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Case 1:05-cv-01020-MMS

Document 39-18

Filed 01/05/2007

Page 1 of 51

CONFIDENTIAL
VELSICOL CHEMICAL CORPORATION
LABORATORY REPORT
SUBJECT:
Applicator and Inhabitant Exposure
to

UNITERM NO:

Chlordane During and After Termiticide

PROJECT NO: REPORT NO:
SECTION:

480018

Applications in California

AUTHOR:

W. P. Cahill___________________

Environmental Studies

DATE TYPED:
PERIOD COVERED: WORK DONE BY:

Or4-obe.r

P, Is\^

)P1ESTO:
Y. H. Atallah L. L. Gingerich A. M. Khasawinah M. 0. Messerschmidt G. s. Nagle L. G. Nickell D. Y. Takade D. M. Whitacre W. P. Cahill
Vailit

W. P. Cahill, M. K. Stumphy and

Raltech

Scientific Services, Inc.

SUPERVISOR:

Y. H. Atallah

DEPARTMENT HEAD:. D. Y. Takade

(2)

REFERENCES:

OBJECT: To determine

the exposure of PCO^ and inhabitants to chlordane and deodorized kerosene during and after treatment of homes for termite control.

SUMMARY:See

next

page.

SIGNATURE:
91.00-430

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gummary
A study was conducted to determine the inhalation and dermal exposure
of applicators and inhabitants to chlordane and deodorized kerosene from typical tenniticide treatments of crawl-space and slab houses. Applicators were monitored during preparation and application of the tenniticide. The potential applicator dermal exposure was similar for the crawl-space and slab treatments although large variations among applications were detected (796 to 0.89 ug chlordane per 100 cm2 denim patch). Potential applicator inhalation exposure was approximately 30 tiroes greater for crawl-space than slab treatments.
Potential inhabitant inhalation and surface samples were collected before, during and after treatment. Samples were also collected 22 days after treatment of the crawl-space houses. Air residues of chlordane in crawl-space treated homes ranged from about 0.001 to 0.049 mg/m3 in the living quarters and from 0.0014 to 0.015 mg/m3 in the crawl-spaces. Surface residue in living quarters ranged from 0.010 to 0.094 mg/m2. The chlordane air and surface residue remained fairly uniform through 22 days post-treatment. Deodorized kerosene was not detected in the living quarters. Levels in the crawl-space ranged from 1.68 to 6.95 mg/m3 and were lowest for the 48 hr posttreatment samples. Chlordane (potential inhabitant inhalation exposure) was detected in 5 of 18 air samples (slab treatment) at low levels ( 0.00083 to 0.0023 mg/ms). However, chlordane surface and deodorized kerosene air residues were not detected.

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METHODS AND MATERIALS
I.
Tenniticide Applications

(See Appendix I for protocol containing description of the termiticide and general application procedures; See Appendix II for a description of specific application techniques used by PCO's).
II.
Sampling

A.

PCO Exposure Samples
1.
Inhalation samples
a.

Deodorized kerosene
The sampling method used was that described in the U.S. Dept. of Health, Education and Welfare (NIOSH) Publication No. 77192, "Criteria for a Recommended Standard...Occupational Exposure to Refined Petroleum Solvents" (Appendix III).

An activated charcoal tube, lot no. 107, SKC, Inc. was attached near the tip of the collar beneath each applicators' chin and connected by Tygon(R) tubing to a battery powered air pump (MSA model G or S) such that sampled air first passed through the charcoal tube. The flowrate was adjusted to 1.0 L/min (See Appendix HI, p 217) Immediately prior to application and confirmed after sampling. Flow rates were determined using an air mass flow calibrator (Kurz Instruments, Inc. Carmel Valley, CA). After sampling charcoal tubes were sealed with plastic caps and placed in labeled vials.
b.
Chlordane
i.

Crawl-space treatment

A spillproof midget impinger without a sintered glass frit (Daco Products, Inc. Montclair, N.J.) containing 10 mL of ethylene glycol was attached to the applicators lapel and connected to a battery powered air pump as described above. Upon completion of the treatment the ethylene glycol was transferred, using two 5 inL rinses, to a labeled 8 oz glass bottle. The bottle was closed with a poly-seal cap.
ii.

Slab treatment

A midget impinger with a sintered glass frit containing 15 to 20 mL of ethylene glycol (Ace Glass Inc., Vineland, NJ) was secured beneath the chin of the applicator with nylon fiber reinforced tape (3M Inc.) and connected to the pump as described previously. Samples were collected
as described for the spillproof impinger. Each rinse was allowed to penetrate the frit and drain before transfer.

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2.

Dermal Samples

Denim-patches (10 x 10 cm) were attached to the outer surface of the applicators' coveralls just above each knee and elbow, the inner surface of the coveralls at the elbow but not overlapping the outer patch and to the inner surface of the work pants (pants worn under coveralls) at the knees. A denim patch (5.1 x 35 cm) was also attached to the upper collar surface of the coveralls. After the application the patches were removed and placed in separate, labeled vials. Prior to the experiment several randomly selected denim patches were selected and placed in sealed vials to act as "blanks".
Hand washes were obtained after each treatment by directing a stream of 2:1 acetone/water (about 250 mL) over the hands of

the applicator. Each washing was collected through a funnel The into a 16 ounce bottle equipped with a. poly-seal cap. hands were rubbed together during washing.
B.
Inhabitant Potential Exposure Samples

A*ir (deodorized

kerosene and chlordane) and surface residue samples (chlordane) were collected in the kitchen at each of the 6 homesites and in the master bedroom at 5 of the 6 homesites. The living room was sampled instead of the master bedroom at the 8982 homesite since the former was closer to the treatment location. At the 3706

homesite, samples were also collected from the living room and hallway to duplicate the California Department of Food and Agriculture sampling. Air samples (deodorized kerosene and ehlordane) were collected in each of the 3 treated crawl-spaces. However crawl-space surface residue samples were not collected. The sampling periods for the inhabitant potential (as opposed to actual) exposure were as follows:
a 2-hour period proceeding application

(control).

a 2-hour period within 4 hours after completion of the application, a 2-hour period on the day following treatment. a 2-hour period on the second day following treatment. a 2-hour period on the twenty second day following treatment

(crawl-space homesites only).
1.
Inhalation samples

The equipment, and flowrates for the homesite sampling (inhabitant exposure) were the same as those described for the applicator inhalation exposure. The sampling devices were placed on the refrigerator in the kitchen, dresser tops in the master bedroom and on the dirt floor of the crawl-space near the entry way. In all cases the door to the crawl-space entry was closed during sampling. The sampling equipment was placed on table tops in the living room and hallways.

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2.

Surface samples
Denim patches (10 x 10 cm) were placed adjacent to the air sampling devices. However crawl-space surface residue samples were not collected.

III.

Analysis
Scientific Services, Inc. Analyses were conducted by Raltech 53707) for Velsicol Chemical (P.O. Box 7545, Madison, Wisconsin Corporation. See Appendix I and IV for methods of analysis. The limits of detection for chlordane and deodorized kerosene per sample were 0.10 and 50 ug respectively.

RESULTS
The analytical results (total chlordane or deodorized kerosene residue per sample) for the PCO applicator exposure samples are presented in Table 1. The ratio of the potential dermal applicator exposure and the actual exposure (residues on outer patches to residues on inner patches at the knees and elbows was about 30 and 3 respectively. These data show that the potential applicator exposure was greatly reduced by an additional layer of clothing since the outer and inner knee patches were separated by the coveralls and work pants while 'those at the elbow were separated only by the coverall sleeve. Although new rubber gloves extending halfway to the elbow were worn during mixing and treatment, inadvertent hand contamination was reported, The analytical results (total quantity of chlordane or kerosene per sample) for the inhabitant exposure samples are listed in appendices V and VI. Inhabitant exposures (mg/ma and mg/m3) are presented in Tables 2 and 3. In general, the air sample values were approximately 12 to 300 fold less than the OSHA recommended permissable exposure limit of 0.5 mg/m3 for chlordane. In many instances chlordane was not detected. The potential applicator dermal exposure was similar for the crawl-space and slab treatments although large variations among applications were detected (796 to 0.89 ug chlordane per 100 cm2 denim patch). Potential applicator inhalation exposure was approximately 30 times greater for crawl-space than slab treatments.

Potential inhabitant inhalation and surface samples were collected before, during and after treatment. Samples were also collected 22 days after treatment of the crawl-space houses. Air residues of chlordane in crawl-space treated homes ranged from about 0.001 to 0.049 mg/m3 in the living quarters and from 0.0014 to 0.015 mg/m3 in the crawl-spaces. Surface residue in living quarters ranged from 0.010 to 0.094 mg/ma. The chlordane air and surface residue remained fairly uniform through 22 days post-treatment. Deodorized kerosene was d6t detected -in the'living quarters. Levels in the crawlspace ranged from 1.68 to 6.95 mg/m3 and were lowest for the 48 hr post-treatment samples. Chlordane (potential inhabitant inhalation exposure) was detected in 5 of 18 air samples (slab treatment) at low levels ( 0.00083 to 0.0023 mg/m3). However, chlordane surface and deodorized kerosene air residues were not detected.

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Case 1:05-cv-01020-MMS
Table 1

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Analysis of PCO Applicator Exposure Samples Collected During Typical Termiticide Treatments in the Los Angeles Area,

(ug chlordane per sample)

House No House Typ e
knee, r.o .i./ knee, r.i .-i
knee, 1.0 .j knee, l.i .j

370 6
era wl

3826
crawl

390 1
erawl

896 1
sla b

898 1
slab

8982
slab

96 .2

54.7 7.3
222

17 .5
0 .97

356 .0 3 .5 404 .0
1 .5

1 .5
0 .53

23.9
0.84 34.2 0.82

2 .3
796 .0
2 .2

7 .5

49 .5 0 .79

6.2

0 .89

elbow, r.

a.^

10 .7
2 .5
6 .0

17.5 4.3
10.5

11 .1 1 .6
32 .4

12 .1 12 .5
9 .5

10 .1

11.9 7.3
19.0

elbow, r. +/-.^
elbow, 1. c.^

3 .4
5 .7

elbow,

1. +/->l

2 .0

5,4
41.5
92.0
Mt 9 (0.1181

0 .73

12 .7

4 .2

7.7

collar patch hand wash

10 .4

4 .2

2 .7

2 .0

2.4
59.6

579

22 .7 4 .0 (0 .033)
820 (6 .83)

103 ,0 0 .16

30 .8

EG impineer

7 .3
(0

5/

.oen^

(0 .0013)

ug kerosene per sample

charco.al tube

1.86

(1.55)
1/

Z50 <( o .42)

<<

Z50
0 .42)

<(

<^50 0.42)

denim patch attached to right knee outside (r.o.) or left knee outside (l.o.)

of-coverall.
z/ denim patch, attached to right knee inside (r.i.) or left knee inside of workpants beneath coverall.

(l.i.)

3/

denim patch attached to right elbow outside

(r.o.) or left elbow outside (l.o.)

of coverall.

^
&-

denim patch attached to the right elbow inside (r.i.) or left elbow inside (l.i.)

of coverall.
sample lost during analysis
values in parenthesis in mg/m3 (average air concentration for 2 hour sampling

period).

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Case 1:05-cv-01020-MMS

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Case 1:05-cv-01020-MMS

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Case 1:05-cv-01020-MMS

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Filed 01/05/2007

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Case 1:05-cv-01020-MMS
Table 4

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Analysis of Air Samples Representing Potential Inhabitant Exposure to Chlordane (impinger trap) and Kerosene (charcoal trap) from Typical Slab Te-naiticide Treatments.

House No.

Room
kitchen bedroom

Sample

Pretreat mg/m3

Treat

Immed Post

3961 8961 8961
8961

kitchen
hedrnoin

impinger impinger charcoal
charr-nfll

N.D.-^

3^-

mg/m3

N.D..^
N-n-

N.D.

N.D. 0.0019 N.D.
w n

24h Post mg/m3 N.D. N.D. N.D.
M n

8981 8981 8981 8981 8981

kitchen bedroom
kitchen bedroom liv. rm.

impinger impinger charcoal charcoal charcoal

N.D.
N.D.

0.00083

0.0023 N.D.
N.D. N.D. N.D.

N.D. N.D.
N.D. N.D.

N.D. N.D.

8982 8982 8982
8982

kitchen
liv. rm. kitchen liv. rm.

impinger impinger charcoal charcoal

N.D.

N.D.

N.D. N.D.
N.D.

0.0017 0.0010 N.D. N.D.

Limit of detection for

ethylene glycol impinger sample (chlordane air sample)

0.00083 mg/m3

2/

Limit of detection.for charcoal trap (deodorized kerosene air

sample)

0.42 mg/m3

s/ Indicates no

sample collected

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Case 1:05-cv-01020-MMS
Table 5

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Analysis of Surface Samples (Denim Patches, d.p.) Representing Potential Inhabitant Dermal Exposure to Chlordane From Typical Slab Termiticide Treatments

House No.____Room____Sample____Pretreat____Treat____Immed Post____24h Post

mg/m2_____mg/m2____mg/m^______mg/mg
8961

8961

kitchen bedroom

d.p. d.p.

N.D.-^
N.D.

^
N.D,

N.D. N.D.

N.D. N.D.

8981 8981

kitchen bedroom

d.p. d.p.

N.D. N.D.

N.D.
0.014

N.D, N.D,

8982

kitchen
liv. rm.

8982

d.p. d.p.

N.D, N.D,

N.D.

N.D

N.D.

N.D

1

Limit of detection 0.010

mg/m2

H^

3-

No sample collected

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Case 1:05-cv-01020-MMS

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APPENDIX I

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.-1Protocol

Pest Control Operator (PCO) and Inhabitants Exposure to Chlordane in Homes Treated for Termite Control.

OBJECTIVE

To determine the exposure of PCO and inhabitants to chlordane and deodorized kerosene during and after treatment of homes for termite control.
INTRODUCTION
Termites annually cause extensive damage to homes in the U.S. However, the introduction of prophylactic treatment of homes with persistent insecticides such as chlordane has minimized but not eliminated monetary loss caused by these pests. In fact, chlordane is the major insecticide used for soil treatment to control subterranean termites in homes. While data on the exposure of applicators and inhabitants are limited, two studies have attempted to estimate the levels of chlordane and heptachlor in habitation areas. Malina et. al. have determined the chlordane levels in air habitations treated for insect control (I). In addition, data are available on heptachlor residues in air and on surfaces in homes and business establishments treated for termite control (2). Both studies yielded interesting results but neither study provided adequate information concerning PCO and inhabitant exposure.

Because of concerns about the human health effects of chlordane, QSHA. has established an occupational permissible, exposure limit of 0.5 mg/m3 (skin, ref. 4) to chlordane. NIOSH has recommended an occupational exposure limit of 100 mg/m3
for kerosene.

This test is intended to determine the exposure levels of Pest Control Operators (PCO) and inhabitants to chlordane and deodorized kerosene during and after soil treatment with chlordane to control termites in homes.

EXPERIMENTAL
I.
Chlordane
Gold Crest(R), C-100, emulsiftable concentrate, E.P.A. Reg. No. 876-63-AA, E.P.A. Est. No. 876-TN-l. Chlordane will be used in compliance with

label directions. Volumes and percentages of active ingredient will be at or below the specified rate which ever will control the target pest (termites).

II.

Homes

A.
B.

Crawl-space construction-with all duct work passing through the crawl-space (3 homes).
Concrete slab construction (3 homes).

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III.

Location

Torrance and Westminster (Los Angeles area), California. IV.
Application

A.

Personal Protection

1.

Applicators shall wear respirators, approved by NIOSH/MSHA for protection against pesticides while mixing, loading, or applying finished spray mix in confined spaces, such as crawl spaces and basements. Eye protection shall be provided.

2.
3.

Clean outer clothing shall be worn daily. Clothing shall cover the body, arms to the wrist, and legs to the ankles.

Neoprene gloves shall be worn when mixing, loading or applying
chlordane pesticides.

4.

Adequate supply of water, soap, and towels shall be provided at the work site, and the locale where the working day is
finished.

5.

Applicators shall be instructed as to safety requirements to be observed in the handling of chlordane.

B.

Application Equipment

1.

Pump pressures and nozzle type shall be of such combination
and design so as to prevent formation of droplet size of the finished spray mix that would cause significant drift or run-off from the intended specific application site.

2.

Concentrate chlordane material shall be carried on the service vehicle in properly labeled containers of a size required to prepare a full tank of finished spray mix for the application equipment. Concentrated material shall not be transferred, other than into the application tank, from one container to another at the treatment location site.

C.

Application Procedure

The soil of the inside and outside perimeters of the crawlspace and around the piers will be treated. The soil beneath the concrete slab construction will be treated. For more details see appendix I.

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V.

Sampling

Samples will be collected to of the Pest Control Operator In addition, air samples and in the home to determine the
A.
PCO Exposure Samples

determine inhalation and dermal exposure "(PCO) to chlordane and deodorized kerosene,

surface residue samples will he collected potential exposure of the inhabitants.

Samples collected from the applicator shall be representative of a complete treatment cycle (i.e., from the time of arrival at the treatment site to departure from the site at completion of the job).
1.
Inhalation exposure samples
a.

Deodorized kerosene
The method of collection shall be that described in the U.S. Department of Health, Education and Welfare (NIOSH) Publication No, 77-192, "Criteria for a Recommended Standard... Occupational Exposure to Refined Petroleum Solvents'*. The method requires drawing a known volume of air through a charcoal tube, attached in the workers breaching zone, to trap the organic pollutant (Appendix II).

b.

Chlordane
This method involves drawing a known volume of air through a midget impinger containing 15-20 ml of ethylene glycol. i.

Before use, each sampling pump shall be calibrated using an integrating volume meter or other suitable means.

ii.

Pour 15-20 ml of the ethylene glycol into the midget impinger. A graduated cylinder may be used to measure
the volume.

iii.

Connect the impinger to the pump with a short piece of flexible tubing. The air being sampled must not pass through any tubing or other equipment before
entering the impinger.

iv.

Attach the impinger to the collar or lapel of the worker and turn the pump on to begin collection. Measure the flow rate, time and/or volume accurately. Record the temperature, humidity and the wind speed and direction (if wind is a factor affecting potential exposures). The sample shall be collected at a flow rate of 1.0 liters per minute.

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VI.

ANALYTICAL PROCEDURE:
A.

Chlordane
Extraction and Cleanup

1.

Air Samples

Transfer the ethylene glycol from the sample bottle to a. 50 ml glass stoppered graduated cylinder. Rinse the bottle twice with 5 ml portions of fresh ethylene glycol and add to the graduate cylinder Adjust the volume to 50 ml, stopper and shake.

Add 300 ml of distilled water, 20 ml of a saturated aqueous sodium chloride solution, a 20 ml aliquot of the ethylene glycol trapping solution and 100 ml of n-pentane to a 500 ml separatory funnel and shake vigorously for 1 minute. Allow phases to separate and discard the aqueous layer. Pass the pentane layer through a bed of anhydrous sodium sulfate (5-lOg) and collect in a 125 ml Kuderna-Danish concentrator. Add 2 ml of n-hexane, a boiling stone and concentrate the extract to 2 ml on a 50C water bath. Add 0.5 ml of a 1:1 (concentrated sulfuric acid:fuming sulfuric acid) solution to the concentrated extract and agitate vigorously for I minute and allow the phases to separate.
Transfer the n-hexane extract using a Pasteur pipette to a 50 ml volumetric flask and dilute with hexane. Quantitate the chlordane residue in the extract by GC/EC. Previous

recovery-studies using this method yielded about 90Z recovery,

2.

Denim Patches Denim patches prevashed with hexane will be used for monitoring the dermal exposure and surface residues.
Add 100 ml of hexane to the 8 oz bottle (poly-seal caps) containing the denim patch. Shake sample on a platform shaker for 30 min. Inject an aliquot of the extract directly into the GC-EC to determine the proper dilution or concentration prior to analysis. In case cleanup is needed, the hexane extract will be acid washed as previously

described.

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Identification and Quantification
1

1.

Gas Chromatograph:

Hewlett Packard 5710A with electron capture detector.

Ni

Column:

3% SE-30 on Gas Chrom Q, 80/100 mesh, 1.8 m x 4 mm i.d. glass column.

Carrier:

argon

+

methane (95 + 5) at 40 ml/min.

Temperatures:

175C. injector. 250C. detector, 300C.
oven,

Attenuation:

x8
3

2.

Gas Chromatograph:

TRACOR MT-220 with
detector.

Ni electron capture

Column:

3% SE-30 on Gas Chrom Q 80/100 mesh, 1.2 m x 4 mm i.d. glass column.
nitrogen at 20 ml/min.

Carrier Gas:

Temperatures:

oven, 155C.
injector,

250C.

detector, 285C.
Attenuation:

x2

G. C. Conditions
3.
Standard Curve
The standard curve will be constructed by plotting the sum of the peak heights of the 6 components characteristic of technical chlordane (compound C. heptachlor, compound E, gamma and alpha chlordane and nonachlor) versus the nanograms 'of technical chlordane injected into the gas chromatograph The total amount of technical chlordane (References 4 and 5) in the impinger is determined from the expression.

0

^

-------------6------------

A

x

VTT

ul

x

x Va

Vs

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where

Q A

amount of technical chlordane in the sample (in micrograms). aTDOunt of technical chlordane in the injected aliquot in

nanograms.

^ul Vp
Vs

volume of extract injected into GC in microliters. volume of ethylene glycol from impinger + rinses (50 ml). volume of solution from which GC aliquot taken in milliliters

(50 ml).

Va

volume of ethylene glycol taken for cleanup (20 ml).

The total amount of chlordane in the denim patch was determined from the expression.

Q
when

A x Vt
jul

Q, A and ^il are as above total volume of hexane extract in milliliters (100 ml) Vt
or final volume of extract requires dilution or concentration.

B.

Kerosene
Analysis will be conducted as described in the U.S., HEW, NIOSH publication Ko. 77-192 "Criteria for a Recommended Standard... Occupational Exposure to-Refined Petroleum Solvents". The recommended method essentially involves the desorption of the kerosene from the charcoal using carbon disulfide 'followed by GC/FXD analysis of the extract (Appendix III).

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References

1.

Malina, M.A., J,M. Kearny and P.B, Polen. Chem. 7:30-33.

1959.

J. Agric. Food

2.

Stumphy, M.K. and Y.H. Atallah. 1975. Velsicol Chemical Corporation, Report No. 190, Project No. 406000.
U. S. Department of Health, Education, and Welfare (NIOSH). 1978. Occupational Exposure During the Manufacture and Formulation of Pesticides, XI, Appendix III, p. 378.

3.

4.

D. M. Whitacre and B. L. Hoo 1979. Toxicol. 22:570-74. Contam.
Atallah

Y.H..

Bull. Environ.

5.

McMahon, D.M. and L.D. Sawyer (Editors). Manual (PAM). Vol. I. PDA, HEW.

1977. Pesticide Analytical

YHA/yc September 25, 1979

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APPENDIX II

Application Equipment and Methods

The termiticide applications were made by low pressure spray, rodding and sub-slab injection techniques. For low pressure sprays, the nozzle pressure was 40 psi. For rodding and sub-slab injection, the pump pressure was 60 psi.
Crawl Space

A surface application was made Co the soil area within 18 inches, horizontally, from the Interior foundation wall, piers and pipes. The low pressure spray nozzle was a "shower head" type with 43 orafices each 1 mm in diameter. A Spraying System "36" valve and a 2^ foot aluminum extension were used.
Exterior Foundation

foundation.

A rodding application was made to the perimeter of the exterior A B & G Extenda Rod(R) attachment was used.

Slab Construction

Applications were made by sub-slab injection to all probable termite entry points, including cracks. pipes and voids. A B & G Sub-Slab Injector attachment was used. All treatment holes were sealed with
concrete.

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APPENDIX III

criteria for a recommended standard

OCCUPATIONAL EXPOSURE TO REFINED PETROLEUM SOLVENTS

U.S. DEPARTMENT OF HEALTH, EDUCATION, AND WELFARE
Public Health Service Center for Disease Control National Institute for Occupational Safety and Health

JULY 1977
fw
by
'SupjrlnrHd.nt Daewnr. U.S. Ca*mn--t Printl-c CMftCt. W
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XI.

APPENDIX HI

METHOD FOR SAMPLING REFINED PETROLEUM SOLVENTS IN AIR

In

order

to evaluate

conformance with the recommended environmental

limits, air concentrations of rubber solvent, varnish makers* and painters*

naphtha,

mineral spirits, Stoddard

solvents., and kerosene
Sampling

must be measured

withln-.the individual worker's breathing zone.
conform with the following criteria.

procedures

.must

Atmospheric Sampling

Collect

breathing' zone

or

personal

samples representative of the

individual employee's exposure*

At the time of sample collection, record a

description

of

sampling location and conditions, equipment used, time and

rate of sampling, and any

other -pertinent- information. of

Collect

enough

samples

to

permit

calculation

a TWA exposure for every operation or

location in which there is exposure to any refined

petroleum solvents.

(a)

Equipment

The sampling-train-consists of-a charcoal. tube and a vacuum-pump.--.;.

(1)

'Charcoal

tubes:

Glass

tubes,

with both ends' flame-

sealed, 7-cn long with a 6-naa OD and a 4-mm ID, containing two sections

of

20/40 mesh activated charcoal separated by

a 2-inm portion of urethane foam.

The primary section contains 100 mg of charcoal, the backup section, 50 mg,

A 3-min portion

of

urethane"^oam is placed between the outlet end of the

tube and the backup section. the
primary section.

A plug of glass wool is placed

in

front

of

Tubes with the above specifications are connnercially

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available.

It should be noted that when conditions of very

high

humidity

exist,

evident by the visible condensation within the tube, the collection

efficiency of the sampling tube will be seriously reduced..

(2)
attachment, to the

Pump:

A battery-operated pump, complete with clip for
at 200

employee's belt, capable of operating

ml/minute or

less.

(b)
The

Calibration
accurate

calibration

of

a

sampling pump is essential for the

correct interpretation of the volume sampled.. The frequency of calibration
is dependent on the

use, care, and handling to which the pump is subjected.

Pumps should also be recalibrated if they have been misused or if they have
just

been

repaired or received from a manufacturer.

If the pump receives
Maintenance

hard usage, more frequent calibration may be

necessary.

and

calibration

should be performed on a regular schedule and records of- these

should be kept.
Ordinarily,

pumps should be calibrated in the laboratory both before

they are used in the field and after they have been used to collect a large
number of

field samples.

The accuracy of calibration is dependent on the
as a

type of

instrument

used

reference. "-The

choice

of

calibration

instrument will depend largely on where the calibration is to be performed.

For laboratory testing, a soapbubble meter is recommended,
standard

although

other

calibrating

instruments

can be used.

The actual setups will be

similar for all instruments. Instructions

for

calibration

with the soapbubble meter follow.

If
be

another calibration device is selected, used. The
calibration

equivalent

procedures

should

setup for personal

sampl'ing pumps

with a charcoal

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tube is shown in Figure XIV-1.

Since the

flowrate

given

by

a

pump

is

dependent
charcoal

on

the pressure drop across the sampling device, in this case a the

tube,

pump

must

be

calibrated

while

operating

with

a

representative charcoal tube in, line*

(1)
to

Check

the voltage of the pump battery with a voltmeter

ensure

adequate

voltage

for

calibration.

.Charge

the -battery

if

necessary.

(2)

Break

the

tips of a charcoal tube to produce openings

of at least 2 mm In diameter.

(3) (4)

Assemble the sampling train as shown in Figure XIV-1.

.Turn

on

the

pump

and

moisten

the

inside

of

the

soapbubble meter by immersing the buret in the soap solution.

Draw bubbles

up the inside until they are able to travel the entire buret length without

bursting.

(5)flowrate.

Adjust

the

pump

flowmeter

to

provide

the

desired

(6)

-Check the mercury manometer to ensure that the pressure

drop across the sampling train does not exceed

I

Inch

of

mercury

at

1

llter/mlnute or less*
(7)
'Start
a

soapbubble

up

the

buret and measure'with a

stopwatch the time it takes the bubble to move from one calibration mark to
another.

(8)

Repeat the procedure la (7) above
flowrate

at .least three times,

average the results, and calculate the

by

dividing

the volume

between

the

preselected

marks by the time required for the soapbubble to

traverse the distance.

If, for the. pump being calibrated,
218

the

volume

of

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air

sampled

is calculated as the product of the number of strokes times a.

stroke factor (given in units of
quotient

volume/stroke), the

stroke factor

is

the

of

the

volume

between the two preselected marks divided by the

number of strokes.

(9)
elapsed time

Data
number

for of

the calibration include-the volume measured,
strokes
of the

or

pump,

pressure

drop,' air

-temperature,

atmospheric

pressure,

serial

number of the pump, date, and

name of the person performing the calibration.

(c)

Sampling Procedure

(1)

Break

both

ends

of

the

charcoal
the

tube tube*

to

provide

openings of at least 2 mm, which is half the ID of

A

smaller

opening causes a limiting orifice effect which reduces the flow through the

tube.
section

The smaller section of charcoal in the tube and

is

used

as

a

backup

therefore is placed nearest the sampling pump.

Use tubing to
put
in

connect the back of the tube to the pump, but tubing must never be

front

of

the charcoal tube.

The tube is supported in a. vertical position

within the employee's breathing zone.

(2)

Sample

a maximum of 10 liters of air at a flowrate not

In excess of 200 ml/minute.
a

A sampling rate of 20 ml/minute would
in
an 8-hour period.

collect

volume

of

9.6

liters

For the determination of
sampling
rate

ceiling concentrations the sampling time is 15 minutes at a
of
air

200 ml/minute.

In addition to the personal and ceiling samples, a bulk
This 'air

sample may also be collected.

sample

should

be

taken

by

drawing air through a charcoal tube at 200 ml/minute for 4-6 hours.

(3)

Measure

and record the temperature and pressure of the

atmosphere being sampled.

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(4)

Treat

at least one charcoal tube in the same manner as

the sample tubes (break, seal, and ship), except do not

draw

air

through

it.

This tube .serves as a blank.

(5)

Immediately-

after

samples

are

collected,
caps.
in

cap

the

charcoal tubes with plastic caps.

Do not use

rubber

To
a

minimize

breakage
container.

during

transport,, pack

capped

tubes

tightly

shipping

Shipping Samples

Prior

to

shipping,

the charcoal tubes should be'packed tightly and

padded to minimize breakage during shipping.

A sample of the bulk material

(approximately

20

ml), of the
the

same batch of material which was being used

in the plant at the time of

sampling,

should

be

submitted

to

the

laboratory

in

a

glass

container

with'

a

polymer-lined cap.

This sample

should not be transported in the same container as the charcoal tubes,

220

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criteria for a recommended standard , . .

OCCUPATIONAL EXPOSURE TO REFINED PETROLEUM SOLVENTS

U.S. DEPARTMENT OF HEALTH. EDUCATION., AND WELFARE Public Health Service Center for Disease Control National Institute for Occupational Safety and Health

JULY 1977
Fif
by

SupTinrndcnl

Docuaifnu. U.S. Ga-m>Ant
1D403

PrUMfn, Offic*.

W**hlllKlon. D.C.