Quality assurance project plan (QAPP) remedial investigation ... · Revision No.: 0 Date: 1/12/88 Page: 2 2.0 PROJECT DESCRIPTION The RI/FS is designed to gather the specific information

SFUND RECORDS CTR

88014850

SFUND RECORDS CTR

V 0222-p0282____

January 29, 1988 A R O S I ?

QUALITY ASSURANCE PROJECT PLAN (QAPP) REMEDIAL INVESTIGATION/FEASIBILITY STUDY

HAZARDOUS HASTE AREA, HASSAYAMPA LANDFILL SITE MARICOPA COUNTY, ARIZONA

ERROL L. MONTGOMERY & ASSOCIATES, INC. CONSULTANTS IN HYDROGEOIOGY

1075 EAST FORT LOWELL ROAD, SUITE B

TUCSON, ARIZONA 85719 (602)881-4912

TELEX: 165597 MONTE TUC

Consulting Engineers

CONESTOGA-ROVERS & ASSOCIATES 382 WEST COUNTY ROAD D

ST. PAUL, MINNESOTA 55112

TELEPHONE (612)639-0913

HfiSSflYflMPfi LANDFILL 4410044

I

I E January 29, 1988

QUALITY ASSURANCE PROJECT PLAN (QAPP) REMEDIAL INVESTIGATION/FEASIBILITY STUDY

HAZARDOUS WASTE AREA, HASSAYAMPA LANDFILL SITE MARICOPA COUNTY, ARIZONA

I I

I I

I

I B

I B

B QUALITY ASSURANCE PROJECT PLAN (QAPP)

• REMEDIAL INVESTIGATION/FEASIBILITY STUDY

HAZARDOUS WASTE AREA, HASSAYAMPA LANDFILL SITE

MARICOPA COUNTY, ARIZONA

B

B January 1988 2141

B

TABLE OF CONTENTS

Page

1.0 INTRODUCTION 1

2.0 PROJECT DESCRIPTION 2

2.1 BACKGROUND 2

2.2 PREVIOUS INVESTIGATIONS 6

2.2.1 Investigations Prior to Formation of

Hassayampa Steering Committee 5

2.2.2 Investigation After Formation of

Hassayampa Steering Committee 7

2.3 SITE HYDROGEOLOGIC CONDITIONS 7

2.4 PROJECT OBJECTIVES 9

2.5 SCHEDULE 10

2.6 DATA USAGE 10

2.7 SAMPLING NETWORK DESIGN 11

2.8 SAMPLE MATRICES/PARAMETERS/FREQUENCY 11

3.0 PROJECT ORGANIZATION AND RESPONSIBILITY 13

4.0 QUALITY ASSURANCE OBJECTIVES FOR MEASUREMENT DATA 16

4.1 ANALYTICAL METHODS 16

4.2 DETECTION LIMIT REQUIREMENTS 17

4.3 LEVEL OF QA EFFORT 17

4.4 ACCURACY, PRECISION AND SENSITIVITY OF ANALYSES 20

4.5 COMPLETENESS, REPRESENTATIVENESS AND COMPARABILIT 20

4.6 FIELD MEASUREMENTS 22

5.0 SAMPLING PROCEDURES 23

6.0 SAMPLE CUSTODY 24

TABLE OF CONTENTS

7 . 0 CALIBRATION PROCEDURES AND FREQUENCY

Page

27

8.0 ANALYTICAL PROCEDURES 28

9 . 0 DATA REDUCTION, VALIDATION, ASSESSMENT, AND REPORTING 30

1 0 . 0 INTERNAL QUALITY CONTROL PROCEDURES 34

11.0 SYSTEMS AUDITS 35

12.0 PREVENTIVE MAINTENANCE 36

13.0 CORRECTIVE ACTION PROCEDURES 37

14.0 QA REPORTS 38

LIST OF FIGURES

FIGURE 1 REGIONAL LOCATION MAP

Following Page

FIGURE 2 SITE LOCATION MAP enclosed

FIGURE 3 SCHEMATIC DIAGRAM OF DISPOSAL PIT LOCATIONS IN HAZARDOUS WASTE AREA

FIGURE 4 QAPP ORGANIZATIONAL CHART 13

LIST OF TABLES

TABLE 1 SUMMARY OF WASTES DISPOSED

TABLE 2 ANALYTICAL METHODS AND DETECTION LIMITS FOR HAZARDOUS SUBSTANCES 16

TABLE 3 ANALYTICAL METHODS FOR GENERAL WATER QUALITY PARAMETERS 17

TABLE 4 QUALITY ASSURANCE OBJECTIVES FOR WATER AND SOIL 20

LIST OF ATTACHMENTS

ATTACHMENT 1 PRIORITY POLLUTANT COMPOUNDS/HAZARDOUS SUBSTANCE LIST COMPOUNDS

ATTACHMENT 2 ADDITIONAL WATER QUALITY PARAMETERS

ATTACHMENT 3 LABORATORY FACILITIES

ATTACHMENT 4 SAMPLING PLAN

ATTACHMENT 5 HYDROCARBON CHARACTERIZATION (MODIFIED 8015)

ATTACHMENT 6 ANALYTICAL METHODS FOR ANALYSIS OF AIR SAMPLES

Project Title: Prepared by:

Hazardous Waste Area - Hassayampa Landfill Errol L. Montgomery and Associates, Inc. Conestoga-Rovers & Associates Limited

Approved by: Date: Project Manager E.L. Montgomery

Approved by: Date Quality Assurance/Quality Control Coordinator L.G. Strauss

Approved by; Date: Analytical Project Manager G. McCullough

Approved by: Date: USEPA Quality Assurance Officer

Approved by: Date! USEPA Remedial Project Manager J. Dunn

Revision No.: 0 Date: 1/12/88 Page: 1

1.0 INTRODUCTION

This Quality Assurance Project Plan (QAPP)

gives the organization, objectives, functional activities,

and specific Quality Assurance (QA) and Quality Control (QC)

activities designed to achieve the specific data quality

goals associated with the Hazardous Waste Area Remedial

Investigation/Feasibility Study (Rl/FS), Hassayampa Landfill

(the Site).


2.0 PROJECT DESCRIPTION

The RI/FS is designed to gather the specific

information necessary to evaluate the potential impacts on

the quality of air, surface water and groundwater, and on

public health, from the former hazardous waste disposal pits

located in the northeast corner of the Hassayampa Landfill.

2.1 BACKGROUND

Figure 1 is a regional location map for the

Hassayampa Landfill (the Landfill). Figure 2 (included in a

pocket at the back of this QAPP) shows the area presently

designated for the Rl/FS together with the disposal pit

locations. The Landfill is located in the southeast quarter

of Section 3, Township 1 South, Range 5 West, Maricopa

County, Arizona.

, The Landfill was designated Arizona's interim

hazardous waste disposal facility for a period of

approximately 18 months, from April 20, 1979 to October 28,

1980. During this period, disposal of hazardous wastes in

the northeast part of the Landfill was authorized by Arizona

Department of Health Services and by Maricopa County via a

manifest program. Waste generators submitted the manifests

for approval by Arizona Department of Health Services for

R.5 W R.4 W.

FIGURE I. REGIONAL LOCATION MAP


specified wastes. Waste haulers submitted the approved

manifests to Landfill personnel at the time of disposal. The

approved manifests were subsequently returned to Arizona

Department of Health Services. Compilations of these

manifests were reported by Arizona Department of Health

Services (1982 and 1985). These manifests indicate that a

wide range of hazardous wastes, including about 3.28 million

gallons of liquid wastes and about 4,150 tons of solid

wastes, were disposed in Pits 1, 2, 3 and 4, and in Special

Pits. Types and quantities of wastes disposed in these pits

are summarized in Table 1.

Two additional pits, Pits A and B, in the

hazardous waste area were intended for disposal of

non-hazardous wastes. Pits A and B were not included in the

hazardous waste manifest program. Cesspool waste and septic

tank waste are the principle wastes reported to have been

disposed in Pit A (Ecology and Environment, Inc., 1981).

Although the waste disposed in Pit B has not been fully

determined, hydrate waste is reported to have been disposed

in Pit B (Ecology and Environment, Inc., 1981).

The approximate former area of hazardous

waste disposal and the general location of Pits 1, 2, 3, 4, A

and B, and Special Pit areas, were determined from:

Revision No.: 0 Date: 7/8/87 Page: 3.1

TABLE 1

SUMMARY OF WASTES DISPOSED HASSAYAMPA LANDFILL MARICOPA COUNTY, ARIZONA

(MODIFIED FROM ARIZONA DEPARTMENT OF HEALTH SERVICES, 1985)

PIT

Special Pit

Pit 1

Pit 2

Pit 3

Pit 4

WASTE TYPE

Incompatible Hazardous Waste

Organics & Oils

Acids & Acid Sludges

Alkaline & Metallic Sludges

Pesticides & Alkaline Sludges

TOTAL

QUANTITY Liquid Waste

(gallons)

134,578

360,805

125,597

1,362,636

1,295,022.2

3,278,638.25

3

4

Solid Waste (tons)

308.64

0

0.1

24.5

,816.46

,149.7


. Inspection of aerial photos for the Landfill for 1976,

1979, 1981, 1982, 1985 and 1986;

. Inspection of a hand-drawn sketch of the former hazardous

waste disposal area given by Ecology and Environment, Inc.

(1981), which was based on results of a Site inspection on

January 15, 1981; and

. Interviews with Maricopa County Landfill Department

personnel.

Results of these investigations indicate that the former area

of hazardous waste disposal encompassed an area of

approximately 10 acres in the northeast part of the

Landfill.

Figure 2 (included in a pocket at the back of

this QAPP) shows the 10-acre area presently designated for

the Remedial Investigation, together with disposal pit

locations. The area that is presently fenced and posted as

the hazardous waste area is shown on Figure 2 and comprises

about 8 1/2 acres. The entire area used for the Landfill

operations is shown on Figure 2, and comprises about

47 acres. The base for Figure 2 is an aerial photo of the

Landfill taken on January 26, 1981, 11 days after the Site

inspection by Ecology and Environment, Inc. Figure 3 is a

sketch of the Landfill area prepared by Ecology and

HcAtr •ior- U i i f * 3Aa*d i&«f>K VJA^^V

&lu<l3e.

»9b l

FIGURE 3 SCHEMATIC DIAGRAM OF DISPOSAL PIT LOCATIONS IN HAZARDOUS WASTE AREA, HASSAYAMPA LANDFILL ( FROM ECOLOGY AND ENVIRONMENT, INC., 1981)


Environment, Inc. from a Site inspection conducted

January 15, 1981.

Inspection of Figures 2 and 3 indicates that

the Ecology and Environment, Inc. sketch (Figure 3) is

problematic due to the following:

. No scale is shown.

. North arrow points to northeast.

. Although the entire area of the Landfill operations if

about 47 acres, the sketch shows two 15-acre areas

southeast from the hazardous waste area.

. Relative sizes of the 80-foot long "special pits area",

shown south of Pit 4 on the sketch, and the "15"-acre

"special pits area" shown to the east suggests that the

"15" acres may actually be 1.5 acres.

. Interviews with Maricopa County Landfill personnel, who

worked at the Site during the 18-month disposal period,

indicate that areas south from the present fenced hazardous

waste area were used solely for disposal of sanitary waste.

These personnel also indicate that the present south fence

line of the hazardous waste area lies about 75 feet south

from any of the former hazardous waste disposal pits.


2.2 PREVIOUS INVESTIGATIONS

Results of previous investigations for the

Hassayampa Landfill are sources of information for

hydrogeologic conditions, historic disposal practices,

disposal pit locations, types of substances disposed, and for

locations of off-Site and on-Site wells. Results of previous

investigations for the Landfill include, in chronological

order:

2.2.1 Investigations Prior to Formation of Hassayampa Steering Committee

. Hydrogeologic Conditions and Waste Disposal at the Hassayampa, Casa Grande and Somerton Landfills, Arizona. Report prepared by Kenneth D. Schmidt and Robert C. Scott for Arizona Department of Health Services, Dated January 1977.

. Site Inspection Report on Hassayampa Landfill, Hassayampa, Arizona. Prepared by Ecology and Environment, Inc. for U.S. Environmental Protection Agency, dated February 10, 1981.

. Arizona Department of Health Services inter-office memorandum, dated October 27, 1981, from Bob Hollander to Tibaldo Canez. Re: Alternatives and cost estimates for completion of monitoring wells at the Hassayampa Landfill.

. Letter, dated November 19, 1981, from James Angell, Arizona Department of Health Services, to William Wood, City of Phoenix Engineering Department. Re: Monitoring well specifications.

. Geotechnical Evaluation of the Influence of Hassayampa Landfill Hazardous Wastes on the PVNGS Conveyance Pipeline. Report prepared by Ertec Western, Inc. for Arizona Nuclear Power Project and NUS Corporation, dated March 17, 1982.


. Open Dump Inventory of Hassayampa Landfill, Ground Water Criterion. Report prepared by Arizona Department of Health Services, dated September 1982.

. "Site Inspection and Sampling Documentation Report, Hassayampa Landfill". Prepared by Ecology and Environment Inc. for U.S. Environmental Protection Agency, dated August 5, 1983.

. Hassayampa Landfill Site Inspection Report. Prepared by Arizona Department of Health Services, dated May 1, 1985.

. Study of Waterlogging Problems in the West Salt River and Hassayampa Sub-Basins of the Phoenix Active Management Area: Task IA - Evaluation of Past Hydrogeologic Conditions. Report prepared by Montgomery & Associates for Arizona Department of Water Resources, dated August 25, 1986.

2.2.2 Investigation After Formation of Hassayampa Steering Committee

. Results of Preliminary Hydrogeologic Investigations, Hassayampa Landfill, Maricopa County, Arizona. Memorandum Report prepared by Montgomery & Associates for the Hassayampa Steering Committee, dated April 22, 1987.

2.3 SITE HYDROGEOLOGIC CONDITIONS

On-site monitor wells (C-1-5)3daa[HS-l],

(C-1-5)3dac[HS-2], and (C-1-5)3ddal[HS-3] were constructed by

Arizona Department of Health Services. Lithologic

descriptions (Arizona Department of Health Services, 1985)

for drill cuttings obtained during drilling of these monitor

wells indicate that basin-fill deposits were penetrated by


the monitor wells. These basin-fill deposits may be

classified, in order of increasing depth, as follows:

a. Upper alluvial deposits unit: consists chiefly of

clayey, silty, or gravelly sand, with some interbedded

silty clay and clayey sand; thickness ranges from 39 to

55 feet.

b. Basalt/fanglomerate unit: reported to consist chiefly of

interbedded black basaltic lava-flow rocks and coarse

alluvial deposits; top of the unit was penetrated at

depths ranging from 39 to 55 feet; thickness ranges from

13 to 29 feet.

c. Unit A (sandy silt/silty clay unit); reported to consist

chiefly of interbedded sandy silt and silty clay with

thin sand/gravel layers; top of the unit was penetrated

at depths of 67 and 68 feet; thickness ranges from 33 to

44 feet; water table and uppermost saturated zone occurs

in Unit A at the site.

d. Unit B (gravelly sand unit): reported to consist chiefly

of silty, gravelly sand; top of the unit was penetrated

at depths ranging from 101 to 111 feet; thickness is

projected to be about 130 feet; Unit B is saturated at

the site.


On April 1, 1987, water levels were measured

by Montgomery & Associates and altitude and location of

measuring points were surveyed for monitor wells

(C-l-5)3daa[HS-l], (C-1-5)3dac[HS-2], and (C-1-5)3ddal[HS-3].

Analyses of results indicate that direction of groundwater

flow in the uppermost groundwater zone of Unit A (sandy

silt/silty clay unit) is to the southwest; average hydraulic

gradient is about 0.005, or about 26 feet per mile. This

direction of groundwater movement is similar to directions

cited in previous investigations for the Landfill, and to the

direction given by Montgomery & Associates (1986) for the

Hassayampa area. Comparison of water level contour maps and

water level change maps prepared by Stulik and Laney (1976)

with recent water level contour maps and water level change

maps prepared by Montgomery & Associates for the Hassayampa

region indicates that groundwater levels and direction of

groundwater movement in the Landfill area have been

relatively constant for several years.

2.4 PROJECT OBJECTIVES

The objective of the Remedial Investigation

(RI) is to identify and define potential impacts to air,

surface water, sediment, soil and groundwater quality, and to

public health which may have resulted from the disposal of

hazardous wastes at the Site.


The objective of the Feasibility Study (FS)

is to evaluate remedial requirements and alternatives, and to

recommend a remedial action.

2.5 SCHEDULE

The tentative schedule for conduct of the

Rl/FS and estimated project timing are given in the RI Work

Plan.

2.6 DATA USAGE

Data will be used to;

(i) identify and define impacts to surface sediment

within drainage paths from the Site,

(ii) identify and define the extent of subsurface soil

contamination within the vicinity of the Site,

(iii) identity and define the extent of groundwater

contamination from the Site,

(iv) evaluate risks to public health and impacts to the

environment, and

(v) provide data to scope remedial alternatives.


2.7 SAMPLING NETWORK DESIGN

The sampling network consists of:

- subsurface soil intervals surrounding the Site,

- air at monitoring stations at the Site,

- sediment from surface water drainage courses from the Site,

and

- groundwater downgradient of the Site accessed through

monitoring wells.

The Rl/FS Work Plan provides specific details

on sampling locations.

2.8 SAMPLE MATRICES/PARAMETERS/FREQUENCY

Sample matrices include:

- sediment from drainage channels,

- organic vapors adsorbed on charcoal filters,

- subsurface soil, and

- groundwater.

The parameters to be analyzed for the

evaluation of impacts from hazardous waste disposal include

volatile organic compounds, base/neutral and acid compounds.


pesticide compounds, PCBs, cyanide, and metals. These

parameters are listed on Attachment 1.

Additionally, parameters to assess general

water quality will be included as listed on Attachment 2.

Laboratory facilities are described in Attachment 3.

Sample collection frequency will be conducted

in accordance with the Rl/FS Work Plan. To summarize:

- subsurface soil samples will be collected once,

- air samples will be collected once,

- surface sediment samples will be collected once, and

- groundwater samples will be collected a minimum of four

times.


3.0 PROJECT ORGANIZATION AND RESPONSIBILITY

3.1 OPERATIONAL/LABORATORY/QA RESPONSIBILITIES

Figure 4 presents the organizational chart

for the RI/FS Project. In addition, the functional

responsibilities of each of the key technical personnel

listed below.

E.L. Montgomery - Project Manager

- corporate quality control and quality assurance

- managerial guidance to technical group

- technical representation at meetings

- liaison between technical group and

Hassayampa Steering Committee

- report preparation and review

L.J. Strauss - QA/QC Coordinator

- system audits of laboratory

- overview and review of field and Laboratory QA/QC

- data validation and assessment

- advise on data corrective action procedures

- review of tentatively identified compounds

- QA/QC representation of project activities

PROJECT MANAGER E. MONTGOMERY

TECHNICAL SUPPORT HYDROGEOLOGY W. VICTOR TOXICOLOGY P. NEES FEASIBIUTY AND REMEDIAL CONSTRUCTION R.G. SHEPHERD

QA/QC COORDINATOR L STRAUSS

PROJECT MANAGER LABORATORY ACTIVITIES

G. McCULLOUGH

HELD STAFF W. VICTOR J. KEAY

E. PEACOCK R. DALTON J. DAVIS

M. GREENE

QA OFRCER LABORATORY ACTIVITIES

L DAVIS

TECHNICAL DIRECTORS LABORATORY ACTIVITIES

M. BARRY J. HUMPHRESS

8. PROFFITT

CRA

figure 4 QAPP ORGANIZATION Hassayampa Landftll

2 1 4 1 - 2 9 / 0 7 / 8 7 - 1 - D - 1


W.R. Victor - Hydrogeologist

- hydrogeologic interpretation

- technical representation at meetings

- report preparation and review

- coordinate field activities

- inspect installation of monitoring wells

- assisted by field technicians

- project specific orientation and supervision

of sampling personnel

- ensure that chain-of-custody implemented in field

- hydrogeologic interpretation

- report preparation

Dr. P. Nees - Toxicology

- provide input on data requirements for risk assessment

- conduct review of USEPA risk assessment

- data interpretation

- report preparation

- technical representation

R.G. Shepherd - Construction

- provide input on data requirements to scope remedial

alternatives

- data interpretation


L. Davis - Quality Assurance Officer - Laboratory

- Periodic review and inspection of all laboratory activities

as independent Quality Assurance Unit officer

R.G. McCullough - Project Manager - Laboratory

- corporate technical review of laboratory requisites, study

design, and data review

- managerial guidance to laboratory technical groups

Primary responsibility for project quality

rests with the Project Manager. The responsiblity for

obtaining a validated data base rests with the QA/QC

Coordinator. Independent quality assurance is provided by

the laboratory QA officer, and appropriate Section

Supervisors. All of these people report to the Project

Manager.


4.0 QUALITY ASSURANCE OBJECTIVES FOR MEASUREMENT DATA

The overall QA objective is to develop and

implement procedures for field sampling, chain-of-custody,

laboratory analysis and reporting that will provide accurate

data and legally defensible results in a court of law.

Specific procedures to be used for sampling,

chain-of-custody, calibration, laboratory analysis,

reporting, quality control, audits, preventative maintenance

and corrective actions are given in other sections of this

QAPP.

The purpose of this section is to define

goals for the level of QA effort (accuracy, precision and

sensitivity of analyses), and completeness,

representativeness, and comparability of measurement data

from the analytical laboratories. QA objectives for field

measurements are also discussed.

4.1 ANALYTICAL METHODS

Table 2 summarizes the analytical methods to

be utilized for analysis of water and soil/sediment samples

for hazardous substances.


TABLE 2

ANALYTICAL METHODS AND DETECTION LIMITS FOR HAZARDOUS SUBSTANCES

VOLATILE COMPOUNDS

CAS No.

74-87-3 74-83-9 75-01-4 75-00-3 75-09-2 67-64-1 75-15-0 75-35-4 75-35-3 156-60-5 67-66-3 107-06-2 78-93-3 71-55-6 56-23-5 108-05-4 75-27-4 78-87-5 10061-02-6 79-01-6 71-43-2 124-48-1 79-00-5 10061-01-05 75-25-2 591-78-6 127-18-4 79-34-5 108-88-3 108-90-7 100-41-4 108-10-1 108-42-5 1330-20-7

HSL Compound

chloromethane bromomethane vinyl chloride chloroethane methylene chloride acetone carbon disulfide 1,1-dichloroethene 1,1-dichloroethane trans-1,2-dichloroethene chloroform 1,2-dichloroethane 2-butemone 1,1,1-trichloroethane carbon tetrachloride vinyl acetate bromodichloromethane 1,2-dichloropropane trans-1,3-dichloropropene trichloroethene benzene dibromochloromethane 1,1,2-trichloroethane cis-1,3-dichloropropene bromoform 2-hexcinone tetrachloroethene 1,1,2,2-tetrachloroethame toluene chlorobenzene ethylbenzene 4-methyl-2-pentanone styrene total xylenes

USEPA Method Reference

Water

624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624 624

Soil

8240 8240 8240 8240 8240 8240 8240 8240 8240 8240 8240 8240 8240 8240 8240 8240 8240 8240 8240 8240 8240 8240 8240 8240 8240 8240 8240 8240 8240 8240 8240 8240 8240 8240

Target Detection Limits*

Low Water (ug/L)

10 10 10 10 5 10 5 5 5 5 5 5 10 5 5 10 5 5 5 5 5 5 5 5 5 10 5 5 5 5 5 10 5 5

Low Soil/Sediment

(ug/kg)

10 10 10 10 5 10 5 5 5 5 5 5 10 5 5 10 5 5 5 5 5 5 5 5 5 10 5 5 5 5 5 10 5 5

continued....


TABLE 2


BASE/NEUTRAL ACID COMPOUNDS

CAS No.

111-44-4 108-95-2 95-57-8 541-73-1 106-46-7 95-50-1 100-51-6 39638-32-9 95-48-7 67-72-1 621-64-7 98-95-3 106-44-5 78-59-1 88-75-5 105-67-9 111-91-1 120-83-2 120-82-1 91-20-3 106-47-8 87-68-3 65-85-0 91-57-6 59-50-7 77-47-4 95-95-4 88-06-2 91-58-7 208-96-8 131-11-3 606-20-2 83-32-9 99-09-2 132-64-9

HSL Compound

bis(2-chloroethyl) ether phenol 2-chlorophenol 1,3-dichlorobenzene 1 ,4-dichlorobenzene 1 ,2-dichlorobenzene benzyl alcohol


Water

625 625 625 625 625 625 625

bis (2-chloroisopropyl) ether 625 2-methylphenol hexachloroethane N-nitrosodi-dipropylamine nitrobenzene 4-methylphenol isophorone 2-nitrophenol 2,4-dimethylphenol bis (2-chloroethoxy) methane 2,4-dichlorophenol 1,2,4-trichlorobenzene naphthalene 4-chloroaniline hexachlorobutadiene benzoic acid 2-methylnaphthalene p-chloro-m-cresol hexachlorocyclopentadiene 2,4,5-trichlorophenol 2,4,6-trichlorophenol 2-chloronaphthalene acenaphthylene dimethyl phthalate 2,6-dinitrotoluene acenaphthene 3-nitroaniline dibenzofuran

625 625 625 625 625 625 625 625 625 625 625 625 625 625 625 625 625 625 625 625 625 625 625 625 625 625 625

Soil

8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270


Low Water (ug/L)

10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 50 10 10 10 50 10 10 10 10 10 10 50 10

Low Soil/Sediment

(ug/kg)

400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 2000 400 400 400 2000 400 400 400 400 400 400 2000 400

continued....


TABLE 2


BASE/NEUTRAL ACID COMPOUNDS (continued)

CAS No.

51-28-5 121-14-2 86-73-7 100-02-7 7005-72-3 84-66-2 534-52-1 86-30-6

100-01-6 101-55-3 118-74-1 87-86-5 85-01-8 120-12-7 84-74-2 206-44-0 129-00-0 85-68-7 218-01-9 56-55-3 117-81-7 117-84-0 205-99-2 207-08-9 50-32-8 193-39-5 53-70-3 191-24-2 91-94-1 88-74-4

HSL Compound

2,4-dinitrophenol 2,4-dinitrotoluene fluorene 4-nitrophenol 4-chlorophenyl phenyl ether diethyl phthalate 4,6-dinitro-2-methylphenol N-nitrosodiphenylamine (diphenylamine) 4-nitroaniline 4-bromophenyl phenyl ether hexachlorobenzene pentachlorophenol phenanthrene anthracene di-n-butyl phthalate fluorcinthene pyrene butyl benzyl phthalate chrysene benzo(a)anthracene


Water

625 625 625 625 625 625 625

625 625 625 625 625 625 625 625 625 625 625 625 625

bis (2-ethylhexyl) phthalate 625 di-n-octyl phthalate benzo (b) fluorcinthene benzo (k) fluorcinthene benzo(a)pyrene indeno(1,2,3-cd)pyrene dibenz(a,h)anthracene benzo(g,h,i)perylene 3,3'-dichlorobenzidine 2-nitroaniline

625 625 625 625 625 625 625 625 625

Soil

8270 8270 8270 8270 8270 8270 8270

8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270 8270


Low Water (ug/L)

50 10 10 50 10 10 50

10 50 10 10 50 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 50

Low Soil/Sediment

(ug/kg)

2000 400 400 2000 400 400 2000

400 2000 400 400 2000 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 2000

continued....

Revision No.: 0 Date: l / % / ^ l Page: 16.4

TABLE 2


PESTICIDES AND PCBs

CAS NO.

319-84-6 58-89-9 319-85-7 319-86-8 76-44-8 309-00-2 1024-57-3 959-98-8 72-54-8 7421-93-4 1031-07-8 60-57-1 72-20-8 50-29-3 33213-65-9 72-55-9 57-74-9 8001-35-2 72-43-5 12674-11-2 11104-28-2 11141-16-5 53469-21-9 12672-29-6 11097-69-1 11096-82-5

HSL Compound

alpha-BHC gamma-BHC (Lindane) beta-BHC delta-BHC heptachlor aldrin heptachlor expoxide endosulfan I 4,4'-DDD endrin aldehyde endosulfan sulfate dieldrin endrin 4,4'-DDT endosulfan II 4,4'-DDE chlordane toxaphene methoxychlor aroclor 1016 aroclor 1221 juroclor 1232 aroclor 1242 aroclor 1248 aroclor 1254 aroclor 1260

USEPA 1 Refer-

Water

608 608 608 608 608 608 608 608 608 608 608 608 608 608 608 608 608 608 608 608 608 608 608 608 608 608

Method ence

Soil

8080 8080 8080 8080 8080 8080 8080 8080 8080 8080 8080 8080 8080 8080 8080 8080 8080 8080 8080 8080 8080 8080 8080 8080 8080 8080


Low Water (ug/L)

0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.5 1.0 0.5 0.5 0.5 0.5 0.5 0.5 1.0 1.0

Low Soil/Sediment

(ug/kg)

8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 16.0 16.0 16.0 16.0 16.0 16.0 16.0 16.0 80.0 160.0 80.0 80.0 80.0 80.0 80.0 80.0 160.0 160.0

continued....

Detection limits listed for soil/sediment are based on wet weight. Specific detection limits are highly matrix dependent. The detection limits listed here in are provided for guidance and may not always be achievable.


TABLE 2


Parameter

Aluminum* Calcium* Chromium* Barium* Beryllium Cobalt* Copper Iron* Nickel Magnesium* Manganese* Potassium* Zinc Silver Sodium* Arsenic Antimony Selenium Thallium Mercury Tin* Cadmium Lead vanadium* Cyanide

Low Water (ug/L)

Method

202.1 215.1 218.1 208.1 210.1 200.7 220.1 236.1 249.1 242.1 243.1 258.1 289.1 272.2 273.1 206.2 204.2 270.2 279.1 245.1 282.1 213.2 239.2 286.1 335.2


Low Soil/Sediment

(ug/kg)

Prep./Method

3050/ 202.1-AA 3050/ 215.1-AA 3050/7190 -AA 3050/7080 -AA 3050/7090 -AA 3050/6010, -ICP 3050/7210 -AA 3050/ 236.1-AA 3050/7520 -AA 3050/ 242.1-AA 3050/ 243.1-AA 3050/ 258.1-AA 3050/7950 -AA 3050/7760 -AA 3050/ 273.1-AA 3050/7060 -AA 3050/7041 -AA 3050/7740 -AA 3050/7840 -AA 3050/7471 -AA 3050/ 282.1-AA 3050/7130 -AA 3050/7420 -AA 3050/7910 -AA 9010

Target Detection** Limits (ug/L)

200 5,000

10 200 5 50 25 100 40

5,000 15

5,000 20 10

5,000 10 60 5 10 0. 40 5 5 50 10

* hazardous substances not on the priority pollutant list Specific detection limits are highly matrix dependent. The detection limits listed herein are provided for guidance and may not always be achievable.

Revision No.: 0 Date: 1/Q/Ql Page: 16.6

TABLE 2



E.P. Toxicity Test

Target Detection Limits (ug/L)

Arsenic Barium Cadmium Chromium Mercury Lead Selenium Silver

Prep./Method

1310/7060 1310/7080 1310/7131 1310/7190 1310/7470 1310/7421 1310/7740 1310/7760

10 200 5 10 0.2 5 5 10


Analytical methods for analysis of air samples are given in

Attachment 6 of this QAPP.

Table 3 summarizes the analytical methods to

be utilized for analysis of groundwater for general water

quality parameters.

Section 8.0 provides a further discussion of

analytical procedures.

4.2 DETECTION LIMIT REQUIREMENTS

The data used to conduct all phases of the

study will have detection limits that are consistent with the

standard method detection liinits for the analytical methods

specified and must meet the objectives of the study. The

unique target detection limits for each parameter in soil and

water samples are given in Tables 2 and 3.

4.3 LEVEL OF QA EFFORT

To assess the quality of data resulting from

the field sampling program, duplicate samples and field

Revision No.: 0 Date: l l Q / Q l Page: 17.1

TABLE 3

ANALYTICAL METHODS FOR GENERAL WATER QUALITY PARAMETERS

Parameter Method Reference

Target Detection Limits

Groundwater

Chloride Ammonia (NH3) as N pH Conductivity Total Petroleum Hydrocarbons Carbonate Bicarbonate Sulfate Fluoride Nitrate as N Phosphate Silica Alkalinity (as CaCO^) Total Dissolved Solids (residue at 180°C)

325.3 350.3^ 150.1^ 120.1^

Modified 8015^ 310.1 310.1 375.4 340.2 300.0 365.1 370.1 310.1 160.1

0.1 mg/L 0.01 mg/L

1 mg/L 1 mg/L 1 mg/L 0.1 mg/L 0.1 mg/L 0.1 mg/L 0.05 mg/L 0.5 mg/L 1 mg/L

10 mg/L

Notes:

a = These measurements also taken in the field

b = Methods for Chemical Analysis of Water and Wastes, EPA-600/4-79-020, Revised March 1983

c = SW-846 "Test Methods for Evaluating Solid Waste. Physical/Chemical Methods". 3rd Edition. November 1986 (To be used only on contingency basis as described in the RI/FS Work Plan.). A description of the modifications to Method 8015 is presented as Attachment 5.


blanks will be obtained and submitted to the analytical

laboratory for analysis. In addition, trip blanks and

duplicate matrix spike samples will be analyzed by the

laboratory. The frequency with which field QA/QC samples

will be submitted for analysis is given in Attachment 4 and

is summarized as follows:

i) Groundwater - Stage I Investigation (Task D - Rounds 1 and 2, and Task E - Round 1).

For every 10 water samples a field duplicate and a

field blank will be collected and submitted for

analysis of volatile organics, semi-volatile organics,

pesticides, PCBs, trace elements, cyanide and routine

constituents. In addition, a trip blank will be

analyzed for volatile organics.

ii) Groundwater - Monitoring Program

(Task E - Round 2).

For every 10 water samples, a field duplicate and a

field blank will be collected and analyzed for volatile

organics. In addition, a trip blank will be analyzed

for volatile organics. This program assumes that

results from the analysis of previous groundwater

samples will indicate that only volatile organic

compounds need be analyzed during the monitoring

program. If the results obtained from previous

groundwater analyses indicate contamination by other


compounds, additional analyses will be required

accordingly for the duplicates and field blanks.

iii) Soil Samples - Soil Borings, Surface Sediment, HS-1

Abandonment and lined excavation.

For soil borings, the HS-1 Abandonment, and

the lined excavation, one duplicate for every 10 soil samples

will be prepared in the laboratory and analyzed for the same

parameters as the soil samples.

For surface sediments, one sample will be

collected from a "background location" and analyzed for the

same parameters as for the other surface sediment samples.

In addition, a duplicate will be analyzed for the same

parameters.

Duplicate matrix spike samples will be

analyzed for organic compounds and inorganic constituents at

a frequency of one per ten (10) samples.

Field blanks and trip blanks for water

samples will be analyzed to check procedural contamination

and/or naturally occurring conditions at the site that may

cause sample contamination. Duplicates for water and soil

samples will be analyzed to check for sampling and analytical

reproducibility.


Laboratory QA for the geotechnical testing

will require that all equipment used in the analyses be

calibrated not more than six months prior to actual testing,

that all solutions be not more than one month old, and that

all calculations be checked by someone other than the person

conducting the actual testing.

4.4 ACCURACY, PRECISION AND SENSITIVITY OF ANALYSES

The fundamental QA objective with respect to

accuracy, precision and sensitivity of laboratory analytical

data is to achieve the QC acceptance criteria of the

analytical protocols. The accuracy and precision

requirements for all samples will be in accordance with the

specified EPA analytical methods.

4.5 COMPLETENESS, REPRESENTATIVENESS AND COMPARABILITY

It is expected that all analyses conducted in

accordance with EPA methods will provide data that meets QC

acceptance criteria in 95 percent of all samples tested.

Completeness required for all samples analyzed is summarized

in Table 4.


TABLE 4

QUALITY ASSURANCE OBJECTIVES FOR WATER AND SOIL

Measurement Parameter

VOCs

Total Petroleum Hydrocarbons

BNAs

Pest./PCB

Metals and Cyanide

General Water Quality Parameters

Experimental Conditions

water/soil

water

water/soil

water/soil

water/soil

water

Precision Standard Deviation

as per

as per

as per

as per

as per

as per

ref.

ref.

ref.

ref.

ref.

ref.

Accuracy

as per ref.

as per ref.

as per ref.

as per ref.

as per ref.

as per ref.

Completeness

90

90

90

90

90

90

Notes:

VOCs BNAs Pest./PCB

- Volatile Orgeuiic Compounds - Base/Neutral and Acid Extractable Organic Compounds - Pesticides amd PCBs See Table 2 for Methods and Attachments 1 and 2 for Parameter Lists

Revision No.: 0 Date: , 1/12/88 Page: 21

The sampling network was designed to provide

data representative of Site conditions. During development

of this network, consideration was given to past disposal

practices, existing analytical data, remedial activities to

date and physical setting. The extent to which existing and

planned analytical data will be comparable depends on the

similarity of sampling and analytical methods. The

procedures used to obtain the planned analytical data are

documented in this QAPP. Following completion of data

collection, the data base will be evaluated for

representativeness.

The Quality Assurance objectives for

representativeness cannot be quantified. The data will be

reviewed to determine if the data is representative of site

conditions and will provide adequate information to meet

project objectives.

If a sample has acceptable accuracy,

precision and sensitivity and also does not demonstrate

potential artificial contamination based on field, lab or

trip blanks, then the sample results will be considered

representative.


4.6 FIELD MEASUREMENTS

Measurement data will be generated in many

field activities that are incidental to collecting samples

for analytical testing or unrelated to sampling. These

activities include, but are not limited to, the following:

documenting time and weather conditions,

determining pH, specific conductance, and temperature of

groundwater samples,

determining depth to water in a well,

verifying pre-'Sampling purge volumes, and

conduct pumping tests.

The general QA objective for such measurement

data is to obtain reproducible and comparable measurements to

a degree of accuracy consistent with the intended use of the

data through the documented use of standardized procedures.


5.0 SAMPLING PROCEDURES

The procedures for collecting samples and for

conducting all related field activities are described in

detail in Attachment 4.


6.0 SAMPLE CUSTODY

Sample custody protocols for the study

program will be consistent with standard Montgomery &

Associates procedures as follows. All samples will be in the

custody of a responsible person and a record will be

completed via a field chain-of-custody form. The

chain-of-custody form consists of two copies which are

distributed to the receiving laboratory and the Montgomery &

Associates office file. The person relinquishing custody to

the shipper will maintain his copy while the other copy is

enclosed within the sample shipment. The laboratory upon

receiving the samples will complete the chain-of-custody

form, retain a copy for their records, and forward the

original form to Montgomery & Associates. This copy will

also be used for internal laboratory chain-of-custody

procedures. Field custody procedures are further described

in Attachment 4.

Laboratory custody procedures and document

control for all samples will be in a manner consistent with

the intent of the Contract Laboratory Program (CLP), as

outlined in the appropriate CLP Statements of Work (SOWs).

Laboratory custody procedures for the general water quality

parameters will also be consistent with the intent of the

CLP.


The sample custodian will be responsible for

checking the contents of the shipment. Samples will be

distributed to respective areas in the laboratory by the

sample custodian and will be relinquished via a

chain-of-custody form to the data generators and back to the

sample custodian as required. Samples shall be maintained

within the respective laboratory area under the custody of

the data generator responsible for that area while the work

is being carried out. Sample tags will be used to identify

samples within trays, ovens, beakers, etc. Extra sample

material which is not in use will be returned to a central

secure storage area by the sample custodian at the end of

each day.

Document control will be as follows. All

observations and results recorded by the laboratory, but not

on preprinted data sheets, are entered into permanent

logbooks specific to the project. All documents relevant to

the work, including logbooks, chart recordings, custody

records, correspondence, etc., will be inventoried and

assembled in a permanent file for submittal to Montgomery &

Associates, on an as-required basis.

Evidentiary files for the entire project

shall be inventoried and maintained by Montgomery &

Associates and shall consist of the following:


A. Project Plan

B. Project Logbooks

C. Field Data Records

D. Sample Identification Documents

E. Chain-of-Custody Records

F. Lab Reports and Supporting Data

G. Correspondence

H. Report Notes, Calculations, etc.

I. References, Literature

J. Miscellaneous - photos, maps, drawings, etc

K. Final Report

The evidentiary file materials shall be the

responsibility of the project coordinator with respect to

maintenance and document removal. The file will be stored in

a filing room at the secured office of Errol L. Montgomery &

Associates, Inc., in Tucson, Arizona, or in a secure storage

room in Tucson, Arizona, for a minimum period of 6 years.


7.0 CALIBRATION PROCEDURES AND FREQUENCY

Calibration procedures and frequency for

analytical services for the groundwater quality parameters

will be in accordance with their individually specified EPA

analytical methods.

Tape measures used to obtain water levels

will be examined prior to each period of sustained use to

verify their calibration.


8.0 ANALYTICAL PROCEDURES

Samples collected for chemical analysis will

be tested for the parameters listed on Attachments 1 and 2 in

a manner consistent with the intent of CLP RAS protocols.

The methods for performing these analyses are specified in

the appropriate CLP SOWs for organics and inorganics and are

summarized on Tables 2 and 3 of Section 4. The testing will

also conform to EPA guidelines, as appropriate. The

analytical results for metals in soils and sediment will be

reported on a dry weight basis. Soil samples that are

shipped shall be assumed to contain low level contamination

unless specified otherwise.

As part of the organic analyses listed in

Table 2, computer assisted library searches will be executed

for non-Hazardous Substance List (HSL) sample components for

the purpose of tentative identification. Up to ten (10)

substances of greatest apparent concentration for the

purgeable organic fraction and ten (10) substances of

greatest apparent concentration for the BNA extractable

fraction will be tentatively identified via a forward search

of the most recent, available version of the EPA/NIH Mass

Spectral Library.

Coraputer generated library search routines

should not use normalization routines that would misrepresent


the library or unknown spectra when compared to each other.

It should also be noted that only after visual comparison of

sample spectra, with the nearest library searches, will the

mass spectral interpretation specialist assign a tentative

identification.


9.0 DATA REDUCTION, VALIDATION, ASSESSMENT, AND REPORTING

Laboratory chemists will perform analytical

data reduction and validation in-house for submittal to the

laboratory QA officer. The laboratory QA officer is

responsible for assessing data quality and advising of any

data which were rated "preliminary" or "unacceptable" or

other notations which would caution the data user of possible

unreliability. Data reduction, validation, and reporting by

the laboratory will be conducted as follows:

Raw data produced by the analyst is turned over to the

respective area supervisor.

- The area supervisor reviews the data for attainment of

quality control criteria as outlined in CLP protocols

and/or established EPA methods and for overall

reasonableness.

- Upon acceptance of the raw data by the area supervisor, a

report is generated and sent to the laboratory quality

assurance officer.

- The laboratory quality assurance officer will complete a

thorough audit of reports at a minimum frequency of one in

teh and an audit of every report for consistency.


- The laboratory QA officer will decide whether any sample

re-analysis is required.

- Upon acceptance of the preliminary reports by the

laboratory QA officer, final reports are generated and

signed by the laboratory project manager.

The laboratory QA officer will conduct an

evaluation of data reduction and reporting by the laboratory.

These evaluations will consider the finished data sheets,

calculation sheets, document control forms, blank data,

duplicate data, and recovery data for matrix and surrogate

spikes. The material will be checked for legibility,

completeness, correctness, and the presence of necessary

dates, initials, and signatures. The results of these checks

will be assessed and reported to the laboratory project

manager noting any discrepancies and their effect upon

acceptability of the data.

Validation of the analytical data will be

performed by the QA/QC Coordinator in accordance with the

following documents:

i) "Laboratory Data Validation Functional Guidelines for

Evaluating Organics Analyses", Technical Directive

Document, prepared by the USEPA Data Validation Work

Group, NUS Corporation Superfund Division.


ii) "Laboratory Data Validation Functional Guidelines for

Evaluating Inorganics Analyses", prepared by the USEPA

office of Emergency and Remedial Response.

Assessment of analytical and in-house data will also include

checks for data consistency by looking for comparability of

duplicate analyses, comparability to previous data from the

same sampling location (if available), adherence to accuracy

and precision criteria, transmittal errors, and anomalously

high or low parameter values. The results of these data

validations will be reported to the project manager, noting

any discrepancies and their effect upon acceptability of the

data. Additional reporting is described in Section 14.0.

Data validation for measurements taken in the

field will be carried out by the QA/QC Coordinator and/or

Hydrogeologist, who will check for consistency by looking for

comparability of duplicate analyses, comparability to other

available data, adherence to accuracy and precision criteria,

transmittal errors, and anomalously high or low parameter

values.

Where laboratory measurements of pH and

conductance essentially corroborate field measurements, the

field measurements will be used. Where laboratory

measurements do not corroborate field measurements, the field


instruments will be inspected and tested. The field or

laboratory results will be used depending on the results of

this inspection.


10.0 INTERNAL QUALITY CONTROL PROCEDURES

Internal quality control procedures for

analytical services for groundwater parameters will be

conducted by the laboratory quality assurance officer in

accordance with their standard operating procedures and the

individual method requirements in a manner consistent with

the intent of the CLP. These specifications include the

types of audits required (sample spikes, surrogate spikes,

reference samples, controls, blanks), the frequency of each

audit, the compounds to be used for sample spikes and

surrogate spikes, and the quality control acceptance criteria

for these audits.

Internal quality control procedures for

analytical services for the additional water and soil quality

parameters will be in accordance with their individually

specified EPA standard method and standard laboratory

operating procedures.

Quality control of field sampling will

involve collecting field duplicate samples and field blanks

in accordance with the applicable procedures.


11.0 SYSTEMS AUDITS

The QA/QC Coordinator and Hydrogeologist will

monitor and audit the performance of QA/QC procedures to

ensure that the project is executed in accordance with this

QAPP.

Laboratory

Systems audits are based on an on-site

inspection of the laboratory. Audits of the laboratory will

be executed by the QA/QC Coordinator.

Field

Two system audits of the sampling activities

will be conducted to ensure that the sampling plan is being

adhered to and/or that variances are justified and

documented. These audits will be scheduled to oversee as

many different field activities as possible.


12.0 PREVENTIVE MAINTENANCE

This section applies solely to field

equipment. For this project, this includes water level

sounders, a field pH and temperature meter, and a specific

conductance meter. Specific preventive maintenance

procedures for this equipment will be consistent with the

manufacturer's guidelines.


13.0 CORRECTIVE ACTION PROCEDURES

Corrective action indicated by audit results

or detection of unacceptable data will be determined by the

project manager in consultation with the QA officers.

Corrective action may include, but is not limited to:

- reanalyzing the samples, if holding time criteria permit,

- resampling and analyzing

- evaluating and amending sampling and analytical

procedures,

- accepting data with qualifications, and

- qualifying data as unuseable.

The type of corrective action required for

field activities will be outlined by the Hydrogeologist,

QA/QC coordinator, and the laboratory QA officer in

consultation with the project manager.


14.0 QA REPORTS

QA reports will contain a discussion on QA/QC

summarizing the quality of the data collected and/or used as

appropriate to each phase of the project. Data Validation

Reports can be available on request.

Reports of QA activities will be prepared and

will include:

1. Report from the laboratory project managers of data

reduction.

2. Report from the QA Officer of data validation.

3. Report from the QA/QC Coordinator on field audits.

4. Laboratory documentation, including:

- Sample Data Summary Package

- Sample Data Package

The laboratory will maintain the following documentation for

review on an as-required basis, for a minimum period of

six years:


For the Inorganic Analyses;

- Data.

- All Quality Control Checks run during the analysis and the

acceptance levels established either by the originators of

the check sample (for example, EPA) or established by

Analytical Technologies, Inc., using historical data.

- All duplicates with the relative percent deviation (RPD)

determined and all spikes with percent recovery determined

which were run during the analysis.

- A record of all reagent duplicates and reagent spikes and

their values. This will include the RPD and percent

recoveries.

- A record of all reagent blanks and their values.

- Standard calibration curves.

- Calculated ion balances.

- The dates of analysis shall be included.


For the Organic Analyses:

- Data.

- All matrix spikes and matrix spike duplicates which were

run during the analysis. This will include the relative

percent deviation (RPD) determinations.

- A record of all trip blanks, system blanks, and reagent

blanks and their values.

- A record of all reagent spikes.

- Raw sample quantitation reports and chromatograms.

- Tuning reports.

- Surrogate data.

- All Quality Control Checks run during the analysis and the

acceptance levels established either by the originators of

the check sample (for example, EPA) or established by

Analytical Technologies, Inc., using historical data.

- Dates of extractions and analysis will be included.


General:

- Copies of all supporting documentation (for example,

chain-of-custodies).

- a letter describing any problems, if any, encountered

during the analysis ad the corrective action taken to

resolve the problems.

Montgomery & Associates reports regarding

laboratory chemical results will include the following QA/QC

documentation:

- Data Summaries for Analyses of Groundwater Samples,

Duplicate Groundwater Samples, Field Blanks, Trip Blanks,

and System Blanks.

- Matrix Spike and Matrix Spike Duplicates.

- Surrogate Spike.

- Internal Quality Control Check.

ATTACHMENT 1

PRIORITY POLLUTANT COMPOUNDS/

HAZARDOUS SUBSTANCE LIST COMPOUNDS

ATTACHMENT 1

HAZARDOUS SUBSTANCE LIST

VOLATILES

Compound

acrolein acrylonitrile chloromethane bromomethane vinyl chloride chloroethane methylene chloride 1,1-dichloroethene 1,1-dichloroethane trans-1,2-dichloroethene chloroform 1,2-dichloroethane 1,1,1-trichloroethane carbon tetrachloride bromodichloromethane 1,2-dichloropropane trans-1,3-dichloropropene tr ichloroethene benzene chlorodibromomethane 1,1,2-trichloroethane cis-1,3-dichloropropene bromoform tetrachloroethene 1,1,2,2-tetrachloroethane toluene chlorobenzene ethylbenzene acetone* total xylenes* carbon disulfide* 2-butanone* vinyl acetate* 2-hexanone* 4-methy1-2-pentanone* styrene*

*Hazardous Substance List (HSL) Compounds, not on priority pollutant list.

ATTACHMENT 1 (cont'd)

HAZARDOUS SUBT ANCE LIST

BASE/NEUTRAL/ACID COMPOUNDS

Compound

bis(2-chloroethyl) ether phenol 2-chlorophenol 1,3-dichlorobenzene 1,4-dichlorobenzene 1,2-dichlorobenzene bis (2-chloroisopropyl) ether hexachloroethane N-nitrosodi-n-propylamine nitrobenzene isophorone 2-nitrophenol 2,4-dimethylphenol bis (2-chloroethoxy) methane 2,4-dichlorophenol 1,2,4-trichlorobenzene naphthalene hexachlorobutadiene p-chloro-m-cresol hexachlorocyclopentadiene 2,4,6-trichlorophenol 2-chloronaphthalene acenaphthylene dimethyl phthalate 2,6-dinitrotoluene acenaphthene 2,4-dinitrophenol 2,4-dinitrotoluene fluorene 4-nitrophenol 4-chlorophenyl phenyl ether benzyl alcohol* 2-methylphenol* 4-methylphenol* Benzoic acid* 2-methylnapthalene* 2,4,5-trichlorophenol* 3-nitroaniline* dibenzofuran* 4-nitroaniline* 2-nitroaniline*

*Hazardous Substance List (HSL) Compounds not on Priority Pollutant List.

ATTACHMENT 1 ( c o n t ' d )


B A S E / N E U T R A L / A C I D COMPOUNDS ( c o n t ' d )

Compound

diethyl phthalate 4,6-dinitro-2-methylphenol 4-bromophenyl phenyl ether hexachlorobenzene pentachlorophenol phenanthrene anthracene di-n-butyl phthalate fluoranthene pyrene butyl benzyl phthalate chrysene benzo(a)anthracene bis (2-ethylhexyl) phthalate di-n-octyl phthalate benzo(b)fluoranthene benzo(k)fluoranthene benzo(a)pyrene indenod , 2, 3-cd)pyrene dibenzo(a,h)anthracene benzo(g,h,i)perylene N-nitrosodiphenylamine 3,3'-dichlorobenzidine 4-chloroanaline

ATTACHMENT 1 ( c o n t ' d )


PESTICIDES AND PCB'S

Compound

alpha-BHC gamma-BHC (Lindane) beta-BHC heptachlor delta-BHC aldrin heptachlor expoxide endosulfan I 4,4'-DDD dieldrin endrin 4,4'-DDT endosulfan II 4,4'-DDE chlordane toxaphene endrin aldehyde aroclor 1016 aroclor 1221 aroclor 1232 aroclor 1242 aroclor 1248 aroclor 1254 aroclor 1260 endosulfan sulfate* endrin ketone* methoxychlor*

*Hazardous Substance List Pollutant List.

(HSL) Compounds not on Priority

ATTACHMENT 1 (cont'd)


TOTAL METALS AND CYANIDE

Antimony Arsenic Beryllium Cadmium Chromium Copper Lead Mercury Nickel Selenium Silver Thallium Zinc Aluminum* Iron* Magnesium* Manganese* Calcium* Barium* Cobalt* Potassium* Sodium* Tin* Vanadium* Cyanide

*Hazardous Substance List (HSL) Compounds, not on Priority Pollutant List.

E.P. TOXICITY METALS

Arsenic Barium Cadmium Chromium Lead Mercury Selenium Silver

ATTACHMENT 2

ADDITIONAL WATER QUALITY PARAMETERS

ATTACHMENT 2

ADDITIONAL WATER QUALITY PARAMETERS

Compound

Chloride Ammonia (NH2) as N pH - lab and field Conductivity - lab and field Temperature - field Carbonate Bicarbonate Sulfate Fluoride Nitrate as N Phosphate Silica Alkalinity (as CaC03) Total Dissolved Solids (at ISCC) Total Petroleum Hydrocarbons

ATTACHMENT 3

LABORATORY FACILITIES

TEMPE, ARIZONA FACIUTY

(£WIR(5NM'EN' CL MANAGER

ADMINISTRATIVE OFFICES LABORATORY

ENVIRONMENTAL LABORATORY

ANALYTICAL TECHNOLOGIES, INC.

ATTACHMENT 3


MAJOR EQUIPMENT TEMPE FACILITY

INSTRUMENTATION/MODEL

1 . GC/MS/DS F i n n i g a n 1020-OWA

2 . Gas C l i romatographs :

Tracor 565 Varian 4600 Tracor 545

3. Liquid Chromatographs:

Tracor

4. Atomic Absorption (AA)

Perkin Elmer 2380

5. TOC Analyzer

6. Spectrophotometer Beckman 34

7. Ion Chromatograph Dionex 20101

8. Liquid Scintillation Counter (2) TM Analytic Delta 300 (6891)

9. Compaq Desk Pro Computer/20MB

10. IBM CLONE COMPUTER/20MB

11. Compaq Portable Computer

Other laboratory equipment includes:

EP Extractors Hoods Ovens Balances Specific Ion Meter pH Meters PERKIN-ELMER IR

DESCRIPTION

Capillary/packed column GC with 10-sample Auto Liquid Sampler (ALS-10)

HALL/ECD/Purge & Trap/PID FID/ECD-2 HALL/PID/Purge & Trap/ALS

UV/Fluoresence

HGA/Flame/Cold Vapor Autoscimpler

O.I. Instrument

UV/VIS with Autosampler

Conductivity/Amperometric Detectors

Epson Printer/Graphics

Citizen MP/lO Printer

ATTACHMENT 3


MAJOR EQUIPMENT SAN DIEGO FACILITY


1. Gas Chromatograph/Mass Spectrometer/Data System (GC/MS/DC) Finnigan 1020-OWA

2. GC/MS/DS Finnigan 1020-OWA

GC/MS/DS Finnigan 1030-OWA

DESCRIPTION

Capillary/packed column GC

Capillary/packed column GC with 10-sample Auto Liquid Sampler (ALS-10)

Capillary/packed column GC with ALS-10

8.

9.

Data System, Stand alone Finnigan 2000

Gas Chromatographs:

Varian 3700 Varian 3700 Varian 3700 Hewlett Packard 5880 Perkin Elmer 300 Perkin Elmer 300 Tracor 565 Varian 4600 Varian 6000

Liquid Chromatographs:

Perkin Elmer, Series 4 Perkin Elmer, Series 10 Tracor

Laboratory Computer Perkin Elmer DIMS/200

Inductively Coupled Plasma (ICP) Perkin Elmer 5500

Atomic Absorption (AA) Perkin Elmer 3030 Perkin Elmer 2380

INCOS

ECD NPD/FID TCD/FID (gas analysis) ECD/ECD ECD/ECD ECD/FID HALL/ECD/purge & trap FID/ECD HALL/PID/purge & trap

Dual UV UV UV

300 MB Storage

Sequential

HGA HGA/Flame/Cold Vapor

ATTACHMENT 3


MAJOR EQUIPMENT SAN DIEGO FACILITY


10. Infrared Spectrophotometer Beckman 252 MX

DESCRIPTION

Computerized

11. Mercury Analyzer Coleman 50

12. Optical Microscope American Optical 110

13. TOC Analyzer Xertex/Dohrmann DC-80

14. TOC Analyzer (2) Xertex/Dohrmann DX-20

15. Gel permeation Chromatograph Analytical Biochemistry Labs

16. Technicon Auto II

(Sample clean-up)

Cyanide, Phenolics, Sufacte, Chloride, TKN, Nitrite, Nitrate, Phosphate, Total Phorophous, Alkalinity

ATTACHMENT 4

SAMPLING PLAN FOR REMEDIAL INVESTIGATION / FEASIBILITY STUDY

HAZARDOUS WASTE AREA HASSAYAMPA LANDFILL


AHACHMENT 4 CONTENTS

Page

INTRODUCTION 4.1 DATA MANAGEMENT 4.2

SAMPLING PROCEDURES 4.4 CHAIN OF CUSTODY AND SAMPLE CONTROL PROCEDURES 4.4 SAMPLE CONTAINERS 4.15 AIR SAMPLING METHODS 4.15 SOIL SAMPLING METHODS 4.16

Soil Boring Samples 4.16 Surface Sediment Samples 4.19 Landfill Soil Cover Samples 4.21 Monitor Well Soil Samples 4.21 Lined Excavation Samples 4.22

WATER SAMPLING METHODS 4.23 Drill Water Samples 4.26 Measurement of Groundwater Levels 4.26 Parameters Measured in the Field 4.27 Samples for Organic Analyses 4.28 Samples for Routine, Trace Element, and Cyanide Analyses . 4.29

LABORATORY PROCEDURES 4.31

ANALYTICAL METHODS . 4.32

TABLES

Table

4-1 SUMMARY OF SAMPLING PROGRAM, HASSAYAMPA LANDFILL, MARICOPA COUNTY, ARIZONA

4-2 SUMMARY OF SAMPLING REQUIREMENTS, HASSAYAMPA LANDFILL, MARICOPA COUNTY, ARIZONA

ILLUSTRATIONS

Figure

4-1

4-2

4-3

4-4

4-5

4-6

FIELD DATA FORM FOR PUMPED WELL

CHAIN OF CUSTODY TRAFFIC REPORT

CHAIN OF CUSTODY LETTER OF TRANSMITTAL

CHAIN OF CUSTODY ANALYSES REQUEST SCHEDULE FOR ORGANICS

CHAIN OF CUSTODY ANALYSES REQUEST SCHEDULE FOR ROUTINE PARAMETERS

CHAIN OF CUSTODY ANALYSES REQUEST SCHEDULE FOR TRACE ELEMENTS

SAMPLING PLAN FOR REMEDIAL INVESTIGATION / FEASIBILITY STUDY

HAZARDOUS WASTE AREA HASSAYAMPA LANDFILL


INTRODUCTION

The following Sampling Plan describes procedures for obtaining air,

soil, and water samples for the RI/FS (Remedial Investigation / Feasibility

Study) for the Hassayampa Landfill, Maricopa County, Arizona. This Sam

pling Plan should be used in conjunction with the associated Work Plan,

QAPP (Quality Assurance Project Plan), and Health and Safety Plan to con

duct proper sampling operations. Figure 2 (located in a pocket at the back

of the QAPP) shows locations for sampling sites for soil and groundwater

samples.

Topography across the Hassayampa Landfill is undulatory due to the

frequent reworking of landfill pits in the active part of the property.

However, the hazardous waste area is covered by a graded soil cover that is

reported to be several feet in thickness, and is relatively flat to gently

sloping. Access for vehicles is generally good in the hazardous waste

area, where surficial soils are relatively compacted and firm. Surficial

soils in parts of the active landfill are loose and are generally passable

only to four-wheel drive vehicles. Access to existing monitor wells,

proposed monitor wells, and proposed soil borings is good.

4,2

DATA MANAGEMENT

Data management procedures will be required to document results of

field operations, chain of custody, laboratory analyses, and other project

related activities. Data management will include maintenance of field

notebooks, instrument calibration notebooks, QA/QC (Quality Assurance /

Quality Control) notebooks for laboratory results, and project files.

Field notebooks will be used to record notes on field operations and to

record field data obtained during project TASKS. Items to be recorded for

data management documentation will include, but not be limited to, the

following:

site conditions, including weather and location;

personnel on-site during field operations;

observations during drilling of soil borings and monitor wells;

lithologic descriptions of drill cuttings;

all sampling data and forms, including chain of custody and sample control data;

time that pertinent sampling operations occur and equations used to calculate volume of water pumped prior to sampling wells;

QA/QC reviews for data;

pumping test data and analysis;

well development data; and

calibration data for field instrumentation, such as water level sounders, pH meters, conductivity meters, etc.

Entries in field notebooks and calibration notebooks will be made using

indelible ink, and will be initialed and dated.

Photographs will be taken of pertinent field operations and site

areas, such as trenches, monitor wells, soil borings, surface sediment

4.3

sampling sites, etc. The frame number and film roll number corresponding

to the photographed location will be recorded in the field notebook. The

film roll will be identified by taking a photograph of a clipboard on the

first frame. The project name, film roll number, date, and photographers'

names will be written on the clipboard. All such photographs will be

developed and retained in the project files.

4,4

SAMPLING PROCEDURES

Sampling and QA/QC procedures for the RI/FS are designed to ensure

that collection, identification, preservation, and transportation of sam

ples will result in properly representative data for site conditions.

Quantities, types, and frequency of water, air, and soil samples to be

obtained during the RI/FS, including QA/QC samples, are summarized in Table

4-1. A list of sample containers, preservatives, and holding times for

parameters to be analyzed is given in Table 4-2.

CHAIN OF CUSTODY AND SAMPLE CONTROL PROCEDURES

Chain of custody and sample control procedures will be required to

ensure the integrity and preservation of samples during their collection,

transportation, and storage prior to laboratory chemical analysis. Exam

ples of typical chain of custody and sample control documents are shown on

Figures 4-1 through 4-6. These documents will include: field data form

(Figure 4-1); chain of custody traffic report (Figure 4-2); chain of custo

dy Tetter of transmittal (Figure 4-3); chain of custody analysis request

schedules with signatures for transfer of custody (Figures 4-4, 4-5, and 4-

6); and records and receipts for delivery or shipment of samples. All per

tinent data concerning each sample will be recorded on the traffic report

(Figure 4-2), including:

traffic report sample numbers

sample description

sampling personnel

description of sampling point and sampling methods

sample site name and number

date and time of collection

field observations

number and volumes of samples

TABLE <.-!. SUMMARY OF SAHPLlHG PROGRAM

HASSAYAMPA LANOFILL, MARICOPA COUMTY, ARIZONA

4.5

OA/OC SAMPLES

..INVESTIGATIVE SAMPLES DUPLICATE SAMPLES^ FIELD BLANKS*' ...TRIP BLANKS'^

HUMBER FREQUENCY TOTAL NUMBER FREQUENCY TOTAL IIUMBER FREQUENCY TOTAL NUMBER FREQUENCY TOTAL

GRAND

TOTAL

ASSUMED

CONCENTRATION TYPE OF ANALYSIS

WATER SAMPLES"

Task D Round 1

A UB t ie l t s

5 UA w e l I s

w/o HC phase

w/HC phase

Wel l HS-1

Task 0 Round 2

4 UB We l l s

5 UA U e l l s

H/o HC phase

w/HC phase

4

5

5

1

4

5

5

1

1

1

1

1

1

1

4 1 1 1

5

5

1 1 1 1

4 1 1 1

5

5

1 1 1 1

1 1 1 1

1 1 1 1

624, 625, 608, cyanide, routine, trace


624, 8015 (modified)

8015 (modified)

624




8015 (modified)

Task E Round 1

4 UB WelIs

5 UA WelIs

u/o KC phase

w/HC phase

Uells HS-2 t HS-3

1 1

- - - 5 L

- - - 5 H

1 3 H

1 5 L




8015 (modified)


Task E Round 2

4 UB U e l I s

5 UA U e l l s

w/o HC phase

w/HC phase

U e l l s HS-2 e, HS-3

4

5

5

2

1

1

1

1

4

5

5

2

1

---

1

1

1 1

---

1 1

1 1

t 1 1

—

1 1 1

1 \ 1

1 1

...

1 1

1 1

1

5

1

1

7

5

5

3

S

L

L

H

H

L

624 (plus any previously detected

parameters)


parameters)


8015 (modified)


parameters)

Or i n inq Uater 624

TABLE 4-1. SUHMARY OF SAMPLING PROGRAM

HASSAYAMPA LANDFILL, MARICOPA COUNTY, ARIZONA

4.6

AIR SAMPLES

OA/QC SAMPLES

..IMVESTIGATIVE SAHPLES DUPLICATE SAMPLES^ FIELD BLANKs'' TRIP BLANKS'^ GRAND ASSUMED

MUMBER FREQUENCY TOTAL MUMBER FREQUENCY TOTAL HUMBER FREQUENCY TOTAL NUMBER FREQUENCY TOTAL TOTAL CONCENTRATION

1 1

TYPE OF ANALYSIS

EPA TOI

SOIL SAMPLES

6 SoiI Borinqs

6 Soil Borinqs

8 Soil Borinqs

Surface Sediment

Monitor UelIs

Uell HS-1

Lined Excavation

24

24

S

6

S

3

1

24

24

8

6

8

3

1

3

2

...

1

...

1

1

1

1

...

1

...

1

1

3

2

--

•-

27

26

8

L-M

L-M

L-M

8240

8240, EP Toxicity metals

vertical hydraulic condu

moisture content

L 8080, metals by sample digestion

L-H vertical hydraulic conductivity

L-M 8240

L-M 8240, 8270, 8080. EP Toxicity, CERCLA

characteristics of hazardous waste

SoiI Cover Sieve analysis

Duplicates of soil samples for laboratory chemical analyses will be prepared by the laboratory

Field blanks for water chemical analyses will be prepared using bottled deionized water

^ Trip blanks for water chemical analyses will be prepared by the laboratory prior to field operations

UB - Monitor Uells completed in Unit B

UA - Monitor Wells completed in Unit A

HS - Existing on-site monitor welts

HC - Nonaqueous hydrocarbon phase

NOTE: Frequency indicates the number of t imes the sample source will be sampled for the indicated

sampli ng round and/or analys i s.

T A B L E 4 - 2 . S U M H A R Y OF S A M P L I N G R E Q U I R E M E N T S

H A S S A Y A M P A L A N D F I L L , M A R I C O P A C O U N T Y , A R I Z O N A

4.7

P A R A M E T E R

V o l a t i l e O r g a n i c C o m p o u n d s

( E P A m e t h o d s 6 2 4 / 8 2 4 0 )

S e m i - V o l a t i l e O r g a n i c s ,

P e s t i c i d e s , or P C B ' s

( E P A m e t h o d s 6 2 5 / 8 2 7 0

a n d 6 0 8 / 8 0 8 0 )

T o t a l P e t r o l e u m H y d r o c a r b o n s

( m o d i f i e d E P A m e t h o d 8 0 1 5 )

T r a c e E l e m e n t s ( g e n e r a l )

M A T R I X

S o i l

C O N T A I N E R

S o i l

W a t e r

S o i l

R o u t i n e C o n s t i t u e n t s ( g e n e r a l ) W a t e r

C y a n i d e ( t o t a l ) U a t e r

A m m o n i a , N i t r a t e W a t e r

T u o 4 0 - m t g l a s s v i a l s

w i t h T e f l o n - l i n e d s e p t a

4 0 0 - m l m a s o n jar u i t h

T e f l o n - l i n e d l i d , or

4-6 inch b r a s s t u b e w i t h

T e f I o n / a I u m i n u m l i n e d e n d c a p s

F o u r l - l i t e r a m b e r g l a s s

b o t t l e s w i t h T e f l o n - l i n e d

s c r e u c a p s

4 0 0 - m l m a s o n jar w i t h

T e f l o n / a l u m i n u m l i n e d lid

P R E S E R V A T I ON

U a t e r T w o 4 0 - m l g l a s s v i a l s w i t h

T e f l o n - l i n e d s e p t a

1 - l i t e r p l a s t i c b o t t l e

O n e m a s o n jar w i t h T e f l o n /

a l u m i n u m l i n e d l i d , or 4-6

i n c h b r a s s t u b e w i t h

T e f I o n / a I u m i n u m l i n e d e n d c a p s

1 - l i t e r p l a s t i c b o t t l e

l - l i t e r p l a s t i c b o t t l e

l - l i t e r p l a s t i c b o t t l e

A d d 4 d r o p s 1:1 H C l ,

R e f r i g e r a t e




A d d 4 d r o p s 1:1 H C l ,


f i l t e r i m m e d i a t e l y , '

a d d 1 : 1 H N O 3 to p H < 2 ,




A d d N a O H to p H > 1 2


R e f r i g e r a t e , a n a l y z e as

s o o n as p o s s i b l e

R E C O M M E N D E D

H O L D I N G T I M E

FOR P R O J E C T

14 d a y s

14 d a y s

7 d a y s p r i o r to

e x t r a c t i o n ; 21 d a y s

a f t e r e x t r a c t i o n

7 d a y s p r i o r to

e x t r a c t i o n ; 21 d a y s

a f t e r e x t r a c t i o n

14 d a y s

2 8 d a y s

28 d a y s

2 8 d a y s

14 d a y s

4 8 h o u r s

Co*puting linutes required

to punp five B.H. voluaes:

(T.D.-P.W.L.)l ^ Q ) -

( )(

ginutes

Measuring Point

which is

)

Top of

ERROL L. MONTGOMERY & ASSOCIATES, INC.

WATER LEVEL RECORD SHEET (Previous measured W.L.

Sampling Round

4.8

) Page.

PUMPED WELL.

Elevation of Measuring Point above mean sea level.

_ft. above lanci surface.

Well Location: T .

Well Coordinates:

Computed Sampling Time Hrs.

R Sec.

.ft N.

_ft E.

STATIC WATER LEVEL:. Punp Intake ft.BNP

D A T E / T I M E AFTER PUMPING

STARTED (MINUTU)

SOUNDER USED

CONDUCTIVITY

pH METER/PRO!

HOUR

#

METER/P

IE USED:

DEPTH TO WATER (FIKT)

HELD w e r DEPTH

{QBE USED: # / §

it / #

PUMPING RATE

(GPH)

•

DRAMOOWN

( F T . )

REMARKS (INCLUDE HETHOD

OF MEASUREMENT)

sees per gal.discharge

-

I

FIGURE 4-1 FIELD DATA FORM FOR PUMPED WELL

ERROL L. MONTGOMERY A ASSOCIATES, INC. 4 CONSUITANTS IN HYDROGEOIOGY 1075 EAST FORT LOWELL ROAD, SUITE B TUCSON, ARIZONA 85719 (602) 881 4912 TELEX: 165597 MONTE TUC

CHAIN OF CUSTODY TRAFFIC REPORT

Project No.

D Organic ° Grab a Soil DInorganic a Composite • Water

a Other Sample Number

Sampling Site Name/Code/We11 No.

Sampling Date and Time of Collection

Sampling Personnel:

Name Signature

Name Signature

Name Signature

Sampling Point ___^__________^___ and Method of Sampling

Field Observations

Sample, Sample Container Data

Volume No. Used Lot No. Preservatives Analyses Needed Destin. Ship. Method/Date

Special Handling Procedures

FIGURE 4-2 CHAIN OF CUSTODY TRAFFIC REPORT

ERROL L. MONTGOMERY & ASSOCIATES, INC. CONSULTANTS IN HYDROGEOLOGY

1075 EAST fORT LOWELL ROAD, SUITE B

TUCSON, ARIZONA 85719 (602) 881-4912

TELEX: 165597 MONTE TUC

4.10 ESROL I . MONTGOMERY, P.O.

JOHN W. HARSHBARGER, P.G., P.E. DONALD K. GREENE, P.E. WILLIAM R. ViaOR, P.G.

EDWARD W. PEACOCK, P.G. RONALD H. DEWin

CHAIN OF CUSTODY LETTER OF TRANSMITTAL

Date:

Job No. TO:

ATTENTION:

On in

water sample(s) was (were) shipped to you parcel(s). The sample(s) was (were)

container(s). via shipped in „ _ _ _ _ _ ^ _ _ _ , ^_______ Custody seals were (were not) attached to the sampie and/or shipping container (s). Upon receipt, the laboratory representative accepting custody of the samples must sign and date the attached Chain of Custody/Analyses Request Schedule. The laboratory representative must remark on the number and integrity of the sample(s) (i.e., condition of custody seal and container, relative temperature of each sample, or other conditions which may affect credibility of laboratory results) in the space provided at the bottom of the Chain of Custody/Analyses Request Schedule. If the integrity of the sample(s) is in question, please notify us immediately.

Please perform the analyses indicated in the attached Chain of Custody/Analyses Request Schedule within the maximum allowable holding times indicated or, if not indicated, those recommended by federal regulatory agencies. The final laboratory report should include at a minimum: all data indicated on sample container labels; date sample was received at the laboratory; date of analysis for each parameter reported; and detection limits. Results of your analyses and the attached Chain of Custody/ Analyses Request Schedule should be sent to our Tucson office.

If you have any questions regarding the shipment or the analyses requested, please contact us.

Very truly yours,

ERROL L. MONTGOMERY & ASSOCIATES, INC.

Attachment(s).

By:

Title:

FIGURE 4-3 CHAIN OF CUSTODY LETTER OF TRANSMITTAL

4.11

CHAIN OF CUSTODY ANALYSES REQUEST SCHEDULE

ORGANICS

ERROL L. .MONTGO.VIERY Jt , \SSOCI.*TE3, INC. CONSUirANI] IN HrOBOCIOlOCr 1075 EASl r o e i LOWELL DOAO, SUIIE > TUCSON. ARIZONA 85719 1602) 981 4912 TELEX; 165597 MONTE TUC

Project No,

SftHPLE IDENTIFIER

SAMPLE COLLECTION DATE TIHE

PRIORITY VOLATILE ORGANICS

ONLY

PRIORITY BNA, AND

PESTICIDES ONLY OTHER

NAXIHUN ALLOWABLE HOLDING IIHE,

STARTING FROM TIHE OF COLLECTION REMARKS

Relinquished by: Affiliation: Oate: Tiie: Received by: Affiliation: Date: Tiae:

LABORATORY COHHENTS ON SAMPLE INTEGRITY UPON RECEIPT:

FIGURE 4 -4 CHAIN OF CUSTODY ANALYSES REQUEST SCHEDULE FOR ORGANICS

4 .12 ERROL L. MO.VTGOMERY & ASSOCIATES, INC,

CONtUlTANTl IN HYDtOOIOlOOY

I07S lAST rORT lOWf l l ROAD. SUITI 1

TUCSON. ARIZONA I I 7 l f (602) t a M 9 l ]

K l t X i l6iS»7 AAONTE TUC


ROUTINE PARAMETERS

TO:

FROM:

DATE OF SHIPMENT: NUMBER OF SAMPLES SHIPPED: ^

SHIPPED VIA:

Sample No. Identification

CONTAINER:

IDENTIFICATION OF SAMPLES

Sampling Date (Time) Sample Temp./Conductivity/pH

•BSBBanassaaBBBsaasssBSBSSBSssBBBsaBsassasaaaaBBsassBBS

PRE-TREATMENT OF SAMPLES: E 3 3 3 3 3 3 3 S 3 S 3 S 8 a S S 3 3 S a S 3 a s 3 S 3 S 3 :

OETERHINATIONS TO BE HADE:

« i n > « i u i i i < kf t

• o c t i i i d kyi

A f f lKa t tea i

C l . KeatgoMry I A t M t l t t M , I » .

A r f l l l a t U a i

Oati i

Ottai

l l a i i

T l i i i

LABORATORY COMMENTS ON SAMPLE INTEGRITY UPON RECEIPT:

Routine Constituents

Calcium Sulfate S i l i ca

Hagnesium Ni t ra te pH

Sodium Boron

Potassium Fluoride

Carbonate E lec t r ica l Conductance

Bicarbonate Total Dissolved Solids

Chloride (Residue 9 180'C)

FIGURE 4 - 5 CHAIN OF CUSTODY ANALYSES REQUEST SCHEDULE FOR ROUTINE PARAMETERS

ERROL L. MONTGOMERY & ASSOCIATES, INC. CONtUlTANTS IN HrDROOIOlOCY

107} lAST rORt l O W t l l ROAO. SUIT! B

TUCSON. ARIZONA IS7I9 |M2) 611-191]

T d l X i I6SS97 AAONTI TUC

4 . 1 ;


TRACE ELEMENTS

TO:

FROM:

•SSaBSBBSS ssasssS3BBBssaasaaa3BBseas=assa8ss3a8SBBSBaa8sa«svas3S3S3B33S=s=aB33sas333Bsascsaa

OATE OF SHIPMENT: NUHBER OF SAMPLES SHIPPED:

SHIPPED VIA: CONTAINER:

Sample No. Identification

IDENTIFICATION OF SAMPLES

Sampling Date (Time) Sample Temp./Conductivity/pH

• B 8 a a a a B a B B a a a B 0 a B a s B a s B 8 S B B a a « B a a s a 3 8 S 3 s s B B 8 a a s a a a 3 a 8 a a e s a s a s a s = 3 3 s s 3 3 3 s B 3 3 E a s s B a B 3 s s a s 3 B 3 8 s s s a s 3 a

PRE-TREATMENT OF SAMPLES:

DETERMINATIONS TO BE MADE:

RiliaquUktd by:

Rtc«l<rtd byi

A r r i l l t t l o a i

C l . lloat|Oi<ry ( A t i a c i a t i i , Uc .

t r n U a t U a i

Oatti

Oatii

T la i i

I l a i i

LABORATORY COMMENTS ON SAMPLE INTEGRITY UPON RECEIPT:

Trace Metals and Other Constituents

I r o n Manganese Copper Molybdenum Lead Antlaony Beryl l ium Cadmiun T o t a l Chromium

Arsen ic S i l v e r Mercury Selenium Zinc Nicke l Thal l ium Aluminum Barium

FIGURE 4 - 6 CHAIN OF CUSTODY ANALYSES REOUEST SCHEDULE FOR TRACE ELEMENTS

4.14

container lot numbers, if applicable

analyses required

method and date of delivery or shipment

preservatives used

sample destination

special handling procedures

Immediately after obtaining a water, air, or soil sample, a unique, pre

printed, pre-numbered, adhesive sample label will be affixed to the sample

container and traffic report by the field hydrogeologist. Sample lids and

sample labels will be secured with tape, and the samples will, be put on ice

in an ice chest. Vials for volatile organic analyses will be placed in

zip-lock bags and the supply of ice in the ice chest will be maintained to

provide proper cooling of the samples. The field hydrogeologist will

maintain custody of the samples from the time of collection to time of

delivery or shipment to the chemical laboratory. At the end of each sam

pling day, samples will be hand delivered or will be shipped to the chemi

cal laboratory via bus or via overnight air freight service. If the sam

ples are shipped, receipts for shipment will be obtained. The laboratory

will be notified prior to delivery or shipment of samples.

Prior to relinquishing sample custody for shipment, a minimum of two

custody seals marked with the sample custodian's initials will be placed

across the opening of the shipping container to detect unauthorized opening

of the container. Clear tape will be placed over the custody seals to

prevent accidental breakage of the seals during shipment. Samples will be

preserved by cooling with refrigeration, ice, or artificial substances

(such as "Blue Ice") from the time of collection to the time of receipt by

the laboratory. Thereafter, the laboratory will preserve the samples in

accordance with protocol of analytical methods. Chain of custody and

sample control procedures followed by the laboratory will be consistent

with the QAPP.

4.15

One original copy of the chain of custody documents will accompany the

sample shipping container to the laboratory; the sample custodian will

retain a copy of these docunients. On receipt of the samples at the labora

tory, the laboratory will complete the original chain of custody documents,

retain a copy for their records, and forward the completed originals to the

Tucson, Arizona, office of Errol L. Montgomery & Associates, Inc.

SAMPLE CONTAINERS

For laboratory chemical analyses of water and soil samples, clean

unused sample containers will be provided by the chemical laboratory.

Requirements for volume, type, and cleanliness of sample containers will be

consistent with requirements of the laboratory and with the analytical

methods to be used. A list of sample containers, preservatives, and hold

ing times for parameters to be analyzed is given in Table 4-2.

AIR SAMPLING METHODS

Air samples will be obtained at five monitoring stations at the hazar

dous waste area during TASK B. One station will be established upwind from

the site and will measure background air quality. Three monitoring sta

tions will be established at the downwind site perimeter. The fifth moni

toring station will be established over Pit 1. One duplicate sample will

be obtained over Pit 1 and one blank will be analyzed for quality assur

ance.

The air quality survey will be conducted during daylight hours, which

is the time when atmospheric conditions would be most favorable for vola

tilization of volatile organic compounds. The monitoring stations will be

4.16

equipped with air pumps that draw air through a TENAX tube. Each station

will be established on top of a supporting device and will sample air at a

height of four to six feet above land surface. Procedures described in the

previous section of Attachment 4 titled "CHAIN OF CUSTODY AND SAMPLE CON

TROL PROCEDURES" will be followed.

Volatile organic compounds in air are adsorbed onto the TENAX resin

and are subsequently desorbed in a chemical laboratory. Analytical methods

for analysis of the air samples are specified in Attachment 6 of the QAPP.

SOIL SAMPLING METHODS

Soil samples will be obtained during TASKS A, B, C, and D. Soil

samples will be obtained from soil borings, surface sediments, landfill

soil cover, and monitor wells. In addition, samples of drill cuttings,

drilling mud, etc., placed in the lined excavation in the hazardous waste

area will be obtained after several months of exposure to the atmosphere.

Quantities and frequency of soil samples and QA/QC samples to be obtained

are given in Table 4-1.

Soil Boring Samples

During soil boring operations (TASK A), four soil samples for labora

tory chemical analyses will be obtained from each of as many as 12 soil

borings. Nine of the soil borings will be located along the perimeter of

the hazardous waste area; three optional soil borings may be located in the

interior of the hazardous waste area (Figure 2). The three optional inter

ior soil borings will be drilled and sampled if results from drilling any

of the perimeter borings do not indicate obvious soil contamination based

on visual inspection of soil samples.

4.17

Soil samples for laboratory chemical analyses will be obtained from

each of the borings at four depth intervals, beginning at about 30 feet

below land surface. Number of soil boring samples to be obtained for

laboratory chemical analyses will be 36 for the nine perimeter borings and

12 for the three optional interior borings. Vertical spacing between

sampled intervals will be selected by the on-site hydrogeologist based on

data obtained during drilling; however, a spacing of five to 10 feet is

anticipated. Low permeable zones, where contaminants in the vadose zone

may tend to accumulate, will be targeted for sampling.

All soil boring samples obtained for laboratory chemical analyses from

soil borings will be analyzed for volatile organic compounds using EPA

method 8240. In addition, soil samples from the three optional interior

borings, from the perimeter boring southeast from Pit 2, and from the two

perimeter borings along the south boundary of the hazardous waste area

(Figure 2) will be analyzed for eight metals (arsenic, barium, cadmium,

chromium, lead, mercury, selenium, and silver) using the EPA EP Toxicity

method. For every 10 soil samples analyzed, a duplicate sample will be

prepared from the soil samples by the chemical laboratory (Table 4-1).

Duplicate soil samples will also be analyzed using EPA method 8240 and,

where obtained from a boring designated for metals analysis, for the EP

Toxicity metals. Individual compounds and metals to be analyzed with these

methods are listed in the QAPP.

An additional soil sample will be obtained from each of eight of these

borings for laboratory geotechnical analyses. These eight additional soil

samples will be analyzed for vertical hydraulic conductivity and moisture

content, and will be obtained from depths and borings selected by the on-

site hydrogeologist based on data obtained during drilling (Table 4-1).

Soil samples will be obtained in one of two ways, depending on the

drilling method selected. If the continuous-core hollow-stem flight auger

rig is used, soil samples will be removed from the core barrel, using clean

4.18

stainless steel scoops, and placed in glass jars. After the auger has

advanced to the specified depth, the core barrel will be removed and opened

at a sample processing station located near the drilling rig. Soil samples

will be obtained from a selected interval within the core barrel and placed

into clean wide-mouth glass jars. The sample interval within the core

barrel will be selected, based on appearance and texture, to provide a

sample that is most representative for the depth cored. The jars will be

filled as completely as possible to minimize air space, and will be sealed

with Teflon-lined or aluminum-lined lids. Procedures described in the

previous section of Attachment 4 titled "CHAIN OF CUSTODY AND SAMPLE CON

TROL PROCEDURES" will be followed. A lithologic description will be pre

pared for the interval recovered by the core barrel.

If a conventional hollow-stem flight auger rig is used, soil samples

will be obtained using California modified or split-spoon samplers with

clean four-inch or six-inch brass tube inserts. After the auger has been

advanced to the specified depth, the sampler will be driven ahead of the

auger. The sampler will be removed and opened at a sample processing

station located near the drill rig. The brass inserts will be removed from

the sampler, and a lithologic description will be prepared for soils in the

inserts. Based on appearance and texture of soils in the brass inserts,

brass insert samples considered to be representative for the depth sampled

will be selected for laboratory chemical analyses. Each selected insert

will be capped on both ends with Teflon or aluminum foil, sealed with tape,

marked with sample identifiers, and put in clean glass mason jars. The

mason jars will also be marked with sample identifiers and the chain of

custody and procedures described in the previous section titled "CHAIN OF

CUSTODY AND SAMPLE CONTROL PROCEDURES" will be followed. After the brass

inserts are removed, the samplers will be cleaned and equipped with addi

tional clean brass inserts for the collection of subsequent soil samples.

Soil samples obtained for laboratory geotechnical analyses will be

collected using a split-spoon sampler with brass tube inserts. The sampler

4.19

will be removed and opened at a sample processing station located near the

drill rig. The brass inserts will be removed from the sampler, and a

lithologic description will be prepared for soils in the inserts. Based on

appearance and texture of soils in the brass inserts, brass insert samples

considered to be representative for the depth sampled will be selected for

laboratory geotechnical analyses. Each selected insert will be sealed on

both ends with wax to prevent moisture loss, marked with sample identifi

ers, and put in clean glass mason jars. The mason jars will also be marked

with sample identifiers and procedures described in the previous section

titled "CHAIN OF CUSTODY AND SAMPLE CONTROL PROCEDURES" will be followed.

After the brass inserts are removed, the samplers will be cleaned and

equipped with additional clean brass inserts for the collection of subse

quent soil samples.

All brass tube inserts will be pre-cleaned by the chemical laboratory,

and will be used once and not reused. The core barrel, split-spoon sam

plers, and other sampling tools will be cleaned before and after the col

lection of each sample for laboratory chemical analyses, according to the

following procedure:

1. Clean with hot, high-pressure tap water spray;

2. Wash with trisodiumphosphate solution;

3. Rinse with tap water; and

4. Rinse with deionized water.

Surface Sediment Samples

During TASK C, samples of surface sediment for laboratory chemical

analyses will be obtained along representative potential drainage routes

from the hazardous waste disposal pit area to determine if past impacts on

surface sediment occurred. A maximum of five off-site composite surface

4.20

sediment samples from the selected drainages shown on Figure 2 (located in

a pocket at the back of the QAPP), and one sample from an off-site "back

ground" area, will be obtained and analyzed. The background sample will be

obtained at a topographically high point, outside any drainage ways, and a

minimum of 500 feet in an upwind direction from the Hassayampa Landfill.

Each sampling site will be marked with a wooden stake and located on a map

for future reference. Each surface sediment sample will be analyzed for

pesticides and PCB's using EPA method 8080, and for metals using sample

digestion (Table 4-1). Individual constituents to be analyzed with these

methods are listed in the QAPP.

The samples will be obtained using a stainless steel scoop, a stain

less steel bowl, and clean wide-mouth glass jars. At each sampling site, a

minimum of 10 scoops of surface sediment will be obtained from land surface

to a depth of about two inches within an area about two feet in diameter

and will be placed in a clean stainless steel bowl. The contents of the

bowl will then be thoroughly mixed. A jar will be filled with this mixture

as completely as practicable to minimize air space, and will be sealed with

a Teflon-lined or aluminum-lined lid. Procedures described in the previous

section titled "CHAIN OF CUSTODY AND SAMPLE CONTROL PROCEDURES" will be

followed. A lithologic description will be prepared for the samples. A

duplicate soil sample for QA/QC laboratory chemical analyses will be pre

pared by the chemical laboratory from the soil samples submitted.

Sampling tools will be cleaned before and after the collection of each

sample, according to the following procedure:

1. Rinse with tap water;




4.21

Landfill Soil Cover Samples

During TASK B, shallow holes will be dug into the soil cover over Pits

1, 2, 3, and 4 using a shovel or backhoe. At each of these pits, litholo

gic descriptions will be prepared, thickness will be measured for the soil

cover penetrated, and a representative composite sample of the soil cover

will be obtained for grain size analyses by a soil laboratory. Special

care will be taken to avoid complete penetration of the soil cover during

these inspections. The sample will be obtained using a stainless steel

scoop, a stainless steel bowl, and clean wide-mouth glass jars. At each

location for the shallow holes, a minimum of 10 scoops of soil will be

obtained from land surface to total depth of the soil cover and will be

placed in a clean stainless steel bowl. The contents of the bowl will then

be thoroughly mixed. A jar will be filled with this mixture. After the

four jars are obtained, labeling and custody procedures described in the

previous section titled "CHAIN OF CUSTODY AND SAMPLE CONTROL PROCEDURES"

will be followed. Standard grain size analyses will be conducted for each

sample by a soil laboratory using U. S. standard sieves. After sampling,

the shallow holes will be filled with the soil removed.

Monitor Well Soil Samples

During drilling operations for each of four selected monitor wells

(TASK D), two soil samples will be obtained from the Unit A (sandy

silt/silty clay unit) for laboratory geotechnical analyses for vertical

hydraulic conductivity. In addition, three soil samples for laboratory

chemical analyses will be obtained during abandonment (TASK D) of existing

on-site monitor well (C-l-6)3daa[HS-l]. The borings for geotechnical soil

samples and chemical soil samples will be advanced using rotary drilling

methods. Each sample will be obtained using California modified or split-

spoon samplers with brass tube inserts. Labeling and custody procedures

described in the previous section titled "CHAIN OF CUSTODY AND SAMPLE

4.22

CONTROL PROCEDURES" will be followed. Procedures for obtaining these

samples and for cleaning sampling equipment will be in accordance with

procedures given in the previous section titled "Soil Boring Samples".

Lined Excavation Samples

At the start of field operations, a lined excavation will be made in

an unused part of the fenced hazardous waste area and will be used for

placement of drill cuttings, drilling fluids, and rinsate. Materials in

this lined excavation will remain exposed to the atmosphere for a period of

several months, preferably summer months, after which a composite sample of

the materials will be obtained.

The composite sample will be obtained using a stainless steel scoop, a

stainless steel bowl, and a clean wide-mouth glass jar. Scoops of material

will be obtained from a minimum of 10 evenly spaced locations along the

length of the excavation. An effort will be made to obtain the scoops

midway between the top and bottom of the material. The scooped material

will be placed in a clean stainless steel bowl and the contents of the bowl

will then be thoroughly mixed. A jar will be filled with this mixture as

completely as practicable to minimize air space, and will be sealed with a

Teflon-lined or aluminum-lined lid. Procedures described in the previous

section titled "CHAIN OF CUSTODY AND SAMPLE CONTROL PROCEDURES" will be

followed. A description of the sampled material will be prepared. A

duplicate sample for QA/QC laboratory chemical analyses will be prepared by

the chemical laboratory from the soil samples submitted. The composite

sample and duplicate will be analyzed using: EPA method 8240 for volatile

organic compounds; EPA method 8270 for base-neutral and acid organic com

pounds; EPA method 8080 for pesticides and PCB's; EPA method for the char

acteristic of EP Toxicity; and appropriate tests for determining charac

teristics of hazardous wastes as defined under CERCLA.

4.23

Sampling tools will be cleaned before and after collection of the

sample, according to the following procedure:

1. Rinse with tap water;




WATER SAMPLING METHODS

Groundwater samples will be obtained during four sampling rounds as

follows:

TASK D ROUNDS 1 AND 2: All new UA and UB monitor wells will be sampled. Groundwater samples will be analyzed for: volatile organic compounds using EPA method 624; semi-volatile organic compounds using EPA method 625; pesticides and PCB's using EPA method 608; cyanide; routine constituents; trace elements; pH; and specific electrical conductance. Individual constituents to be analyzed with these EPA methods are listed in the QAPP.

TASK E ROUND 1: All new UA and UB monitor wells, and existing on-site monitor wells (C-l-3)3dac[HS-2] and (C-l-5)3ddal[HS-3] will be sampled. Groundwater samples will be analyzed for: volatile organic compounds using EPA method 624; semi-volatile organic compounds using EPA method 625; pesticides and PCB's using EPA method 608; cyanide; routine constituents; trace elements; pH; and specific electrical conductance.

TASK E ROUND 2: All new UA and UB monitor wells, and existing on-site monitor wells (C-l-3)3dac[HS-2] and (C-l-5)3ddal[HS-3] will be sampled. Groundwater samples will be analyzed for volatile organic compounds using EPA method 624 and any other potential contaminants detected and verified during the three previous sampling rounds.

4.24

For every 10 groundwater samples obtained for organic and/or inorganic

analyses, a duplicate and a field blank will be obtained and will be anal

yzed for the same parameters as the groundwater samples. As a check for

possible cross contamination or third source contamination, a trip blank

prepared by the chemical laboratory will accompany each group of samples

submitted for volatile organic analysis. Field blanks will be prepared by

the sampling personnel using bottled deionized water. Quantities and

frequency of groundwater samples and QA/QC samples to be obtained are given

in Table 4-1. A list of sample containers, preservatives, and holding

times for parameters to be analyzed is given in Table 4-2.

In addition, during TASK D round 1, a groundwater sample will be

obtained from existing on-site monitor well (C-l-5)3daa[HS-l] during aban

donment operations (TASK D) and will be analyzed for volatile organic com

pounds using EPA method 624. A duplicate will be obtained from this well

and will be analyzed for volatile organic compounds using EPA method 624.

If a nonaqueous hydrocarbon phase occurs in a UA monitor well, samples

of the nonaqueous phase will be bailed from the well and will be analyzed

solely for: volatile organic compounds using EPA method 624; and TPH

(Total Petroleum Hydrocarbons) using modified EPA method 8015.

The following procedures will be followed for collection of ground

water samples from the monitor wells:

1. At the beginning of each day of a sampling round, operation of large capacity wells located within one-half mile from the monitor wells to be sampled will be observed and recorded.

2. With the possible exception of groundwater samples obtained during well development operations (TASK D round 1), each well will be sampled using a submersible pump. A water level measurement, using an electrical water level sounder, will be obtained prior to pumping each well. The wellhead assembly for sampling operations at the new UA and UB monitor wells is shown on Figure 9 of the RI/FS Work Plan. A pump will be dedicated to each well.

4.25

3. A minimum volume of water equal to three borehole volumes will be pumped from each well prior to sampling. The minimum volume, in gallons, will be calculated using the following equation:

71 X (hole radius, in ft.)^ x (height of water in hole, in ft.)

Time when pumping starts and stops will be recorded in a field notebook.

4. During the pumping period, measurements of water level, pumping rate, and pH, temperature, and specific electrical conductance of pumped water will be obtained at intervals determined by the pumping rate and the volume to be pumped. Pumping rate will be determined by'measuring the time required to fill a container of known volume. After measurements of specific electrical conductance are stable (within +/- 10 percent of the average), and after a minimum of three borehole volumes have been pumped, water samples will be obtained from the discharge line. Temperature, pH, and conductance of pumped water will be measured immediately before samples are obtained.

5. All samples will be put on ice at the time of collection and procedures described in the previous section titled "CHAIN OF CUSTODY AND SAMPLE CONTROL PROCEDURES" will be followed. After groundwater samples are collected, a final water level measurement will be obtained and the pump will be turned off.

6. On arrival at a monitor well, the well vault, lock, and protective barrier posts will be inspected for security, damage, and vandalism. The well vault will be locked whenever authorized sampling personnel are not present.

7. If a hydrocarbon phase occurs on the water surface in a UA monitor well, the well will not be equipped with a permanent submersible pump and samples will be obtained from the well by bailing. Bailers will be dedicated to each of these wells.

a. Prior to sampling, a measurement of water level and free product thickness will be made using an ORS Interface Probe.

b. Samples will be obtained by bailing using a dedicated two-inch by five-foot clear Teflon or acrylic bailer equipped with a check valve. Water withdrawn with the first full bailer will be inspected for character and thickness of the hydrocarbon phase. A sample for laboratory chemical analyses will then be obtained from the hydrocarbon phase in the first full bailer and from as many subsequent bails as are necessary to obtain a sufficient volume of the hydrocarbon phase.

4.25

To minimize contact of sampling equipment with surficial soils, sampling

equipment will be placed on the cement pad at each well site or on the

tailgate of the sampling vehicle.

Water removed from each monitor well during development operations

(TASK D round 1) will be discharged to a lined excavation adjacent to the

well and will be allowed to evaporate naturally. Results of laboratory

analyses for the TASK D round 1 samples will be used to screen for con

taminants and to determine if water removed from the wells during subse

quent sampling operations should be also contained in the lined excava

tions. For subsequent sampling operations at each well, if potential

contaminants are not detected or are detected below Maximum Contaminant

Levels in the most recent sample from the well, the water removed during

sampling operations will be discharged via a perforated hose or pipe to the

land surface for evaporation.

Drill Water Samples

As a precautionary check and documentation for drilling water to be

used during construction of the UA and UB monitor wells, water samples from

the water truck used for drilling operations will be obtained prior to

drilling the first monitor well and after drilling the last Stage I monitor

well. These samples will be analyzed for volatile organic compounds using

EPA method 624. Individual compounds to be analyzed with this method are

listed in the QAPP.

Measurement of Groundwater Levels

Groundwater level measurements will be made using an electrical water

level sounder and a steel tape. Prior to groundwater level measurement,

the sounder will be rinsed with deionized water and wiped with a clean

4.27

paper towel. Groundwater levels will be recorded to the nearest 0.01 foot

on water level record forms (Figure 4-1). Site identifier, weather condi

tions, date and time of measurement, elevation and description of measuring

point, and distance of measuring point from land surface will be included

in the information recorded. Sounders will be dedicated to the project.

The sounders will be calibrated with a steel surveyor chain before each

round of water level measurements and when repairs are made. A calibration

notebook will be maintained for each sounder and will include: date and

time calibrated; points of calibration; personnel conducting the calibra

tions; and method of calibration. In addition, manufacturer recommended

maintenance of the instruments will be conducted and results recorded.

Parameters Measured in the Field

Specific electrical conductance, temperature, and pH of water will be

measured in the field during pumping test and sampling operations. Speci

fic electrical conductance of water will be measured using a Beckman Solu

Bridge conductivity meter, or equivalent. Measurements of pH will be made

using a Beckman pHI 20 or pHI 21 digital pH meter, or equivalent. These pH

meters also measure temperature. Measurement of pH and temperature will

also be made using pH paper and a laboratory grade thermometer. The con

ductivity meter and pH meter will be calibrated with standard solutions

before each pumping test and sampling round. Notes from the calibrations

will be recorded in the field notebook. In addition, manufacturer recom

mended maintenance of the instruments will be conducted and results re

corded.

Water samples for measurement of these parameters in the field will be

obtained in a wide-mouth one-liter polyethylene bottle. The bottle will be

rinsed three times with the water to be sampled. After rinsing, the bottle

will be filled and measurements of the parameters will be made and record-

4.28

ed. Before and after each measurement, the meter probes and the therm

ometer will be rinsed with deionized water.

Samples for Organic Analyses

Water samples for volatile organic analyses will be obtained from each

monitor well in two 40-miniliter screwcap glass vials fitted with Teflon-

coated silicon septa. The vials (no. 13074) and septa (no. 12722) are sold

by Pierce Chemical Company, Rockford, Illinois, and will be obtained from

the chemical laboratory in a clean and new condition. Sampling will be

conducted so as to minimize exposure of the sample to air. First, the vial

and cap will be rinsed three times with the water stream to be sampled.

After rinsing, four drops of reagent grade 1:1 hydrochloric acid will be

added to the vial. The vial will then be filled with the sample water to

attain a convex meniscus at the top of the vial. Only the sample water

will contact the inside of the vial or cap. The vial will be sealed im

mediately after filling by placing the septum, Teflon side down, on the

meniscus and screwing the cap firmly in place. The vial will be checked

for trapped air by inverting the vial, tapping it gently, and inspecting

for headspace (air bubbles). If headspace is present, the vial will be

emptied and the process will be repeated until no headspace is observed.

If it is necessary to analyze for TPH (Total Petroleum Hydrocarbons)

for any UA monitor well, samples for TPH analyses will be obtained in the

same manner as water samples for volatile organic analyses.

Groundwater samples for analyses of semi-volatile organic compounds,

pesticides, and PCB's will be obtained in four one-liter, screwcap, amber

glass bottles with Teflon-coated caps. Sampling will be conducted so as to

minimize exposure of the sample to air. Methods for filling the bottles

will be the same as described above for the vials, except that hydrochloric

4.29

acid will not be used, a septum will not be used, and the occurrence of

headspace will not be cause for refilling the bottle.

For every 10 groundwater samples obtained for organic analyses, a

duplicate and a field blank will be obtained and will be analyzed for the

same parameters as the groundwater samples. As a check for possible cross

contamination or third source contamination, a trip blank prepared by the

chemical laboratory will accompany each group of samples submitted for

volatile organic analysis. Field blanks will be prepared by the sampling

personnel using bottled deionized water.

Samples for Routine. Trace Element, and Cyanide Analyses

Groundwater samples for analysis of routine parameters, trace ele

ments, and cyanide will be obtained in new, clean, one-liter polyethylene

bottles. The bottles will have relatively long screwcaps with a positive

seal lip on the bottle. Prior to filling, the bottle and cap will be

rinsed three times with the water stream to be sampled. After rinsing, the

bottle will be filled and sealed immediately by screwing the cap firmly in

place. Only the sample water will contact the inside of the bottle or cap.

Separate bottles will be used for each routine parameter, cyanide, or trace

element analysis.

Groundwater samples for trace element analyses will be filtered im

mediately in the field and will be acidified by adding a sufficient amount

of reagent grade 1:1 nitric acid to each bottle to lower the pH to less

than two. The bottles will be shaken gently after capping to evenly dis

perse the acid. Acid preservation and amount of acid used will be noted in

the sample custody documents.

Groundwater samples for cyanide analysis and routine analysis will not

be filtered in the field. Groundwater samples for cyanide analysis will be

4.30

treated with sodium hydroxide to raise the pH to 12. The bottles for

cyanide analyses will be shaken gently after capping to evenly disperse the

sodium hydroxide. Method of preservation for the cyanide sample will be

noted in the sample custody documents.

For every 10 groundwater samples obtained for inorganic analyses, a

duplicate and a field blank will be obtained and will be analyzed for the

same parameters as the groundwater samples. Field blanks will be prepared

by the sampling personnel using bottled deionized water.

4.31

LABORATORY PROCEDURES

All samples submitted for analyses during this project will be handled

and analyzed by the chemical laboratories in accordance with standard

procedures and methods established by the laboratories and in accordance

with the intent of the EPA Contract Laboratory Program. These procedures

and methods include requirements for: purity of standards, solvents, and

reagents; glassware; analytical methods; data requirements; laboratory

performance; and analytical data review. Detailed discussions for these

procedures and methods are given in the QAPP. The chemical laboratories

selected for the RI/FS are:

LABORATORY

Analytical Technologies, Inc. 2113 South 48th Street, Suite 108 Tempe, Arizona 85282

Clayton Environmental Conslts, Inc, 1252 Quarry Lane Pleasanton, California 94566

Brown and Caldwell 373 South Fair Oaks Avenue Pasadena, California 91105

BC Laboratories, Inc. 4100 Pierce Road Bakersfield, California 93308

INTENDED USE

Principal laboratory for analyses of organic and inorganic parameters in water and soil samples.

Alternate laboratory for analyses of organic and inorganic parameters in water and soil samples.

Alternate laboratory for analyses of organic and inorganic compounds in water and soil samples.

Alternate laboratory for analyses inorganic parameters in water and soil samples.

The laboratories will follow QA/QC procedures and methods, and will provide

QA/QC documentation, which provide reliability of data equivalent to that

intended by the EPA Contract Laboratory Program. All laboratory chemical

analyses will be conducted in accordance with standard protocols applicable

to each method.

4.32

e

QA/QC protocols for the principal laboratory (Analytical Technologies,

Inc.) are given in "Analytical Technologies, Inc. Laboratory Quality As

surance Plan". This document is available for review on request. In

addition, the QA/QC protocols for the principal laboratory and the alter

nate laboratories will be consistent with the QAPP and with the intent of

the following publications:

1. "Laboratory Data Validation Functional Guidelines for Evaluating Organics Analyses", Technical Directive Document No. HQ-8410-01, prepared for the Hazardous Site Control Division of the U. S. Environmental Protection Agency, April 11, 1985.

2. "Laboratory Data Validation Functional Guidelines for Evaluating Inorganics Analyses", U. S. Environmental Protection Agency Office of Emergency and Remedial Response.

3. "Statement of Work for Organics Analysis", U. S. Environmental Protection Agency Contract Laboratory Program, October 1986.

4. "Statement of Work for Inorganics Analysis", U. S. Environmental Protection Agency Contract Laboratory Program, SOW No. 787, July 1987.

ANALYTICAL METHODS

Methods to be used for laboratory chemical analyses for water and soil

samples are listed in Table 4-1; individual constituents to be analyzed

using these methods are listed in the QAPP. Analytical methods for anal

ysis of the air samples are specified in Attachment 6 of the QAPP.

ATTACHMENT 5

HYDROCARBON CHARACTERIZATION

(MODIFIED 8015)

HYDROCARBON CHARACTERIZATION/FUEL FINGERPRINT ANALYSIS (Modified EPA 8015)

by GC-FID

[REVISION 4A]

1.0 Scope and Application:

This method is used to determine the concentration of Fuel Hydrocarbons (Cs - C30 ) in solid and aqueous matrices. Method detection limits for solids and waters are 5mg/Kg and Img/L, respectively. It is used to detect the following substances:

Gasoline * Benzene

Diesel Toluene

Xylene Naptha

Ethyl Benzene Stoddard Solvent

Jet Fuel Paint Thinner Kerosene Mineral Spirits

Excludes the hydrocarbon fraction C5 and below, will be insignificant in weathered gasoline.

which

2.0 Summary of Method:

This method provides an extraction procedure and chromatographic conditions for the detection of fuel hydrocarbons in the carbon range of C5 " ' 30. A weighed amount of solid matrix is extracted using pentane as the extraction solvent by shaking for 1 minute. A measured volume of aqueous matrix is extracted with pentane. Quantitative analysis is done using direct injection of 2.0 uL of organic solvent extract into a gas chromatograph (GC). A temperature program is used in the GC to separate the organic compounds. Detection is achieved by a flame ionization detector (FID). Quality control is monitored by the matrix spike and matrix spike duplicate for precision and accuracy.

3.0 Apparatus and Materials:

Gas Chromatograph with Flame Ionization Detector

Integrator

GC Column: Bonded RSL-200 one (1) micron; 30m X 0.25mm Heliflex

Mettler Balance (top-loader)

4 0-ml screw-cap vial with teflon cap liner

20-ml screw-cap vial with teflon cap liner

Graduated Cylinder

Spatula

4.0 Reagents

Pentane - Pesticide quality

Sodium Sulfate (Na2S04) - granular, kiln-dried

Organic-free Water

Gasoline Standard - prepared from Unocal regular unleaded

Diesel Standard - prepared from Chevron

BTXE Standards - mixture of benzene, toluene, xylenes and ethyl benzene neat standards obtained from Chem Services

5.0 Procedures:

5.1 Extraction:

5.1.1 For aqueous matrix:

Measure 25 ml of aqueous sample into a 40-ml teflon-lined, screw-capped vial. Add 50 ul of ICOOO ppm Di-N-Octylphthalate as surrogate compound. Extract with 5.0 ml pentane as organic extraction solvent. Rotate on a mechanical rotator for 5 minutes. Adjust speed of rotator to approximately 40 revolutions per minute (+5). Set timer for 15 seconds, count the number of revolutions (between 9 and 11 is acceptable). Let layers

Analyze the organic layer by direct of 2.0 uL pentane extract into GC-

separate. injection FID.

5.1.2 For solid matrix:

Weigh out approximately 10.0 g of solid sample into a 20-ml teflon-lined, screw-capped vial. Add about 2.0 g of Na2S04 (ashed). Add 100 ul of IOOOO ppm Di-N-Octylphthalate as surrogate. Shake to mix. Extract with 10.0 ml pentane as organic extraction solvent by shaking for 1 minute. Let layers separate. Analyze the organic layer by direct injection of 2.0 uL pentane extract into GC-FID.

5.2 Gas chromatographic column and operating conditions for the instrument are:

Column: Bonded RSL-200 One (1) micron; 30m X 0.25 mm I.D. Heliflex

Detector: Flame Ionization Detector

Injection Method: Splitless mode with vent time at

t = 1.5 minutes

Programmed Temperature:

Initial Temperature = 45 C, hold for t = 4 minutes Rate =12.0 C/min. to Final Temp. = 280 C, hold for 22 min.

Run Time: 44 minutes

Gas Flows:

H =30 ml/min

Air = 3 00 ml/min

Split (He) = 100 ml/min

Septum Sweep = 5 ml/min

Column Pressure = 15 psi

5.3 Calibration

Adjust sensitivity of the instrxoment for the compounds or substances being analyzed to see at least 1.0 ng/uL BTXE and 5.0 ng/ul Diesel and/or Gasoline on column. A standard will be analyzed at these concentrations to confirm this method detection limit.

5.3.1 Calibrate using external standard calibration

5.3.1.1 External Standard Calibration Procedure

Prepare calibration standards at a minimum of three concentration levels. One of the external standards should be at concentration near, but above, the detection limit. The other concentrations should correspond to the working range of the detector.

a) For Gasoline Calibration:

Prepare 10 ppm, 150 ppm, 500 ppm and 1500 ppm of Gasoline Standards in pentane.

b) For Diesel/BTXE Calibration:

Prepare a BTXE Standard mixture of benzene, toluene, xylenes and ethyl benzene neat standards in pentane. Make a Diesel/BTXE combined standard mixture by preparing 3 0/1 ppm, 150/5 ppm, 500/10 ppm and 1500/20 ppm respectively.

5.3.1.2 Using 2.0 uL injection of each calibration standard, calculate the ratio of the response to the mass injected of the standard of column which is defined as calibration factor (CF). The calibration curve is linear if the relative standard deviation (RSD) of the calibration factor is less than or equal to 10% (RSD < 10%).

5.3.1.3 The working calibration curve is verified each eight-hour shift by the measurement of one or more calibration standards. If the response varies more than + 15%, the analysis is repeated using a fresh calibration standard. If this response does not meet criteria, a new calibration curve is analyzed.

5.4 Gas Chromatographic Analysis:

5.4.1 Inject 2.0 uL of the pentane extract of the sample into GC.

5.4.2 If the peak areas or peak height exceed the linear range of the system, dilute the extract and reanalyze.

5.4.3 Quantitation is done by ratio of total peak area of the sample versus the standard. Peak integration is started after the solvent peak returns to baseline. If significant peaks appear as shoulders on the solvent peak, these peaks can be included in the total area at the discretion of the analyst.

5.4.4 All chromatograms are manually inspected by the analyst to insure that extraneous background peaks (heavies) are not included in the total area calculation of the sample. Raw data is reintegrated, with new basepoints manually inserted by the analyst using graphical analysis on the CLAS system.

5.4.5 Chromatograms of our gasoline and BTXE/diesel standards are included as Attachment 1 and Attachment 2.

6.0 Quality Control:

6.1 Each time a set of samples is extracted or there is a change in reagents, a method blank is done to check for laboratory contamination. It should be carried through all the stages of sample preparation and measurement steps.

6.2 Matrix spike and matrix spike duplicate is done for each batch of ten samples (10%) of a similar matrix to check for precision and accuracy. Spiking is done directly into the sample prior to extraction. The spiking levels of fuel hydrocarbons are 500 mg/Kg for soils, and 100 mg/L for waters.

6.3 Surrogate spike recovery is quantitated for each reagent blank, matrix spike/matrix spike duplicate, and each sample. Surrogate recoveries should be within 70-120% for soils and 55-110% for water samples. This applies to samples we are able to run without dilution. Matrix spike precision and accuracy limits are included as Attachment 3.

6.4 If surrogate recoveries fall outside of the established limits, the individual sample is reextracted. If recovery is outside of limits the second time, sample matrix interference is assumed.

6.5 If the matrix spike precision or accuracy data falls outside of the warning limits but within the control limits, the data is reviewed by a senior analyst. Required action will be up to the discretion of the senior analyst.

If the matrix spike precision or accuracy data falls outside the control limits, the supervisor is informed. All data are reviewed. All affected samples are reextracted, with matrix spike and matrix spike duplicate samples prepared from reagent soil. If QA/QC limits are still not met, analysis of samples is halted until the problem is resolved.

IjfPj S I IJ I i n r E 1:^-^11.0 1 GAS STANDARD

500ppm

IAPAO ri

'\ . 6 0

- e». 5'?

ATTACHMENl 1

111:5 I R U t l E I i r : t j ^

U M T E T I M E : e i

P H G E n o . : 0 1

0 . 0 0 - I . I O 8 . 3 0 1 ? . 2 0 i r . t " 0 2 2 . 0 0 2 ' S . 10 ••3n o 0 . 3 0 S" -.

•5 2 2 : 0 3 : ' I '

to r t

a i o I

3 I o n

a 3 -

Dl

01

j -n , Kty .\ J , 1^1

• .v i i l l lL ! : M M . •:

TEST M O . :

ItETMOl- MO. :

2 ^ . 00

2 2 . 4 5

1 '~' . !?0

17. :?

1 - 1 . SO

1 2 . 2 3

9 . 70

7 , I

•1 . t o

Ui. : ) l P P IJ II ••EI t: i2":-M.ut DIESEL/BTXE STANDARD

)P )

i i l 'Ho - t i l lH::

L1 ' . I I

I ULLI.,

lM:En!:'.M!En I • 0^

HnTE T I M E : 0 1 ,

r i i G E Mu . : 01

ATTACHMENT 2

^;p II' : I '2 - 1' ' . ' '

A B C D E F G

Benzene - Sl.Sppm Toluene - 34.3ppin Ethylbenzene - 35.8ppin O & M xylene - Sl.lppm P-xylene - 19.6ppm Diesel - SOOppm Di-n-octylphthalate surrogate - lOOppm

G

.'irfiiri.-i.-

o . no -I . -10 '?0 I:?. 20 .<. 7.b0 22.00 2iC.-10 :30.-Ô .?v.20 3"?. y'i} -M.OO

ATTACHMENT 3

MATRIX SPIKE QA/QC LIMITS

Modified 8015 (Water)

Precision Limits (RPD) Warning Control

Accuracy Limits (% Recovery) Warning Control

Diesel Gasoline

26 13

34 16

55-114 67-99

44-129 59-107

Modified 8015 (Soil)

Diesel Gasoline

29 28

37 36

60-125 54-130

44-141 35-150

% RECOVERY = (SPIKE SAMPLE RESULT - SAMPLE RESULT)

SPIKE CONCENTRATION X 100

RPD (RELATIVE % DIFFERENCE) =» (SPIKED SAMPLE - DUPLICATE SPIKE) RESULT SAMPLE RESULT

AVERAGE OF SPIKED SAMPLE 100

ATTACHMENT 6

ANALYTICAL METHODS FOR

ANALYSIS OF AIR SAMPLES

TARGET DETECTION LIMITS FOR

ANALYSIS OF AIR SAMPLES

USING EPA METHOD TOI

Air samples obtained during TASK B of the RI/FS Work Plan will be

analyzed using EPA method TOI, as described in the following excerpt from

EPA publication 600/4-84-041, dated April 1984 and entitled:

COMPENDIUM OF METHODS FOR THE DETERMINATION OF TOXIC ORGANIC COMPOUNDS IN AMBIENT AIR

The target detection limit for analysis of air samples by this method is

one microgram per cubic meter. The actual detection limit for this method

may be affected by background concentrations, matrix interference, and

volume of sample obtained, and may be somewhat higher or lower than the

target detection limit.

METHOD TOI Revision 1.0 April, 1984

METHOD FOR THE DETERMINATION OF VOLATILE ORGANIC COMPOUNDS IN AMBIENT AIR USING TENAX* ADSORPTION AND

GAS CHROMATOGRAPHY/MASS SPECTROMETRY (GC/MS)

1. Scope

1.1 The document describes a generalized protocol for collection

and detennination of certain volatile organic compounds

which can be captured on Tenax® GC (poly(2,6-Diphenyl

phenylene oxide)) and detennined by thermal desorption

GC/MS techniques. Specific approaches using these techniques

are described in the literature (1-3).

1.2 This protocol is designed to allow some flexibility in order

to accommodate procedures currently in use. However, such

flexibility also results in placement of considerable

responsibility with the user to document that such procedures

give acceptable results (i.e. documentation of method performance

within each laboratory situation is required). Types of

documentation required are; described elsewhere in this method.

1.3 Compounds which can be determined by this method are nonpolar

organics having boiling points in the range of approximately

80" - 200°C. However, not all compounds falling into this

category can be detennined. Table 1 gives a listing of

compounds J o r which the method has been used. Other compounds

may yield satisfac^sory results but validation by the individual

user is required.

2. Applicable Documents

2.1 ASTM Standards:

01356 Definitions of Terms Related to Atmospheric Sampling

and Analysis.

E355 Recommended Practice for Gas Chromatography Terms and

Relationships,

TOl-2

2.3 Other documents:

Existing procedures (1-3).

U.S. EPA Technical Assistance Document (4).

3. Summary of Protocol

3.1 Ambient air is drawn through a cartridge containing '\.l-2

grams of Tenax and certain volatile organfc compounds are

trapped on the resin while highly volatile organic compounds

and most inorganic atmospheric constituents pass through the '•

cartridge. The cartridge is then transferred to the

laboratory and analyzed.

3.2 For analysis the cartridge is placed In a heated chamber and

purged with an inert gas. The inert gas transfers the

volatile organic compounds from the cartridge onto a cold trap

and subsequently onto the front of the GC column which is held

at low temperature (e.g. - y C C ) . The GC column temperature is

then increased (temperature programmed) and the components

eluting from the column are identified and quantified by mass

spectrometry. Component identification is normally accomplished,

using a library search routine, on the basis of the GC retention

time and mass spectral characteristics. Less sophistacated

detectors (e.g. electron capture or flame ionization) may be

used for certalii applications but their suitability for a given

application niust be verified by the user.

3.3 Due to the complexity of ambient air samples only high resolution

(i.e. capillary) GC techniques are considered to be acceptable

In this protocol.

4. Significance

4.1 Volatile organic compounds are emitted into the atmosphere from

a variety of sources including Industrial and commercial

facilities, hazardous waste storage facilities, etc. Many of

these compounds are toxic; hence knowledge of the levels of

TOl-3

such materials in the ambient atmosphere is required in order

to determine human health Impacts.

4.2 Conventional air monitoring methods (e.g. for workspace

monitoring) have relied on carbon adsorption approaches with

subsequent solventdesorption. Such techniques allow

subsequent injection of only a small portion, typically 1-5%

of the sample onto the GC system. However, typical

ambient air concentrations of these compounds require a more

sensitive approach. The thermal desorption process, wherein

the entire sample is introduced into the analytical (GC/MS)

system fulfills this need for enhanced sensitivity.

5. Definitions

Definitions used In this document and any user prepared SOPs should

be consistent with ASTM Dl356(6). All abbreviations and symbols

are defined with this document at the point of use.

6. INTERFERENCES

6.1 Only compounds having a similar mass spectrum and GC retention

time compared to the compound of interest will Interfere in

the method. The most commonly encountered interferences are

structural Isomers.

6.2 Contamination of the Tenax cartridge with the compound(s)

of interest is a commonly encountered problem in the method.

The user must be extremely careful in the preparation, storage,

and handling of the cartridges throughout the entire sampling

and analysis process to minimize this problem.

7. Apparatus

7.1 Gas Chromatograph/Mass Spectrometry system - should be capable

of subambient temperature programming. Unit mass resolution

or better up to 800 amu. Capable of scanning 30-440 amu region

every 0.5-1 second. Equipped with data system for Instrument

control as well as data acquisition, processing and storage.

TOI-4

7.2 Thermal Desorption Unit - Designed to accommodate Tenax

cartridges in use. See Figure 2a or b.

7.3 Sampling System - Capable of accurately and precisely

drawing an air flow of 10-500 ml/minute through the Tenax

cartridge. (See Figure 3a or b.)

7.4 Vacuum oven - connected to water aspirator vacuum supply.

7.5 Stopwatch

7.6 Pyrex disks - for drying Tenax.

7.7 Glass jar - Capped with Teflon-lined screw cap. For

storage of purified Tenax.

7.8 Powder funnel - for delivery of Tenax into cartridges.

7.9 Culture tubes - to hold individual glass Tenax cartridges.

7.10 Friction top can (paint can) - to hold clean Tenax cartridges.

7.11 Filter holder - stainless steel or aluminum (to acconmodate

1 inch diameter filter). Other sizes may be used if desired,

(optional)

7.12 Thermometer - to record ambient temperature.

7.13 Barometer (optional).

7.14 Dilution bottle - Two-liter with septum cap for standards

preparation.

7.15 Teflon stirbar - 1 inch long.

7.16 Gas-tight glass syringes with stainless steel needles -

10-500 nl for standard Injection onto GC/MS system..

7.17 Liquid microliter syringes - 5,50 nL for injecting neat

liquid standards Into dilution bottle.

7.18 Oven - 60 + S' C for equilibrating dilution flasks.

7.19 Magnetic stirrer.

7.20 Heating mantel.

7.21 Variac

7.22 Soxhlet extraction apparatus and glass thimbles - for purifying

Tenax.

7.23 Infrared lamp - for drying Tenax.

7.24 6C column - SE-30 or aUernative coating, glass capillary or

fused silica.

i.

TOI-5

7.25 Psychrometer - to determine ambient relative humidity,

(optional).

8. Reagents and Materials

8.1 Empty Tenax cartridges - glass or stainless steel (See

Figure la or b).

8.2 Tenax 60/80 mesh (2,6-dlphenylphenylene oxide polymer).

8.3 Glasswool - silanized.

8.4 Acetone - Pesticide quality or equivalent.

8.5 Methanol - Pesticide quality, or equivalent.

8.6 Pentane - Pesticide quality or equivalent.

8.7 Helium - Ultra pure, compressed gas. (99.9999%)

8.8 Nitrogen - Ultra pure, compressed gas. (99.9999%)

8.9 Liquid nitrogen.

8.10 Polyester gloves - for handling glass Tenax cartridges.

8.11 Glass Fiber Filter - one inch diameter, to fit in filter holder,

(optional)

8.12 Perfluorotributyl amine (FC-43).

8.13 Chemical Standards - Neat compounds of interest. Highest

purity available.

8.14 Granular activated charcoal - for preventing contamination of-

Tenax cartridges during storage.

9. Cartridge Constructl-on and Preparation V

9.1 Cartridge Design

9.1.1 Several cartridge designs have been reported in the

literature (1-3). The most common (1) is shown in

Figure la. This design minimizes contact of the

sample with metal surfaces, which can lead to

decomposition in certain cases. However, a

disadvantage of this design is the need to rigorously

avoid contamination of the outside portion of the

cartridge since the entire surface is subjected to the

purge gas stream during the desorption porcess.

TOI-6

Clean polyester gloves must be worn at all times

when handling such cartridges and exposure of the

open cartridge to ambient air must be minimized.

9.1.2 A second common type of design (3) is shown in

Figure lb. While this design uses a metal (stainless

steel) construction, it eliminates the need to avoid

direct contact with the exterior surface since only

the Interior of the cartridge is purged.

9.1.3 The thermal desorption module and sampling system

must be selected to be compatible with the particular

cartridge design chosen. Typical module designs

are shown in Figures 2a and b. These designs are

suitable for the cartridge designs shown in Figures

la and lb, respectively.

9.2 Tenax Purification

9.2.1 Prior to use the Tenax resin is subjected to a

series of solvent extraction and thermal treatment

steps. The operation should be conducted in an area

where levels of volatile organic compounds (other than

the extraction solvents used) are minimized.

9.2.2 All glassware used in Tenax purification as well as

cartridge materials should be thoroughly cleaned by

water rinsing followed by an acetone rinse and dried

in an oyeh at 250''C.

9.2.3 ûlk Tenax is placed in a glass extraction thimble

and'held in place with a plug of clean glasswool.

The resin is then placed in the soxhlet extraction

apparatus and extracted sequentially with methanol

and then pentane for 16-24 hours (each solvent) at

approximately 6 cycles/hour. Glasswool for cartidge

preparation should be cleaned in the same manner as

Tenax.

9.2.4 The extracted Tenax is immediately placed in an open

glass dish and heated under an infrared lamp for two

TOl-7

hours In a hood. Care must be exercised to avoid

over heating of the Tenax by the infrared lamp.

The Tenax is then placed in a. vacuum oven (evacuated

using a water aspirator) without heating for one hour.

An inert gas (helium or nitrogen) purge of 2-3

ml/minute is used to aid in the removal of solvent

vapors. The oven temperature 1s then Increased to

110°C, maintaining inert gas flow and held for one

hour. The oven temperature control is then shut

off and the oven is allowed to cool to room temperature.

Prior to opening the oven, the oven is slightly

pressurized with nitrogen to prevent contamination

with ambient air. The Tenax Is removed from the oven

and sieved through a 40/60 mesh sieve (acetone rinsed

and oven dried) into a clean glass vessel. If the Tenax

is not to be used immediately for cartridge preparation

It should be stored in a clean glass jar having a

Teflon-lined screw cap and placed in a desiccator.

9.3 Cartridge Preparation and Pretreatment

9.3.1 All cartridge materials are pre-cleaned as described

In Section 9.2.2. If the glass cartridge design shown

in Figure la is employed all handling should be

conducted wearing polyester gloves.

9.3.2 The cartridge is packed by placing a 0.5-lcm glass-

wool plug in the base of the cartridge and then

" filling the cartridge to within approximately 1 cm

of the top. A 0.5-lcm glasswool plug is placed in

the top of the cartridge.

9.3.3 The cartridges are then thermally conditioned by

heating for four hours at 270''C under an inert gas

(helium) purge (100 - 200 ml/min).

m

' TOI-8

9.3.4 After the four hour heating period the cartridges

are allowed to cool. Cartridges qf the type shown

in Figure la are immediately placed (without cooling)

in clean culture tubes having Teflon-lined screw caps

with a glasswool cushion at both the top and the bottom.

Each tube should be shaken to ensure that the cartridge

Is held firmly in place. Cartridges of the type shown

in Figure lb are allowed to cool to room temperature under

inert gas purge and are then closed with stainless steel

plugs.

9.3.5 The cartridges are labeled and placed in a tightly

sealed metal can (e.g. paint can or similar friction

top container). For cartridges of the type shown

In Figure la the culture tube, not the cartridge,!s

labeled.

9.3.6 Cartridges should be used for sampling within 2 weeks

after preparation and analyzed within two weeks after

sampling. If possible the cartridges should be stored

at -20''C in a clean freezer (i.e. no solvent extracts

or other sources of volatile organics contained in the

freezer).

10. Sampling

10.1 Flow rate and Total*-Volume Selection

10.1.1 Each compound has a characteristic retention volume

(liters of air per gram of adsorbent) which must not

be exceeded. Since the retention volume is a function

of temperature, and possibly other sampling variables,

one must include an adequate margin of safety to

ensure good collection efficiency. Some considerations

and guidance in this regard are provided in a recent

report (5). Approximate breakthrough volumes at 38*'C

(lOO'F) in liters/gram of Tenax are provided in Table 1,

These retention volume data are supplied only as rough

guidance and are subject to considerable variability, depending on cartridge design as well as sampling

parameters and atmospheric conditions.

TOl-9

10.1.2 To calculate the maximum total volume of air which

can be sampled use the following equation:

V M A X = I b ^ 1.5

where

VMAX is the calculated maximum total volume in liters.

V|3 is the breakthrough volume for the least retao'ned

compound of interest (Table 1) in liters per gram

of Tenax.

W is the weight of Tenax in the cartridge, in grams..

1.5 is a dimensionless safety factor to allow for

variability in atmospheric conditions. This factor

is appropriate for temperatures in the range of

25-30°C. If higher temperatures are encountered the

factor should be increased (i.e. maximum total volume

decreased).

10.1.3 To calculate maximum flow rate use the following

equation:

QHAX = - ^ - '""o

where

QMAX '"""is the calculated maximum flow rate in milli-

<i leters per minute.

t is the desired sampling time in minutes. Times

greater than 24 hours (1440 minutes) generally

are unsuitable because the flow rate required

is too low to be accurately maintained.

10.1.4 The maximum flow rate QMAX should yield a linear flow

velocity of 50-500 cm/minute. Calculate the linear

velocity corresponding to the maximum flow rate

using the following equation:

B - ^MAX

irr

TOl-10

where

B is the calculated linear flow velocity in

centimeters per minute.

r is the internal radius o f the cartridge in

centimeters. If B is greater than 500 centimeters per minute

either the total sample volume (^MAX) should be

reduced or the sample flow rate (QMAX) should be

reduced by increasing the collection time. If B is

less than 50 centimeters per minute the sampling rate

( Q M A X ) should be increased by reducing the sampling

time. The total sample value (^MAX) cannot be

increased due to component breakthrough.

10.1.4 The flow rate calculated as described above defines

the maximum flow rate allowed. In general, one should

collect additional samples in parallel, for the same

time period but at lower flow rates. This practice

yields a measure of quality control and is further

discussed in the literature (5), In general, flow

rates 2 to 4 fold lower than the maximum flow rate

should be employed for the parallel samples. In

all cases a constant flow rate should be achieved

for each cartridge since accurate integration of the

analyte codcentration requires that the flow be

coQStant'over the sampling period.

10.2 Sample Collecti on

10.2.1 Collection of an accurately known volume of air

is critical to the accuracy of the results. For

this reason the use of mass flow controllers,

rather than conventional needle valves or orifices

Is highly recommended, especially at low flow

velocities (e.g. less than 100 milliliters/minute)

Figure 3a illustrates a sampling system utilizing

mass flow controllers. This system readily allows

for collection of parallel samples. Figures 3b

shows a commercially available system based on r lecWle.,Va/ve "r/ow con-fr-o fle.rs.

TOI-11

10.2.2 Prior to sample collection insure that the sampling

flow rate has been calibrated over a range including

the rate to be used for sampling, with a "dummy"

Tenax cartridge in place. Generally calibration

is accomplished using a soap bubble flow meter

o r calibrated wet test meter. The flow calibration

device is connected to the flow exit, assuming

the entire flow system is sealed. ASTM Method

D3686 describes an appropriate calibration scheme,

not requiring a sealed flow system downstream

of the pump.

10.2.3 The flow rate should be checked before and after .

each sample collection. If the sampling interval

exceeds four hours the flow rate should be checked

at an intermediate point during sampling as well.

In general, a rotameter should be included, as

showed in Figure 3b, to allow observation of the

sampling flow rate without disrupting the sampling

process.

10.2.4 To collect an air sample the cartridges are removed

from the sealed container just prior to initiation

of the collection process. If glass cartridges

(Figure la) are employed they must be handled

only with polyester gloves and should not contact

any other surfaces.

10.2.5 A,particulate filter and holder are placed on

the inlet to the cartridges and thc exit end

of the cartridge is connected to the sampling

apparatus. In many sampling situations the use

of a filter is not necessary if only the total

concentration of a component is desired. Glass

cartridges of the type shown in Figure la are

connected using teflon ferrules and Swagelok

(stainless steel or teflon) fittings. Start the

pump and record the following parameters on an

appropriate data sheet (Figure 4 ) : data, sampling

location, time, ambient temperature, barometric

TOl-12

pressure, relative humidity, dry gas meter reading

(if applicable) flow rate, rotameter reading (if

applicable), cartridge number and dry gas meter

serial number.

10.2.6 Allow the sampler to operate for the desired time,

periodically recording the variables listed above.

Check flow rate at the midpoint of the sampling

Interval if longer than four hours.

At the end of the sampling period record the

parameters listed in 10.2.5 and check the flow

rate and record the value. If the flows at the

beginning and end o f the sampling period differ

by more than 10% the cartridge should be marked

as suspect.

10.2.7 Remove the cartridges (one at a time) and place

in the original container (use gloves for glass

cartridges). Seal the cartridges or culture tubes

in the friction-top can containing a layer of

charcoal and package for immediate shipment to

the laboratory for analysis. Store cartridges

at reduced temperature (e.g. - 20°C) before analysis

if possible to maximize storage stability.

10.2.8 Calculate and record the average sample rate for

each cartridge according to the following equation:

where

Q Ql Q2 - .-.QN ' ' N

Q/\ = Average flow rate in ml/minute.

Q ] , Q2. Qn= Flow rates determined at

beginning, end, and immediate points

during sampling.

N = Number of points averaged.

10.2.9 Calculate and record the total volumetric flow for

each cartridge using the following equation:

Vm = T X QA 1000

TOl-13

where

Vm = Total volume sampled in liters at measured 'm temperature and pressure.

T2 = Stop time.

T] = Start time.

T = Sampling time = T2 - T ] , minutes

10.2.10 The total volume (Vj) at standard conditions,

25°C and 760 mmHg, is calculated from the

following equation:

' m X _PA. i l l 760 273 + t;

where

P/\ = Average barometric pressure, mmHg

t/\ = Average ambient temperature, "C.

11. GC/MS Analysis

11.1 Instrument Set-up

11.1.1 Considerable variation from one laboratory to

another is expected in terms of instrument configuration.

Therefore each laboratory must be responsible

for verifying that their particular system yields

saHsfactory results. Section 14 discusses specific

*• performance criteria which should be met.

11.1.2 A block diagram of the typical GC/MS system

required for analysis of Tenax cartridges is

depicted in Figure 5. The operation of such

devices is described in 11,2.4. The thermal

desorption module must be designed to accommodate

the particular cartridge configuration. Exposure

of the sample to metal surfaces should be

minimized and only stainless steel, or nickel metal

surfaces should be" employed.

TOl-14

The volume of tubing and fittings leading from

the cartridge to the GC column must be minimized

and all areas must be well-swept by helium carrier

gas.

11.1.3 The GC column inlet should be capable of being

cooled to -70°C and subsequently increased rapidly

to approximately 30°C. This can be most readily

accomplished using a GC equipped with subambient

cooling capability (liquid nitrogen) although

other approaches such as manually cooling the

inlet of the column in liquid nitrogen may be

acceptable.

11.1.4 The specific GC column and temperature program

employed will be dependent on the specific compounds

of interest. Appropriate conditions are described

in the literature (1-3). In general a nonpolar

stationary phase (e.g. SE-30, OV-1) temperature

programmed from 30''C to 200°C at 8°/minute will

be suitable. Fused silica bonded phase columns

are preferable to glass columns since they are

more rugged and can be inserted directly into

the MS ion source, thereby eliminating the need

for a GC/MS transfer line.

11.1.5 Capillary column dimensions of 0.3 mm ID and 50

meters long are generally appropriate although

sf\prter lengths may be sufficient in many cases,

n.l.6 Prior to instrument calibration or sample analysis

the GC/MS system is assembled as shown in Figure

5. Helium purge flows (through the cartridge)

and carrier flow are set at approximately 10 ml/

minute and 1-2 ml/minute respectively. If applicable,

the Injector sweep flow is set at 2-4 ml/minute.

TOI-15

11.1.7 Once the column and other system components are

assembled and the various flows established the

column temperature is Increased to 250°C for

approximately four hours (or overnight if desired)

to condition the column.

11.1.8 The MS and data system are set according to the

manufacturer's instructions. Electron impact

ionization (70eV) and an electron multiplier gain

of approximately 5 x 10^ should be employed.

Once the entire GC/MS system has been setup the

system is calibrated as described in Section 11.2.

The user should prepare a detailed standard

operating procedure (SOP) describing this process '•

for the particular instrument being used.

11.2 Instrument Calibration

11.2.1 Tuning and mass standarization of the MS system

is performed according to manufacturer's instructions

and relevant information from the user prepared

SOP. Perfluorotributylamine should generally

be employed for this purpose. The material

is introduced directly into the ion source

through a molecular leak. The instrumental

parameters (e.g. lens voltages, resolution,

etc.) should be adjusted to give the relative

ion'-abundances shown in Table 2 as well as

" acceptable resolution and peak shape. If

- these approximate relative abundances cannot

be achieved, the ion source may require cleaning

according to manufacturer's instructions.

In the event that the user's instrument cannot

achieve these relative ion abundances, but

is otherwise operating properly, the user

may adopt another set of relative abundances

as performance criteria.

TOl-16

However, these alternate values must be repeatable

on a day-to-day basis.

11.2.2 After the mass standarization and tuning process

has been completed and the appropriate values

entered into the data system the user should

then calibrate the entire system by introducing

known quantities of the standard components

of interest into the system. Three alternate

procedures may be employed for the calibration

process including 1) direct syringe injection

of dilute vapor phase standards, prepared

in a dilution bottle, onto the GC column,' 2)

Injection of dilute vapor phase standards

into a carrier gas stream directed through the

Tenax cartridge, and 3) introduction of permeation

or diffusion tube standards onto a Tenax cartridge.

The standards preparation procedures for each

of these approaches are described in Section

13. The following paragraphs describe the

instrument calibration process for each of

these approaches.

11.2.3 If the instrument is to be calibrated by direct

injection of a gaseous standard, a standard

is prepared in a dilution bottle as described

in êction 13.1. The GC column is cooled

to -70°C (or, alternately, a portion of the

column inlet is manually cooled with liquid

nitrogen). The MS and data system is set

up for acquisition as described in the relevant

user SOP. The ionization filament should be turned

off during the initial 2-3 minutes of the run to

allow oxygen and other highly volatile components

to elute. An appropriate volume (less than 1 ml)

of the gaseous standard is Injected onto the GC

system using an accurately calibrated gas tight syringe.

TOl-17

The system clock is started and the column is

maintained at -70°C (or liquid nitrogen inlet cooling)

for 2 minutes. The column temperature is rapidly

increased to the desired ini'tial temperature (e.g. 30°C).

The temperature program is started at a consistent

time (e.g. four minutes) after injection. Simultaneously'

the ionization filament is turned on and data acquisition

is initiated. After the last component of interest has"

eluted acquisi ton is terminated and the data is processed

as described in Section 11.2.5. The standard injection

process is repeated using different standard volumes.as

desired.

11.2,4 If the system is to be calibrated by analysis of

spiked Tenax cartridges a set of cartridges is

prepared as described in Sections 13.2 or 13.3.

Prior to analysis the cartridges are stored as

described in Section 9.3. If glass cartridges (Figure la)

are employed care must be taken to avoid direct contact, as described earlier. The GC column is

cooled to -70°C, the collection loop is immersed in

liquid nitrogen and the desorption module is

maintained at 250°C. The inlet valve is placed in the

desorb mode and the standard cartridge is placed in

the desorption module, making certain that no leakage

of purge gas occurs. The cartridge is purged

for 10 minutes and then the inlet valve is placed in

the inject mode and the liquid nitrogen source removed

from the collection trap. The GC column.is maintained

at -70°C for two minutes and subsequent steps are as

described in 11.2.3. After the process is complete the

cartridge is removed from the desorption module and

stored for subsequent use as described in Section 9.3.

TOl-18

11.2.5 Data processing for instrument calibration involves

determining retention times, and integrated characteristic

ion Intensities for each of the compounds of interest.

In addition, for at least one chromatographic run,the

individual mass spectra should be inspected and

compared to reference spectra to ensure proper

instrumental performance. Since the steps involved

in data processing are highly instrument specific, the

user should prepare a SOP describing the process for

Individual use. Overall performance criteria for

Instrument calibration are provided in Section 14. If

these criteria are not achieved the user should refine

the Instrumental parameters and/or operating

procedures to meet these criteria.

11.3 Sample Analysis

11.3.1 The sample analysis process is identical to that

described in Section 11.2,4 for the analysis of standard

Tenax cartridges.

11.3.2 Data processing for sample data generally involves

1) qualitatively determining the presence or absence

of each component of interest on the basis of a set

of characteristic ions and the retention time using

a^reverse-search software routine, 2) quantification

of each identified component by integrating the. intensity

of a characteristic ion and comparing the value to

that of the calibration standard, and 3) tentative

identification of other components observed using a

forward (library) search software routine. As for

other user specific processes, a SOP should be prepared

describing the specific operations for each individual

laboratory.

TOl-19

12. Calculations

12.1 Calibration Response Factors

12.1.1 Data from calibration standards is used to calculate

a response factor for each component of interest.

Ideally the process involves analysis of at least

three calibration levels of each component during a

given day and determination of the response

factor (area/nanogram injected) from the linear

least squares fit of a plot of nanograms injected

versus area (for the characteristic ion).

In general quantities of component greater

than 1000 nanograms should not be injected

because of column overloading and/or MS response

nonlinearity.

12.1.2 In practice the daily routine may not always

allow analysis of three such calibration standards.

In this situation calibration data from consecutive

days may be pooled to yield a response factor,

provided that analysis of replicate standards

of the same concentration are shown to agree

within 20% on the consecutive days. One standard

concentration, near the midpoint of the analytical"

range of interest, should be chosen for injection

every day to determine day-to-day response

reproducibility.

12.''1.3 If substantial nonlinearity is present in

- the calibration curve a nonlinear least squares

fit (e.g. quadratic) should be employed.

This process involves fitting the data to

the following equation:

Y = A + BX + CX2

where

Y = peak area

X = quantity of component, nanograms

A,B, and C are coefficients in the equation

TOI-20

12.2 Analyte Concentrations

12.2.1 Analyte quantities on a sample cartridge are calculated

from the following equation:

where

12.2.2

12.2.3

YA = A + BXA + CXA

YA is the area of the analyte characteristic ion for

the sample cartridge.

XA is the calculated quantity of analyte on the sample

cartridge, in nanograms.

A,B, and C are the coefficients calculated from the

calibration curve described in Section 12.1.3.

If instrumental response is essentially linear over the

concentration range of interest a linear equation

(C=0 in the equation above) can be employed.

Concentration of analyte in the original air sample is

calculated from the following equation:

CA

where

XA

C A is the calculated concentration of analyte in

nannograms per liter.

V^ atid X. are as previously defined in Section

10.2.10 and 12.2.1, respectively.

13. Standard Preparation

13.1 Direct Injection

13.1.1 This process involves preparation of a dilution

bottle containing the desired concentrations

of compounds of interest for direct Injection

onto the GC/MS system.

TOl-21

13.1.2 Fifteen three-millimeter diameter glass beads

and a one-inch Teflon stirbar are placed in a

clean two-liter glass septum capped bottle and

the exact volume is determined by weighing the

bottle before and after filling with deionized water.

The bottle is then rinsed with acetone and dried at 200°C.

13.1.3 The amount of each standard to be injected into the

vessel is calculated from the desired injection quantity

and volume using the following equation:

W. = Wi_x VB VI

where

Wj is the total quantity of analyte to be injected

into the bottle in milligrams

WJ is the desired weight of analyte to be injected

onto the GC/MS system or spiked cartridge in

nanograms

VJ is the desired GC/MS or cartridge injection

volume (should not exceed 500) in microliters.

VB is total volume of dilution bottle determined

in 13.1.1, in liters.

13.1.4 The volume of the neat standard to be injected

into the dilution bottle is determined using

the following equation:

W

where

VJ is the total volume of neat liquid to be injected

in microliters,

d is the density of the neat standard in grams per

milliliter.

TOl-22

13.1.6 The bottle is placed in a 60°C oven for at

least 30 minutes prior to removal of a vapor

phase standard.

13.1.7 To withdraw a standard for GC/MS injection

the bottle is removed from the oven and stirred

for 10-15 seconds. A suitable gas-tight microber

syring warmed to 60''C, is inserted through

the septum cap and pumped three times slowly.

The appropriate volume of sample (approximately 25%

larger than the desired injection volume) is drawn

into the syringe and the volume is adjusted to the

exact value desired and then inmediately injected

over a 5-10 seconds period onto the GC/MS system as

described in Section 11.2.3.

13.2 Preparation of Spiked Cartridges by Vapor Phase Injection

13.2.1 This process involves preparation of a dilution

bottle containing the desired concentrations

of the compound(s) of interest as described

in 13.1 and injecting the desired volume of

vapor into a flowing inert gas stream directed

through a clean Tenax cartridge.

13.2.2 A helium purge system is assembled wherein

the helTum flow 20-30 mL/minute is passed

''through a stainless steel Tee fitted with

a-septum injector. The clean Tenax cartridge

is connected downstream of the tee using

appropriate Swagelok fittings. Once the cartridge

is placed in the flowing gas stream the appropriate

volume vapor standard, in the dilution bottle,

is Injected through the septum as described in

13.1.6. The syringe is flushed several times

by alternately filling the syringe with carrier

gas and displacing the contents into the flow

stream, without removing the syringe from the septum.

Carrier flow is maintain through the cartridge for

approximately 5 minutes after injection.

TOl-23

13.3 Preparation of Spiked Traps Using Permeation or Diffusion

tubes

13.3.1 A flowing stream of inert gas containing known

amounts of each compound of interest is generated

according to ASTM Method 03609(6). Note that

a method of accuracy maintaining temperature

within _+ 0.1°C is required and the system

generally must be equilibrated for at least

48 hours before use.

13.3.2 An accurately known volume of the standard

gas stream (usually 0.1-1 liter) is drawn

through a clean Tenax cartridge using the

sampling system described in Section 10.2.1,

or a similar system. However, if mass flow

controllers are employed they must be calibrated

for the carrier gas used in Section 13.3.1

(usually nitrogen). Use of air as the carrier

gas for permeation systems is not recommended,

unless the compounds of Interest are known

to be highly stable in air.

13.3.3 The spiked cartridges are then stored or inmediately

analyzed as in Section 11,2.4,

14. Performance Criteria and Quality Assurance

This sectton summarizes quality assurance (QA) measures and

provides guidance concerning performance criteria which, should be

achieved within each laboratory. In many cases the specific

QA procedures have been described within the appropriate section

describing the particular activity (e.g. parallel sampling).

TOI-24

14,1 Standard Opreating Procedures (SOPs)

14.1.1 Each user should generate SOPs describing the

following activities as they are performed

in their laboratory:

1) assembly, calibration, and operation of

the sampling system,

2) preparation, handling and storage of Tenax

cartridges,

3) assembly and operation of GC/MS system including

the thermal desorption apparatus and data

system, and

4) all aspects of data recording and processing,

14.1.2 SOPs should provide specific stepwise instructions

and should be readily available to, and understood

by the laboratory personnel conducting the

work,

14.2 Tenax Cartridge Preparation

14.2.1 Each batch of Tenax cartridges prepared (as

described in Section 9) should be checked for

contamination by analyzing one cartridge iinnediately

after preparation. While analysis can be accomplished

^by GC/MS, many laboratories may chose to use

GC/FID due to logistical and cost considerations,

14.2.2 Analysis by GC/FID is accomplished as described

for GC/MS (Section 11) except for use of-FID

detection.

TOl-25

14.2.3 While acceptance criteria can vary depending

on the components of interest, at a minimum

the clean cartridge should be demonstrated

to contain less than one fourth of the minimum

level of interest for each component. For

most compounds the blank level should be less

than 10 nanograms per cartridge in order to

be acceptable. More rigid criteria may be

adopted, if necessary, within a specific laboratory.

If a cartridge does not meet these acceptance

criteria the entire lot should be rejected.

14,3 Sample Collection

14.3.1 During each sampling event at least one clean

cartridge will accompany the samples to the

field and back to the laboratory, without being

used for sampling, to serve as a field blank.

The average amount of material found on the

field blank cartridge may be subtracted from

the amount found on the actual samples. However,

if the blank level is greater than 25% of the

sample amount, data for that component must

be identified as suspect.

14.3.2 DCTring each sampling event at least one set

" of parallel samples (two or more samples collected

simultaneously) will be collected, preferably

at different flow rates as described in Section

10.1, If agreement between parallel samples

is not generally within ^ 25% the user should

collect parallel samples on a much more frequent

basis (perhaps for all sampling points). If

a trend of lower apparent concentrations with

increasing flow rate is observed for a set

TOI-26

of parallel samples one should consider using

a reduced flow rate and longer sampling Interval

if possible. If this practice does not Improve

the reproducibility further evaluation of the

method perfonnance for the compound of interest

may be required,

14.3,3 Backup cartridges (two cartridges in series)

should be collected with each sampling event.

Backup cartridges should contain less than

20% of the amount of components of interest

found in the front cartridges, or be equivalent

to the blank cartridge level, whichever is

greater. The frequency of use of backup cartridges

should be increased if increased flow rate

is shown to yield reduced component levels

for parallel sampling. This practice will

help to identify problems arising from breakthrough

of the component of interest during sampling.

14.4 GC/MS Analysis

14.4.1 Perfonnance criteria for MS tuning and mass

calibration have been discussed in Section

11.2 and Table 2, Additional criteria may

be used by the laboratory if desired. The <t

following sections provide performance guidance

and suggested criteria for detennining the •

acceptability of the GC/MS system.

14.4.2 Chromatographic efficiency should be evaluated

using spiked Tenax cartridges since this practice

tests the entire system. In general a reference

compound such as perfluorotoluene should be

spiked onto a cartridge at the 100 nanogram

level as described in Section 13.2 or 13.3.

The cartridge is then analyzed by GC/MS as

TOI-27

described in Section 11.4, The perfluorotoluene (or

other reference compound) peak is then plotted on an

expanded time scale so that its width at 10% of the

peak can be calculated, as'shown in Figure 6, The

width of'the peak at 10% height should not exceed

10 seconds. More stringent criteria may be required

for certain applications. The assymmetry factor

(See Figure 6) should be between 0,8 and 2.0. The

assymmetry factor for any polar or reactive compounds

should be determined using the process described above.

If peaks are observed that exceed the peak width o r

assymmetry factor criteria above, one should inspect

the entire system to determine if unswept zones or

cold spots are present in any of the fittings and

is necessary. Some laboratories may chose

to evaluate column performance separately by

direct injection of a test mixture onto the

GC column. Suitable schemes for column evaluation

have been reported in the literature (7).

Such schemes cannot be conducted by placing

the substances onto Tenax because many of

the compounds (e,g, acids, bases, alcohols)

contained in the test mix are not retained,

or degrade, on Tenax.

14.4.3 The system detection limit for each component

is"calculated from the data obtained for

" calibration standards. The detection limit

- is defined as

DL = A + 3,3S

' TOI-28

where

DL is the calculated detection 1/imit in

nanograms injected.

A is the intercept calculated in Section

12.1.1 or 12.1,3.

S is the standard deviation of replicate

determinations of the lowest level standard

(at least three such detenninations are

required.

In general the detection limit should be 20

nanograms or less and for many applications

detection limits of 1-5 nanograms may be required.

The lowest level standard should yield a signal

to noise ratio, from the total ion current response,

of approximately 5.

14.4.4 The relative standard deviation for replicate

analyses of cartridges spiked at approximately

10 times the detection limit should be 20%

or less. Day to day relative standard deviation

should be 25% or less.

14.4.5 A useful performance evaluation step is the

use of an internal standard to track system

performance. This is accomplished by spiking

each caKtridge, including blank, sample, and

^calibration cartridges with approximately 100

nanograms of a compound not generally present

in ambient air (e.g. perfluorotoluene).. The

integrated ion intensity for this compound

helps to identify problems with a specific

sample. In general the user should calculate

the standard deviation of the internal standard

response for a given set of samples analyzed

under identical tuning and calibration conditions.

Any sample giving a value greater than + 2

?t.?ndard deviations from the mean (calculated

i

TOI-29

excluding that particular sample) should be

Identified.as suspect. Any marked change in

internal standard response may indicate a need

for instrument recalibration.

TOI-30

REFERENCES

Krost, K. J,, Pellizzari, E, D., Walburn, S. G,, and Hubbard, "Collection and Analysis of Hazardous Organic Emissions", Analytical Chemistry, 5£, 810-817, 1982.

S. A.

2. Pellizzari, E. 0. and Bunch, J, E., "Ambient Air Carcinogenic Vapors-Improved Sampling and Analytical Techniques and Field Studies", EPA-600/2-79-081, U.S. Environmental Protection Agency, Research Triangle Park, North Carolina, 1979,

3. Kebbekus, B. B. and Bozzelli, J. W., "Collection and Analysis of Selected Volatile Organic Compounds in Ambient Air", Proc. Air Pollution Control Assoc, Paper No. 82-65.2, Air Poll. Control Assoc, Pittsburgh, Pennsylvania, 1982,

4. Riggin, R, M., "Technical Assistance Document for Sampling and Analysis of Toxic Organic Compounds in Ambient Air", EPA-600/ 4-83-027, U.S. Environmental Protection Agency, Research Triangle Park, North Carolina, 1983,

5. Walling, J. F,, Berkley, R. E,, Swanson, D. H,, and Toth, F, J. "Sampling Air for Gaseous Organic Chemical-Applications to Tenax", EPA-600/7-54-82-059, U.S. Environmental Protection Agency, Research Triangle Park, North Carolina, 1982.

6. Annual Book of ASTM Standards, Part 11,03, "Atmospheric Analysis", American Society for Testing and Material, Philadelphia, Pennsylvania.

7. Grob, K., Jr., Grob, G,,-and Grob, K., "Comprehensive Standardized Quality Test for Glass Capillary Columns", J, Chromatog,, 156, 1-20, 1978,

TOI-31

TABLE 1, RETENTION VOLUME ESTIMATES FOR COMPOUNDS ON TENAX

COMPOUND ESTIMATED RETENTION VOLUME AT 100°F (38°C)-LITERS/6RAM

Benzene

Toluene

Ethyl Benzene

Xylene(s)

Cumene

n-Heptane

1-Heptene

19

97

200

^ 200

440

20

40

Chloroform

Carbon Tetrachloride

1,2-Dichloroethane

1,1,1-Trichloroethane

Tetrcchloroethylene

Trichloroethylene

1,2-Dichloropropane

1,3-Dichloropropane

Chlorobenzene

Bromofonn

Ethylene Dibromide

Bromobenzene

8

8

10

6

80

20

30

90

150

100

60

300

TOI-32

TABLE 2. SUGGESTED PERFORMANCE CRITERIA FOR RELATIVE ION ABUNDANCES FROM FC-43 MASS CALIBRATION

M/E % RELATIVE

ABUNDANCE

51

69

100

119

131

169

219

264

314

1.8 + 0.5

100

12.0 + 1.5

12.0 + 1.5

35.0 + 3.5

3.0 + 0 .4

24.0 + 2.5

3.7 + 0 .4

0.25 + 0.1

TOl-33

Ttnax ~1.5 Grami (6 cm B«d Dapth)

Glau Wool Plugs (0.5 cm Long)

GIMS Cartridge

(13.5 mm OD x 100 mm Long)

\

.(a) GlauCartrldga

MT'. Swagdok Z janax

Glau Wool Plugs (0.5 cm Long)

\

1/8" End Cap.

Fitting ~-1.5 Grams (7 cm Bad Dtpth)

Matal Cartridga (12.7 mm 0 0 x 100 mm Long)

(b) Matal Cartridga

FIGURE 1. TENAX CARTRIDGE DESIGNS

TOI-34

Cavity for • Tanax Cartridga

Latch for Comprawlon

Effluant to 6-Port Valva

To GC/MS

Liquid Nitrogen Coolant

(a) Glass Cartridges (Compression Fit)

Purya O M " •

8wag«lQ& End Fftdnvi

>Tenax Trap

Heated Block Liquid

Nitrogen Coolant

(b) Metal CartrMges (Swagelok Fittings)

FIQURE 2. TENAX CARTRIDGE DESORPTION MODULES

TOI-35

/Oi l lMs\ yPumpy

Mau Flow Controllers

Vent

Couplings to Connect Tenax Cartridges

o

Vent

Rotometer

(a) Mass Flow Control

t Pump ^

Needle Valve

(b) Needle Valve Control

Coupling to Connect Tenax Cartridge

FIGURE 3. TYPICAL SAMPLING SYSTEM CONFIGURATIONS

TOI-36

SAMPLING DATA SHEET (One Sample Per Data Sheet)

PROJECT:

SITE:

LOCATION:

INSTRUMENT MODEL NO:

PUMP SERIAL NO:

SAMPLING DATA

Sample 1

Start Time:

Time

1.

2.

3.

4.

N.

Total

Dry Gas Meter Reading

Volume Dat

Rotameter Reading

a**

dumber:

Flow Rate.*Q ml/Min

DATE(S) SAMPLED:_

TIME PERIOD SAMPLED:

OPERATOR:

CALIBRATED BY:

Stop

Ambient Temperature

°C

Time:

Barometric Pressure, mmHg

Illative Humidity, % Comments

-

Vn, « (Final - I n i t j a l ) Dry Gas Meter Reading, or

. Q T -t- Qz ^ Q 3 - - - - Q N

" N 1

1000 x (Sampling Time in Minutes)

Liters

Liters

* Flowrate from rotameter or soap bubble calibrator (specify which).

** Use data from dry gas meter if available.

FIGURE 4. EXAMPLE SAMPLING DATA SHEET

TOI-37

Purge Gas

Thermal Desorption Chamber

6-Port High-Temperature Valve

Mass Spectrometer

Carrier

Gas

Vent

Freeze Out Loop

Liquid

Nitrogen

Coolant

FIGURE 5. BLOCK DIAGRAM OF ANALYTICAL SYSTEM

TOI-38

Asymmetry Factor • BC AB

Example Calculation:

Peak Hetbht - DE - 100 mm „ 10% Peak Height - BO - 10 mm

Peak Width at 1 0 \ Peak Height - AC - 23 mm A B - I I m m BC • 1 2 mm

Tftercfore: Asymmetry Factor " "TT " l - l

FIGURE 6. PEAK ASYMMETRY CALCULATION

1

•I i

V'

FIGURE 2

J i

m I ' M