MRI.REPORT A _,.> __ ~_" _'W""" ._,,-,__., __ ~. __,_.....'

Consumer Exposure to Paint Stripper Solvents

Final Repor1

For U.S. Environmental Protection Agency

EPA Contract No. 68-00-0137

Work Assignment No. 4-06

MRI Project No. 9803-A(06)

February 28. 1994

MIDWEST RESEARC'..; l~, ,~ -, ". ffJ:

---.--- I·~ _"~__~- , • ._.._
This document has bE el~ oreoarec for HIP

.r.S Environmenta: F rurl~ctlon Aqenc,

oroducts does not ')I S''1 Jte AqerH:y E"l!j

1fT E' of Pollution Prevention and T)(I'

,5e )f trade names or COfYln-'e r ( d

-r'pn' )f mcommendation fc u:+

This documer : , unntec)n rI':) " I-lOP
MAl. REPORT

Consumer Exposure to Paint Stripper Solvents

Final Report

For U.S. Environmental Protection Agency

Technical Program Branch, 7404

Chemical Management Division

OffIce of Pollution Prevention and Toxles

Northeast Mall, Room G012

401 M Street, SW

Washington, DC 20460

EPA Contract No. 68-00-0137

Work Aaalgnment No. 4-06

MRI Project No. 9803-A(06)

February 28, 1994

MIDWEST RESEARCH INSTITUTE 425 Volker Boulevard, Kansas City, MO 64110-2299 • (816) 753--7600

I
PREFACE

The objective of this project is to detennine consumer exposures to

solvents contained in chemical paint stripping products that have been

fonnulated to reduce or eliminate me1hytene chloride content. This report details

the results of 15 experimental runs conducted in the Air Consumer Exposure

(ACE) Laboratory at Midwest Research Institute (MAt) to measure airborne

exposures to solvents dUring the application of commercially available paint

strippers.

This project was prepared for the Environmental Protection Agency (EPA),

Office of Pollution Prevention and Toxics (Oppn, Chemical Management

Division, Technical Programs Branch under EPA Contract No. 68-00-0137, Work

Assignment No. 4-06. The EPA Project Officer was Ms. Janet Remmers.

Dr. Gordon Cash served as the EPA Work Assignment Manager.

This report was prepared by Mr. James McHugh, MRI Work Assignment

Leader. The MRI Program Manager was Mr. Paul Constant. Dr. George Scheil,

Mr. Scott Klamm, and Mr. William C. Bailey assisted with the ACE laboratory

experiments. Mr. Jack Balsinger served as the Senior Quality Assurance Officer.

MIDWEST RESEARCH INSTITUTE

I

Approved:

~;[(~ Program Manager

Jack Balsinger

Senior Quality Assurance Officer

February 28, 1994

MRI-0Pf'1iR06-01.FFl

()""-.MJ . )7"';

LlHnHJ:S M. McHugh, CIH

ior Industrial Hygienist

iii
CONTENTS

Preface iii

list of Tables vi

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

2. Product Selection 3

2.1 Shelf survey 3

2.2 Product selection. . . . . . . . . . . . . . . . . . . . . . .. 3

2.3 Product testing 4

3. MRI ACE laboratory Facilities .. . . . . . . . . . . . . . . . . . . . . .. 5

3.1 Temperature measurements and controls 6

3.2 Relative humidity measurements and controls. .. 6

3.3 Barometric pressure measurements 8

3.4 Air change rate measurements and controls 8

3.5 Air mixing 9

4. Experimental Procedures. . . . . . . . . . . . . . . . . . . . . . . . . . .. 11

4.1 Test protocol " 11

4.2 Preparation of the test chamber 12

4.3 Sampling equipment 12

4.4 Product application method 13

5. Air Sampling Procedures " 19

5.1 Nearly real-time air samples " 19

5.2 Integrated air samples 19

6. Analytical Methods 23

6.1 MIDAC Fourier transform infrared analyzer 23

6.2 Integrated air samples .,. . . . . . . . . . . . . . . . .. 25

7. Results and Discussion . . . . . . . . . . . . . . . . . . . " 27

7.1 Integrated air samples 27

7.2 Nearty real-time air samples. . . . . . . . . . . . . . .. 36

7.3 Quality control samples 37

7.4 Quality assurance activities 37

8. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 39

9. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 41

Appendices:

A. Limited shelf survey of paint stripping products in the Kansas

City metropolitan area A-1

B. Operating procedures for the MIDAC FTIR closed cell

system B-1

C. Analytical methods C-1

D. FTIR results-air concentrations vs. time 0-1

MRI-OPPi\R06-01.FR V

I
LIST OF TABLES

Table Page

1 Test chamber environmental conditions 7

2 Duration of test runs .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 16

3 Quantities of product applied and residue removed . . . . . . . . . . . . .. 18

4 Air sampling and analytical methods . . . . . . . . . . . . . . . . . . . . . . . .. 20

5 Concentrations of standards 24

6 Integrated air sampling results-Bix Stripper . . . . . . . . . . . . . . . . . .. 28

7 Integrated air sampling results-Bix Spray-On Stripper 29

8 Integrated air sampling results-Strypeeze ..... . . . . . . . . . . . . . .. 30

9 Integrated air sampling results-Wood Finishers Pride 31

10 Integrated air sampling results-3M Safest Stripper . . . . . . . . . . . . " 32

11 Occupational exposure limits .. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 33

12 Blind spiked sample results .. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 38

I

vii
SECTION 1

INTRODUCTION

The Toxic Substances Control Act (TSCA) mandates the assessment of

risks associated with the manufacture and use of new and existing chemicals. In

1985, the Interagency Committee of Indoor Air Quality called for an effort

directed at developing an understanding of the magnitude of human exposure to

indoor air pollutants, the contributions of various energy conservation measures.

and the impact of introducing new consumer products and bUilding materials. As

part of this effort, exposure to chemical releases under various conditions from

consumer products and building materials in indoor environments must be

assessed.

Chemical paint strippers used by consumers have primarily contained

methylene chloride (dichloromethane). Because of concerns about the toxicity of

methylene chloride, new paint stripper formulations have been developed that

eliminated this chemical or significantly reduced its content. However, there is

concern about the toxicity of these new fonnulations. The Office of Pollution

Prevention and Toxies (OPPT) received a referral from the Consumer Product

Safety Commission about one such substitute, N-methyl pyrrolidone (NMP). The

OPPT RM1 process has determined that there is a reasonable basis for the

concern about the use of NMP in paint strippers; however, other new formulations may also pose some degree of risk.

The paint-stripping solvents selected for this study represent the largest

share of the market. They are:

• Methylene chloride (dichloromethane)

• Toluene

• Acetone

• Methanol

• N-Methyl pyrrolidone (NMP)

• Dibasic esters (e.g., dimethyl glutarate. dimethyl adipate, dimethyl succinate)

The objective of this study is to determine consumer exposure to solvents

contained in commercially available paint strippers under typical product-use

scenarios. The products that were tested are those that have been formulated to

reduce the content of methylene chloride.

Mf:ll·OPPl\R06·01.FR ,
Each of the selected products was tested in triplicate under controlled

environmental conditions inside MAl's Air Consumer Exposure (ACE) Laboratory

exposure chamber for a total of 15 experiments. The paint strippers were used

according to the manufacturers' instructions printed on the label. Product

application procedures were consistent with previous laboratory studies of

methylene chloride paint strippers conducted at the Lawrence Berkeley

Laboratory (Girman and Hodgson, 1986).

2
SECTION 2

PRODUCT SELECTION

2.1 SHELF SURVEY

A shelf survey was conducted at retail stores in the Kansas City, Missouri,

metropolitan area to compile a list of chemical paint stripping products available

to consumers (Appendix A). Ten retail stores were surveyed, which included

home improvement, paint, and hardware stores.

A total of 38 paint stripping products distributed by 19 manufacturers were

found on the store shelves. The product contents were detennined from the

label and from the material safety data sheet requested from the manufacturers.

Thirty-five of the products contained one or more of the target compounds. None

of the products contained dimethyl succinate.

A total of 29 products contained methylene chloride. Of these, only one

product contatned methylene chloride as the sole active ingredient. Twenty-eight

products contained other active ingredients in addition to methylene chloride. Of

these, 27 contained methanol, 14 contained toluene, and 8 contained acetone.

A total of 23 products contained ingredients other than the target compounds

selected for this study. Some of the product fonnulations included: xylene,

ethanol, lsobutane, petroleum distiltants, minerals spirits, stoddard solvent,

monochlorotoluene, ethylene glycol, monobutyl ether, glycol ethers, sodium

carbonate, calcium hydroxide, and ammonia.

Of the products that did not contain methylene chloride, two contained a

mixture of volatile organic compounds (i.e., methanol, toluene, and acetone), two

contained a mixture of dibasic esters, and one contained NMP.

2.2 PRODUCT SELECTION

From the list of available paint strippers on the market, the following five

products were selected by the MRI Work Assignment Leader (WAL) and

approved by the EPA Work Assignment Manager (WAM):

MRI-OPPT\R08-01.FR 3
• SIX Stripper, Six Manufacturing Co., Inc., Ashland City, TN

• BIX Spray-on Stripper, Bix Manufacturing Co., Inc., Ashland City, TN

• Strypeeze, Savogran, Norwood, MA

• Wood Finisher's Pride, Creative Technologies Group, GreensviJIe, SC

• 3M Safest Stripper, 3M Corporation, St. Paul, MN

Each of the selected products was found on the shelves of at least two

retailers and contained one or more of the target compounds. A total of nine

products met the selection criteria, however, only five were selected due to cost

considerations. The fonnulations of the four products that were eliminated were

similar to those selected. All of the paint strippers are applied to the substrate

with a brush, except for BIX Spray-on Stripper. This product was specifically

selected for this study because of its unique application method.

Two of the five selected products contained methylene chloride fonnulated

with other volatile organic compounds. Strypeeze contained a mixture of

methylene chloride, methanol, acetone, and toluene. SIX Spray-On Stripper

contained a mixture of methylene chloride and methanol. The fonnulations of

these two products are similar to 25 products included in the shelf survey (i.e.,

products containing methylene chloride and one or more volatile organic

compounds).

One of the product selected contained a mixture of organic compounds

other than methylene chloride. BIX Stripper, which contained a mixture of

methanol, acetone, and toluene, is similar to two other products included in the

shelf survey.

Two of the five setected products contained semi-volatile compounds.

Wood Finisher's Pride was the only product found in the shelf survey that

contained NMP as active ingredient. 3M Safest Stripper, which contained a

mixture of dibasic esters, was also chosen for the study. One other products

included in the shelf survey have a similar formulation.

2.3 PRODUCT TESTING

Each of the selected products were analyzed by gas chromatography!

mass spectrometry (GS/MS) to confirm the presence of the target compounds.

The target volatile organic compounds of each of the selected products were

analyzed using EPA Method 8260A, Volatile Organic Compounds by GC!MSCapillary Column Technique. The target semivolatile compounds were analyzed

using EPA Method 8270A, Semivolatile Organic Compounds by GC/MS-Capillary

Column Technique. The presence of all of the target compounds listed on the

product labels were confirmed by the GC/MS analyses.

'if

,~i

4 MRI·0PFl'\R08-0',FR
SEcnoN3

MRI ACE LABORATORY FACILITIES

This studywas conducted in a room-size test chamber located in MAl's

ACE Laboratory (room no. 214/216-E). The volume of the test chamber is

1,261 ns (floor dimension of 14 x 11.4 ft with a ceiling height of 7.9 ft). The test

chamber is equipped with temperature, humidity, and ventilation controls required

to conduct consumer exposure studies under stable conditions.

Real-time temperature, humidity, and barometric pressure measurements

were collected at 1-min intervals dUring all experimental test runs using

WEATHERtronics sensors mounted inskte the test chamber. A Compaq portable

computer recorded the temperature, humidity, and barometric pressure data,

together with the clock time, onto an internal hard disk drive. A dot-matrix printer

printed the data in real time.

The following instruments were used for measurements of environmental

conditions inside the test chamber:

• MIDAC Fourier-transform infrared analyzer

• MAl-built analog-to-digital converter based on Wintek micro control system

module with 12-bit resolution and RS-232 host computer interface

• Compaq portable computer with GWBASIC logging program

• Dot-matrix printer to record all logger operations

• WEATHERtronics SG-21 hydrothermograph

• WEATHERtronics 7105-A analog output barometer

• WEATHERtronics 5120-8 portable humidity probe

• Thermocouples (type K) with Omega TAC 80 thennocouple-to-millivolt

converters

5
3.1 TEMPERATURE MEASUREMENTS AND CONTROLS

The temperature within the ACE Laboratory was monitored using two

thermocouples connected to an Omega TAC 80 thermocouple amplifier and

Iinearizer. The temperature probes were located on the east wall of the test

chamber. The temperature was set between 75° and nOF and controlled within

±1.5°F. The temperature in the ACE Laboratory was controlled with dual

thermostats using a dedicated air-conditioning unit.

The accuracy of the Omega thermocouple~to~millivolt converter is listed by

the manufacturer as ±7.2° over its entire operating range of 4° to 1832°F. The

output of the instrument is listed as 1 mY/OF. The temperature probe was cali~

brated over a much narrower operating range (32° to 212°F) using ice water and

boiling water to achieve an accuracy of ±1OF.

The temperature measuring equipment was checked prior to each run

against a mercury thermometer. The mercury thermometer was checked against

a set of certified thermometers (No. 9848), which are traceable to the National

Institute of Standards and Technology (NIST).

Table 1 summarizes the average. maximum. and minimum temperatures

that were measured inside the test chamber during each experimental run.

3.2 RELATIVE HUMIOtTY MEASUREMENTS AND CONTROLS

The relative humidity within the test chamber was measured at 1-min

intervals using a WEATHERtronics 5120~B portable humidity probe located on

the east wall of the test chamber. The relative humidity was set at a level

between 55% and 65% and controlled within ±10%. The humidity in the test

chamber was regulated by a dedicated air~conditioning unit, which dehumidifies

the supply air entering the test chamber. Due to the low volume of air entering

the chamber. control of the humidity within the chamber was limited. The relative

humidity within the chamber tended to increase when the person performing the

paint stripping operation entered the room. No attempt was made to dehumidify

the air once it entered the test chamber.

The accuracy of the WEATHERtronics humidity probe is listed by the

manufacturer as ±2% in the operating range of 0% to 80% relative humidity. The

instrument was tested and fully calibrated at the factory. The humidity probe was

calibrated at a low humidity point of 12% inside a glass container using a saturated salt solution of lithium chloride in water, and a high humidity point of 75%

using a saturated salt solution of sodium chloride in water. Calibration of the

humidity recording equipment was conducted once, immediately prior to the ACE

Laboratory experimental runs.

6
...., MRI-oPPnR06-01

Table 1. TEST CHAMBER ENVIRONMENTAL CONDITIONS

r.~ .-•••;.::-> !til )"}':'.- r, . _.________

1 0.76 76.6 77.2 76.1 59.2 64.4 55.1

2 0.62 76.8 77.5 76.3 56.8 62.9 54.3

3 0.61 76.6 77.2 76.1 61.4 63.9 58.0

4 0.57 75.9 76.7 75.1 60.2 65.6 57.9

5 0.57 75.8 76.6 75.3 60.0 65.1 57.6

6 0.58 76.2 77.0 75.5 56.1 58.9 54.3

7 0.56 75.8 76.6 75.0 60.6 66.8 58.0

8 0.54 76.7 77.3 75.9 57.9 64.7 54.7

9 0.55 76.3 77.0 75.2 59.3 62.2 56.1

10 0.56 76.5 77.5 75.9 61.9 65.5 56.0

11 0.54 75.9 76.8 75.3 65.4 69.6 57.3

12 0.57 76.6 77.5 76.0 62.7 68.2 55.3

13 0.55 76.6 77.4 76.0 55.9 67.7 46.3

14 0.54 76.1 76.9 75.6 56.6 70.2 47.8

15 0.54 75.8 76.6 75.1 54.6 63.8 46.2
The humidity recording equipment was checked against a wet bulb/dry

bulb psychrometer prior to each experimental run. The thermometers in this unit

were checked against NIST traceable thermometers.

Table 1 summarizes the average relative humidity measured inside the

test chamber during each experimental run. The maximum and minimum relative

humidities that were recorded dUring each experimental run are also presented.

3.3 BAROMETRIC PRESSURE MEASUREMENTS

The barometric pressure was monitored using a WEATHERtronics 7105·A

analog output barometer located on the east wall of the test chamber. The

barometric pressure was not controlled.

The accuracy of the WEATHERtronics analog output barometer is listed

by the manufacturer as ±O.08% over an operating range of 17.72 to 32.48 in Hg

including hysteresis, thermal shift, and nonlinearity. Each sensor was tested by

the manufacturer inside a pressurized chamber and compared to an NISTtraceable standard. Calibration adjustments to this sensor are not possible.

The barometer was checked against a mercury Fortin-type barometer.

This instrument check was conducted once immediately prior to the first

experimental run.

3.4 AIR CHANGE RATE MEASUREMENTS AND CONTROLS

Air change rates within the test chamber were controlled for all

experimental runs. Air was exhausted from the test chamber using a General

Metal Works (GMW) vacuum pump controlled with a critical orifice. The critical

orifice was sized to achieve an air change rate (ACH) of approximately 0.5 per

hour within the test chamber.

Air change rates were estimated for each experimental run by measuring

tracer-gas decays. Immediately prior to an experiment, the sulfur hexafluoride

(SFe) tracer gas was uniformly mixed in the test chamber by injecting pure gas

with a syringe. A sample of test chamber air was continuously drawn from the

breathing zone of the worker and measured with the MIDAC Model 2400 Fourier

transform infrared (FTIR) spectrometer at 4-min intervals.

A decay curve, Ct

=Co e-AI, was fitted to the SF6 air concentration data

collected at regular intervals after injection of SF6 gas was stopped and the

source removed from the test chamber. The parameter estimates, COl the SF6

concentration at time t = 0, and A, the air change rate, were estimated by linear

8 MRI-OPPl\R06-01
regression of the log-transformed SF6 concentrations VS. time. The SFa concentration at time t = 0, Co. and the air change rate, A, were both estimated

simUltaneously by least-squares method.

The air change rate during each experimental run is presented in Table 1.

3.5 AIR MIXING

Air mixing characteristics of the ACE Laboratory test chamber were

investigated using tracer gas decays as part of EPA-OPPT, Work Assignment 03

(McHugh and Bauer, 1992). The study found that adequate air mixing in the

chamber is achieved using two commercially available box fans positioned at two

adjacent comers along the long wall. Each fan was mounted on a tubular stand,

which positioned the fans to a 30-degree tilt from the vertical at a height of 32 in

from the floor. The fan speed was adjusted to 800 rpm.

9
11

SEcnON4

EXPERIMENTAL PROCEDURES

4.1 TEST PROTOCOL

Each of the selected products was tested in triplicate under controlled

environmental conditions inside MAl's Air Consumer Exposure (ACE) Laboratory

exposure chamber for a total of 15 experiments. The paint strippers were used

according to the manufacturers' instNetions printed on the label. The application

procedure was consistent with previous laboratory studies conducted at the

Lawrence Berkeley Laboratory (Girman and Hodgson, 1986).

The substrate selected for paint removal consisted of a plywood panel

(8 ff with dimensions of 2 x 4 ft) painted on one side with a primer coat and two

finish coats of an oil-base enamel (white). This is the same substrate as that

used for a previous study of methylene chloride exposure from controlled use of

a paint remover in residences that was sponsored by the U.S. Consumer Product

Safety Commission (Girman and Hodgson, 1987).

The ventilation rate within the test chamber was set at approximately

0.5 air changes per hour (ACH). The selected air change rate was one of the

two ventilation rates used in the Lawrence Berkeley Laboratory study of

methylene chloride paint stripper. The selected ACH represents the ventilation

rate in an enclosed room (no open doors or windows) in a typical residence.

The performance of a paint-stripping operation in such an enclosed room

approximated the "woret-case' scenario. The ventilation rate was measured

using a tracer-gas decay method.

Airborne concentrations of paint stripper solvents were measured dUring

actual paint stripping operations using two sampling methods-integrated air

sampling onto solid sorbent tubes for subsequent analysis, and nearly real-time

air concentration measurements using the MIDAC FTIR spectrometer. The air

sampling procedures are detailed in Section 5.

MRH)PPT\R06-01
4.2 PREPARAnON OF THE TEST CHAMBER

The following procedures were performed prior to each experimental run

to prepare the environment controls and sensors:

• The vacuum exhaust pump was tumed on to maintain the appropriate air

change rate within the test chamber.

• The temperature sensors in the test chamber were checked against a NISTtraceable thermometer.

• The temperature within the chamber was adjusted to between 750 and 77°F.

• The WEATHERtronics 5120-8 humidity sensor in the chamber was checked

against a psychrometer with the wet/dry-bulb thermometers traceable to NIST.

• The relative humidity within the chamber was adjusted to between 55% and

65%.

The test chamber was equipped with the following items:

• Product container

• 1-qt can

• 7.6-cm-wide brush

• 7.6-cm-wide scraper

• Cheese cloths

• Thin polyethylene plastic sheet

• Plywood panel (8 fr! with dimensions of 2 x 4 ft) painted on one side with a

primer coat and two finish coats of an oil-base enamel

• Support stand for the plywood panel

• Fisher Scientific balance (Model No. 2-116), capable of weighing up to 5 kg

4.3 SAMPLING EQUIPMENT

A MIDAC Model 2400 FTIR spectrometer was set up on a benchtop in the

instrument room adjacent to the test chamber. The instrument was equipped

with a White cell with a fixed path length of 20 m. A flexible, 12-ft Teflon

sampling line from inside the test chamber was routed through the wall of the

12 MRI·QPPTlR06-01
chamber and attached to the inlet of the White cell. A Gast vacuum pump

(Model No. MAA-V109-MB) was attached to the outlet of the White cell with a

short length of Tygon tubing. The vacuum pumped putted air from the test

chamber through the cell at a constant rate. The air exhausted from the White

cell was directed back into the test chamber using Teflon tUbing. A valve

attached to the outlet of the White cell was used to adjust the vacuum within the

White cell to less than 2 in Hg. During all experimental runs, the inlet of the

Teflon sampling line to the White cell was attached to the breathing zone of the

person performing the stripping operation inside the test chamber.

Stationary air samplers were positioned at three locations within the test

chamber. The air sampters consisted of a battery-operated pump that pulled air

at a constant rate through an activated charcoal tube. Sampling inlets were

placed at breathing zone height on both the sides of the plywood panel at a

centerline distance of 3 ft. The sampler located nearest to the exhaust outlet of

the test chamber was designated as the "outlet·1 sampler. The one nearest the

air inlet to the chamber was designated as the 'Iinlet" sampler. An additional

stationary sampler was positioned at breathing height in the center of the test

chamber, immediately adjacent to the plywood panel. The supply air to the test

chamber was sampled during each experimental run by placing a stationary air

sampler within the air stream. When the paint stripper contained methanol, a

second set of samplers equipped with a silica gel sorbent tube was placed at

each location.

The stationary samplers were turned on immediately prior to the start of

the paint stripping operation. The lIinletll and "outlet" samplers inside the test

chamber were turned off and removed from the test chamber when the test subject left the chamber at the end of the paint stripping and cleanup operations.

The samplers positioned at the center of the chamber and in the supply air of the

chamber were run for an 8-h period. A built-in timer shut off the samplers

automatically at the end of the sampling period.

In addition to the stationary sampler, a portable, battery-operated air

sampler was attached to the person performing the stripping operation. The

sampling inlet was positioned in their breathing zone. The personal air sampler

was started immediately prior to the start of the paint stripping operation and

turned off when the test subject left the chamber.

4.4 PRODUCT APPLICATION METHOD

The paint strippers were used according to the manufacturers' instructions

on the container label. The application of the paint removers was similar to that

detailed in a study conducted at the Lawrence Berkeley Laboratory (Girman

and Hodgson, 1986).

MRI-QPPM06-01 13
Prior to each experimental run, polyethylene plastic sheets were placed on

the floor of the test chamber and beneath the support stand to collect the paint

scraping. The plywood p8fl8I was ptaced on the support stand which poaitioned

the panel at a 45-degree angle. The product container, 1-qt can, brush, scraper,

cloths, and plastic sheet were individually weighed on Fisher-Scientific balance

(Model No. 2-116).

The procedure was as follows:

• Each product was shaken or stirred as recommended by the manufacturer and

transferred to a 1-qtmetal can. For the BIX Spray.()n Stripper, a portion of

the stripper was transferred to the sprayer that was supplied with the product.

• The can and the application brush (or sprayer) were weighed on the balance

and the weight recorded on data sheet.

• Thick coats of the product were applied to one-quarter of the panel with a

7.6-cm-wide brush (or with a sprayer).

• The can and the brush (or sprayer) were weighed again on the balance and

the weight recorded.

• After the product remained undisturbed on the first quarter section for 10 min,

the product was applied to the second quarter using the same technique as

described above.

• After the stripper was in contact with the paint for 15 min (longer for some

products), the softened paint was scraped from the first quarter with a

7.6-cm-wide scraper. The scrapings were transferred to a polyethylene sheet.

• The above sequence was repeated until each quarter of the panel had been

stripped twice.

• During the periods between application of the product or scraping of the

softened paint, the test subject sat on a stool approximately 1 m from the

substrate.

• At the conclusion of the final scraping, the substrate was wiped with clean

cheese cloths.

• The used metal can, brush, scrapper, and cloths were weighed on the balance

and the weights recorded.

• The polyethylene sheets that contained the paint scrapings were gathered,

folded, and weighed on the balance. The weights were recorded.

14 MRI·0PPTIFI06-01
• All containers, tools, and the folded plastic sheets were placed into a plastic

bag and sealed.

• At the comptetion of the paint stripping operation and cleanup, two of the three

air samplers were removed from the chamber when the test subject left the

chamber. The remaining sampler in the test chambers ran for an 8-h duration.

The duration of each experimental run is presented in Table 2. The paint

stripper was allowed to remain in contact with the paint for the minimum time

recommended on the label. SIX Stripper, SIX Spray-Qn Stripper, and Strypeeze

were in contact with the paint for 15 min before scrapping. Wood Finisher's

Pride and 3M Safest Stripper were in contact with the paint for 30 and 60 min,

respectively.

Table 2 also presents the durations of time that the test subject spent

inside the chamber. The time spent inside the chamber for experimental run

nos. 1 through 9 was approXimately 1"Y.z h. The duration of exposure for run

nos. 10 through 12 was approximately 2 h because the stripper was required to

be in contact with the paint for 30 min prior to scrapping. The duration of

exposure for run nos. 13 through 15 was approximately 2 h due to a 60-min

contact time required for the strippers.

Table 3 presents the amount of the product applied during each experimental run and the amount of residue scraped off the plywood panel. The

residue consisted of the removed paint and that portion of the paint stripper that

did not volatilize during the stripping operation.

MRI-oPP'NlO8-01 15
Table 2. DURATION OF TEST RUNS

&IX

Date 07127193 07129193

Entered Chamber 14:50 13:48

Start Time 14:55 13:53

Stop Time 16:25 15:24

Exited Chamber 16:40 15:38

Duration of Stripping

Operation (hr:min) 01:30 01:30 01:31

Duration Subject Inside

Test Chamber hr:min 01:50 01:50 01:50

16

&IX -on S r

Date

Entered Chamber

Start Time

Stop Time

Exited Chamber

Duration of Stripping

Operation (hr:min)

Duration Subject Inside

Test Chamber hr:min

s •

Date

Entered Chamber

Start Time

Stop Time

Exited Chamber

Duration of Stripping

Operation (hr:min)

Duration Subject Inside

Test Chamber hr:min

01:25

01:39

01:25

01:45

01:25

01:36

01:31

01:48

01:25

01:36

08127/93

10:44

10:55

12:25

12:41

01:30

01:57

MAl-oPP1\R06-01
Table 2 (Continued)

Wood F........ Prt.

Date 09101193 09103193

Entered Chamber 12:47 12:47

Start Time 12:43 12:55

Stop Time 14:35 14:48

Exited Chamber 14:55 15:05

Duration of Stripping

Operation (hr:min) 01:47 01:52 01:53

Duration Subject Inside

Test Chamber hr:min 02:05 02:08 02:18

3M Sllreat StrI

Date

Entered Chamber

Start Time

Stop Time

Exited Chamber

Duration of Stripping

Operation (hr:min)

Duration SUbject Inside

Test Chamber hr:min

MAI-OPPl\R06-01

09108193

13:37

13:42

16:21

16:40

02:39 02:40

03:03 02:53

02:40

03:03

17
Table 3. QUANTmES OF PRODUCT APPLIED AND RESIDUE REMOVED

SIX Stripper 1 664 574

2 724 635

3 703 662

Average 697 624

SIX Spray-on Stripper 4 537 408

5 497 484

6 586 450

Averaae 540 447

Strypeeze 7 724 808

8 676 710

9 765 800

Average 722 773

Wood Finishers' Pride 10 884 1104

11 805 1125

12 908 1124

Average 866 1118

3M Safest Stripper 13 837 778

14 775 669

15 786 761

Average 799 736

18
19

SECTION 5

AIR SAMPLING PROCEDURES

Airborne concentrations of the paint stripper solvents were measured in

the test chamber during paint stripping procedures by collecting both nearly realtime and integrated air samples.

5.1 HEARLV REAL-TIME AIR SAMPLES

Airborne concentrations of the paint stripper solvents and the tracer gas

were measured in nearly real-time at the breathing zone of the paint stripper

applicator using a MIDAC Model 2400 Fourier transform infrared (FTIR)

spectrometer. The instrument was equipped with a closed-path White cell with a

path length of 20 m. Air from the breathing zone of the product user was drawn

to the White cell with a sampling pump via Teflon tUbing. Repetitive highresolution spectra were averaged every 4 min over the range of 400 to

4,000 em:' with resolution of 0.5 em". Operating procedures for the MIDAC

FTIR closed-cell system are detailed in Appendix B.

5.2 INTEGRATED AIR SAMPLES

Integrated air samples were collected by drawing air through activated

charcoal and/or silica gel sorbent tubes with battery-operated, constant-flow

samplers. The air sampling methods used for this study are present in Table 4.

When available, sampling was conducted according to National Institute of

Occupational Safety and Health (NIOSH) standard methods. NIOSH-approved

methods were not available for N-methyl-2-pyrrolidone or for the dibasic esters

(dimethyl adipate and dimethyl glutarate). A GAF Chemical Corp. method, which

is currently used by OSHA, was used for N-methyl pyrrolidone. The dibasic

esters were sampled using a Du Pont-developed method.

Two air sampling devices were used for this study; the Ametek

Model Alpha 2 constant-flow sampler and the Gilian Model HFS 113 sampling

system operated in the low-flow constant pressure mode. The Ametek Alpha 2

is a personal air-sampling instrument that moves a constant volume airflow

through an external collection device (e.g., charcoal or silica gel tube). An

MRI·OPPnR06-01
I\)

o Table 6. AIR SAMPUNG AND ANALYTICAL METHODS

Methylene chloride I NfOSH IActivated charcoalI0.01 to 0.2 Umin IGas chromatography, FlO 0.01 mg per

1005 sorbent tube sample

Acetone I NIOSH Activated charcoal 0.01 to 0.2 Umin Gas chromatography, FlO 0.02 mg per

1300 sorbent tube sample

Toluene I NIOSH Activated charcoal 0.01 to 0.2 Umin Gas chromatography, FlO 0.01 mg per

1501 soment tube sample

Methanol I NIOSH Silica gel sorbsnt 0.02 to 0.2 Umin Gas chromatography, FlO 0.01 mg per

2000 tube sample

Dibasic esters I Du Pont I Activated charcoal 0.01 to 0.2 Umin Gas chromatography, FlO 0.01 mg per

sorbent tube sample

N--Methyl I GAFf Activated charcoal 0.01 to 0.2 Umin Gas chromatography, FlO 0.01 mg per

pyrrolidone OSHA sorbent tube sample

MRK>PPl\R06-()1
automatic flow control system maintains the rate within ±50/0 over pressure drop

changes up to 25 in H20 . The sampler features two tight--emitting diodes that

indicate constant flow and battery charge. The Gilian sampling system consisted

of a Gitian air sampler attached to the Gilian triple variable-flow sampling

manifotd. The universal sampling manifold allowed one sampling pump to collect

up to three sorbent-tube samples simultaneously. The airflow through each

sorbent tube was controlled individually with separate needle valves.

Both the Ametek and GUian sampJing pumps were calibrated before and

after each use with a Gilibrator primary flow calibrator (GUian Instrument Corp).

The Gilibrator calibration system is based on the thin-film volumetric method, a

primary calibration procedure. The Gilibrator is a battery-operated, electronic

bubble flowmeter that provides instantaneous air flow readings and a cumulative

averaging of multiple flow measurements. The unit consists of a flow cell

assembly, control unit (base), and battery charger. The flow cell assembly

consists of a flow tube. bubble generator, and sensor blocks located on each end

of the tube. The Gilibrator was calibrated by Gitian Instruments Corp. on

February 2. 1993, using a film flowmeter (MCS-102) calibrator traceable to NIST,

per circular No. 602.

The flow rate of each sampling pump was calibrated before and after each

use by attaching the flow celt (outlet) of the Gilibrator to the pump inlet with

flexible rubber tubing. The appropriate sorbent tube (activated charcoal or silica

gel tube) was placed in line between the GiJibrator and the pump. The bubble

generator was activated on the flow cell to form a bubble film across the

diameter the flow tube. The sampling pump draws the thin-film bubbles up the

flow tube. As the bubble traverses past the two infrared sensors, each sensor

transmits a signal to the control unit indicating the passage of the film. The

control unit contains a crystal-controlled timing system, a microprocessor control

system, and an LCD reading for displaying flow and other messages. The flow

rate of the sampler is calculated by the internal microprocessor and displayed

automatically on the LCD screen. Triplicate flow measurements were performed.

The calibration results were recorded on the Air Sampling Data Sheet.

During each experiment the following integrated air samples were

collected:

• One stationary sample inside the test chamber prior to each run for a period of

8 h (pretest background sample).

• One air sample from the breathing zone of the test subject conducting the

paint-stripping procedure (personal breathing zone sample).

• Two stationary air samples within the test chamber for the duration of the

paint-stripping task (Iength~of-task sample).

21
• One stationary air sample within the test chamber, beginning at the start of the

paint-stripping task and running for an 8-h period (8-h, time-weighted average

sample).

• One stationary air sample outside of the test chamber (supply air sample).

22 MRHJPPnA06-01
SECTION 6

ANALYTleAl METHODS

6.1 MIDAC FOURIER TRANSFORM INFRARED ANALYZER

6.1.1 Analysis of the Volatile Organic Solvents in the Paint StrIpper

Airborne concentrations of the paint stripper solvents were measured in

nearly real-time at the breathing zone of the paint stripper applicator using a

MIDAC Model 2400 Fourier transform infrared (FTIR) spectrometer. The instrument was equipped with a closed-path White cell with a path length of 20 m. Air

from the breathing-zone of the product user was drawn to the White cell via

Teflon tUbing with a GAST vacuum pump. Repetitive high-resolution spectra

were collected and averaged at 4-min intervals over the range of 400 to

4,000 em" with resolution of 0.5 em". The FTIR spectrometer was operated

from a portable computer.

The FTIR was calibrated using a series of standards prepared in Tedlar

gas sampling bags (Nutech Corporation). The standards were prepared by

diluting an aliquot of appropriate solvent with high purity air to a volume of 20 L

in Tedlar bags. The following chemical were used for calibration of the FTIR:

• N-Methyl-2-pyrrolidonet Aldrich Chemical Co" high purity, 99+%, HPLC grade

• Toluene, Aldrich Chemtcal Co., high purity, 99.8%, HPLC grade

• Acetone, Aldrich Chemical Co., high purity, 99+%, HPLC grade

• Methanol, Aldrich Chemical Co., high purity, 99.9%

• Dichloromethane, Aldrich Chemical Co" high purity, 99.9%, HPLC grade

• Dimethyl adipate, Aldrich Chemical Co., high purity, 99+%

• Dimethyl glutarate, Aldrich Chemical Co., high purity, 98%

The resulting concentrations of the standard series are presented in

Table 5. The dilution volume was metered using a calibrated dry gas meter

(Singer Company, MAl No. 9044) into clean, dry Tedlar gas sampling bags.

23
Methylene chloride 10, 100, 3,000 100

Acetone 5,60,2,000 60

Toluene 10, 100, 1,000 100

Methanol 3,30,3,000 30

N-Methyl pyrrolidone 30,60,180 60

Dimethyl adipate 30,60,180 60

Dimethyl glutarate 30,60,180 60

Dimethyl succinate 30,60,80 60

Sulfur hexafluoride 0.3,3.6 3

Each Tedlar bag containing the standard series was attached to a

sampling inlet and pumped into the FTIR White cell. Analysis of the samples

was performed as detailed in Appendix B.

A mid-point check standard (prepared independently from the standard

series) was prepared and pumped into the White for analysis prior to each

experimental run to monitor the accuracy and precision of the system over the

entire project. If the analytical results of the check standard fell outside of the

instrument performance objective, calibration of the FTIR was repeated with the

full standard series.

6.1.2 Analysis of Sulfur Hexafluoride Tracer Gas

Tracer gas concentrations within the test chamber were measured in

nearty real-time using a MIDAC FTIR. Repetitive high-resolution spectra were

collected and averaged every 4 min over the range of 400 to 4000 em" with

resolution of 0.5 em",

The FTIR was calibrated using a series of SF6 standards prepared in

Tedlar gas sampling bags (Nutech Corporation). The TOOfar bags have

Swagelok fittings that allow the injection of liquids or gases through silicone septa

using Hamilton gastight syringes. A neat concentration of SF6 was prepared by

24
evacuating a 500-ml Tedlar bag and filling it with pure SFs gas from a

compressed gas cylinder (sulfur hexafluoride gas, Matheson Gas Products,

> 99.8% pure). Atiquots of the neat SFs were drawn from the Tedlar bag using a

Hamilton gastight syringe to prepare working standards. The series of SFs

standards in air were prepared by diluting aliquot of the working standard with

high purity air to a volume of 20 L to produce standards in clean, dry Tedlar

bags. The dilution volume was metered using a calibrated dry gas meter (Singer

Company, MRI No. 9044). The resulting air concentrations of SFa are presented

in Table 5.

A blank was prepared with the standard series using the preparation

procedures specified above, except that no SFs was injected into the Tedlar bag.

Each Tedlar bag containing the SFs gas standards and blank were attached to a

Teflon sampling line and pump into the FTIR White cell. Analysis of the samples

were performed as specified in Appendix B.

A mid-paint check standard (prepared independently from the standard

series) was prepared and pumped into the White cell for analysis prior to each

experimental run to monitor the accuracy and precision of the system over the

entire project. If the analytical results of the check standard fell outside of the

instrument pertormance objective, calibration of the FTIR was repeated with the

full standard series.

6.2 INTEGRATED AIR SAMPLES

Stationary integrated air sample and personal breathing-zone air samples

were col/ected using the sampling methods presented in Table 4. Air samples

were col/ected by drawing air through the appropriate solid absorbent tube

(activated charcoal or silica gel) with a battery-operated, constant-flow pump. The

sorbent tube samples were analyzed by DataChem Laboratories, Inc. using

NIOSH methods, except for N-methyl pyrrolidone and the dibasic esters.

N-Methyl pyrrolidone samples were analyzed using a method developed by GAF

and partially validated by OSHA. The dibasic esters samples were analyzed

using method developed by Du Pont. The analytical methods are presented in

Appendix C.

Immediately after sampling, the solid sorbent tubes were placed in a

freezer at -18°C until they were shipped to DataChem Laboratories. The

samples were shipped inside a foam-insulation container that was cooled with

blue ice. Blind field spikes were shipped with the samples.

25
where:

SEcnON 7

RESULTS AND DISCUSSION

7.1 INTEGRATED AIR SAMPLES

The results of the integrated air sampling are presented in Tables 6

through 10 for each of the paint stripping products tested. The airborne

concentrations are presented in units of milligrams per cubic meter of air (mg/m3

)

and parts per million (ppm). The results in ppm were calculated using the

following equation:

ppm = mg/m 3

x 24.5

M.W.

M.W. = molecular weight of the analyte

24.5 = liters of vapor per mole of contaminant at 25°C

and 760 mm Hg

In Tables 6 through 8, the air sampling results for methanol are presented on a

separate line from the corresponding results for the other organic compounds

collected at the same location. Since methanol was collected on a separate

silica-gel sorbent tube, the sample volumes are not the same as those for the

other compounds.

The first three paint stripping products that were tested contained two or

more chemicals with relatively high vapor pressure (e.g., methylene chloride,

acetone, methanol, toluene). The last two products tested contained one or

more chemicals with lower vapor pressures (e.g., N-methyl pyrrolidone, dimethyl

adipate, dimethyl 9Iutarate).

Published occupational exposure limits for methylene chloride, toluene,

methanol, acetone, and N-methyl pyrrolidone are presented in Table 11. No

exposure limits were found for the dibasic esters. The threshold limit vatues

(TLVs) are issued by the American Conference of Govemmental Industrial

Hygienists (ACGIH). The permissible exposure limits (PEls) are regulatory limits

promulgated by the Occupational Safety and Health Administration for working

adults. The maximum concentration values (MAKs) are workplace standards set

by Germany.

MRI-OPP1\R06-01 27
I\)

(X) Table 6. INTEGRATED AIR SAMPLING RESULTS-BIX STRIPPER

RunNo. 1

PrWst t.cIcQround 16 0480 148 71.0 NO (<0.1) NO (<0.06) NO (<0.1) NO (<0.04)

Prelilet beckground 17 e> 149 71.5 NO (<0.1) NO « 0.1)

T..ct..1bM, cenIiIr 19 48D 10.3 4.94 180 76 650 170

Test et.nber. ariIr 18 480 10.1 4.as 250 191

Testa.,_, iNMtide 23 128 24.8 3.10 310 130 870 230

Testc:MI••, inIIIt .... 22 126 25.8 3.25 920 703

Teetctwnbel, ouItItaide 21 126 25.9 3.26 310 130 aeo 230

Testdwnber, autIIItaide 20 126 31.1 3.92 760 581

BrwIhing zane 25 126 24.5 3.09 310 130 810 220

BAIlIfhing zone 24 128 29.7 3.74 750 574

SUpply... 10test chamber 26 480 153 73.4 NO (<0.1) NO «0.06) NO (<0.1) NO (<0.04)

SuPDtY ...to tMt ctwnber 27 0480 148 71.0 NO '<0.1) NO 1<O.1l

RunNG.2

Pree.t~ 29 48D 152 73.0 NO «0.1) NO (<0.06) NO (<0.1) NO (<0.04)

PtWet beckgrol.ni 28 480 151 n,S NO «0.1) NO «0.1)

Testd*W_. cenw 35 480 10.6 5.09 180 80 630 170

Tea ctwnt.. centIr 34 480 9.2 •.4 290 220

Tea chM_, inIIItaide 39 112 25.7 2.88 380 160 1000 270

Test ch8mber. inlet side 36 112 26.2 2.93 1200 918

Testct..__, outIM side 38 112 25.0 280 390 160 1000 270

Teetctwnber, outtlIt side 37 112 25.8 2.89 1100 841

ere.4hlng lOne 33 112 24.6 2.76 310 130 830 220

8nMIthing zone 32 112 27.2 3.05 1100 841

Supply ..to... chamber 30 480 156 74.9 NO (<0.1) NO (<0.05) NO (<0.1) NO (<0.03)

ISuclclIY lIir to test cMnlber 31 480 152 73.0 NO (<0.1) NO (<0.1)

RunNo. 3

P"'" bIcqround 40 480 151 72.5 NO «0.1) NO «0.06) 0.28 0.074

Pr8tIIstt.ckground 41 480 150 72.0 NO «0.1) NO«0.1)

Test ctwnb«. CWlW 47 480 10.8 5.18 230 100 600 160

Test etwnber, cenW 46 480 9.2 4.4 360 280

Teet ct••*-, inIMtide 50 112 25.2 2.82 350 150 710 190

Test chImbeI. inlet.. 51 112 25.7 2.88 800 612

T.-t et.nber, ouItIt side 49 112 25.9 2.90 140 720 190

T_ctwnber. outletside 48 112 26.1 2.92 790 604

Brwthing zone 44 112 25.6 2.87 350 150 660 180

Br..ching zone 45 112 24.7 2.n 790 604

Supply IIir toWst ch8mbeI 43 480 153 73.4 0.3 0.1 1.4 0.37

SuPOlY air to tast chamber 42 480 151 12.5 NO (<0.1) NO (<0.1)
N

co

MRI-QPf'1\R06-01

Table 7. INTEGRATED AIR SAMPLING RESULTS-SIX SPRAy-oN STRIPPER

Run No.4

bIIc:kQround 5~ 480 150 72.0 1 0.3 Pr*It~ 54 480 150 12.0 NO«O.1) NO«0.1) T..chwnber,canter 55JS6 480 10.8 5.18 1900 SSO Ttit chwnber,canter 57 480 9.7 4.7 160 120

T..chM1ber, inlItside 61182 96 26.0 2.50 3100 890 r..ctwnber, inlItside 63 96 26.2 2.52 2SO 190

T" dwnber, ouliIt Iide S&59 96 25.2 2.42 3100 890

Ttit ctIMIber, ouIIItside Sl 96 26.6 2.55 2SO 190

Bl-ehiIgZMe 67168 99 26.4 2.61 3000 670 8NIIlfq zone 69 99 204.9 2.47 200 150

Supply iii' totestch8mber 64I6S 480 1<49 71.5 0.3 0.09

NO(<O.n NO(<0.1) :SuDill¥ IirtotestctlImber 66 480 151 12.5

~~

RunNo.'

72/73 ... 153 13.4 1 0.3 Prt6IIIl~ 74 ... 151 72.5 NO«0.1) NO«0.1) r..dwnbIr. cerW 81/82 ., T. 9.9 4.8 1700 490 chM1I:ler, '*1W 83 ., T. 8.7 4.2 160 120

ctwnbw, inIIt.. 15178 94 25.5 2.<tO 2900 6<tO T. ctwnbIr, ilIIt tide n 94 26.7 2.51 220 170

T. chImbIr, 0UIIt side 79180 94 26.0 2.44 3000 670

T. chMIber,outJlIt slde 78 94 26.6 2.50 220 170

er.ttqzone 87181J 96 27.0 2.59 . . ~zone 89 96 204.7 2.37 . . Supply.totiel ctwnber IW85 480 152 13.0 0.27 0.078 I~ • to..chIImber 86 480 149 71.5 NO(<O.1l NO(<O.n

Run No.I

PrWetbIdr;round 92193 ., 155 704.4 0.4 0.1

P"'~ 94 .-0 151 n.s NO«0.1) NO«0.1) TMtctwmer, center 9&'98 480 8.4 4.0 2000 580

T..chImber, center 97 480 1.2 3,5 170 130

T..ctwmer, inIIt side 101/102 92 26.2 2.41 3200 920

T.. ctwnber. iIiItside t03 92 25.0 2.30 310 2-«)

Tett chMIDIr, editside 9Ml9 92 24.8 2,28 3600 1000

T. cfwnber.0IMet IIde 100 92 26.1 2.<tO 280 210

an.aqzone 10041105 92 26.8 2.47 3400 980

Breethfng zone 106 92 24.6 2.26 310 240

SuppI'f Iir to test chamber 1071108 ... 161 n.3 NO«0.1) NO(<0.1) suiJOlY NO«o.n NO(<O.1) Iirto..c:hIrnber 109 480 158 15.8

• Airsampler failed cUIngrun.
U>

o Table 8. INTEGRATED AIR SAMPLING RESUlTS-STRYPEEZE

Run No.7

Pretelt lJecIVound 113/114 480 151 n.S 1.5 0.43 NO«0.1) NO(<0.04) NO(<0.1) NO (<0.06) P"'" bIlckgRIUnd 115 <480 151 n.s NO«0.1) NO« 0.1)

Tftt ctwnber, C*1ter 1221123 0480 8.4 4.0 230 70 240 64 130 55

Tat ctwnber, eerier 12" 480 8.8 4.2 64 49

Testdwnber, in6It.. 12Ot'121 107 25.2 2.70 370 110 340 90 260 110

TeetchImber. inIIt.. 116 107 26.4 2.82 200 150

Tat c:hM1ber, outletside 1181119 107 25.2 2.70 300 90 230 61 180 76

Tat chImber, outletside 117 107 25.8 2.78 210 181

8I'eIItq zone 12501126 6 26.2 0.16 . . . . . . Bl'elIIhlng zone 127 6 26.3 0.16 . . SUpply air totestchamber 128/129 480 152 73.0 1 0.3 NO«0.1) NO(<0.04) NO« 0.1) NO (<0.06)

SuPDIV airtotestchlImber 130 480 149 71.5 HOl<o.n Noe<O.l)

Run No. I

Pnllwt bKtqJround 133/134 480 153 73.4 NO(<0.14) NO«0.04) NO (<0.1) NO(<0.04) NO(<0.1) NO (<0.06)

PnItIIIt~ 135 480 148 71.0 NO« 0.1) NO«0.1)

TeMctwnber. eerier 13&'137 <480 9.1 4.4 270 80 300 80 160 61

T" dwnber. cerier 138 480 9.3 4.5 61 51

Telt c:twnMr,inIItute 142/143 110 25.3 2.78 470 1040 430 110 310 130

Tat c:hMlbIr, inIIIl.... 144 110 26.5 2.92 2040 180

Tat c:Nmbw. ouatt aide 14()j'141 110 25.4 2.79 490 140 430 110 310 130 T_chImber, outletside 138 110 26.0 2.88 240 180

8I'eIItq zone 1«il'1.es 110 25.6 2.82 430 120 390 100 280 120

8reIIlhing zone 147 110 25.1 2.78 230 180

Supplyairtolett chamber 1481149 480 145 69.6 0.1 0.03 NO« 0.1) NO (<0.04) NO«0.1) NO (<0.06)

IsuiXlIY Ilrtotestch8mber 150 480 143 68.8 NO«0.1) NO«0.1)

Run No.'

PrMeat bKtqJround 153/154 480 147 70.6 NO (<0.14) NO(<0.04) NO (<0.1) NO (<0.04) NO(<0.1) NO (<0.06)

PretIIIIt~ 155 480 147 70.8 NO«0.1) NO«0.1)

TeMchamber, center 15W160 480 9.1 4.4 230 70 250 66 130 55

Telt chImber. oenter 161 480 9.2 4." 68 52

T_ cIwnber, inIIIt side 185/166 118 25.2 2.97 400 120 340 90 2SO 110

Telt c:hMlb«. Inletside 189 118 26.4 3.12 83 63

Telt cNmbIr. outletside 16711f18 118 25.1 2.96 400 120 330 88 290 120

T" cMmber,outletside 170 118 25.7 3.03 190 150

BrwIIIt*Ig zone 182/163 118 26.5 3.13 380 110 310 82 260 110

Brelthing zone 164 118 25.0 2,96 180 140

Supply ...totestchwnber 15&'157 480 U59 81.1 0.2 0.06 NO «0.1) NO (<0.03) NO«0.1) NO (<0.05)

IsuDdV ...to..chIImber 158

- 1f18 80.6 MOt<O.n MOt<O.n

• Air sempler f1IIIed duringrun.
cu..... MAI-oPPM06-01

Table 9. INTEGRATED AIR SAMPLING RESULTS-WOOD FINISHER'S PRIDE

Run No. 10

PretestbtIekground 171 480 151 72.5 NO «0.1) NO «0.03)

Test chamber, center 172 480 148 71.0 74 18

Testchamber, inlet side 174 126 148 18.6 38 9.4

Test chamber, outletside 173 126 150 18.9 45 11

Breathing zone 175 129 148 19.1 39 10

Suppty airto test chamber 176 480 150 72.0 NO «0.1) NO «0.03)

Run No. 11

Pretestbedtground 192 480 148 71.0 1.7 0.42

Test chamber, center 193 480 26.1 12.5 46 11

Test chamber, inlet side 194 128 149 19.1 41 10

Test chamber, outfetside 195 128 147 18.8 42 10

Breathing zone 197 130 150 19.5 37 9.1

Supplvair to test chamber 196 480 145 69.6 NO «0.1) NO «0.03)

Run No. 12

Pretest blIctcground 199 480 150 72.0 2.2 O.~

Teat chamber. center 200 480 25.9 12.4 46 11

Test chamber, inlet side 202 139 144 20.0 40 10

Test chamber. outletside 201 139 146 20.3 44 11

Breathing zone 204 143 145 20.7 37 9.1

Supplyair to test chamber 203 480 149 71.5 NO «0.1) NO «0.03)
(,,)

I\)

MRI-OPPl\R06-01

Table 10. INTEGRATED AIR SAMPLING RESULT5--3M SAFEST STRIPPER

IIlr:':Lr

Run No. 13

Pretest background 221 480 152 73.0 NO «0.01) NO«0.1) 0.16 0.02

Test chamber, center 222 480 26.1 12.5 8.8 1.2 4.2 0.64

Test chamber', inlet side 223 187 145 27.1 7.0 1.0 4.0 0.61

Test chamber, outlet side 224 187 149 27.9 6.8 1.0 3.9 0.60

Breathing zone 226 187 137 25.6 7.8 1.1 4.7 0.72

Supply air to test chamber 225 480 150 72.0 NO «0.01) NO «0.1) NO(<0.01) NO «0.1)

Run No. 14

Pretest background 227 480 150 72.0 NO «0.01) NO «0.1) NO «0.01) NO «0.1)

Test chamber, center 228 480 25.1 12.0 12 1.7 5.4 0.83

Test chamber, inlet side 231 176 145 25.5 9.0 1.3 4.7 0.72

Test chamber, outiet side 229 176 147 25.9 8.9 1.3 4.6 0.70

Breathing zone 232 184 121 22.3 9.4 1.3 4.9 0.75

SUDolv air to test chamber 230 480 142 88.2 4.5 0.6 NO«0.01) NO {<0.1)

Run No. 15

Pretest background 234 480 150 720 NO «0.01) NO«0.1) NO «0.01) NO «0.1)

Test chamber, center 235 480 25.8 12.4 8.9 1.3 4.0 0.61

Test chamber, irnet side 238 184 153 28.2 8.5 1.2 4.6 0.70

Test chamber, outlet side 239 184 144 26.5 7.9 1.1 4.2 0.64

Breathing zone 237 186 145 27.0 7.8 1.1 4.1 0.63

Supply air to test chamber 236 480 143 68.6 NO «0.01) NO«0.1) NO «0.01) NO «0.1)
Table 11. OCCUPATIONAL EXPOSURE LIMITS

750 I 2380 I 1000 I 2400 I 1000

200 I C1885 I C500 I 375

400 I 100

100

100

200

360

380

260

2400 1 1000

150

250

560

325

100

250

200260

590

500 I C3480 IC1000

260 200

752

1740

150

250328

565

50

50

200

174

188

262

1780

ACGIH TLVs - American Conference of Govemmentallndustrial Hygienists Threshold Limit Values

OSHA PELs - Occupational safety and Health Administration Permlssi~e Exposure limits

NIOSH RELs - National Institute for Occupational Safety and Health Recommended Exposure limits

German MAKS - German Maximum Concentration Values in the Workplace

TWA - Time-weighed average exposure concentration for a normal8-hour (TLV,PEL) or up to 10-hour (REL) workday.

STEL - Short-term Exposure Limit is usually a 15-minute time-weighted average exposure that should not be exceeded.

Ceiling (C) - The concentration that should not be exceeded at any time.

w

c..>

MRI-OPPl\R06-01
The ACGIH TLVs are guidelines that are based on the best available

information from industrial experience, and from experimental human and animal

studies. These guidelines are intended for the workplace exposures for working

adults and are applicable for the general population. The time-weighted average

(TWA) exposure limit is the time-weighted average concentration for a nonnal

8-h workday and a 40-h work week, to which nearly all adult workers may be

repeatedly exposed, day after day, without adverse effects. The short-term

exposure limit (STEL) is the air concentration to which workers can be exposed

continuously for a short period of time without suffering from irritation; chronic or

irreversible tissue damage; or narcosis of sufficient degree to increase the

likelihood of accidental injury or impair self-rescue. A SrEL is defined as a

15-min TWA exposure that should not be exceeded at any time during a workday

even if the 8-h TWA is within the TWA-TLV.

The "pretest backgroundM

results represent the background air

concentrations within the test chamber prior to each experimental runI averaged

over an 8-h period. The results demonstrate that the background air concentrations of acetone, methanol, and the dibasic esters were below the detection

limit « 0.1 mglm3

) of the analytical method. The background concentration of

N-methyl pyrrolidone (NMP) was below the detection limit prior to the first run in

the series (run no. 10). The background levels measured prior to SUbsequent

runs (nos. 11 and 12) were 1.7 and 2.2 mglm3

, respectively. The N-methyl

pyrrolidone background concentration appears to be from low-level residual NMP

in the test chamber from the previous run. The background air concentrations of

methylene chloride and toluene ranged from below the limit of detection « 0.1)

to 1.5 mg/m3

. Methylene chloride and tofuene were det$ded in the air supply to

the chamber during some of the runs; theretore, the background air concentrations measured prior to the runs may be due either to the supplied air to the

chamber or to residual chemicals from the previous run. In all cases, the pretest

background air concentrations were low relative to the levets measured during

the runs. The air concentration data were not corrected for the background.

The first product tested in the ACE Laboratory was SIX Stripper, which

contained acetone, toluene, and methanol. The air concentration of toluene

measured in the breathing zone of the product user ranged from 660 to

830 mglm3

. The stationary air samples collected during paint stripping and

cleanup task (i.e., length-ot-task samples) ranged from 710 to 1000 mglm3

. The

8-h TWA air concentration of toluene ranged from 600 to 650 mg/m3

, which

exceeds the PEL established by OSHA and the recommended limits pUblished

by the ACGIH and NIOSH. The ACGIH TLV for toluene is 188 mglm3 (8-h

TWA). The OSHA PEL is 754 mglm3 (8-h TWA) with an acceptable ceiling

concentration of 1885 rng/m3

• The breathing-zone concentration of methanol

ranged from 750 to 1100 mglm3 • The length·of-task stationaJY samples yielded

similar results ranging from 760 to 1200 mglm3

• Both the breathing-zone and

length-of-task air concentrations for methanol exceeded the ACGIH short-term

34 MRI·OPPnR06-01
exposure limit (STEL) of 328 mglm3

, The 8-h TWA air concentration of methanol

ranged from 250 to 360 mglm3

, Two of the three 8-h time-weighted samples

exceeded the ACGIH TLV-TWA for methanol of 262 mglm3

, The acetone level

were found to be within occupational exposure limits. The breathing zone and

length-ot-task air samples for acetone ranged from 310 to 390 mglm3. The 8-h

TWA sampling results ranged from 180 to 230 mglm3

•

The SIX Spray-On stripper, which contained methylene chloride and

methanol, was the only product selected for this study that was not applied with

a brush. The stripper was sprayed onto the ptywood substrate with a sprayer

supplied with the product. The airbome concentrations of methylene chloride and

methanol measured in the breathing zone of the product user were found to be

3000 and 3400 mglm3

•and 200 and 310 mglm3, respectively. The breathingzone sampler failed during run no, 5 and was not reported. The stationary

length-ot-task air samples ranged from 2900 to 3600 mglm3 for methylene

chloride and from 220 to 310 mglm3 for methanol. The methylene chloride 8-h

TWA air concentration ranged from 1700 to 2000 mg/m3

, which exceeds the PEL

set by OSHA (1740 mglm3

) and the recommended TLV published by ACGIH

(174 mglm3

) . The 8-h TWA air concentration of methanol ranged from 120 to

130 mglm3.

Strypeeze, the third product tested, contained methylene chloride, toluene,

acetone, and methanol. The results of the breathing-zone and stationary lengthof-task samples for methylene chloride ranged from 380 and 490 mglm3

. The

breathing zone sampler failed dUring run no. 7 and was not reported. The 8-h

TWA air concentrations ranged from 230 to 270 mglm3

, which exceeds the

ACGIH TLV-lWA for methylene chloride (174 rngIm3

) . The results of the

breathing-zone and stationary length-of-task samples for toluene ranged from

230 and 430 mglm3

• The 8-h TWA air concentrations ranged from 240 to

300 mglm3

, which exceeds the ACGIH TLV-TWA for toluene (188 mglm3) . The

levels of airborne acetone and methanol were both within published occupational

limits. The 8-h TWA air concentrations of methanol and acetone ranged from 64

to 68 mg/m3 and 130 to 160 mglm3

, respectively.

Wood Finisher's Pride, which contained N-methyl pyrrolidone (NMP), was

the fourth product tested. The air concentration of NMP measured in the

breathing zone of the product user ranged from 37 to 39 mglm3

. The stationary

air samples collected during paint stripping and cleanup (i.e.,length-of-task

samples) ranged from 38 to 45 mg/m3

• The 8-h TWA air concentration of NMP

ranged from 46 to 74 rng/m3

, These results are higher than those found during a

study conducted in 1991 by the GAF Chemical Corporation of a similar NMP

paint stripping product (Hylan, 1991). Airbome concentrations of NMP of 7.3 and

6.1 mglm3 were measured at distances of 1 and 2 ft, respectively, dUring the

application of the paint stripper to a 40- by 30-in plywood sheet. In 1987, GAF

researchers measured airborne concentrations of NMP during the removal at

flocr-tlle adhesive from a 4- by 4-ft section of a concrete basement floor (Hylan,

MRI-QPPnR06·01 35
1989). NMP air concentration in the breathing zone of the worker was found to

be 2.3 mglm3

• The air exch8nge rates during these tests were not specified.

The air concentrations of NMP were wett betowthe maximum concentration

value in the workplace (MAK) of 400 mglm3 8lItabti8hed by Germany. Exposure

limits for NMP have not been established by OSHA, NIOSH, or ACGJH.

3M Safest Stripper, the final product tested, contained dibasic esters

(dimethyl adipate and dimethyl glutarate). The air concentration at the breathing

of the product user ranged from 7.8 to 9.4 mglm3 for dimethyl adipat., and from

4.1 to 4.9 mglm3 for dimethyl glutarate. The length-of·task statjonary samples

ranged from 6.8 to 9.0mglm3 for dimethyt adipste, and from 3.9 to 4.7 mglm3 to

dimethyl glutarate. The a.h TWA air concentrations were slightty higher than the

length-of-task results, ranging from 8.8 to 12 for dimethyt adipate, and from 4.0

to 5.4 for dimethyl gkJtarate. Exposure limits for the dibasic esters have not

been estabJished by OSHA, NIOSH, or ACGIH.

7.2 HEARLY REAL-TIME AIR SAMPLES

The air concentration of each of the target compounds were plotted

against time. The plots for each experimental run are presented in Appendix D.

The air concentrations of both the volatile and semivojatile compounds appeared

to rise rapidly wjthin the test chamber during the paint stripping operations. After

the stripper operation was completed, the air concentration of the less volatUe

compounds decreased at a lower rate relative to the more volatile components.

The semivolatile compounds appeared to adsorb andlor absorb onto the test

chamber surfaces. This Msink effect" extended the decay of the less volatile

components over time.

The infrared spectra for dimethyl adipate and dimethyl glutarate were too

similar to be resolved by the FTIR. The air concentration of total dibasic esters

is plotted against time.

The NMP air concentration data collected during run no. 11 sharply

increases at approximately 2.7 h into the run. The vacuum in the White cell was

above 2 in. Hg dUring the first period. The vacuum was corrected at 2.7 h by the

FTIR operator. All data collected prior to the adjustment have a negative bias.

The air concentrations measured by the FTIR appeared to agree with the

integrated samples, with the exception of N-methyl pyrrolidone. The FTIR NMP

air concentration data were higher than the data measured by the integrated air

sample results. This may have been due to difficulties in preparing standards of

semivolatile compounds in air. The NMP that was injected into the Tedlar bag

may not have fully vaporized due to saturation. This would have created positive

bias to the data.

36 MRI-Of>PT\R06-01
A combined plot of the air concentration vs. time for experimental run

nos. 3, 6, 9, 12, and 15 is presented in AppendiX 0, pg. 0-18. This plot presents

comparative air concentrations levels of the target compounds for all five paint

stripping products tested.

7.3 QUALITY CONTROL SAMPLES

Blind spikes samples were prepared at MAl and submitted to DataChem

Laboratories, Inc. with the regular air sampling media. The blind spikes were

prepared by injecting a known votume of each of the target anatytes onto the

appropriate sorbent tube with a microliter syringe. Table 12 presents the results

of the spiked samptes as reported by DataChem. The percent accuracy,

averaged over the three spike levels, were within an acceptable range (80% to

120%) for all analytes, except for dimethyl adipate. The percent accuracy for the

dimethyl adipate ranged from 57% to 147%. In general, the accuracies of the

more viscous semivolatile spikes were less than the accuracies of the volatite

spike samples. The difficulty of delivering microliter quantities of a viscous

chemical to the sorbent tube may have contributed to a wider accuracy range for

the semivolatile compounds.

7.4 QUALITY ASSURANCE ACTlVmES

A system audit was conducted by the Senior Quality Assurance Officer

during an experimental run in the ACE Laboratory. No systematic bias was

found. An audit of randomly selected data was conducted and the project report

was reviewed by the Senior Quality Assurance Officer.

MRI-oPf'MOtHl1 37
Table 12. BLIND SPIKED SAMPLE RESULTS

Methylene Chloride 1~ 1.0 1.3 1.4 7.7 108

MoI.~. = 84.93 185 4.0 5.3 5.2 -1.9 98

Den = 1.325 186 7.0 9.3 9.0 -3.2 97

Acetone 181 1.0 0.79 0.72 -8.9 91

MoI.INf. = 58.08 182 6.0 4.7 4.7 0 100

Den = 0.791 183 10 7.9 7.7 -2.5 98

Toluene 178 1.0 0.87 0.89 2.3 102

MoI.INf. :=: 92.14 179 2.0 1.7 1.7 0 100

Dena = 0.867 180 4.0 3.5 3.3 -5.7 94

Methanol 189 1.0 0.79 0.76 -3.8 96

MoI.INf. = 32.04 190 2.0 1.6 1.6 0 100

= 0.791 191 4.0 3.2 3.0 -6.3 94

N-MMhyt Pyrrolldone 241 1.0 1.0 0.9 -10 90

MoI.~. = 99.13 242 1.5 1.5 1.7 13 113

Denali = 1.033 243 2.0 2.1 2.4 14 114

Dlmethyt atutarate 247 0.5 0.54 0.67 24 124

MoI.IM. = 160.2 248 1.0 1.1 1.2 9 109

= 1.087 249 1.5 1.6 1.9 19 119

Dlmethyt Adlpate 244 0.5 0.50 0.73 46 146

MoI.WI. = 174.2 245 1.0 1.0 1.3 30 130

= 1.0063 246 1.5 1.5 0.85 -43 57

38 MRI-oPP1\R06-01
SECTION 8

CONCLUSIONS

Due to concerns about the toxicity of methylene chloride, chemical paint

strippers with new fonnulations are currently available at some retail stores.

Some of these new formulations reduced the methylene chloride content by

adding other volatile organic chemicals to the mixture, such as acetone,

methanol, and toluene (e.g., Strypeeze and SIX Spray-On Stripper). Other

formulations contain mixtures of volatile organic compounds and no methylene

chloride. SIX Stripper, which contains acetone, toluene, and methanol, is an

example of this type of formulation. Other new formulations have been

developed that contain less volatile compounds, such as N-methyl pyrrolidone

(Wood Finisher's Pride) and dibasic esters (3M Safest Stripper).

These new formulations were tested in a controlled environment to assess

consumer exposures to these new formulations. The air exchange rate (ACH)

selected for this study represents the ventilation rate of a closed room within a

typical residence. Using chemical paint strippers in an environment that lacks

adequate ventilation represents a "worst-case" situation and is not recommended

by product manufacturers.

The results of this study indicate that airborne exposures to paint stripping

products with reduced methylene chloride content may exceed occupational

exposure limits when the paint strippers are used in unventilated residential

rooms. Airborne exposures to substitute compounds, such as toluene and

methanol, were found to exceed occupational exposure limits when used with

low ventilation rates. In addition, the new formulation substitutes a nonflammable

chlorinated compound with flammable organic chemicals, such as toluene,

acetone, and methanol.

As expected, the formulations with the less volatile substitutes resulted in

lower airborne exposures; however, the toxicity of these compound are less

known. No U.S. occupational exposure limits have been set for N-methyl

pyrrolidone, dimethyl adipate, or dimethyl glutarate; however, a maximum

concentration limit for N-methyl pyrrolidone has been by established by

Germany. The N-methyl pyrrolidone airborne concentrations generated during

this study did not exceed this exposure limit.

MRI-OPI'1\R06-0t 39
The lower volatile compounds (N-methyl pyrrolidone and dibasic esters)

appeared to adsorb and/or absorb onto the surfaces of the test chamber. At the

completion of the paint stripping operation. the air concentrations of N-methyl

pyrrolidone and dibasic esters decayed at a lower rate relative to the more

volatile compounds. A higher number of air exchanges is required to reduce the

air concentrations of lower volatile compounds to background levels after the

paint stripping operation is completed. This ·sink effecf' may extend the duration

of exposure of these compounds to bUilding occupants.

Airbome exposure limits for N-methyl pyrrotidone and dibasic esters

should be established for the general public (consumers) and in the workplace

based on currently availabte human exposure and animal studies. The fire risk

of the formulations containing acetone. toluene. and methanol also should be

evaluated.

40
secnoN9

REFERENCES

Girman, J. R., and A. T. Hodgson (1986). "Source Characterization and

Personal Exposure to Methylene Chloride for Consumer Products." Proceedings

79th Annual Meeting of the Air Pollution Control Assoc. Paper No. 86-52.7.

Hodgson, A. T., and J. A. Girman (1987). "Exposure to Methylene Chloride from

Controlled Use of a Paint Remover in Residences." Proceedings 80th Annual

Meeting of the Air Pollution Control Assoc.

Hylan, A. C. (1991). Correspondence to F. Fusiak. 8 March 1991.

Hylan, R. C. (1987). Correspondence to P. Taylor. 26 March 1989.

Matthew, T. G. (1987). "Environmental Chamber Test Methodology for

Characterizing Organic Vapor for Solid Emission Sources." Atmas Environ

21:321-329.

McHugh, J. M., and K. M. Bauer (1992). "Indoor Air Quality Sink Chamber

Tests.' Environmental Protection Agency, Office of Pollution Prevention and

Toxics, Washington, DC. EPA 600/R·92-094.

"Guide to Occupational Exposure Values." Compiled by the American

Conference of Governmental Industrial Hygienists. 1990.

"Threshold Limit Values for Chemical Substances and Physical Agents and

Biological Exposure Indices." American Conference of Governmental Industrial

Hygienist. 1993-1994.

MRI·QPP1\R06-o1 41
APPENDIX A

LIMITED SHELFSURVEY OF PAINTSTRIPPING PRODUCTS

IN THE KANSAS CITY METROPOLITAN AREA

A-1
Limited Shelf Survey of Paint Stripping Products

in the Kansas City Metropolitan Area

Product Name: Bix Tuff Job Remover

Product Number: 14002, #7485680220

Manufacturer's Name and Address:

Bix Manufacturing Co, Inc.

P.O. Box 69

Ashland City, Tn 37015

Contents Listed on Label:

Methylene Chloride

Methanol

Product Found at:

Ace Hardware

Payless Cashways

True Valve Hardware

Product Name: Six Stripper

Product Number: 1002, # 74856 10220

Manufacturer's Name and Address:

Bix Manufacturing Co, Inc.

P.O. Box 69

Ashland City, Tn 37015

Contents Listed on Label:

Methanol

Toluene

Acetone

Product Found at:

Ace Hardware

Paylass Cashways

True Value Hardware

MRI·OPPTIR<J6..01 A-3
Product Name: Bix Spray on Stripper

Product Number: #74856 60220

Manufllcturer's Name and Address:

Bix Manufacturing Co, Inc.

P.O. Box 69

Ashland City, Tn 37015

Contents Listed on Label:

Methytene Chloride

Methanol

Product Found at:

True Value Hardware

Sherwin-Williams

Product Name: Goof off

Product Number: # 23494 00005

Manufacturer's Name and Address:

Atlanta Sundries

Lithonia Ga 30058

Contents Listed on Label:

Xylene

Product Found at:

Payless Cashways

Sears

True Value Hardware

Sentry Hardware

Product Name: Oops

Product Number: # 33873 00045

Manufacturer's Name and Address:

Diy Products Division

Rhodes American

2825 W. 31 st Street

Chicago II 60623

Contents Listed on Label:

Ethanol

Vm&P Naptha

Xylene

Monochlorotoluene

Product Found at:

True Valve Hardware

A-4 MRI.()PPT\R06-01
Product Name: Klean-Clean

Product Number: # 30192 07399

Manufacturer's Name and Address:

Klean-Strip

Division of W.m. Barr Inc.

Memphis, Tn 38101-1879

Contents Ll8ted on label:

Xylene

Methylene Chloride

Ethylene Glycol

Monobutyl Ether

Product Found at:

True Value Hardware

Product Name: Formby's -Wood Formula- Paint Remover

Procluct Number: # 32053 30035

Manufacturer's Name and Address:

Thompson and Formby Inc.

P. O. Box 667

Olive Branch, Ms 38654

Contents Listed on Label:

Methylene Chloride

Methanol

Product Found at:

True Value Hardware

Product Name: Powder/Plus+ Paint Stripper

Product Number: # 27046 00421

Manufacturer's Name and Addre.s:

H.f. Staples and Company,inc.

Merrimack, Nh 03054

Contents Listed on Label:

Sodium Carbonate

Calcium Hydroxide

Product Found at:

True Value Hardware
Product Name: Safest Stripper

Product Number: # 5111 10101

Manu1llcturer'. Name and Add.....:

Do-It-Yourself Div

3m Consumers Product Group

Box 33053

St. Paul, Mn 55133-3053

Contents Listed on Label:

Dimethyl Adipate

Dimethyl Glutarate

Product Found at:

Payless Cashways

Ace Hardware

True Value Hardware

Sherwin-Williams

Servistar Hardware

Product Name: Klean Strip Paint Remover

Product Number: Ks-221, # 5111 10101

Manufacturer'. Name and Addre.s:

Klean-Strip

P.O. Box 1879

Memphis, Tn 38101

Contents Listed on Label:

Methylene Chloride

Isopropanol

Ethanol

Methanol

Product Found at:

Ace Hardware
Product Name: Strypeeze

Product Number:# 49542 01102

Manufacturer's Name and Address:

Savogran

P.O. Box 130

Norwood, Ma 02062

Contents Listed on Label:

Methylene Chloride

Acetone

Toluene

Methanol

Petroleum Distillates

Product Found at:

True Value Hardware

Ace Hardware

Sherwin-Williams

Product Name: Zip Strip

Product Number:# 38514 72004

Manufacturer'. Name and Address:

Star Bronze Company

P.O. Box 2206

Alliance, Oh 44601 0206

Contents Listed on Label:

Methylene Chloride

Methanol

Ethanol

Mineral Spirits

Product Found 8t:

Payless Cashways

Ace Hardware

True Value Hardware

Beverly Lumber

Sentry Hardware

"'Rl~' A-7

I
Product Name: Wood Finisher's "Pride" Paint Stripping Gel

Product Number: # 54000 76520

Manufacturer's Name .net Address:

Creative Technologies Group

Greenville, Sc 29601

Contents Listed on Label:

N-Methyl PyrrOlidone

Product Found at:

Sears

True Value Hardware

Graggs Paint Co.

Product Name: Nasca Liquid Stripper Paint and Wamish Remover

Product Number: # 737n 07120

M8I1ufacturer's Name and Address:

National Solvent Corp.

Medina, Oh 44256

Contents Listed on Label:

Methanol

Methylene Chloride

Acetone

Toluene

Mineral Spirits

Product Found at:

Sears

Product Name: Quick Strip Refinisher

Product Number: 4002, # 74856 30220

Manufacturer's Name and Address:

Bix ManufactUring Co. Inc.

P.O. Box 69

Ashland City, Tn 37015

Contents Listed on Label:

Methanol

Toluene

Acetone

Product Found at:

Payless Cashways

A-a MRI·QPPl\R06-01
Product Name: Klean Kutter liquid Paint Remover

Product Number: Kk-5 # 3019200515

Manufacturer's Name and Address:

Klean Strip

Memphis, Tn 38101-1879

Contents Listed on Label:

Methanol

Toluene

Acetone

Methylene Chloride

Product Found at:

Payless Cashways

Sutherlands

Servistar Hardware

Product Name: Sears Paint and Vamish Remover

Product Number: My62533

Manufacturer's Name and Address:

Sears, Roebuck and Co.

Chicago, 1\ 60684

Contents Listed on Label:

Methylene Chloride

Product Found at:

Sears

A-9
Product Name: Enrich Paint and Varnish Remover

Product Number: # 42909 40083

Manufacturer's Name and Addre.s:

General Paint and Chemical Co.

Division of Cotter and Co.

201 Jandus Road

Cary, /I 60013

Contents Listed on Label:

Methylene Chloride

Methanol

Toluene

Mineral Spirits

Product Found at:

True Value Hardware

Product Name: Kutzit Paint and Varnish Remover

Product Number: # 49542 01112

Manufacturer's Name and Addr.ss:

Savogram Co.

Norwood, Ma 02062

Contents Listed on Label:

Methylene Chloride

Methanol

Toluene

Acetone

Product Found at:

True Value Hardware

Sherwin-Williams

Sentry Hardware

A-10

I
Product Name: Ace Extra Strength Stripper

Product Number: Ace 1182,# 82901 11825

Manufacturer's Name and Address:

Ace Hardware Corp.

Oak Brook, II 60521

Contents Listed on Label:

Methylene Chloride

Isobutane

Isopropyl Alcohol

Stoddard Solvent

Product Found at:

Ace Hardware

Product Name: Ace liquid Stripper

Product Number: Ace 1118,# 82901 11189

Manufacturer's Name and Address:

Ace Hardware Corp.

Oak Brook," 60521

Contents listed on label:

Methylene Chloride

Acetone

Methanol

Toluene

Product Found at:

Ace Hardware

Product Name: Ace Heavy Bodied Stripper

Product Number: Ace 12058,# 82901 12058

Manufacturer's Name and Address:

Ace Hardware Corp.

Oak Brook, II 60521

Contents Listed on Label:

Methylene Chloride

Xylene

Methanol

Toluene

Product Found at:

Ace Hardware

A-11

I
Product Name: Zip Strip2 Paint and Finish Remover

Product Number: # 38514 70032

MlII1ufacturer's Name and Address:

Star Bronze Co.

P.O. Box 2206

Alliance, Ohio 44601

Contents Listed on Label:

No Components Were Listed on Label

Product Found at:

Sentry Hardware

Product Name: Duffy's Paint and Varnish Remover

Product Number: # 50431 35753

Manufacturer's Name and Address:

Duffy's Refinishing Co.

Cedar Rapids, la 52402

Contents Listed on Label:

Methanol

Toluene

Methylene Chloride

Product Found at:

Sentry Hardware

Product Name: Zing Paint and Vamish Remover

Product Number: None Identified on Label.

Manufacturer'. Name and Address:

C and M Coatings

Division the Valspar Corp

Kansas City, Mo 64127 and Minneapolis Mn 55415

Contents Listed on Label:

Methylene Chloride

Methanol

Ethanol

Aliphatic Hydrocarbons

Wax and Wetting Agents

Product Found at:

Servistar Hardware

A-12 MRI·OPPT\R06-01
Product Name: Parks Pro Stripper

Product Number: # 75955 15140

Manufacturer's Name and Address:

Parks Corp.

SomersetMa

Contents Listed on Label:

Methylene Chloride

Toluene

Methanol

Stoddard Solvent

Propylene Glycol Monomethyl Ether

Ammonia

Dipropylene Glycol Monomethyl Ether

Product Found at:

Servistar Hardware

Product Name: All Pro Marine Paint Stripper

Product Number: # 21204

Manufacturer'. Name and Addr•••:

All Pro Corp.

Tampa FI 33619

Contents Listed on Label:

Methylene Chloride

Isopropanol

Ethylene Glycol Monobutyl Ether

Methanol

Product Found at:

Gragg Paint Co.

MRH)PPM06-01 A-13

II
Product Name: All Pro Semi Paste Paint Remover

Product Number: # 21404

Manufacturer's Name and Address:

All Pro Corp.

Tampa FI 33619

Contents Listed on label:

Methylene Chloride

Methanol

Xylene

Toluene

Product Found at:

Gragg Paint Co.

Product Name: All Pro Sprayable Paint Remover

Product Number: -# 21924

Manufacturer's Name and Address:

All Pro Corp.

Tampa FI 33619

Content. Listed on Label:

Methylene Chloride

Isopropanol

Ethanol

Methanol

Product Found at:

Gragg Paint Co.

Product Name: All Pro Heavy Body Paint Remover

Product Number: -# 21104

Manufacturer'. Name and Address:

All Pro Corp.

Tampa FI 33619

Contents Listed on label:

Methylene Chloride

Isopropanol

Ethanol

Methanol

Product Found at:

Gragg Paint Co.

A-14

I
Product Name: Super Strip

Product Number: SSc, #49542 01132

Manufacturer'. Name and Address:

Savogran

P.O. Box 130

Norwood Ma 02062

Contents Listed on Label:

Toluene

Methylene Chloride

Methanol

Product Found at:

Sherwin-Williams

Product Name: Six Quick Strip

I

Product Number: 4002 # 74856 30220

Manufacturer's Name and Address:

Six ManUfacturing Co.

P. O. Box 391

Old Hickory, Tn

Contents Listed on Label:

Methylene Chloride

Methanol

Toluene

Acetone

Product Found at:

Sutherlands

MRI-OPPT\R06-0\ A-15
Product Name: Klean-Strip Heavy Bodied Paint Remover

Product Number: Hb~2, #30192 00210

Manufacturer's Name and Address:

Klean-Strip

Division W.m. Barr, Inc.

Memphis, Tn 38101-1879

Contents Listed on Label:

Methylene Chloride

Ethanol

Methanol

Isopropanol

Product Found at:

Sutherlands

Product Name: Easy off Paint Stripper

Product Number: Sf-200, #3079220025

Manufacturer's Name and Address:

Klean~Strip

Division W.m. Barr, Inc.

Memphis, Tn 38101-1879

Contents Listed on Label:

Alipahatic Dibasic Acid Esters

Petroleum Distillates

Product Found at:

Sutherlands

A-16

I
Product Name: Strip-X Creamy Paint Stripper

Product Number: Sx-6, #3019200610

Manufacturer'. Name and Addres.:

Klean-Strip

Division W.m. Barr, Inc.

Memphis, Tn 38101-1879

Contents Listed on Label:

Methylene Chloride

Ethanol

Methanol

Xylene

Product Found at:

Suther/ands

Product Name: Klean Strip Semi Paste Paint Remover

Product Number: Ks-3, #30192 00310

Manufacturer's Name and Address:

Klean-Strip

Division W.rn. Barr, Inc.

Memphis, Tn 38101-1879

Contents Listed on Label:

Methylene Chloride

Ethylene Glycol Monobutyl Ether

Methanol

Isopropanol

Product Found at:

Sutherlands

Product Name: Plasti-Kote Paint Stripper

Product Number: 289, #7191500289

Manufacturer's Name and Address:

Plasti-Kote

Medina, Ohio 44256 and

Upland, ca 91786

Contents Listed on Label:

Methylene Chloride

Product Found at:

Sutherlands

A-17

I
Product Name: Klean Strip Aerosol Spray Paint Remover

Product Number: Sr-72, #30192 07210

Manufacturer's Name and Address:

Klean-Strip

Division W.m. Barr, Inc.

Memphis, Tn 38101·1879

Contents Listed on Label:

Methylene Chloride

Methanol

Monyl Phenoxy Polyethoxyethanol

Product Found at:

Sutherlands

A-18 MRI-OPPTIRQ6.01

I
APPENDIX B

OPERAnNG PROCEDURES FOR THE MIDAC rnR CLOSED CELL SYSTEM

II

B-1
Nearty real-time sampting and analysis of air at breathing zone of the test subject

was conducted using the MIDAC FTIR in the closed-eell operating mode. The

system is mounted on an optical bench and consists of:

• 20-m unheated fixed-alignment White cell with a folded path mirror

• Nemst glower and power supply

• MIDAC spectrometer

• Transfer mirrors (two)

The optical components listed above were bolted to the mounting holes on the

optical bench.

SETUP OF THE FT1R CLOSED CELL SYSTEM

The follOWing procedures were used to set up the MIDAC FTIR closed-cell

system:

• Tum on the power supply to the Nemst glower.

• Depress the ignitor button to light the glower (approximately 30 s).

• Verify that the ZnSe wedged lenses (light yellow color) are installed on the cell

and the spectrometer.

• Dim the room lights and Visually align the beam so that it is reflected off

mirrors through the cell and roughly centered on the spectrometer lenses.

• Flush the cell with dry nitrogen gas.

• Remove the breather cap from the MIDAC spectrometer and fill the detector

with liquid nitrogen; do not overfill.

• Replace the breather cap.

• Connect the power supply and computer to the spectrometer.

• Power up the computer and determine the storage space remaining of the

hard drive. About five spectra can be recorded for each megabyte of space

available on the hard drive.

• Start the Labcalc program.

• Select the F2 function key or the backslash key on the computer to bring up

the menu.

MRI·OPPT\R06-01
• Select ENVIRONMENT and then DIRECTORY from the menu. (NOTE: All

Labcalc menu choices can be setected by either moving the cursor to the

desired item and pressing the ENTER key, or by pressing the first letter of the

menu selection.)

• Enter the path name of the subdirectory to which the data will be recorded

(Example: C:\LC\DATA). Always end the path name with the "V' symbol

(Example: C:\LD\DATA\).

• Select the F2 function key to bring up the menu.

• Select ARITHMETIC and then DOPROGRAM from the menu.

• Select the AUTOCOL program.

• If the printer is attached to the computer, an immediate printed record of each

analysis can be obtained by selecting YES when prompted. If NO is selected

at the prompt, the analysis files will be recorded only to disk and will be briefly

displayed on the computer monitor.

• Enter a short summary phrase and a four-cheracter code for each data set.

This code will be included in each filename generated for the data set.

• Enter the number of the desired scans. The scan number will usually be set at

64 (about 4 min).

ALIGNMENT PROCEDURES FOR THE FTIR CLOSED CELL SYSTEM

The following procedures were used to achieve the final alignment of the closedcell system:

• Select the ALIGN mode from the main menu.

• Select a RESOLUTION of 8 wavenumbers from the secondary menu.

• No other menu items should be altered with the possible exception of GAIN.

Normal gain should be set at 1. Higher multiples (e.g., 2, 4, 8, etc.) are

possible but are not recommended.

• Select ALIGN from the menu. The current interferogram signal will be

displayed on the screen with continuous updates.

I

8-4
• Observe the zero point of the interferogram. The zero point should be stable

at approximately 800 units. An unstable zero point or a reading greater than

about 1,000 or less than about 600 indicates a problem. To correct the

problem, first verify that the autoscaling function has not malfunctioned by

exiting the ALIGN mode and then reentering the mode from the main menu.

• Observe the peak-to-peak reading of the interferogram. The reading should

be less than 30,000 units. A reading of 32,767 indicates that the detector

signal is saturated. In this case, the gain must be reduced (see Section 3.0).

Peak-to-peak readings below 15,000 units indicate that the gain is too low;

however, do not readjust the gain until the alignment of the mirrors has been

optimized to obtain the maximum possible reading.

• SlOWly move the mirror pivots horizontally and vertically to obtain the maximum

signal strength.

• Adjust the poslnon of the spectrometer mounting table to obtain the maximum

signal strength. First, move the spectrometer 'eft and right, then rotate in

place, and finally, adjust the vertical angle with the mounting feet.

• Repeat the series of adjustments (first to the mirrors and then to the

spectrometer) until no further improvements in the signal strength is observed.

• With maximum signal strength set, readjust the instrument gain if the peak-topeak readings are not within the range of 15,000 and 30,000 units.

• Press the ESC key to return to the main menu.

Once the maximum signal had been obtained, the optical alignment was not

changed.

SErrlNG INSTRUMENT GAIN

The following procedures were used to adjust the internal instrument gain:

• Do not attempt to reset the instrument gain unless the sample cell contains

clean, dry nitrogen gas. Lower gain readings are normal when introducing

sample gases or when recording a background spectrum with the source off or

blocked. Before attempting to reset the gain, verify that the gain setting on the

ALIGN mode menu is set to 1. Higher multiples of 2 or more may be used to

increase sensitivity, but this also increases the noise.

• Open the instrument case by releasing the four latches and lifting the cover

straight up and off.

I

MRI-OPFnR06-01 B-5
• Locate the pre-amp board positioned near the center of the case. A small

jumper block is mounted on the board in one of the eight jumper positions

labeled A through H. Each jumper position changes the gain by a factor of

1.5. To increase the gain, repositton the jumper block to a higher position

(toward the letter H). Moving the jumper to a lower position (toward the letter

A) reduces the gain. Avoid dropping the jumper block into the instrument

electronics.

• When the peak-to-peak signal is between 16,000 and 30,000 units, the gain is

optimized.

• Carefully replace the instrument cover.

DATA COLLECTION

The MIDAC FTIR spectrometer is not equipped with a modulated source beam;

therefore, a background spectrum was obtained for each data set. The

background spectrum is subtracted from aU other spectra and corrects for cell

temperature effects. Background spectra were recorded for each data set,

unless valid background spectra have been recorded preViously. The following

procedure were used to record a background spectra:

• Select BCKGRND SELECT from the menu.

• Block the source beam.

• Select COLLECT NEW BCKG and then press ENTER when ready.

• The system will automaticatty record and save the interferogram to the hard

drive in a fife named "XXXXb.spc" where MXXXXMis the four-character base

filename selected dUring the setup procedure The single beam spectrum will

be recorded in a file named I·XXXXbc.spc.II

• Flush the cell with dry nitrogen gas.

• Remove the beam block.

• Select REF SELECT and then COLLECT NEW REF from the menu to record

the reference spectrum which will be saved to the hard drive in a file named

XXXXr.spc and XXXXrc.spc.

• Purge sample gas through the cell.

• Select SAMPLE START from the menu and enter the number of sequential

data sets to be recorded as well as the time interval between sets. For

64 scans the minimum interval should be approximately 300 s.

I

8-6
• Enter the file path name for the sUbdirectory where the calibration files are

located (usually C:\LC\QUANT\). Calibration filenames have a ."cl" file

extension.

• Enter the filename for the analysis result file.

• Select the compounds to be calculated from the menu (maximum of nine

entries). As each compound is selected, a "+11 sign will appear under the

selection. If a mistake is made, use the CLR selection from the menu to clear

the entire list. The selection process must then be started from the beginning.

• Press the number "9" key to end selections.

• When the READY prompt appears on the monitor, start recording the spectra

by pressing any key.

• As each set is collected, the interferogram will be displayed on the monitor and

saved to the hard drive. The concentration data for each compound will be

calculated using the library spectra and predefined calibration files, displayed

on the monitor in units of ppm-meters, and saved to the hard drive. The air

concentration is determined by dividing this value by the path length (20 m).

• After the data set is completed, a new base name can be selected to start

another set.

II

MRI·QI>Pl\R06-01 B-7
APPENDIX C

ANALYTleAl METHODS

C-1

,.
fORMULA: Table

H.W.: Table 1

OSHA/NIOSH/ACGIH: Table 1 PROPERTIES: Table 1

KETONES I

METHOD: 1300

ISSUED: 2/15/84

REVISION #l: 5/l5/89

I

COMPOUNDS:

(Synonyms:

acetone

Table 1) cyclohexanone

diisobutyl ketone

SAMPLING

2-hexanone

methyl isobutyl ketone

2-pentanone

MEASUREMENT

SAMPLER: SOLID SOR8ENT TUBE lTECHNIQUE: GAS CHROMATOGRAPHY, FlO

(coconut shell charcoal, 100 mg/50 mg)!

!ANALYTE: compounds above

fLOW RATE: O.Ol to 0.2 L/min

acetone

VOL-MIN: 0.5 L

-MAX: 3 L

llhui

1 L

10 L

lDESORPTION: 1 mL CS2' stand 30 min

!

!INJECTION VOLUME: 5 ~L

SHIPMENT: HI8K must be refrigerated [lJ

SAMPLE STABILITY: unknown

FIELD BLANKS: 101. of samples

ACCURACY

RANGE STUDIED. BIAS and

OVERALL PRECISION (sr): see EVALUATION OF

METHOD

lCOLUMN: glass (3.5 m x 6 mm), packed with 101.

SP-2100 0.11. Carbowax 1500 on

Chromosorb WHP

!TEMPERATURE-INJECTOR: 250°C

-DETECTOR: 300 °C

-COLUMN: 50°C to 170°C @100/min

!CARRIER GAS: NZ or He. 30 mL/min

lCAlIBRATION: standard solutions of analyte in

C52

!RANGE: 0.06 to 10 mg per sample [2J

!ESTIMATED LOD: 0.02 mg per sample

!PRECISION (sr): see EVALUATION OF METHOD

APPLICABILITY: This is intended as a general method for the ketones listed above. If only

certain compounds are of interest, the instrumental conditions can be changed to maximize

instrument response for these compounds.

INTERfERENCES: None reported. Alternate columns, e.g., 101. SP-2100 or OB-1 fused silica

capillary. can be used.

OTHER METHODS: This ~ethod combines and replaces Methods 51. S18, S19 and 520 [3J, 5178 and

S35B [41. and 1300 (dated 2/15/84).

5/15/89 1300-1 NIOSH Manual of Analytical Methods

C·3
KETONES I

REAGENTS:

1. Carbon disulfide (CS 2 )GC grade.-

2. Analytes, reagent grade.

3. Nitrogen. prepurified.

4. Hydrogen, dry.

5. Air, filtered, dry.

·See SPECIAL PRECAUTIONS.

METHOD: 1300

EQUIPMENT:

1. Sampler: glass tube, 7 cm long, 6-mm 00. 4-mm 10,

flame-sealed ends with plastic caps, containing two

sections of activated (600 GC) coconut shell charcoal

(front = 100 mg; back = 50 mg) separated by a 2-mm

urethane foam plug. A si1ylated glass wool plug

precedes the front section and a 3-mm urethane foam

plug follows the back section. Pressure drop across

the tube at 1 L/min airflow must be less than

3.4 kPa. Tubes are commercially available.

2. Personal sampling pump, 0.01 to 0.2 Llmin, with

flexible connecting tubing.

3. Gas chromatograph equipped with FlO, integrator and

column (page 1300-1).

4. Vials. 2-mL, glass. PTFE-lined crimp caps.

5. Syringe, 10-J.lL, readable to 0.1 lJL.

6. Pipet, TO, l-mL.

7. Volumetric flasks, IO-mL.

--I

SPECIAL PRECAUTIONS: Carbon disulfide is toxic and a serious fire and explosion hazard (flash

point = -30 GC); work with it only in a hood.

SAHPLlNG:

1. Calibrate each personal sampling pump with a representative sampler in line.

2. Break the ends of the sampler immediately before sampling. Attach sampler to personal

sampling pump with flexible tubing.

3. Sample at an accurately known flow rate between 0.01 and 0.2 L/min for a total sample size

of 0.5 to 3 L for acetone or 1 to 10 L for the other ana1ytes.

4. Cap the samplers and pack securely for shipment.

SAHPLE PREPARATION:

5. Place the front and back sorbent sections of the sampler tube in separate vials. Discard

the glass wool and foam plugs.

6. Add 1.0 mL C52 to each vial. Attach crimp cap to each vial.

7. Allow to stand 30 min with occasional agitation.

CALIBRATION AND QUALITY CONTROL:

8. Calibrate daily with at least five working standards over the range 0.02 to 10 mg analyte

per sample.

a. Add known amounts of analyte to C52 in 10-mL volumetric flasks and dilute to the mark.

b. Analyze together with samples and blanks (steps 11 and 12).

c. Prepare calibration graph (peak area vs. mg analyte).

9. Detennine desorption efficiency (DE) at least once for each lot of charcoal used for

sampling in the calibration range (step 8). Prepare three tubes at each of five levels

plus three media blanks.

a. Re-ove and discard back sorbent section of a media blank sampler.

b. Inject a known amount (2 to 20 J.lL) of analyte or of a standard solution of analyte in

C52 directly onto front sorbent section with a microliter syringe.

c. Cap the tube. Allow to stand overnight.

d. Desorb (steps 5 through 7) and analyze together with working standards (steps 11 and 12).

e. Prepare a graph of DE vs. mg analyte recovered.

10. Analyze three quality control blind spikes and three analyst spikes to ensure that the

calibration graph and DE graph are in control.

5/15/89

C-4

1300-2 NIOSH Manual of Analytical Methods
METHOD: ! 300 KETONE5 I

MEASUREMENT:

11. 5et gas chromatograph according to manufacturer's recommendations and to conditions given on

page 1300-1. Inject sample aliquot manually using solvent flush technique or with autosampler.

NOTE: If peak area is above the linear range of the working standards, dilute with C52'

reanalyze and apply the appropriate dilution factor in calculations.

12. Measure peak area.

CALCULAnONS:

13. Determine the mass, mg (corrected for DE) of analyte found in the sample front (Wf) and back

(Wb) sorbent sections, and in the average media blank front (Bf) and back (Bb) sorbent

sections.

NOTE: If Wb > Wf/10. report breakthrough and possible sample loss.

14. Calculate concentration, C, of analyte in the air volume sampled, V (L):

EVALUATION Of METHOD:

The methods were validated under NI05H Contract COC-99-74-45 [5]. Desorption efficiency was

checked by spiking known amounts of the compounds (either neat or in solutions with C52) on

coconut shell charcoal. Samples were generated for acetone, cyclohexanone, 2-pentanone, and

methyl isobutyl ketone by heating a quantity of the liquid to just below its boiling point in a

3-necked, 500-mL round bottom flask. The compound was carried through a fixed-temperature

condenser to the concentrations. Samples were generated for diisobutyl ketone and 2-hexanone

using a syringe pump which delivered the compounds to a heated glass-lined inlet which was

swept with nitrogen, carrying the vapor to the mixing chamber. Results were as follows:

Overall Measurement

Method Range, mg/m3 Breakthrough 1 Range. mglsample

Compound [2-5] (srI (L) (sr) DE2

Acetone 51.127 1200 to 4500 4.3 2.4 to 14.2 0.86

(0.082) (0.024)

Cyclohexanone S19 98 to 392 65 3.8 to 18.0 0.82

(0.062) (0.025)

Oiisobutyl ketone 5358 145 to 582 44 1.8 to 7.0 0.91

(0.070) (0.032)

2-Hexanone 5178 188 to 790 >45 1. 5 to 8.1 0.81

(0.053) (0.018)

MIBK 518 208 to 836 17 2.1 to 8.3 0.91

(0.064) (0.008)

2-Pentanone S20 395 to 1570 19 3.5 to 14.0 0.90

(0.063) (0.011)

15% breakthrough. 0.2 Llmin at high end of concentration range in dry ai r ,

2Averaged over mass range shown.

5/15/89 1300-3 NIOSH Manual of Analytical Methods
KETONES I METHOD; 1300

I

Low-level desorption efficiency checks showed the DEs to be 70% and 761. for 0.024 and 0.096

mg/sample respectively for cyclohexanone and 67% for 0.052 mg/sample of M1BK (2].

REFERENCES;

[1] uall Report, Sequence #552B-J (NIOSH, unpublished, Oct. 2, 1986).

{2] Williams, Karen, Desorption Efficiency Determination for Cyclohexanone and Methyl Isobutyl

Ketone, NIOSH/MRSB, Unpublished (1986).

(3] NlOSH Manual of Analytical Methods, 2nd. ed., V. 2, 51, S18, 519 and 520, U.S. Department

of Health, Education, and Welfare, Publ. (NlOSH) 77-157-8 (\977).

[4] Ibid, V. 3, S178 and 5356, U.S. Department of Health, Education, and Welfare, Pub'. {NIOSH}

77-157-C (1917).

[5] Documentation of the NlOSH Validation Tests, U.S. Department of Health, Education, and

Welfare, Publ. (NlOSH) 17-185 (\977), available as Stock No. PB 274-248 from NTIS,

Springfield, VA 22\6\.

[6] NIOSH Manual of Analytical Methods, 2nd. ed., V. 1, P&eAH 127, U.S. Department of Health.

Education, and Welfare, Publ . (NIOSH) 17-157-A (1977).

METHOD REVISED BV; Edward J. Slick, NIOSH/DPSE; methods originally validated under NIOSH

Contract COC-99-74-45.

Table 1. General Information

COlllpound

(Syoooyms)

A.cetone

2-Propanone;

CAS #67-64-1)

Cyclohexanone

(CAS #108-94-1)

Diisabutyl ketone

(2.6,-dimethyl4-heptanane;

CAS #108-83-8)

2-Hexanone

(methyl n-butyl ketone;

HBK; CA.S #591-78-6)

Methyl isobutyl ketone

(H1BK; hexane; isopropyl

acetone; 4-methyl2-pentanone;

CAS #108-10-1)

2-Pentanone

(methyl propyl ketone;

CAS #107-87-9)

Formula

(M.W, )

CH3COCH3

(58.08)

«CH3)2CHCH2.)lO

( 142.2.4)

CH3{CHZ)3COCH3

( 100.16)

{(H3)2(HCH2COCH3

( 100. 16)

CHlHz'H2COCH3

(86.13)

Properti es*

liquid: ap 56 0(;

d 0,79\ g/ml;

VP 35.5 kPa (266 mm Hg)

liquid; BP 155 oc;

d 0.947 g/mL;

VP 0.3 kPa (2 mm Hg)

1iquid; BP 169 0(;

d 0.847 g/mL;

VP 0.23 kPa (1.7 mm Hg)

liquid; BP 127 0(;

d 0.812 g/ml;

VP 0.4 kPa (3 mm Hg)

liquid; BP 1\7 0(;

d 0.800 g/mL;

VP 2.0 kPa (15 mm Hg)

liquid; BP laO 0(:

d 0.81Z g/ml.

VP 3.6 kPa (27 mm Hg)

Exposure Limits,

OSHA

NIOSH

ACGIH

750; STn lOaD

250

750; STn 1000

25 (skin)

25 (skin)

25 (skin)

Z5

25

25

5

1

5

50; STEL 75

50; STn 75

50; STEl 75

200; STH ZSO

150

200; STEL 250

2.37

4.01

5.82

4.09

4.09

3.52

*Density @25 0(; VP @ ZO 0(.

5/15/89 1300-4 NIOSH Manual of Analytical Methods
FQRIIIJLA: ~; CH40

M.W.: 32.04

OSHA: 200 ppm

HIOSH: 200 ppw; 800 ppml15 min [1]

ACGIH: 200 PPQ: STEl 250 ppm

(1 ppm =1.310 mg/ml • HlP)

METHANOL

IIlETHOO: 2000

ISSl£D: 2/15184

PROPERTIES: liquid: BP 64.5 °c;

d 0.192 glml • 20°C;

VP 15.3 kPa (115 mm Hg; 15.1' v/v) •

20°C;

explosive range 6 to 36\ v/v in air

I

SYJOtYM$; carbinol; methyl alcohol: wood alcohol; rAS 167-S6-1.

SAMPLING

SNIPLER: SOl10 SORBEHT TleE

(silica gel, 100 mg/50 11I9)

FLOW RATE: 0.02 to 0.2 Llmin

VOL-"IN: 1 l i' 200 ppm

-fW(: 5 l

SHIMHT: routi ne

SAMPLE STABILITY: 6 weeks

BlANKS: 2 to 10 field blanks per set

BULK SAMPLE: desirable, 1 to 10 ml

RANGE STUDIED: 140 to 540 mg/mll en

(S-L s~les)

BIAS: not significant [2]

OVERAll PRECISION (sr): 0.063 [2]

lTEQlfI~: GAS CHROMTOGRAPHY, FlO

1ANALYTE: methanol

!DESORPTION: 1 ml water; stand 4 hrs

1INJECTION VOlI.IE: 5 loll

!TEfft:RAT~E-INJECTION: 200 °C

-DETECT~: 250 - 300 °C

-COllA!: 80 °C

!CARRIER GAS: HZ or He, 30 mllmin

1

!COLUMN: glass, 2 m x 2 Inn 10, 60/80 mesh

Tenax GC or equi valent

!CALIBRATIOH: solutions of methanol in water

!RANGE: 0.1 to 6 11I9 per ~le

l~STlMATEO LOO: 0.01 mg per sample [51

lPRECISION (sr): 0.032 [2] I

APPLICABILITY: The working range is 25 to 900 mgllIl (19 to 690 ppn) for a 5-L air ~le.

The method is applicable to ceiling detemtinations. At high concentrations of methanol or at

high relative hllllldity, a large silica gel tube is required (700 mg front section).

INTERfERENCES: None identified. ~itive identification by _ss spectl"CJftetry Illly be necessary

in Sale cases. Alternative gas chranltographic C01UM5, e.g.• SP 1000, SP-2l00 or FFAP are

also confirmation aids. High relative h""idity drastically decreases the capacity of the

~ler.

OTHER METHODS: This method carbines and replaces Methods SS9 (3) and P&CNt 241 [4].

2/15J84 2000-1

C-7
REAGENTS:

1. w.ter. distilled.

2. Methanol.*

3. Nitrogen, purified.

4. Hydrogen. prepurified.

5." Air. filtered.

*See special precautions.

"T.elI): 2000

EQUIPfIIENT:

1. S-.:>ler: glass tube. 1 an long. 4 .. 10. containing

two sections of 20/40 mesh silica gel sep4rated by a

2.... portion of urethane foam (front =100 1119. back

=- SO MI).

NJTE: At high relative hunidlty or high _thanal

~trations. use a larger tube: 15 at

long, 8 Am 10. with three sections of silica

gel (100 IIISI. lSO mg. 150 1119).

2. Personal 5aq)ling ~. 0.02 to 0.2 Llmin. with

fl..ible connecting tubing.

3. Gas chrcllllltograph. FlO, integrator and collJlll'\

(page 2000-1) .

4. Vials. glass. 2-ml. PTFE-lined criMp caps.

5. Syringe. 10-~L. readable to 0.1 pl.

6. Volu.etric flasks, lO-ml.

SPECIAL PRECAUTIONS: Methanol i5 flllllMble and a dangerous fire and explosion risk. It is

noderately toxk by ingestion and inhalation.

SMPLING:

1. Calibrate each perSOf'lil SMPling with a representative ~ler in line.

2. Break the ends of the sanpl.r ilmlediately before s.tq)ling. Attach ~ler to per-sonal

sampling pump with flexible tubing.

3. S~le at an accurately known flow rate beu.en 0.02 and 0.2 Llmin for a total ~le size

of 1 to 5 l.

4. Cap the samplers with plastic (not rubber) caps and pack securely for shipment.

SNfILE PREPARATICIt:

5. Place the front and back sorbent sections of the ~ler tube in separate vials. Discard

the glass wool and fOM! plugs.

6. Add 1.0 ml distilled water to e.ch vial. Attach crilq) cap to each vial.

1. Allow to stand 4 hrs with occasional agitation.

CALIBRATICIt AND QUf\lITY a»ITROl:

8. Calibrate daily with at least flve NOrking standirds over the range 0.01 to 6 1119 methanol

per ~le.

a. Add known iIlIOUnts of methanol to distilled water in lQ....ft. volunetric flasks and dilute

to the _Me.

b. AM.lyze together with $Mples and blanks (steps 11 and 12).

c. Prepare c.llibration grlph (pINk ..... vs.....thanol) .

9. Dete11lline desorption efficiency (DE) at least once for each lot of silica gel used for

S4WJ1Pling in the calibrat;on range (step 8), Prepare three tubes at each of five levels

plus three Media blanks.

a. RenNe and dlscard back $Orbent sectlon of a .'a blank allPler.

b. Inject a known amount of methanol direetly onto front sol"bent section with a microliter

sydnge.

21lS/84

C-8

2000-2
ME1lQl: 2000

II

c. Cip the tube. Allow to stand overnight.

d. Desorb (steps 5 through 7) and analyze together wittl working standards (steps 11 and 12).

e. Prepare a graph of DE vs. IIg ..thana1 recovered.

10. Analyze three quality control blind spikes and three analyst spilces to insure that the

calibration graph and DE graph are in control.

ME:ASlREMENT:

11. Set gas chl"CllMtograph according to manufacturer's ~tionsand to conditions given

on page 2000-1. Inject Ulq)le aliquot manually using solvent flush technique or with

aut~ler.

NOTE: If peak area is above the linear range of the wor1cing standircls, dilute ",ith

distilled water, reanalyze and apply the appropriate dilution factor in calculations.

12. Measure peak area.

CALCUlATIONS:

13. Detemine the mass, mg (corrected for DE) of methanol found in the uqlle front (w,> and

back ("'b) sorbent sections. and in the average media blank front (8f) and back (~)

sorbent sections.

NOTE: If > Wf/lO. report breakthrough and possible ~le loss.

14. calculate concentration. C, of methanol in the air volume sampled. V (l):

------------------------------------- EVALUATION OF METlfJO

Method SS9 (3)was issued on January 11. 1975, and validated over the range 140 to 540 ••'

at 2S ·C and 758 nm Hg. using S-l ~les [2]. Overall precision. sr' was 0.063 with average

recovery for 18 ~les 94.2\, representing a non-significant bias. The atlllospheres were

generated by calibrated syringe pIM'P. Desorption efficiency ~s 0.92 at 1.31119 methanol and

0.84 at 0.65 Ilg methanol per sawple. Breakthrough (51. on back section) occurred at 52 min when

saMpling an atmosphere containing 541 mg/m' in dry air at 0.2 l/min.

Additional data were gathered using a larger (700 mg front section) silica gel tube under high

tulidity condit1ons; thew _re published In P&CAM 241 [4]. A ~rlson of the data is

consistent with a recommended maximum sample volume of 5 L.

Front 8,...kthroullh

Section, Test COnditions capacity.

Method f!IJ!I charcoal 1..BH ms ..thanol W.

S59 [2.3] 100 5-40 0 5.6 10.4

P&CM 247 [4] 700 534 as 4.6 8.15

2/15184 2000-3

c-s
!E!HQO: 2000

I

REFERENCES:

[1] Criteria for a Recantnded Standard...Occupational EXJlO$Ure to !'ethyl Alcohol, U.S.

Depl.r~t of HHlth, Education, and Welfare, P\lbl. (..IOSH) 761-148 0(76).

[2] Doc~tation of the NIOSH Validation Tests, U.S. Departllent of Health, Education, and

Wt1 fare , Publ. (NIOSH) 11-185 (1917).

[3] NIOSH Ptanua1 of Analytlea1 P1ethods, V. 2, SS9, U.S. Depa.rtlnent of Health, Educa t\on, and

WtlfAre, Pub1. (NIOSH) 77-157-8 (\977).

[4] Ibid, V. " NCNI 241, U.S. oepartment of Health, Education, and welfare, Publ. (NIOSH)

11-151-A 0(77).

[5] User check, UBTL, NIOSH sequence 14121-K (Unpublished, November 3, 1983).

IlIEl'HOO REVISED BY: Charles ~ister, NIOSHlDPSE; SSg orlginally validated under NIOSH

Contract CDC-GG-74-4S.

211SIM

C-10
FOfIIIUt.A: CH~12

P1.W.: M.94

OSHA: 500 ....; C 1000 ... P 2GOO ...

NIOSH: l~t feasible; potenti.,

urc\nogen [1]

ACGIH: 50 JlIlII; suspect CU'Ci.....

(l ... 3.47 ..,... • ITP)

S1'NONYMS: dichl~thMe; CAS 1'JS..09-2.

SIftlIW

SMPlER: SOLID SORIEJfT 1laE

(2 coconut shell cMrc:oal tubes,

100 mg and 50 1IIg)

FLOW ~TE: 0.01 to 0.2 ~in

VOl.....IN: 0.5 l • 500 PPM

-MX: 2.5 l

SHIMMT: separate front and blckup tubes

SNPlE STABILITY: not det,rwined

8lN1CS: 101 of s..,1es

ACCLUCY

RMGE STUDIED: 1100 to 7097 MgIm.

(l-l SaMples) [2]

BIAS: not significant [2)

OVERAll PRECISION (sr): 0.073 [2]

"""," ...,.: .... ,. I$SIB: 211S114

REVISI. ,,: "1SlI7

PROPERTIES: 1'quid; d 1.323 tIa • 20 -c;

8P 40 ·C; .. -95 ·C;

yP ., kPa (341 • til; _ v/v) • 20 ec;

not n.....,.

!TECIIIlquE: GAS ctIINTOGRAPHY. FlO

!

I1Mlm: ..thyl.ne chloride

!

!DESOIPTICII: 1 III CSZ. sund 30 .tn

!

! INJECTION VOUJIE: S lit

!

!TBftMTURE-IIIIJ£CTlON: 200 to 225 -e

-DETECTOR: 2SO ·C

-COUIII: 60 to 90 ·C

!C1MIER GAS: HZ or He. 30 lILIJIin

!

!COUIIt: 3 • x 3 _ suinless st..,. 101 SP-looo

on 80/100 -.sh Ch,...sorb ...

!eAlI_nON: standlrd soluttons of CHzC12

! in CS2 "tth internll stAndard

!~: 0.3 to 10 " per slMP,. [3]

!

!E5TnMm LOO: 0.01 III pel" SIIllPle (••5]

!PRECISION (sr): 0.026 , 1.3 to 5.3 .. '-1"

! s-.ple (21

I

APPliCABILITY: The lIIDt"It:i.. ,... h ,. to 3000 ,.. (350 to 10,400 ~) for a l..l air

se1,. l1!t .-tt!od is .".,. " gUi. dItnlMtions.

INTalFEIlINCES: None identif'ed. 1'hI ...... WI vaU.ted using I 6 • x 3 _ statnless st..,

col_ packed w;th lOS FFN' on 1001120 ..,,, SUpelcoport. AlternAte ChrGllltGgrlPhic col.-s are

lOS TCEP on 801100 Chramsorb Pllt. 5P-21oo. SP-21GO with O. carbcNu 1500. or 01-1 'usld

silica ctp;11arx eolll!'

OTHER ..eTl«JOS: This I"ftises "'thads S329 [3)..'005 (dated 21lSIM), PSCM 121 [.]. and the

criteria doc:.-nt ..tttod (6]. OSM ...thod 59 uses larger {350",)sOrbent sections and has been

.¥lluated for 10-L air ,..les at 1 _ .",11M chloride [7],

8/1S/81 1005..1 MIOSH fllanual of Analyt\cal Pltthods

C-11
MET!!'tJ.B CHLORIDE

1. E1..t: -=-- disa1f1d1*.

~~tc..lily. COftutnh'lt

0.11 ,Iv decant. bInzaM or other

sufUbl. internal studard.

2....~1.. chloride.

3. IIttl"Clgln or heli.. purified.

4. H)1dNlln. p....rif....

S. Air. filtered. CClIIPressed.

-see SPECIAL PRECAUTIONS.

fITIII; ,.

EQUlflftEIfT:

1. ~ler: Hfalr.te frant Iftd bide.. glus tuMs with

pllstic ~. 7 c:. '011. ,_ aD. 4 _ 10. fl__

...,ed .... CGl\tlfnh'l Kth.tecI (MO ec) cocanat

shill cMl"COIl (f,..t. 100 ..; Melt • 50 ..). A

sHy11Ud glass ..-1 pl" is placed at eIdl aM of

..ee- tube. PNssuN drop across the tuMI at

1 L/IItn .irl1c:w ..st be less thUI 3.4 Ie,••

Note: 1-.0 tIC IIrcillly..:.vanlbl. tubes, HCh

canuining 150 III CMl'COil in we. beds• .-

be uMd.

2. PersoMl NIIlPltng pIlIP. 0.01 to 0.2 v.tn. wtttl

flexib1. COftRICting tubing.

3. Gis cmo-totriPh. fl_ tOfttuttOft .teetor.

in~tor Iftd col_ (PIlI 1005-1).

4. vi.ls. 2.... mE-lined up_ crt. CliPS.

S. syri.... lo-loll. rodIbl. to 0.1 loll.

6. Volu.etr;c fl.sks, l~.

II

SPECIAL PRECAUTIONS: carbon disulfide is tcucic and • s.rious fire Ind exp1ostoa buard (flash

point., -30 ee); work with it only in • hood.

SMPll.:

1. calibrate udl persoMl HIlIIPHng .... with ......sentltiv. HllP1ar in H ....

2. 8rNt ends of UlllPler ;"i.t.,y before HllPli.... Connect the two SGr'Hnt tubes with a

short piece of flexible tUbing. AtUch ~l.r to personal 5..ling witll fl.tb'.

~tlg.

3. s..le It In accurately kncMI flow rllte betwHn 0.01 Ind 0.2 LlJrin for a total $Mpl. size

of O.S to 2.5 L.

4. separate tile front .nd kckup Wbes and e.tP Me" tube to ,revet .;gral;on of _thyl.-

chloride betwen tubes. ',ck securely for sMllltRt.

SMI'lE PREPARATION:

S. PlIICe the front and back sorbent sections (i .e., front .nd backup tubes) of the 1MP'''' in

SfIPAr.te vials. Discard the glloss wool and fMl plugs.

6. Add 1.0 ..... eluent to each vial. Atueh cri. cap to Mch vill.

1. Allow to stand 30 .in with occaslOMl Agihtion.

CAlIIMntll All) QlMUTY CClfTIQ.:

8. calibrate daily wfth at 'ent fhe working stMdlrds over tN r.,.. 0.01 to 10 III ._,.-

chlorhle per UllPle. .

a. Mel kftOlllt .cMIItts of _ttlyl.ne chlorhle to eluent in 104L YOl...tric flasks'" dUm

to t_..n.

b. Analyze toetther with slllPles and blanks (steps 11 _ 12).

c. ""re calibration grAPh (ratio of peak Iorea of analyte to pHIl area of ;nte.....,

stMdM'd vs • .-g _thyl.... chloride).

9. DeteNine desorption efficiency (DE) It lN5t once for Hch lot of cMrcoal used for

,.11ng in the calibration range (step 8). Prepare tine tubes at each of five leM1I

plus three Media blanks.

1115117

C-12

1005-2 ..IOSH Kiftu41 of AM1yt\cal ~s
!I!W: 1005

I

A. --.w...... disard bIck .........t sectlOll of A ....i.. bl. ~l.r.

b. Illject A It..- _t of .thyl.... chloride diNCtly onto front sortIent section with a

litcroH ter' sm"".

c. CIp tM tIM. An...stall ov.....i ...t.

4. Desorb (steps tInuIiI' 1) .. "'yn "ith worldng stMdlrds (steps 11 and 12).

e........... A gr. of DE ft. III .thyl.. chloride recowerwd.

10. AMl~ thrM ..lily c.trol bHnd spikes _ three a"""yst spikes to insure that the

al; brAtion gr" Ind DE gr_ Ire in control.

flJEASUFLiEJEiUT:

11. set lIS chr-.togr. according to .....factur-.r·s Nee IndlU.S and to conditions given

on ... 1005-1. Inject UlllPl. oil iquat IllnUlilly using solvent flush technique or vi th

IUtosIIIpl.r.

IIJT£: If peU 1m ts .. the 11....1' ringl of the working stMdlrds. dilute vith .'uent,

runalyz. and apply the wroPriAtI dilution fACtor in aleulltions.

12. flluu... PHk ArH. Divide the peak a.... of analyt. by the peU a..... of intemal standlrel

on tew s_ ch.....togr_.

CALCUlATICItS:

13. DI\etWine the MSS. III (corrected for DE) of .thylene chloride found in the UIIIP" front

(w,) and back (....) SOI"MIIt sections. Ind in the aver••lella blank front (8f) and

Met (lit») sorbtnt sections.

'In'E: If Nt. > "'/10. ,...,.t brHkthrough .... possible UlllPle loss.

14. Cllculate concentration. C. of _thylene Chloride in the air vol.. s.-pl.ct. v (L):

EVAL.lMTICil OF fETIIJD:

...thad S329 (3] .5 bsued on June 6. 1975. And VAl idated ower the ruge 1100 to 11GO .."..

It 25 -c and 163 _ Hg usi .. I l-L $.-pl. [2). QIIerI11 prKtsion. sr'.s 0.013 .nth lver.

NCOMry 1S.1S......tilll a non-signtfiant bill. The concentrltion of .thyl... chloride

...s i.....ntly verified by ClHbr.t.ct syringe,.... Desorption effic1Hey .s 0.91 in the 1''''' 1.3 III to 5.3 III _tllyl.. chloride per UIIP". Breakthrougll (SI on bKtt section)

oce""'" at 18.5 .in lIIhIn Y1IPling an aamsphere containing 6126 IIg/III _thyl.... chloride

at O.187 lilli n at OS RH.

REFElHCES:

[1] IJOSH cu......t Ilttl1i.-ee ...11.tln.. filthy).. Qloride. u.s. o.p.r-.nt of HHlth and

-.. Services. Publ. (IJOSH) ....11. (,...n 1.. ,.).

[2] Doc_ntation of t. NJOSH validation Tests. NJOSH. sm. u.s. DIpa......t of Hulth.

EMation. and ...,f.... Ml. (IIOSH) 11-185 (1911).

[3) IJOSH "'nul of AnalytiCil "'tMds. 2nd ed., Y. 3. 5329, U.S. DIpI.....t of HHltb.

EduCltion, and ..., fa..., ,.,. (IIOSH) 17-151-e (1917).

[4] 110SH Rlnul of .'ytical ;"tMds, 2nd .... Y. 1. NCNI 121. U.S. DtpI......t of Hulth.

EdKltion........,f..... ,.,. (NJOSH) 71-151-.\ (1911).

[5] User check. _n, NI05M n99O-R (....,lshed. No""r 3. 1983).

[6] Criteria for a Reca.l_d SUnArd.••occupational Exposure to ...thylene Chloride. u.s,

OtpIrtilftt of Health. Educat'on. and welfa.... Publ. (NIOSH) 76-138 (1916).

1115111 1110511 KlnUl of ""'1)'\\cal Mhods

C-13
!II1A; 1.

, I

[1] OSM Analytical ftlthods ....., 0915'. avan.l. f". ACGIH. 6500 GleNMy Ave••

Cincinnati. Off 45211.

IlETHOO REVISED BY; G. David Fall)'; .,. T. GIgnoft; and I. J. Wi 11iMS. tlIOSHIDPS£; 5329

originally validated under NIOSH COntract CDC-99-74-4S.

8/15187

C-14

lOO5-C NIOSH Pll.JlAl of AMlytical ...thods
tl

F....LA: a; C1Ks

".W.: 92.14

IETHOD: ...

ISSUED: "15181

OSHA: 200,..; C 300 PIlII; P SOO ....

NIOSH: 100 ppn; 200 ""10 lrin [1.2]

ACQIH: 100 PIlI; 150 PIlI (STeL)

(1 PIlI .. 3.17 MgIII8 • NTP)

PROP1:RTIES: 1iquid; d 0.866 g/IIL • 20 ·C;

IP 110.6 ·C; .. -95 ·C;

yP 3.8 kPa (28 _ Mg; 3." v/v) , 2S ·c;

Ixplosive range 1.3 to 7.11 vlv in air

5Y111m1S: _thylbenzene. CAS '108-88-3.

MUNG

SAMPLER: PASSIVE

(Ictivated carbon)

!TECHNIQUE: GAS CHRQIIMTOGRAPHY. FID

SAMPLE TINE-'fIN: 15 .in • 200

-MX: 8 hr • 20 to 200

!ANAlYTE: toluene

!DESORPTION: 1.5 Ill. clrbon disu1f1de; stand

30 .in

SHJPPIEIfT: see step 2 - if necessary. trlnsfer

sorbent pad to sept-..capped vial;

otherwise. routine

SAMPLE STABILITY: It lHst 2 .-.Ies • 2S ·C if

stored in sept-...c:appect vial

!INJECTUII VOLlIE: 5 pl

!TENPERATURE-INJECTI01: 175 ·C

-DETECTOR: 200 ·C

-tOUR: 100 ·C

FIELD 8l.N1(S: 101 of sMP1.s

BULK SNl'LE: desirable

ACCURACY

!CARRIER GAS: He or ~. 30 JIIlIJDin

!

!COUIII: 3.6 • x 3 _ 00 5P-looo on 80/100 mesh

Chramosorb .-tP

AMGE STUDIED: 15 to 2250 1IIlVWI- [3]

BIAS: not significant [3]

!CALJRRATION: alNllyte solutions in CS2

!

!RMGE: 0.05 to 15 II!I per ~1e

OVERALL PRECISION (sr): 0.038 [3] !ESTIMTED lOO: 0.01 IIIg per $~le

!PRECISION (sr): 0.022 (3]

! -----------------~------------------ APPLICABILITY: The WOI"king r..... is 13 to MO (SO to 2500 ..,.-) for a ~hour s.,le.

The _thad is IPPHQbl. to ceili.. _ten.hations. TM _thad deteraines toluene Vlpor only

(not aerosol). tallpetitive adsorption by IMter vapor and other volatile organic solvents

affects sMP'er apacity.

INTERFEltENCES: None identt,ted. ThI chrc.,tographic co1_ or separation conen tions rM'J be

cMnged to circ..ent interference probl_.

OTHU fIETHOOS: NIOSH ...thads 1500 and 1501 tlllploy Icthe 5.,1;09 on charcoal tubes with

overall sensitivity about the Sale IS this ..thad.

8/15187 4000-1 NIOSH Kanua1 of Ana1yt'cal ~thods

C-15
TQU8E

REMENTS:

1. El..-t: oarbon disulfide (C~).

ee.r-t••ic qulity.*

2. Tol_. rMgIIIt gra.

3. Nitrogen or belhll. purified.

4. Hydrogen. prepurlfitd.

5. Air. filtered.

*See SPECIAL PRfCMITICIIS.

fIT!IW: ..

EQUIPlI8T:

1. s.,ler: plssive _itor "ith ~cU.atlld cMrcoI1

collection .,....t. lIIDI'Iitors .st be of k....

SilIIP1\.. rate for toluene.

2. Gas e totr.... flO. integrator and col...

( 1).

3. Vi.ls. ,lass. 2...... "it.. PTFE-lil" sept.. c.ps.

4. Pipet. TO, 1.S-4II.. and.pipet bUlb.

5. Syrifll". 5-. 10-. 2S- and lOO-lit.

6. Volu.etric flasks. l~.

7. Tw.ezers.

I

SPECIAL PRECAUTIONS: brbon disUlfide is tode and extreltl)' fl....,e (flash point. -30 -C);

work with It onl)' in a hood.

SMPLING:

1. -..owe s_'er fl"lll pilCkage and rwm¥e CIPS if WlicAble. Atuclt UlllllPler in wort...·s

brHthing zone. ....s..... u.pler ",'.ts 'N UllGbstructed. Record start of s..Ung

ti.. Follow -.nuflCturer·s ret' .. nAtions to 811-.te appropriate SMPling ti_ based on

relative tuIIidlty ~nd suspected coneentration of toluene.

NOTE: The uptake constant is only valid for ~lers in air with .'ent veloctty higlter

than ca. 10 calsec. For.,... S,,'H. 1!MUf'e adequate air -.v_nt.

l. Te...inate sallpling by sealing the s.'. as Nee 8.nded by the -.nuf.c:turer or by

transferrh'9. in a tol...f .... envit'OlKlftt. the IoCth.ttd charcoal collection .1_t to a

vial and sealing the vial with a sept. Cip. Use weezers for hlndling the collecUon

.'..nt. taking care not to touch any activated cMrcoal.

NOTE: sm. s",'.r desi",s (e.g.• 3ft 35GI [4]) do not require transfer of the COllect1Oft

el-.nt; otbers (e.g_. DuPont G-M and 6-18) require transfer of sorbent pad to I

5811ed vi.'. 5aIe s,,'er designs (e.g.• Druger ORSA-S) use granular sOfil,ent.

SNl'LE PREPARATION:

3. Add 1.5 III CS2 to each collection el...t.

4. Allow to stand at least 30 .'n with occlsional agitation.

CAUBRATION AND QUALITY CONTROL:

5. calibrate daily whit at least five worti... stMdards.

a. Add known MIMIIIts of toluene to in 10.... vol..tric fliSh and di lute to the _rat

to produce toluene concentrations itt tile range 0.01 to 10 1Ig/Itl.

b. Analyze with s...les and bla.s (sqps • thl"OUlh 10).

c. Prepare alibl-.tion tr.(........ vs... tol....).

6. Dete...i. desorption efficiency (DE) in tM oalibr.tion range at least once for efd lot of

$",'en used. Prwpare three ''''.rs at etch of fiye concentrations plus three -.lia

blanks.

a. Pl.ce the collection el_nt of a ••lia bl_ SIlIPler into .. vial and ape

b. Inject a kncMt ..nt of toluene directly onto the collection el....t vith a .Icroliter

syringe.

c. Allow to stand overnight.

d. Desorb (steps 3 .nd 4) .nd .nalyH with working standolrds.

e. Prepare a graph of DE vs. ntg toluene recovered.

8/15/87

C-16

«)O()-2 NIOSH Manual of Analytical Methods
I

1. Anllyze three ~l ity control b1ind spik.s and th,. .ul)'St spikes to ensure that the

cal ibrltton gr. and DE ..... aN in control.

~:

8. set gas cbf"altogr. accordi.. to .nufKturer's NCG.Lndltions and to conditions ghen

011 ..... 4000-1.

9. Inject sa-ple aliquot Mnua11y using solvent fl.sh ~ique or with an autOSllP'.r.

tGTE: If puk area is abo" the Hnur range of the ..wIting standards, dilute an aliquot of

the desorbed liquid w'th CS2' reanalyze, And apply the appropriate dilution factor

'n calculations.

10. ....sure peak arei..

CALCULATIONS:

11. De~iM the .ss, .. (corrected for DE). of toluene found on the s..le collection

.,....t 00 and on the aver. "'ia b1. (8).

NOTE: If \II > s.IIIIP'.r "PICity • 0.33, the SIIIlPler _ be saturated [6). Evalui.te each

rwsu1t on the Nsh of other organics preHftt in the s.,ed a_spMre, the

conc...trltions of 111 thl 1dsorINb1. Of"IIRics present. the _ient re1athe "'-ridity,

the siIIIlPling rite for the organics prwsent and the s."ng tille.

12. Cil1culate concentration. C <..-). of toluene in the air s,..led:

where: t". length of s.., 'ng period (Min)

K • uptake constant (CIt* to1uenelain).

tGTE: The upuke constant .st be k..... accurately (either be supplied by the ~l.r

_nuflcturer or dlltenriMd by the user by c.liwation with standard toluene-"~-a'r

",btures [5)). K can be "ti_ted f,... the dtffus'on coefficient. 0 (an2 /1ti n),

the cross-sectiON1 area. A (C112). and the diffusion pitlllength. L (aI), of the

s..ler:

EVAllMTlON OF fIEnII):

Precisions and bilses listed in the _thod _,.. det.",'Md by analyzing generated a"phlres

COftuining various contentrations of toluene at a r..... of ,..idities and in the presence of

other volatile organics [3]. GeneraUd concentrations were independently verified.

REFEIEIICES:

[1] Criteria for a Reel. LndId SUndard...Oc:cupatloul Eaposure to Toluene. U.S. Deparwnt of

....,th. Education. and ""'a,... Pub\. (NIOSH) 13-11023 (1913).

(2) NIOSH/OSHA OccupatiOftll ",,'t...idelines for Ctt.ic.l Hazards. U.S. 1lepartlllent of Hulth

Mel .....n services. Publ. (..IOSH) 81-123 (1981). available as Stock 1P883-1S4609 fMII NTIS.

Springfield. VA 22161.

(3] Perkins. J. Bo. N. N. price. L. Eggenberger and J. A. Burkart. Evaluation of Passive

Qrginic Vapor ftonitors. available as P883-221028 f,... NTIS. Springfield. VA 22161 (1981).

8115/81 4000-3 NIOSH ~nual of Analytical "tthods

C-17
TOlM

I

[4) Rodriguez, S. T•• O. W. GosseH_. and A. E....lUIIS. ....te.....tton of Dnorption

Efftctenctes 1ft the 3500 Organic V..-or fItonitor,··~. !!!l. !1m. Assoc. ~." 43,569-574

(1982) •

[5) Hull. R. D••nd It. E. cllst..nt., Testing Protocols wit.. £vllutiOlt Cr'ter'~ 1M

Perforwnce Specificltions for Pusi.. Slllplen......tted to AIHAJ (1984).

[6] Woebkenberg, M. l. UnpIIblisMd dltl 0.).

METHOD WRITTEN 8Y: "'ry Lynn .....enberg. NIOSHIDPSE.

B/15/81

C-18

HIOSH Manual of Analytlcal PIIthods
Personal or Area Monitoring for

Dibasic Esters and styrene in Air

(includlna dimethyl glutarate,

dimethyl succinate, dimethyl adipate)

-, -----,------~.~- -------"'--- ,-- --_.

Principle

Air is drawn by a personal battery-operated pump

through a two-section charcoal tube. where DBE

and styrene vapors are adsorbed. The chem'lcals

are desorbed with carbon disulfide/acetone and

analyzed by gas chromatography.

Safety Wear leather gloveSto avoid cuts when handling

broken glass tubes. Handle carbon disulfide In

the hood. Review MSDSs for carbon disulfide,

DBE, styrene and acetone. Avoid chemical contact

with skin. Carbon disulfide is extremely flammable.

Validation

The method for DBE was developed and

validated by AnalyticS, Inc., Richmond, Virginia.

Desorption efficiency for each of the esters when

they were spiked to charcoal tubes over the

range of 0.05-0.23 mg was 98-104%. DynamiC

standards in air were sampled. taking 4-8 L of air

sample at 300 cc/min for 13-26 minute periods.

Recovery of each ester at a feed concentration of

4- 17 mg/m3 was excellent. averaging 101% with

a CV of 0.03 Breakthrough of DBE from the

front section to the back section in the charcoal

tubes did not occur even after six hours of

sampling at 300 cc/minute (108 L of air}. At

Cape Fear, desorption efficiencies averaging 82 0

/

0

were observed when DBE at concentrations of

0.01-1.1 mg were spiked. Capillary column GC

was used at Analyties, packed column GC at

Cape Fear. The method is sim'llar to the validated

OSHA method for styrene.

Analysis

To have samples analyzed. contact Roche

Analytlcs. Richmond. Va., 1-800-888-8061.

Materials

• Alprla 2 ,l\ir Sampler. 5-200 cc!min range.

or eqldvalent

• Charu)al tubes, Lot 120, 100/50 mg. WIth

plastlr sealing caps, SKC 226-01

• PlastIC tubing to connect pump to tube

• Charcoal tube holder and clothing clips

• Tube tip breaker • Bubble tube calibrator or equivalent electron'le

calibrator

• Cas chromatograph equipped with 6-foot x

c-mch stainless steel column packed with

0.1 0'0 SP-1 000 on 80il 00 mesh Carbopack C

(Supelco). plus a peak area 'lntegrator*

• Exhaust trunk over CC to carry away CS1 odor*

• Carbon disulfide, CS~ *

• Styrene*

• Acetone*

• DBE*

• Developing vials with TEFLON!) lined septum

cap, SKC 226-02A+0

• Developing vibrator, SKC, with vial rack*

• Charcoal tube scoring file, and charcoal pick *

• Assorted pipets: 1. 2, 10 mt. etc. *

• Syringe and needle for CC injections, 10 IJI

Hamilton *

• Electrical tape

• Sampling pump battery charger

Solutions·

Make up 100 ml of desorbing solution with

98 ml of carbon disulfide and 2 ml of acetone.

Do this in the hood. Store in closed glass bottle.

• -ecesserv for on·slte analysiS

C-19
3.7 minutes

47

7.5

160

78 psig

200°C

8 minutes

4° Clminute

2200 C

16 minutes

1

4

30 pSlg

30 psig

200°C

Use this solution to make your DBE standards,

too. Do not keep the standards for more than a

few days because of the possibility of loss of

solvent by evaporation.

Standards * DBE

Make up DBE standards in CS2iacetone as follows:

DBE has a specific gravity of 1.09 glml.

1% DBE by volume (0.0109 mg/~I)

0.1 % (0.00109 mg/I-!/J

0.01 % (0.00011 mgil-! I)

Styrene

If styrene is present, make up standards containing both styrene and DBE by also adding 1~'D,

0.1 % and 0.01 % styrene to the DBE standards.

1q6 styrene by volume [0.0091 mg/I-!l)

0.1 0

0 (0.00091 mg/I-!I)

0.01 % [0.00009 mgfllll

Sampler Preparation

1. Start with a fully charged pump battery.

2. Break tips off both ends of a charcoal tube.

3. Calibrate pump with tube attached by

plastic tubing to take air sample at 100-200

cc/minute. The arrow on the tube indicates the

direction of air flow (toward the pump). If the

air sample will be of 4-8 hours duration, use

'" 100 cc.rnmute flow. If of shorter duration.

use r- 200 cc.rninute.

4. Record on Figure 1: pump brand and model

number, pump serial number, calibration date.

and sampling rate. It may be useful to put a

sticker on the pump with its sampling rate

and calibration date

Taking Air Sample

1. Turn on the pump. Note on Figure 1 the time

you started it. Close the case Fasten the pump

to the belt or pocket of the worker you will

monitor. Run the plastic tubing up his (her)

back and clip the charcoal tube holder to the

collar in front so that it samples air from near

the face. Fasten the plastic tubing to the back

of the shirt so that it won't flop around and get

in the way.

2. Write down on Figure 1 also the employee's

name and job description specifics while he

will wear the sampler. Also write down the

average air temperature and barometric pres-

•necessary for on-sue ana'vSIS

C-20

sure while the sample is being taken. Observe

the employee and record spills, leaks, odors.

ventilation, symptoms, etc At the end of the

air sampling turn off the pump, note the time

3. Measure the pump air flow rate again to make

sure that it has not changed significantly. Write

the flow rate on Figure 1 and average the

before and after flow rates. Record the average

flow rate on Figure 1.

4. Disconnect the charcoal tube and immediately

cap the ends with the plastic caps furnished.

Tag the tube with an identifying label or tape it

to the paper with the information on employee

name, etc.

Desorblnc the Charcoal*

1. With a thin wire charcoal pick, remove the glass

wool holding the charcoal in the tube. Pour the

larger section of charcoalmto one developing

vial. After removing the foam plug pour the

smaller section of charcoal Into another vial

Add 2 ml of desorbing solution to each vial

(in the hood) and cap the vials immediately.

Remember that the solution is extremely

flammable, and stinky

2. Label the vials to correspond with the samples

and place them in the developing vibrator for

30-60 minutes.

Cas Chromatocraph Calibration *

1. GC conditions are:

• helium carrier pressure

• initial oven temp.

• initial temp. hold time

• oven temp. rate

• final oven temp.

• final temp hold time

• range

• attenuation

• hydrogen pressure

• air pressure

• injector temp.

• detector temp. 250° C

2. Inject 1 microliter of 1% standard contairung

DBE and/or styrene. Approximate retention

times (see also Figure 2) are:

dimethyl succinate

styrene

dimethyl glutarate

dimethyl adipate
For the DBE standard, the area ratios of

DMS, DMG and DMA should be '" 17 :66: 17.

If retention times need to be increased or

decreased, adjust the helium carrier flow.

3. Also inject 1 III of 0.1 % standard. Areas of each

of the peaks should be about 10% of what

they were with the 1% standard.

4. Inject 1 111 of 0.01 % standard. Areas of each of

the peaks should be about 10% of what they

were with the 0.1 % standard.

Analysis of Samples

1. Inject 1 III of the solution desorbed from the

larger section of charcoal. Compare the areas

of the DBE and styrene peaks with the

standard that is nearest in area.

2. Inject 1 III of the solution desorbed from the

smaller section of charcoal. In our experience

there has never been any DBE or styrene in this

backup section. even with 48 L of air sample. If

there is more than 25°0 of what is found in the

large section, the sample has been overloaded

and should be discarded.

Calculations

1. Calculate the amount of DBE in the solution

injected as follows:

1a. Add together the areas of the DMS, DMG

and DMA peaks in the sample.

1b. Add together the same peaks in the DBE

standard nearest 'In area.

1c. Divide the total DBE area in the sample by

the total DBE area in the standard and multiply

by the mg of DBE in one microliter of that

standard. (See "Standards" section)

1d. Example:

0.1 % DBE Standard

1 11\ - 0.001 09 mg DBE

Areas: OMS 153.000

OMG 677,000

OMA 166,000

total 996.000

Sample from 41 .7 Lair

Areas: OMS 200,000

DMG 397,000

DMA 176.000

total 773.000

773,000 x 0.00109 = 0.00085 mg ~BE in

996,000 1 III sample Injected

2. Do a similar calculation for styrene:

Example:

0.1 % styrene standard

1 111=0.00091 mg styrene

Styrene peak area 1,315,000

Sample from 41 .7 Lair

Styrene peak area 638,000

638,000 x 0.00091 = 0.00044 mg styrene

1,315,000 In 1111 sample Injected

3. Do similar calculations for the small sections

of the charcoal tubes if any DBE or styrene

are present.

4. Calculate the amounts of DBE and styrene

found in each charcoal tube as follows:

Multiply the mg of OBE found in the injections

for each section by 2000. [There are 2000

microliters in the 2 ml of desorbing solution.)

Divide this number by 0.82 (the desorption

efficiency measured in tests, "Validation"

section). This will give you the mg of DBE

and styrene collected on the charcoal tube.

Add the amounts for the large and small

sections together

Example:

DBE found in 1 III = 0.00085 mg

Styrene found in 111\ = 0.00044 mg

000085 x 2000 2.07 mg OBE in charcoal

0.82 = tube large section

(no DBE found in small section)

000044 x 2000 _ 1.07 mg styrene in char0.82 - coal tube large section

(no styrene found in small section)

5. Calculate the average DBE and styrene

concentrations in the air sample as follows:

Sa. Calculate the volume of air sampled by

multiplying average pump flow rate by minutes

of air sampling.

Example:

101 cc/rninute x 406 minutes = 41 ,006 cc air

5b. Convert average barometric pressure

to mm Hg.

Example:

29.70 inches x 25.4 = 754 mm Hg

C-21

I
Figure 1

Exposure Report Form for DBE and Styrene in Air

Date

NOTICE: USE 100 CCMIN FOR 4-8 HR SAMPLES. 200 CUMIN FOR SHORTER

Location Area Name _

Equipment Elevation SS # _

Job assignments remarks, note when respirator IS worn

(V)

Small Section

____ cc3Ir

(Vel

_--.--=:-_ ec air corrected 298

x

Large Section

X - x 760

DBE analytical: Desorb eaen section in 2 ml of 2°0 acetone In es ,

Inject 1 ~I Standard

Standard Used DMS Area

____ 00 DBE DMG Area

- mg DBE DIVIAArea

in 1 III of Standard Total DBEArea

Sampling method: One SKC 22601 charcoal tube, 10050 mg lot

Pump Du Pont Alpha 2 Pump no Date pump last calibrated

Pump rate cc.min before Final time _

cCimll1 after Initial time _

ec min avg Net time _

Volume of air sample collected: average cc.rrun x minutes

Average air temp, 0 e [C)

Average bar, press mm Hg (P)

Volume corrected to standard V x 298

760 x C+ 273

Standard Large Small

Total DBE Area In Large Section

Total DBE Area In Standard x mg DBE in 1 III Standard - mg DBE 111 1 ~I sample

\ ------- mg DBE In 1 III of Large Section

mg DBE In 1 ~I of Smal: Section

total mg DBE In both SOlutions

____ mg DBE rr

______ mg DBE found

mg DBE found x 1000,000 mg DBE m

VC

100000(' = mg DBE X

082

Total mg DBE In both sotn. x 2000 _ mg DBE found In char~oal tube

0.82

x 2000

DBE Concentration 111 ,,4.11

x mg Styrene In 1 III Standard - mg Styrene in 1 1-11 sample

Stvrene Area

Styrene analytical:

Inject I ~I

Standard Used

____ 00 Styrene

____ mg Styrene In I IJI of Standard

Styrene Area In Large SeCtion

Styrene Area in Standard

Standard Large Section Sn'all Section

x

_______ mg Styrene In 1 1-11 of Large Section

_______ mg Styrene 111 1 I!I of Small Section

_______ total mg Styrene In both solutions

Total mg Styrene In both soln x 2000 _ mg Styrene found In charcoal tube

0.82

ppm Styrene

______mg Styrene found

mg Styrene found x 24,450,000 _ ppm Styrene

104 ve

x 2000

0,82

Styrene Concentration In Air -

mg Styrene x 24.450,000

104

REMARKS: Weather. wind direction, speed, employee comments, etc. ----------------

Sampled by Analyzed by _ Date

C·22
6.3 ppm

styrene

or

Sf. Calculate average styrene concentration

as ppm in air sample with this formula:

mg DBE found

in charcoal tube 24,450,000 DBE

x . = ppm

avg. mol. wt. corr. air vol.

of DBE

Example:

2.07 mg DBE x 24,450,000 = 7.9 ppm

159 40,143cc DBE

Sg. Calculate average styrene concentration

as ppm in air sample with this formula:

mg styrene found

In charcoal tube 24 450 000 ------ x . . ' = ppm styrene

molecular weight corr. air vol.

of styrene

Example:

1.07 mg styrene 24,450.000 --~----::..._- x

104 40,143cc

298

avg deg K

Example:

41 006 x 754 x , 760

298 40,143 cc air

= standard temp.

302 and pressure

Se. Calculate average DBE concentration as

rng/rn' in air sample with this formula

mg DBE found

in charcoal tube

x 1,000.000 = mg DBE/m· corrected air

volume in cc

Example:

2.07 mg DBE 1 000 000 51 6 rns/rn DBE 40,143 cc x ivou. ,&'

Sc. Convert average temperature during

sampling from degrees C to degrees K by

adding 273.

Example:

290 C + 273 = 3020 K

Sd. Correct air volume to standard conditions

with this formula:

calculated x avg, bar. pres x

air volume 760

Figure 2 GC Scan

( OMA

J

_:7

( OMG

--.-/

( STYRE~E

l.-.--.-' OMS

.s'

18

15

12

S9

c

.-

6

3

o

100 90 80 70 60 50 40 30 20 10 o

1 III Solution of 1% DBE and 1% Styrene

C-23
•

- I !

f \f I

I

N-Kethyl-2-pyrrolidinone

Matrix: Air

Tarre t

coneantratlont 51 ppe (103 ~/a')

'rocedurel &&apIa. are collected b1 draYin, & known volu.. of air thr-ouab • charcoal tub,. ....1... are de.or~.¥itb "., ..th,leDI chloride•••tbanol

anet analy..ct b)' p. c..~t~..Ph1 yitb ana••

ioalsation ctetector (CC-'ID).

Air vol.... and

".pUne nte

,tudl.etl 10 liter. at 0.2 Lpa.

Statu. of ..thode StoNa, ..tbod. This ..thod bal been oDly

pertially tvaluated and 1. presented lOt

inforaation and trial u•••

•

- II

Orpnl e servlce lranch I

OSRA Technical center

Salt Lake Cit7, Utah

C-24

P.02
... 4- .......... <';\0 ...... k' , . t:::.. ,_, l>-1 ..... ' 1'1 J. ('4 P.o=:. II

~p,N-n-9, r x, :5: 13 OSHA SLC iECH~:CAL C7; ~HX NJ. 801 524 ~C51 r.O; ,,,

1.1. laeklround

1.1.1. 81.tory of procedure

The OSHA technical center hal received .any requests

for a .a.p11na and analyt1cal proeedure for ••thyl

pyrro11dlnone. Charcoal tube .ampl1n, end

de.orption with 1 at carbOD di.ulfide va. tried

ift1t!ally, but the desorpt1on .fficiency avarac_d

3%.7l. Oe••rptloa with 1 aL 9911 carbon

dl.ulf14.:DMF had concentration '.pendent desorption

ran,ln. fro. 73.2 to 1'.4 for concentration. ranrin,

froa 2.066 to 1'.5~8.,. o.lorptloft with 1 aL 9515 ..t~l.n. chlorid.,..thanol averared 9g.4l for

concentration. froe 0.1033 to 2.066 aa. Charcoal

tube, had ,ood .tor.,e aD4 retention .fficlencie•• A tar,et level of 51 ppa Val eho.en as it 1. half

the r.c.....d.d TVA TLV li,ted on "SDS fro~ .everal

Maufaeturul.

1.1.2. Potential workplace expo.ura (Iaf. '.1.)

Kethyl p,rrolld1noa. 1. u,,, al a .olveftt in ..ny appltcatlon.. It 1. u'" .. a .ol~nt to facilitate

tbe fo~t1Oft of -.ny cbealcal.. It i. u.~ al •

• olv«ftt tor ..~j~ axtraction. 1n eraek!n, 011. and

1n further pet~ochealeal reaction.. It i. v••d a. a

MCltua for pol,..rtaatioD, and u ••olvent for fIDi~" pol,..t.. It 1. u••d In .trippinl pottlh1 ,••in. an4 .po.i•••.

1.1.3. Toxic Iffect. (this .ectlon is for inforaatlon

purpo.e. and thould Dot .. taken IS the ba.t, for

OSHA pollcy.)(ltf. '.Z.)

.ethyl pynoli.inone 1n ratt had a tDLo of 7500

./ke tot .kln expo_un .. a LD of 3564 ../q, with ¥allbt 10•• and body t••,.ri9ure d.er••••• noted in the Ivt"Yhora. In h~a"., ..thyl

wrrolldlnone h an lnhut n eya., .kin aDd

INeOU ..bruu. rrol..,.. expolura "1 cau••

headache, NU.... VOlll ti1\l and dhdnelS.

eoapound:

1

1~:16 801 !24 4081 p.e!

C-25
• JAN-n-92 FRI ::: 1~ OSHA SLC TECHN1ChL C1R FH~ ~J. 8Ql 524 ~Cal - U.:. t

SynonY•• 1 l-Metbyl-2-py~rolidlnon•• I-Methyl-'-pyrrolidinone, NHPI

Methyl pyrrolidone; H-Pyrol

"ol.cular vat.ht: 99.13

Denslty, 1.033

fralzinc poiDt' -24'C

1011ina pointl 202'C

Fla.h pointl "'C (204") (open cup)

Colors colo~le.s liquid

OdorJ .ild .mine-llkl

"olecular for.ulal C519NO

CAS: 872-'0-4

ItaSI

RTSCS.

11139

'4451 (VY"90000?

1.2. Ll.1t dlflnin. par••eters

1.2.1. The det.~tion liMit of the analytical procedure

1. 4 ftC wlth a 1 ~L injection volume. Thi. 1. the ••alleat ••ount which could be d~t.cted uDder

nor••l oper.tin. conditions.

1.2.2. The ovu.ll detection Halt 18 0.1 'pll b..ed on •

10 liter air volu... (All ppa a~unt. in thia

.tudy Ire based on a 10 L air volume.)

1.3. Advent....

1.3.1. Tbe ••mpling ptocedure t. eonyenient.

1.3.2. The analytical method I, reproducible and

.endtive.

1.3.3. R.analy_i. of .amples S. po.slble.

1.3.4. It ..y be po.,ible to analyce other co.pound, at

the •••• tillle.

1.3.~. Interferences ~y be avoided by proplr ••l.ct~on of

colu.n .n~ GC plrameterl.

C-26
FA}, t\S, 4"", "" '. ,,-, r:.:. ... A

1.;.), ,",

l

Due to the voi.t1lit~ ot the meth)':x.ene chloride iu the

desorbina solvent, it .., be DICI••lry to have. fan

blovinc on the instrument, in order to have consi.tent

lnjettlon., vben ul1n. an auto.aapler.

2. Sa~pl1R1 procedure

2.1. Apparatl.l.

2.1.1. A calibrated "~Ional 1 ••pI1nl pump. the flow of

which c.n be detarained vithin + 51 at the

reco...nded flov.

2.1.2. Chareoal tubes, lot 120. cantatnina 100 .. ad••rb1nc .eetlon with a 50 .. backup ••ction

leparated ~y • 2 .. portioD of urethane foam, with

a .tlaniaed .1al. wool plUi before the ad.orbi",

.ection and a 3 .. plul of urethane faa. at the

back of the backup ..etlon. Th. eD4h are ne.a ...led and the ,la1. tub. contalnin. tbe ad.orbant

S. ? c. lon,. with a 6 .. O.D. and 4 .m 1.0'1 IKe

tubes or equi.al.nt. •

2.2. Sampllnc technique

2.2.1. Open tbe end. of the charco.l tube. i.~.dt.t.ly

before ...plinc.

2.1.1. Connect the ch.~coal tuba to the ••~pllnl puap

with flexible tubin,.

2.~.3. 'lace the tube, in a vertical po.ition to .inl.t•• chenn.line. vith tbe ...ller ••ction tovard' tha

pUilp.

2.2.6. A1r MiDI •..,led ,houl. ftOt pa.. thl'O\&lh aJ11 ho.. Dr tublna before .~t.l'lft1 tb. charcoal tube.

2.2.5. s.al the charcoal tube vith pl••tic c.p.·

1....i.t.l' after ...pline. ...1 .ach .ampl.

lencthwl•• vith OSIA 'ora-Zl ...11ne tape.

2.2.6. V1tb .ach bateh of .a.plel. lubelt at le••t one

blank tube fro. the .... lot used for ...pl••.

Thi. tube ahould be subjected to exactly the ••~e

handlinl al the •••ple. (break endl, ••al. , transport) except that no .1r 1••rawn thrOUJh It.

2.2.7. Transport the .~plel (and corre.pondlnl paperwork)

to the lab for analys1 •.

C-27

-

•

-I

!

,

I

J I. - 1 7 - ? F' P 1
I· I ....... - .1- - _ tv-.4 ..' .l. 1. : b- l k M • Ii:- '- MOM 1 N I

JAN-P-92 FRI 15: 14 OSHA SLC TECHNICAL CiR FAX NO. SOl 524 4J5i

2.2.8. Bulk••",baitted for an.ly.i. au.t be ehipped in , .ep.rate aail1nc cont.iner from other •••~1 ••.

2.3. Desorption efficiency

Sl~ tube••ere 11.ul••piked at ••ch lo&di~ of 0.103,

0.517, 1.03, &ftd 2.07 ..taL ..thyl p,yrrolidinon.. The, vere

alloved to equilibrate ~eI'ntlht at 1:00II c••perature. They

ver. openad, .aCh ••etion ,lac" into a ._para,e 2 aL vial, •••••••4 -". 1 aL .f ,~. ••o.~I....lution. dftoorhnd fn~

30 .1nut•• v1 tit oceaaional .hakil\l, and ver. analyzed by

CC-fID. the ovu'all a"era,. vu 99." X.('table 1>

...

TUM'

1

2

3

4

5

6

Tabl. 1

De.orption zffielency

i lecoyerecs

0.103 ., 0.'11 III 1.03 .. 2.07 ...

99.9 '9.S 100 100

M •• 100 96.9 99.6 98.~ ".8 100 99.6

99.1 100 100 99.7

98.2 99.' 99.G 100

".0

".. 99.3 99.7

99.0 99.8 99.3 99.7

C-28

overall .ver... 99.4

.tandard devtation 0.73'

2.4. aatentlon efUe1eney

SlX tubel .ere liquid .piked with 2.07 .. ('1.0 ,,.> ..thyl pyrrolldiaon., al1ewed to equilibrate overbl.ht,

an. had 10 liter. hUMi. air (91t II) pulled throuch them.

Th.y .an opened, 'e.orbed an' andy.eel by GC-rtD. Ttl.

ret~tlon efficiency a.arac" ".6%. There v•• no ••thyl pyrro1141none found on the backUp portions of the

tubas. (Table 2)

4

eet ~24 41111 P.P~
... ... _ -J'... ......... t· • • , '.- ,....., .A...'. I .I.- I .. I

OSHA SLC TECHNICAL eTR FAX NS. eOl S2~ 408:

Table 2

aetention !fflc1ency

Tube • %Recovered t Itecovered Total

'A' 'I'

1 99.9 0.0 99.9

2 97.7 0.0 97.7

3 98.9 0.0 98.9

4 99.9 0.0 99.9

5 101 0.0 101

6 100 0.0 100

avera,. 99.6

2.'. Stor.,.

Tub•• vere .piked vith 2.07 .. (Sl.0 ppe> ..th,l

pyrrolidiDOne and Itor" at rooe t..peraturl until opened

and analyzed. The ncoveri....er.,.d 99.3 I for the l'

day. Itored.(Tabl. 3) -

T.ble 3

Stor.,. Study

..

2.6. r~.ch1on

Day

7

7

7

15

15

15

%Ilecoyued

101

97.0 ".9

100

101

101

!be ,reellion va. calculated ullft1 tb, a~.. COuntl fro~

ai. injection. of each .,an4ard at eoncentrationa of

0.103, 0.517, 1.03, and 2.07 ..'.L ..thyl ,yrroltdinone in the .e.orbt~ .olvent. The pooled coefficient of

veriation va. O.OO731.(Tabl. ')

C-29

l " II - 1 7 _ a :'" ~. l
JAN-r7-S2 Fitl 15:is F~X NO. SCi S2~ ~061 F.:: ."

I

Table J.

Pnchlon Study

Injection

NWllber 0.103 lII/lDL 0.517 q/IlL 1.03 III/ilL 2.07 q/IIlL

1 31014 147390 286310 568130

2 31413 147880 283730 '661'0

3 31606 146470 286010 '71550

4 31033 147830 288630 572910

, 31339 147000 288270 ",UO

6 31196 145030 282800 574330

Averal' 31267 146933 285958 569852

Standard

Deviation 2)0 1012 2347 3591

CV 0.00136 0.00730 0.00821 O.OO6!lO

'ooled CV 0.00131 .. •

vberet

CV (Coefficient of Vart.tio") ••taDfard ••"latlon

avera.e

fooled I .1(CV1)'Z • 12(CV2S'2 • A3(CVS)'! • A4(CVl)-}

CV • 1\ I --------------------------------------------- \ I A1 • A' • A3 • A4

't

4(1),A(2),A(3),A(4) •• of injections at ••cb level

CVl,CV2,CV3,CV4 • Coefficients at .ach level

2.7. Air yolu.. and .ampling rate atudied

2.7.1. The atr volu~e atudied ia 10 lttera.

2.7.2. The .ampItnl rate studied 1. 0.2 litera per

lIinute.

2.'. Interference.

Su.pected 1aterference, should b. l!.ted on ...ple ••ta

.h••u.

C-30

J A t~ - \ 7 - 9 2 F R 1

p,ee
. JfLL.j-P-92 ~Ri 15:15 OSHA SLC TECH~;CAL erR FAX NO. BOl 524 4021

r I

L

•

2.9. Satety precautions

2.9.1. Samplin. eGui,.ent .hould be placed on an .~ployee in a ..nner that do•• not interfere vith

work p.rfor~.nt. or .afety.

2.9.2. Safety .1••••••hould be Yorn at all tim••.

2.9.3. 'ollov all ••fety praetiees that apply to the

workplace be1nc •••pled.

3. Analytical ••thod

3.1. .pparatull

3.1.1. Ca. chroMetorr.ph equlp,.d with. 11.-.

ionis.tion detector. • .. 5190 va. u••d in thl• • tudy.

GC coluan capabl. 01 ....r.tine the an.1ft. and

an internal .tandard fro. aD1 interf.rence,. The

eoluan uoed in thi~ .t.~y Y.~ a 60 ..tlr DI-V.~

Yith 0.5 u d.l., 0.32 .. I.D.

3.1.3. An electroftic late,rator or .~ other .uitable

a.thod of .a.urSftI peak ere••.

3.1.4. 'wo ail111iter vial. with teflon-lined cap••

3.1.5. A 10 ~L Iyrin.e or other con••nient .1z. for

.aapl. injection.

3.1.6. Pl~et. for dSspen.ln. the 'e.orbl~ lolutton.

the Gleneo 1 .L d11penslc va. u••d 1ft thl• ••thocl.

3.1.7. Vol~tric flasks - 5 at and other eoftvenient

.lze. for preparinl It.ndard••

3.2 .....nu

3.2.1. Purified GC Irade nitroren, hydro.en, and aSr.

3.2.3. Methylene chlotid., IPte ,rade

3.2.4. Methanol, BPLC .rad.

3.2.5. n-Iexanol. l.agent Irad., u.e' a. the internal

.tandard

7

-

l e 'I _ , '? ;'(:, -, F F' I

-
_._~- ...._----

OSHA SLC iECHNl:AL C;R FA~ N:. Sal 524 4C81

Th~ ~~~nrh1nr ftn1~rinA il J~i~ ..'by~en, r"l~ri~~t~~fh~nn' vi'h 0.1. uL/mL n-h'~RPul

internal etandard.

3.3. Sample preparation

3.3.1. Sample tube. are opened and the front and back

lection of ••eh tube art placed 1n .eparate 2 aL

vi,h.

3.3.2. IIch le~tion 1. de.orbed with 1 aL of the

d••orblna .olytion of ",5 ••thylene ~hlor14.:..thanol with 0.25 ~L/.L n-hexanol

internal ,tandard.

3.3.3. The vial, ar•••aled i ...diately and allowed to

de.orb for 30 einute. with occa.ional ahakin,.

3.4. Standard preparation

3.4.1. Standard, are prepared by dilutlft1 a knovn

Quantity of ..thyl pyrro114inofte with the

de.orblna solution. A Itandard of 1 ~L'aL .ethyl pyrro11d1none in the de.orbin••olution 1a 1033 ~~~. . 3.4.2. At l.a.t tvo leparate stlndard. et the

ealibration level .hould be .ade.

3••• 3. A third analytical atandard .hould be prepare. at

a hl.her concentration to check the lin.arity of

the detection. Por this stud, tvo .tandard. at 1

uL/aL (1'0'3 ../aL) and on••tandard at 4 ~L/~L

(4.1)2 er/.L) .ethyl pyrrolidlnone vera used.

3.5. Analyd.

3.5.1. Gas chroaatolraph condition••

Flov rates (~L/.ln.)

Injoctor1 200

Detectora 225

COlu.nl aO·-lm!n

10·'.1n-160·

10

2

30

350

1 "L ••e 'l,un 1

Rlt~v••n(••ke-ur)1

Brdroc.n(carrier):

Iydrolen(detector):

Airl

InjectiDn dte:

Chroa.to.rall:

3.5.2. ..ak ar••• are _e.lured by an intelrator or other

lui table m.ans.

8

C-32

T to ~l - 1 7 - ~:: F' I el?ll '524 40131 P • 1 et
nOllt DlIJ Imill11 om ;rn

l I

; ,,.. '1' ,"I,,,, _

3.7.4. The above equation. can be con.olidated to form

the follovina for~ul.. To calculate the ppw. of

analytl in the campla baled on a 1" '1t~r air ••lIpl@1

~I/~L • concentration of analyt. in .ampl. or

standard

24.45 - Holar .ol~e (litare/aole) at 25 ·C and

760 all Ia.

MV _ Molecular vallht (1/ao1e)

DV • Desorption volu•• 10 L • 10 liter air .a.pla

DE - Desorption efficiency

3.7.5. Thi. calculation ts done for .ach .action of the •..,11n, tub. and the re.ult. added tOlether.

3.8. Safety precautions

3.'.1. All handliDI of .olvent••hould be .one 1n a hood.

3.8.2. Avoid 'kin contact with all aolvent••

3.8.3. Vear .afety 11••••• at all tta.a.

4. aeco--andatlons for further atudy

Collectlon .tudie. nead to be perforaed.

10

C-33

..

~. , !
, JAH-l7-92 FRI 15:17 OSHA SLC TECHNICAL CiR FF.X Ne. 801 524 40Si

"'"" 0 ...=

I

.I:

...

J..

•

- "

c: ... 0

0 c:

-

u - • - i rc; .... - ... 0 .. .... c

j .. l- e.

.. .... I I

e :-., .,.. l .. .,..

•

Fieur. 1. An analytical .tand.~d ot 1.0~S ~/wL ..th,l "rro11dinone

in the '.sorbin, solvent of 9Sz5 ..thyl.ne

chlorid_,.eth.nol vith n-haxanol internal .tandard .

...... .

11
F'. 1 4

OSHA SLC TECH~:CAL eTR FAX NJ, 8:: 524 ~C8\ p, : 4,':~

5.1. Gr.yson. H., wKirk Oth..r Encyclopedia of Chemical

Teehno10lY", Third Edition, John W11ey , Son, N.Y., 1981,

Vol. 19. p. 616, and Vol. 20t p.220.

5.2. sv••t, D. t ·"Il.try of toxic Effecta of Chemical

Sub.tanc••·, 1985-86 !ditlon, u.s. Depart_ent of Health and.~ft Servic••• Public H••lth Service, Center for

Dl••••• Control, NIOSH, 1987, Vol. 5. p. 4223.

5.3. Sax. N•• "Dana_roue 'ropertie. of Industrial Hatertal. n •

riftti adition, Van Mo.trand a.inhold Co., N,v fork, 1979.

p. 1089.

•

12

C-35

P. 1 4
MFU-OppnA06-<l1

APPENDIX 0

FTlR RESULTS-AIR CONCENTRATIONS VS. TIME

0-1
Air Concentrations vs. Time

RunNO.1 - alx Stripper

2000 I I

1500

-

i

-!! I .r - I I. Methanol

j

.. - .= 1000 I I ... Toluene c:

8 I -' - I I .. Acetone c:

0

0

..

:.i

500

2 2.5 3 3.5 4

Time (hrs)

0.5 1 1.5

o .**~ I I I I I I I

o

10.76 airexchanges per hourl

oI

V>

-
o

Air Concentration vs. Time

Run No.2 - SIXStripper

2000 '~--------------------------l'

1500

-

i

-

i 1~ L I <; I ,_ Methanol

.. Toluene

G> I ..- -- I I*

Acetone u

s

0

:i

500

2 2.5 3 3.5 4

Time (hrs)

0.5 1 1.5

o.........--I I I J I I I ---- I

o

10.62 airexchllng8lS per hourI

-
Air Concentrations vs. Time

Run No.3 - BIXStripper

2000 I I

1500

........

g

c

1~ / • Methanol 0

4:1

g ... Toluene

c

CD

*Acetone o

c

0

0

:if- 500

2 2.5 3 3.5 4

Time (hrs)

0.5 1 1.5

o I ...~- I o I I I I I

10.61 air exchanges perhourI

o

•

01

-
oI

0>

Air Concentrations vs. Time

RunNo.4 - BIXSpray-On Stripper

2000 I--------------------------~I

1500

-E

g,

g,

-I!

,8

1000 J <; I ,_ Methylene Chloride

i .. Methanol ..

u

c

0

0

..

<

500

2 2.5 3 3.5 4

Time (hrs)

0.5 1 1.5

O~I I I I I I I I

o

10.57 air exchanges per hourJ
Air Concentrations YS. Time

Run No.5 - BIXSpray-On Stripper

2000 I I

2 2,5 3 3,5 4

Time (hI'S)

0.5 1 1.5

0...,..."...... i t ( I ( ( I J

o

1500

-E

Q.

S

I)

c:

:8

1000 I <; I I- Methylene Chloride g

c: .. Methanol G)

u

c:

0

0

500

10.57• exchanges per hour'

oI

......

--
oI

CD

Air Concentrations vs. Time

RunNO.6- SIXSpray-On Stripper

2000 , I

2 2.5 3 3.5 4

rune (hrs)

0.5 1 1.5

o~~ t I I o I I I I I

1500

E

8:-!

11000 J '- I I_ Methylene Chloride

... Methanol 3

c:

0

0

..

<

SOD

10.58 airexchanges perhour'

..
Air Concentrations vs. Time

Run No.7 - Strypeeze

600 I \

500

'[ 400

S: I J \. I I- Methanol j _ .. _ .. Toluene

g 300 I I -. r-. · - ......- I 1* Methylene Chloride

a f ,'- B Acetone

o

200

100

2 2.5 3 3.5 4

Time (hrs)

0.5 1 1.5

O~I I I I I I I I

o

10.56 airexchanges perhourI

oI

co

-
o

...... •

o

Air Concentrations vs. Time

Run NO.8-strypeeze

2 2.5 3 3.5 4

Time(hrs)

0.5 1.5

o

o

100

500

600

E 400

8:- I ,r I \ I I- Methanol j ... I U .... .. Toluene

.: 300 _ . I I r ,r~~. I 1::::nech'Oride

o

;l 200

10.54 airexchanges perhousI

,..
Air Concentrations vs. Time

RunNo.9 - Strypeeze

600 i I

500

2 2.5 3 3.5 4

TIme (hrs)

0.5 1.5

o

o

100

I 400

I

I_ Methanol j I ~-,.. ... Toluene i 300 r - ......... I

I*

Methylene Chloride

I B Acetone

0

200

10.55 air exchanges per houri

oI

.....

.....

-
o

•

I\)

Air Concentration vs. Time

RunNo. 10- WoodFinisher's Pride

2.5 3 3.5 4 4.5 5

Time (hI'S)

0.5 1.5 2

o

o

80 , ,

60

-E

g

c

:i

as 140 I I I_NMPI

0

0

..

:.l

IL

20

10.56 airexchanges PMhourI

J
Air Concentration vs. Time

RunNo. 11 - WoodFinisher's Pride

2.5 3 3.5 4 4.5 5

Time (hfS)

0.5 1.5 2

o I - I I I i I I I I

o

80 ,..--------------------------l'

60

-E

e,

a

c

:8

CIlI

§ I I 40 r I-NMPI

0

0

:<

20

10.54 airexchanges per hourI

oI

-"

CJ)

J
o,

Air Concentration vs. Time

RunNo. 12 - Wood Finisher's Pride

80

2.5 3 3.5 4 4.5 5

Time (hrs)

0.5 1 1.5 2

o r- \ I I I t I I J } I

o

60

-E

a.

a.-c

:8L'lI

.:;;

40 j I c

o

• /- NMP I

c:

0

0

...

:.l

Q.

Z

20

10.57 air exchanges per hourI

-
Air Concentrations vs. Time

Run No. 13- 3M Safest Stripper

o

•

C11

5

4.5

4

-E

c.

c. 3.5 -c:

:8 3

lD

o 2.5 s:

0

0

... 2 <...

! 1.5

I 1

0.5

a

-0.5

0 0.5

10.55 air exchanges per hourl

1.5 2 2.5 3 3.5

Time(hrs)

4 4.5 5 5.5 6

I• Dibasic Esters I

-
oI

-"

0>

Air Concentrations vs. Time

RunNo. 14- 3MSafest Stripper

5

4.5

4

--K

Q. 3.5

-

c:

i 3

S 2.5

<3

2

j 1.5 w

j 1

C5

0.5

0

-0.5

0 0.5

(0.54 airexchanges perhourI

1.5 2 2.5 3 3.5

TIme(hrs)

4 4.5 5 5.5 s

I• Oibasic Esters I

--
Air Concentration VS. Time

Run No. 15 - 3M Safest Stripper

a

...... •

"

5

4.5

4

-E

Co

Co 3.5 -

j 3 as

.b

c:

8 2.5

c:

0

0

2

e

1.5

.~ 1

.!

i5

0.5

0

-0.5

0 0.5 1

10.54 air exchanges per hour l

1.5 2 2.5 3 3.5

Time (hrs)

4 4.5 5 5.5 6

I• Dibasic Esters I

-
o,

-"

en

Air Concentrations vs. Time

Combined Plots for Runs 3, 6, 9, 12 & 15

2000 j I

2 2.5 3 3.5 4

Time (hrs)

0.5 1 1.5

o

o

?~

• Methanol,Run 3

1500 ~- I... Toluene, Run 3

-E

.. Acetone, Run 3

g

c

B Methanol, Run 6

:8

g 1000

-o- Math. Cl.. Run 6

c

GI

-fs Methanol.Run 9

u

c:

0

• Meth.CI., Run 9

0

... *

Toluene, Run 9

500 A~

.. Acetone, Run 9

B- NMP,Run12

*DBE,Run15

-