.9 

71.2 

73.6 

76.6 

81.6 

5.55 

3.66 

8.35 

11.2 

3.36 

3.28 

23.5 

Nonylphenol, diethoxy- (total, 

NPEO2)2 

64 

640 

106 

98.6 

106 

93.6 

113 

99.4 

8.93 

2.90 

20.6 

4.04 

6.83 

6.37 

852 

Nonylphenol, monoethoxy- 

(total,NPEO1)2 

32 

320 

93.7 

93.1 

90.6 

89.2 

96.2 

93.8 

8.01 

3.47 

20.8 

6.64 

4.79 

7.15 

336 

Octylphenol, diethoxy- (OPEO2)2 2.8 

28 

103 

99.1 

98.3 

94.2 

109 

98.4 

9.55 

1.36 

24.3 

3.22 

8.58 

1.90 

38.5 

Octylphenol, monoethoxy-

(OPEO1)2 

28 

280 

86.6 

92.3 

83.9 

93.3 

85.3 

91.4 

6.45 

3.28 

17.0 

5.48 

6.34 

5.25 

219 

para-Cresol 4.0 

40 

85.48 

74.2 

124 

115 

76.9 

67.6 

33.6 

5.09 

45.0 

14.9 

11.2 

5.12 

161 

para-Nonylphenol (total)2 72 

720 

79.4 

86.5 

79.9 

86.0 

83.7 

86.3 

6.23 

7.43 

11.5 

5.47 

10.2 

7.21 

499 

Pentachlorophenol1 16 

160 

52.7 

35.2 

445.2 

40.3 

54.2 

40.5 

44.1 

28.0 

35.1 

24.3 

19.8 

26.4 

520 

Phenanthrene 4.0 

40 

78.2 

85.4 

84.9 

86.0 

80.8 

88.0 

4.72 

2.60 

9.98 

5.10 

3.87 

2.20 

20.7 

Phenol1 4.0 

40 

20.9 

41.9 

20.8 

47.0 

87.5 

39.8 

32.8 

16.3 

37.8 

6.2 

76.4 

13.3 

38.2 

Prometon 4.0 

40 

74.7 

88.6 

79.9 

74.4 

66.6 

73.3 

10.6 

5.12 

16.9 

10.2 

10.7 

6.67 

44.2 

Pyrene 4.0 

40 

73.3 

82.7 

91.6 

80.9 

73.2 

83.2 

5.01 

2.14 

36.9 

5.62 

7.22 

3.10 

20.6 
 

Results and Discussion of Method Validation  

Table 5. Wastewater method mean bias and precision of spike recovery data for seven or eight replicates with compounds spiked at 

two concentrations ranging from 4 to 720 micrograms per sample in reagent-sand (including calculated method detection limits), riversediment, and topsoil samples.—Continued 

[μg , micrograms; μg/kg, micrograms per kilogram; RSD, relative standard deviation; MDL, method detection limit] 

Spike Mean recovery (percent) RSD (percent) Initial 

Compound name amount River River MDL 

(μg) Sand Topsoil Sand Topsoil sediment sediment (μg/kg) 

Tetrabromodiphenyl ether 4.0 

40 

79.6 

84.4 

79.0 

87.6 

83.5 

67.0 

4.29 

5.80 

9.88 

8.81 

6.60 

19.3 

19.1 

Tri(2-butoxyethyl)

 phosphate 

4.0 

40 

101 

87.9 

97.7 

87.8 

102 

89.3 

17.5 

2.35 

32.6 

3.74 

9.15 

1.01 

98.5 

Tri(2-chloroethyl) 

phosphate1 

4.0 

40 

49.4 

66.7 

39.3 

48.0 

39.3 

39.8 

25.4 

13.0 

20.8 

16.6 

59.7 

9.36 

70.3 

Tri(dichloroisopropyl) 

phosphate1 

4.0 

40 

47.0 

46.3 

48.1 

49.8 

66.6 

63.9 

27.8 

24.1 

22.3 

18.1 

30.6 

21.8 

73.0 

Tributyl phosphate 4.0 

40 

86.5 

86.9 

84.7 

91.0 

85.7 

87.9 

8.10 

3.59 

18.3 

4.11 

7.02 

4.50 

39.6 

Triclosan 4.0 

40 

82.9 

82.4 

70.9 

74.8 

86.6 

85.3 

10.7 

6.42 

12.2 

3.55 

13.1 

3.07 

49.6 

Triphenyl phosphate1 4.0 

40 

47.8 

49.0 

47.9 

49.0 

61.4 

64.6 

17.2 

18.4 

29.3 

16.5 

29.0 

16.1 

46.0 

Surrogate Compounds 

Fluoranthene-d10 8 

8 

83.4 

84.1 

92.5 

74.6 

85.0 

81.6 

4.42 

11.4 

6.00 

21.4 

3.80 

6.19 

Bisphenol A-d3 8 

8 

68.2 

56.8 

70.5 

44.1 

64.1 

60.7 

9.36 

7.43 

12.0 

9.71 

18.9 

6.67 

Decafluorobiphenyl 8 

8 

56.7 

65.7 

55.2 

44.8 

62.5 

66.6 

12.3 

11.7 

11.6 

9.78 

14.1 

11.4 

1

Concentration is estimated because recovery is less than 60 percent or precision is greater than 25 percent RSD. This can be caused by instrumental or 

extraction difficulties. 

2

Concentration is estimated because the reference standard is from a technical mixture. 

3

Concentration is estimated because of potential blank contamination unless concentration is greater than 10 times the 95th percentile of all blank 

concentrations. 

*

Percent recovery corrected for background concentration in the unfortified sample. 
 

 

 

 

4 Determination of Wastewater Compounds in Sediment and Soil 

Table 6. Wastewater method compounds that failed method acceptance criteria and are not included in this method. Mean bias and 

precision of spike recovery data for seven or eight replicates with compounds fortified at two concentrations ranging from 4 to 720 

micrograms per sample in reagent-sand, river-sediment, and topsoil samples. 

[μg, micrograms; RSD, relative standard deviation] 

Mean recovery (percent) RSD (percent) Spike 

Compound name amount River River Sand Topsoil Sand Topsoil (μg) sediment sediment 

5-Methyl-1H-benzotriazole 16 

160 

11.2 

8.80 

4.50 

8.01 

8.01 

5.76 

98.1 

10.3 

67.4 

12.8 

98.1 

16.4 

Caffeine 4.0 

40 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

Caffeine-13C3 8.0 

8.0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

Cotinine 4.0 

40 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

Triethyl citrate (ethyl citrate) 4.0 

40 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

0 

Carbaryl 4.0 

40 

4.98 

0.10 

8.23 

4.07 

25.7 

28.5 

106 

264 

89.1 

142 

186 

64.0 

Dichlorvos 4.0 

40 

0 

5.83 

0 

5.36 

0 

11.9 

0 

66.7 

0 

71.3 

0 

50.1 

Method detection limits (MDLs) and minimum reporting 

levels (MRLs)—The MDL is defined as the minimum concentration of a substance that can be measured and reported 

with 99-percent confidence that the compound concentration 

is greater than zero (U.S. Environmental Protection Agency, 

1997). Initial MDLs were determined according to the procedure outlined by the U.S. Environmental Protection Agency 

(1997), assuming a 25-g sample size. 

The MDL was calculated according to the equation 

(n–1, 1–α = 0.99) 

MDL = S × t

(n–1, 1–α = 0.99) (5) 

where 

S = standard deviation of replicate 

analyses, in microgram per 

kilogram, at the lowest spike 

concentration; 

n = number of replicate analyses; and 

t = Student’s t-value for the 99-percent 

confidence level with n–1 degrees of 

freedom. 

According to the USEPA procedure, at least seven 

replicate samples are fortified with compounds at concentrations of two to five times the estimated MDL. This concentration range was used to calculate initial MDLs for most of 

the compounds. However, initial MDLs for some method 

compounds were calculated by using concentrations higher 

than the desired spiking level so that the compound would be 

detected in each of the replicate reagent-sand samples. Initial 

MDLs that were calculated from this procedure for singlecomponent compounds ranged from 12.5 to 852 μg/kg. 

The initial minimum reporting levels (MRLs) have been 

set higher than the calculated initial MDLs (table 7). This 

precaution reduces the risk of reporting false positives in complex, varying matrices. All qualitatively identified compounds 

detected less than the MRL are reported as estimated with the 

“E” remark code, regardless of the established MRL, because 

the wastewater method is classified as an “information-rich” 

method, as are other MS methods (Childress and others, 

1999). 

Calculation of the MDL with data over a long time (6 

to 12 months), including results from a sufficient number 

(n >30) of samples to reflect multiple instruments, analysts, 

and calibration curves, is referred to as a long-term method 

detection level (LT–MDL or operational MDL) (Childress and 

others, 1999). The spiking solution at a concentration of 4 μg 

(in reagent sand) will be used routinely throughout the year 

to calculate LT–MDLs for the wastewater method. The initial 

MDLs and initial MRLs will be updated annually by using 

data acquired from the NWQL (Childress and others, 1999). 

Reconnaissance Study—Figure 2 shows the results from 

a small reconnaissance study of 103 sediment and soil samples 

collected during 2003 throughout the United States. The samples are a mixture of river sediments and soils, the majority 

from urban sampling sites. The number of detections is listed 
Results and Discussion of Method V alidation 25 

Table 7. Initial method detection limits for the wastewater method calculated from the precision data reported in table 5 using the 

eight replicate reagent-sand samples fortified with compound concentrations ranging from 4 to 72 micrograms. 

[μg, micrograms; μg/kg, micrograms per kilogram; RSD, relative standard deviation; MDL, method detection limit; MRL, minimum reporting level; “E” 

Coded, remark placed on compounds for recovery greater than 120 percent or less than 30 percent or RSD greater than 25 percent] 

Spike Mean RSD Initial MDL Initial MRL Compound name amount recovery (percent) (μg/kg) (μg/kg) (μg) (percent) 

1,4-Dichlorobenzene 4 70.1 7.0 27.6 50 

1-Methylnaphthalene 4 76.7 6.5 27.8 50 

2,6-Dimethylnaphthalene 4 75.7 5.9 24.8 50 

2-Methylnaphthalene 4 76.7 6.5 27.8 50 

3-beta-Coprostanol 16 106 15.2 360 500 

3-Methyl-1H-indole (skatol) 4 83.1 6.7 30.9 50 

3-tert-Butyl-4-hydroxyanisole (BHA) 4 79.0 22.9 101 100 

4-Cumylphenol 4 85.9 7.0 33.7 50 

4-n-Octylphenol 4 82.3 7.8 36.8 50 

4-tert-Octylphenol 4 85.3 4.8 22.9 50 

Acetyl-hexamethyl-tetrahydro- 4 76.8 3.8 16.5 50 

naphthalene (AHTN) 

Anthracene 4 78.1 4.5 19.8 50 

Anthraquinone 4 84.3 5.2 24.3 50 

Atrazine 4 74.7 13.7 58.9 100 

Benzo[a]pyrene 4 77.8 5.6 24.6 50 

Benzophenone 4 88.8 6.4 31.8 50 

beta-Sitosterol 16 97.4 16.7 363 500 

beta-Stigmastanol 16 96.1 17.1 367 500 

Camphor 4 79.1 6.1 27.0 50 

Carbazole 4 82.9 4.8 22.4 50 

Chlorpyrifos 4 60.4 9.9 33.6 50 

Cholesterol 16 99.3 7.6 168 250 

Diazinon 4 75.8 11.5 48.6 50 

Diethyl phthalate 4 58.2 14.3 46.7 100 

Diethylhexyl phthalate 4 153 16.1 138 250 

Fluoranthene 4 81.0 5.1 23.2 50 

Hexahydrohexamethyl-cyclo-pentabenzo- 4 78.0 2.9 12.5 50 

pyran (HHCB) 

Indole 4 82.0 11.7 53.5 50 

Isoborneol 4 86.5 8.1 39.3 50 

Menthol 4 88.4 8.5 42.0 50 

Metalaxyl 4 57.7 16.5 53.4 50 

Metolachlor 4 83.9 7.9 37.2 50 

Naphthalene 4 75.7 5.6 23.5 50 

para-Cresol 4 85.5 33.6 161 250 

Phenanthrene 4 78.2 4.7 20.7 50 

Prometon 4 74.7 10.6 44.2 50 
6 Determination of Wastewater Compounds in Sediment and Soil 

Table 7. Initial method detection limits for the wastewater method calculated from the precision data reported in table 5 using the 

eight replicate reagent-sand samples fortified with compound concentrations ranging from 4 to 72 micrograms.—Continued 

[μg, micrograms; μg/kg, micrograms per kilogram; RSD, relative standard deviation; MDL, method detection limit; MRL, minimum reporting level; “E” 

Coded, remark placed on compounds for recovery greater than 120 percent or less than 30 percent or RSD greater than 25 percent] 

Spike Mean RSD Initial MDL Initial MRL Compound name amount recovery (percent) (μg/kg) (μg/kg) (μg) (percent) 

Pyrene 4 73.3 5.0 20.6 50 

Tetrabromodiphenyl ether 4 79.6 4.3 19.1 50 

Tri(2-butoxyethyl) phosphate 4 101 17.5 98.5 100 

Tributyl phosphate 4 86.5 8.1 39.3 50 

Triclosan 4 82.9 10.7 49.6 50 

“E” Coded Compounds 

3,4-Dichlorophenyl isocyanate 4 43.3 24.9 60.4 100 

Acetophenone 4 45.0 40.0 100 100 

Bisphenol A 4 64.5 8.8 31.2 50 

Bromacil 16 62.8 20.7 254 500 

d-Limonene 4 65.7 6.5 23.7 50 

Isophorone 4 12.1 64.1 43.4 50 

Isopropylbenzene (cumene) 4 54.4 28.4 86.6 100 

Isoquinoline 4 59.5 25.0 83.1 100 

Methyl salicylate 4 13.4 47.7 35.8 50 

Nonylphenol, diethoxy- (total, 64 106 8.9 852 1,000 

NPEO2) 

Nonylphenol, monoethoxy- (total, 32 93.7 8.0 336 500 

NPEO1) 

Octylphenol, diethoxy-(OPEO2) 28 103 9.6 38.5 50 

Octylphenol, monoethoxy-(OPEO1) 28 86.6 6.5 219 250 

N,N-Diethyl-meta-toluamide(Deet) 4 76.3 13.2 56.2 50 

para-Nonylphenol (total) 72 79.4 6.2 498 500 

Pentachlorophenol 16 52.7 44.1 520 500 

Phenol 4 20.9 32.8 38.3 50 

Tri(2-chloroethyl) phosphate 4 49.4 25.4 70.3 100 

Tri(dichloroisopropyl) phosphate 4 47.0 27.8 73.0 100 

Triphenyl phosphate 4 47.8 17.2 46.0 50 
Units

CC

 

Results and Discussion of Method V alidation 27 

1 

10 

100 

1000 

1E4 

1E5 

1E6 

1,4-dichlorobenzene (6) 1-methylnapthalene (11) 2,6-dimethylnapthalene (40) 2-methylnapthalene (18) 4-cumylph

enol (5)

4-tert-octylph

enol (8)

acetoph

enone (8) anthracene (53) anthraquinone (48) benzo(a)pyrene (60) benzoph

enone (4) beta-sitosterol (87) bisph

enol A (20)

ca

mphor (1) carbazole (39) cholesterol (47) d-limonene (12) tri(2-butoxyethyl) pho

sphate (6) fluoranthene (60) tonalide (

A

H

T

N) (41) indole (47) isophorone (1) menthol (2)

naphthalene (43)

NPEO2-total (16)

para-cresol (34)

para-nonylph

enol-total (25) phenanthrene (61) ph

enol (57) pyrene (62) 3-methyl-1H-indole (skatol) (75) beta-stigmastanol (63) galaxolide (HHCB) (19) tri(2-chloroethyl)pho

sphate (3) triclosan (27) triphenyl pho

sphate (1) 

CONCENTRATION,

MICROGRAMS PER KILOGRAM 

COMPOUND (NUMBER OF DETECTIONS) 

EXPLANATION 

90th 

PERCENTILE 

75th 

50th 

25th 

O 

10th 

DATA 

POINT 

Figure 2. Analysis of 103 environmental sediment and soil samples. The concentration axis is in log scale to accommodate the large 

concentration ranges for the compounds of interest. The number of compound detections is listed after each compound name. 
 

8 Determination of Wastewater Compounds in Sediment and Soil 

after the compound name. The data are reported using a log 

scale to accommodate the large concentration ranges for each 

compound. The results (concentration ranges and detection 

frequencies) demonstrate the ability of the described method 

to determine the compound classes of interest in various sediment and soil types. 

One or more of the compounds in the method were 

found in 90 percent of the samples. This high frequency is 

caused, in part, by samples being collected primarily in urban 

environments. In addition, some of the compounds have 

natural sources, such as the plant sterols beta-sitosterol and 

beta-stigmastanol. The results presented are not necessarily 

representative of all sediments in the United States, but they 

do demonstrate the ability of the described method to measure 

concentrations of compounds of interest in environmental 

sediment and soil samples. 

Thirty-six of 61 compounds of interest were detected in 

at least one environmental sample. The 36 must frequently 

detected compounds represent a wide variety of chemical 

classes and uses. Figure 2 shows the number of detections 

and the concentration ranges for the compounds of interest. 

Again, naturally present compounds as well as anthropogenicsourced compounds are represented. Many of the detected 

compounds are recognized endocrine disruptors (alkylphenols, 

alkylphenols polyethoxlates, bisphenol A), whereas others, 

such as the fragrances, flame retardants, and fecal steroids, are 

excellent indicators of wastewater. 

Summary and Conclusions 

The U.S. Geological Survey (USGS) National Water 

Quality Laboratory has developed an analytical method for the 

determination of 61 compounds in environmental sediment 

and soil samples. This method provides an efficient means 

of detecting important toxic and estrogenic compounds that 

otherwise might not be reported because they are unregulated 

or not included in other USGS or U.S. Environmental Protection Agency methods. Sediment samples are collected and 

the compounds of interest are isolated by pressurized solvent 

extraction, solid-phase isolation, and are determined by capillary-column gas chromatography/mass spectrometry (GC/ 

MS). The method focuses on the determination of compounds 

indicative of wastewater. The compounds were chosen on the 

basis of potential toxicity or endocrine disruption. Analysis of 

the alkylphenol ethoxylate nonionic surfactant compounds is 

particularly important because they are persistent indicators 

of wastewater. Other method compounds are representative 

of fragrances, food additives, antioxidants, phosphate flame 

retardants, plasticizers, industrial solvents, disinfectants, 

fecal sterols, polycyclic aromatic hydrocarbons, and high-use 

domestic pesticides. 

Average recovery of all method compounds for shortterm single-operator results from reagent-sand samples fortified at 4 to72 micrograms was 76 ±13 percent relative standard 

deviation. Initial method detection limits for single-component 

compounds ranged from 12.5 to 852 micrograms per kilogram. 

There are advantages for the analytical laboratory as well 

as the data user by adopting this new method. For the laboratory, (1) short overall sample-extraction times and (2) the use 

of less organic solvent than for previous methods will reduce 

cost and work-place exposure. Data users, on the other hand, 

(3) will gain clean sample extracts, allowing for improved 

method detection limits; (4) will be able to monitor several 

classes of compounds with varied endocrine-disruption potential; and (5) will benefit from demonstrated low bias and high 

precision. 

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Glossary  

Glossary 

Continuing calibration verification (CCV) 

A standard solution that contains method 

compounds and is used to determine the bias 

of the present calibration curve for the method 

compounds. The CCV is an instrumental 

standard only and is not processed through 

preparative steps of the method. 

Internal standard (IS) 

A compound not expected to be found in 

any environmental sample that is added to 

every sample extract in a known amount. The 

internal standard is used to measure the relative gas chromatographic/mass spectrometric 

(GC/MS) responses of other compounds and 

surrogates in each sample. 

Long-term method detection level (LT–MDL) 

The minimum concentration of a substance 

that can be identified, measured, and reported 

with 99-percent confidence that the compound concentration is greater than zero. The 

LT–MDL is calculated from replicate analyses of samples fortified with all the method 

compounds, and includes precision introduced 

by multiple instruments, multiple analysts, 

and multiple calibrations from 6 to 12 months 

(Childress and others, 1999). 

Method detection limit (MDL) 

The minimum concentration of a substance 

that can be measured and reported with 

99-percent confidence that the compound 

concentration is greater than zero (U.S. 

Environmental Protection Agency, 1997). 

The MDL is calculated from at least seven 

replicate analyses of samples fortified with 

all the method compounds. The MDL is used 

to establish initial minimum reporting levels, 

until the long-term method detection level can 

be calculated to include day-to-day precision. 

Minimum reporting level (MRL) 

The lowest measured concentration of a compound that may be reliably reported by using 

a given analytical method (Timme, 1995). 

Surrogate 

A compound not expected to be found in any 

environmental sample that is added to every 

sample in a known amount prior to sample 

processing. The surrogate is used to monitor 

method performance for each sample. 
 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Manuscript approved for publication May 25, 2005. 

Prepared by the Publishing Group, U.S. Geological Survey, 

National Water Quality Laboratory, Denver, Colorado 

USGS Publishing Staff: 

Edited by Jon W. Raese 

Additional evaluation and approval by Keith L. Lucey 

Cover designed by Suzanne C. Roberts 

Report prepared by Barbara L. Kemp 

Technical Reviews: 

Duane S. Wydoski, USGS, National Water Quality Laboratory 

Michael P. Schroeder, USGS, National Water Quality Laboratory 

James A. Lewis, USGS, National Water Quality Laboratory 

Peter F. Rogerson, USGS, Office of Water Quality 

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

National Water Quality Laboratory 

U.S. Geological Survey 

P.O. Box 25046, MS 407 


Denver Federal Center 


Denver, Colorado 80225-0046 


http://nwql.cr.usgs.gov
 
—

 

Burkhardt and others—Determination of Wastewater Compounds in Sediment and Soil Techniques and Methods 5–B2 

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