Standards of Performance for New Stationary Sources; Appendix A Test Methods; Revisions to Methods 18 and 26 and Addition of Methods 25D and 26A to Appendix A

SUMMARY: The purpose of this action is to make revisions to Method 18,

``Measurement of Gaseous Organic Compound Emissions by Gas

Chromatography'' and to Method 26, ``Determination of Hydrogen Halide

and Halogen Emissions from Stationary Sources--Midget Impinger

Method,'' and to add Method 25D, ``Determination of the Volatile

Organic Concentration of Waste Samples'' and Method 26A,

``Determination of Hydrogen Halide and Halogen Emissions from

Stationary Sources--Isokinetic Method,'' to appendix A of 40 CFR part

60. Method 18 is being revised to clarify the phrase ``engineering

judgment'' as it relates to choosing a sampling methodology. Method 26

for an isokinetic determination of hydrogen chloride emissions is being

revised to add provisions for determining emissions of other hydrogen

halides and halogens. Method 25D is being added as the applicable test

method for the determination of the volatile organic concentration of

wastes. Method 26A is being added as an isokinetic version of Method

26.

A result of this action is that these standard methods will be

available to support compliance determinations with regulations being

promulgated in other rulemaking.

DATES: Effective Date: April 22, 1994.

The incorporation by reference of certain publications listed in

this rule is approved by the Director of the Office of the Federal

Register as of April 22, 1994.

See SUPPLEMENTARY INFORMATION section concerning judicial review.

ADDRESSES: Docket. Docket No. A-90-19, containing material relevant to

this rulemaking for Methods 18, 26, and 26A, and Docket No. A-90-23,

containing material relevant to Method 25D, are available for public

inspection and copying between 8 a.m. and 4 p.m., Monday through

Friday, at EPA's Air Docket, room M-1500, 1st Floor, Waterside Mall,

401 M Street, SW., Washington, DC 20460. A reasonable fee may be

charged for copying.

Two additional dockets pertain to development of the method and the

rulemaking for reference method 25D: (1) Docket No. F-91-CESP-FFFFF,

which contains copies of all BID references and other information

related to the development of the reference method 25D proposal; (2)

Docket No. F-92-CESF-FFFFF, which contains copies of all BID references

and other information related to development of the final reference

method 25D following proposal. The public may review all materials in

these dockets at the EPA RCRA Docket Office.

The EPA RCRA Docket Office is located in room 2427 of the U.S.

Environmental Protection Agency, 401 M Street SW., Washington, DC

20460. The Docket Office is open from 9 a.m. to 4 p.m., Monday through

Friday, except for Federal holidays. The public must have an

appointment to review docket materials. Appointments can be scheduled

by calling the Docket Office at (202) 260-9327.

FOR FURTHER INFORMATION CONTACT: For information concerning Method 26

or Method 26A contact Terry Harrison, Emission Measurement Branch,

([919] 541-5233) or Robin R. Segall, Emission Measurement Branch ([919]

541-0893). For information concerning Method 18 or 25D contact Rima

Dishakjian, Emission Measurement Branch, ([919] 541-0443). The address

for each of these contacts is Emission Measurement Branch (MD-19),

Technical Support Division, U. S. Environmental Protection Agency,

Research Triangle Park, North Carolina 27711.

SUPPLEMENTARY INFORMATION:

Judicial Review

Under section 307(b)(1) of the Clean Air Act (CAA), judicial review

of the actions taken by this notice is available only on the filing of

a petition for review in the U.S. Court of Appeals for the District of

Columbia Circuit within 60 days of today's publication of this rule.

Under section 307(b)(2) of the CAA, the requirements that are subject

to today's notice may not be challenged later in civil or criminal

proceedings brought by EPA to enforce these requirements.

Background Information Document

A background information document (BID) summarizing and responding

to legal comments and technical comments pertaining to this rulemaking

may be obtained from either: (1) The National Technical Information

Service (NTIS), 5285 Port Royal Road, Springfield, VA 22161, telephone

(703) 487-4650, or (2) the EPA Technology Transfer Network (TTN). The

TTN is an electronic bulletin board system which is free, except for

the normal long distance charges. To access the HON BID: (1) Set

software to data bits: 8, N, stop bits: 1; (2) Use access number (919)

541-5742 for 1200, 2400, or 9600 bps modems [access problems should be

directed to the system operator at (919) 541-5384]; (3) Specify TTN

Bulletin Board: Clean Air Act Amendments; and (4) Select menu item:

Recently Signed Rules. Please refer to ``Hazardous Air Pollutant

Emissions from Process Units in the Synthetic Organic Chemical

Manufacturing Industry--Background Information for Promulgated

Standards'', and specify volume number(s).

Volume 2E: Comments on Recordkeeping, Reporting, Compliance, and Test

Methods (EPA-453/R-94-003e)

Volume 2F: Commenter Identification List (EPA-453/R-94-003f)

I. The Rulemaking

Method 18 was developed for and is currently applicable to the

speciation of total gaseous organics in a sample to determine emissions

of individual organic compounds. In response to questions from industry

representatives seeking to use the method for compliance

demonstrations, the EPA is clarifying the phrase ``engineering

judgment'' as it relates to choosing a sampling and analytical

methodology. In the revision, an owner or operator will perform an on-

site field and laboratory evaluation of the methodology chosen to

sample and analyze the compounds of interest. This evaluation is used

to characterize the effectiveness of the methodology and correct for

any inefficiency in the chosen technique.

Method 25D is the applicable test method for the determination of

the volatile organic concentration of wastes. The sampling requirements

in the version of Method 25D promulgated today in 40 CFR part 60,

appendix A, have been changed since proposal. The final version of

Method 25D requires that samples of waste be collected from a source

following specific procedures for sampling a single-phase or well-mixed

waste, a multiple-phase waste, and solid materials. Each sample is

suspended in an organic/aqueous matrix, then heated and purged with

nitrogen for 30 minutes to separate certain organic compounds. A

portion of the sample is analyzed for carbon concentration, as methane,

with a flame ionization detector. The other portion of the sample is

analyzed for chlorine concentration, as chloride, with an electrolytic

conductivity detector. The volatile organic concentration of the waste

is then computed as the sum of the measured carbon and chlorine

contents. Responses to comments on the proposed Method 25D are included

in docket A-90-23.

Under subpart G of part 63, EPA is issuing standards to limit

emissions of halides and halogens from incineration or control of

halogenated organic vent streams at SOCMI facilities. Method 26

currently prescribes only measurement of hydrogen chloride emissions

with sampling at a constant rate. The revisions being made in this

action will expand the method's applicability to other hydrogen halides

and halogens. The addition of Method 26A will provide an alternative to

the revised Method 26 and will allow for isokinetic sampling of gas

streams that are saturated with moisture.

Method 26 was developed for and is currently applicable to

determining hydrogen chloride emissions from municipal waste

combustors. Methods similar to Method 26 and Method 26A were developed

for the measurement of hydrogen chloride (HCl) and chlorine (Cl2)

in emissions from hazardous waste incinerators and boilers and

industrial furnaces burning hazardous waste (56 FR 32728).

The revisions to Method 26 as well as Method 26A also extend the

applicability to measurement of hydrogen bromide (HBr), hydrogen

fluoride (HF), and bromine (Br2).

The Agency assessed the methods further, prior to promulgation,

through laboratory and field evaluations. A study concerning the

potential negative bias in Method 26A at HCl levels below 20 ppm was

performed; specifically, the study was to determine the need to replace

certain glass components in the sampling train with Teflon to

reduce surface adsorption effects. Another study to address sample

stability was performed, particularly in regard to the species created

by hydrolysis of the halogens in the alkaline solution in the sampling

train. Finally, a laboratory evaluation of Method 26A was conducted to

assess the bias and precision of the method for the target analyses. To

assist in its assessment, the Agency also solicited comments on

available information on the proposed methodology. Specifically, the

Agency solicited comments with supporting data to better define the

compounds present in the gas matrices which may, for the hydrogen

halides and halogens specified in the methods: (1) Be analytical

interferences, (2) interfere with their quantitative collection in the

impinger solutions, or (3) affect sample stability.

II. Public Participation

The opportunity to hold a public hearing specifically on these

methods was provided, but no one requested a hearing.

III. Significant Comments and Changes to the Proposed Rulemaking

A. Revisions to Methods 18 and 26 and Addition of Method 26A

Several comment letters were received on the proposed test method

changes and additions. These comments have been carefully considered

and, when deemed appropriate by the Administrator, changes have been

made to proposed Method 26A and the proposed revisions to Methods 18

and 26. A detailed discussion of these comments is contained in the

background document which is referred to in the ADDRESSES section of

this preamble.

The following changes were made to Method 18 as a result of public

comments received: Several commenters expressed concern that the

recovery study in the proposal did not take matrix interferences into

account, since it called for studies in the laboratories. In response

to these comments, the recovery study will be carried out on site, on

actual test samples. For bag and adsorbent sampling, spiked and

unspiked samples will be analyzed in order to quantify the fraction of

sample spike recovered. A correction factor will be required, as in the

proposed version of the method. For direct interface sampling, a

calibration gas will be introduced at the probe in order to check for

leaks in the sampling system. In response to a commenter, the

calibration gas can be introduced anywhere on the probe, but before the

filter. The commenter had expressed concern that on tall stacks, it

would be difficult to introduce a gaseous standard at the tip of the

probe.

Five minor changes were made to Method 26 and Method 26A between

proposal and promulgation as a result of the laboratory and field

studies cited earlier.

The use of Teflon probes and filter holders were

optionally allowed as well as quartz and borosilicate glass. This gives

the affected sources more options and does not affect the Agency's

ability to determine compliance. The data gathered was not sufficient

to show that use of Teflon probes and filter holders should

be required however.

The probe and filter temperature requirement was changed for Method

26A from 120 deg.C14 deg.C to require that the

temperature never be less than 120 deg.C during the sampling run.

Again this approach was taken to allow more flexibility. The Agency

determined that a minimum temperature requirement would minimize the

potential for condensation of acid gases in the probe and on the

filter; with these methods the filter is used to separate halide

particulate matter from the acid gases and is not recovered or analyzed

as part of the method. Therefore allowing the option of collection at

higher temperatures would be acceptable from an Agency perspective. The

source owner should be aware, however, that in some cases, operation at

a higher temperature could result in a positive bias by allowing of

certain compounds such as NH4Cl to pass through the filter.

Following a similar logic, the temperature requirement for the post

test sample train purge (required when the optional use of a cyclone is

used in high moisture environments) was changed to a minimum

temperature of 120 deg.C. The Agency concluded from the field and

laboratory studies that it is imperative that all of the moisture

collected in the cyclone be evaporated and captured during this purge

to assure quantitative recovery of the acid gases. Allowing higher

temperatures will allow this to be accomplished in a shorter time than

at 120 deg.C and potentially reduce the economic burden on the source.

There are, however, practical limitations which the tester will need to

consider in establishing an upper limit for that source to avoid

compromising the filter material or vaporizing halide particulate

matter captured on the filter.

A requirement was added that sodium thiosulfate be added, in excess

of theoretical amounts needed, to the alkaline impinger contents and

wash after sample collection to assure that the hypohalous acid formed

would be reacted to form a second Cl- ion. This then lead to the

equation in Section 8.8 being changed by deleting the factor of 2 since

now 2 halide (Cl- and Br-) ions are formed for each molecule

of halogen captured and measured instead of only one.

Maximum allowable absorbing solution blank correction values were

added to assure that large uncertainties in the compliance status of a

source will not result from laboratories employing poor laboratory

practices. The maximum values reflect attainable goals of current

technology.

Similar changes were made in Method 26 since both methods are

intended to measure the same compounds.

One commenter suggested that Method 13 and Method 13A might, in

some cases, be a better alternative to Method 26A for fluoride

emissions. The cited methods are for total fluoride emissions while

Method 26 and Method 26A are intended specifically for the gaseous

hydrogen fluoride (as well as other halogens and halides); some

modification of Method 13A and Method 13B would be needed to accomplish

this and would likely be source specific. Testers always have the

option of requesting alternative methods; requests should be submitted

in writing and should be accompanied by supporting data.

B. Addition of Method 25D

On July 22, 1991, the EPA proposed a new test method (refer to 56

FR 33491) to be added to appendix A of 40 CFR part 60 for determining

the volatile organic concentration of a waste (Method 25D). Based on

public comments on this proposed test method and EPA's evaluation of

additional technical analyses performed after proposal, certain

requirements of the test method were changed by the EPA from those

proposed. The substantive changes since proposal to Method 25D are

summarized below.

Changes since proposal were made to the sampling requirements for

Method 25D, being promulgated today in appendix A to 40 CFR part 60.

The sampling requirements for Method 25D have been revised to include

procedures for single-phase or well-mixed waste, multiple-phase waste,

and solid waste in addition to an alternative to sampling tap

installation. The final test method still provides a provision for

alternative sampling techniques subject to the approval of the EPA

Administrator.

IV. Administrative Requirements

A. Docket

The docket is an organized and complete file of all the information

submitted to or otherwise considered by EPA in the development of this

rulemaking. The principal purposes of the docket are: (1) To allow

interested parties to identify and locate documents so that they can

effectively participate in the rulemaking process and (2) to serve as

the record in case of judicial review (except for interagency review

materials) [Section 307(d)(7)(A)].

B. Paperwork Reduction Act

This rule does not contain any information collection requirements

subject to OMB review under the Paperwork Reduction Act of 1980, 44

U.S.C. 3501 et seq.

C. Executive Order 12866

Under Executive Order 12866 (58 FR 51736), the Agency must

determine whether the regulatory action is ``significant'' and

therefore subject to Office of Management and Budget (OMB) review and

the requirements of the Executive Order. The Order defines

``significant regulatory action'' as one that is likely to result in a

rule that may:

(1) Have an annual effect on the economy of $100 million or more or

adversely affect in a material way the economy, a sector of the

economy, productivity, competition, jobs, the environment, public

health or safety, or State, local, or tribal governments or

communities,

(2) Create a serious inconsistency or otherwise interfere with an

action taken or planned by another agency,

(3) Materially alter the budgetary impact of entitlements, grants,

user fees, or loan programs or the rights and obligations of recipients

thereof; or

(4) Raise novel legal or policy issues arising out of legal

mandates, the President's priorities, or the principles set forth in

the Executive Order.

Because the methods are not used until required in relevant

standards, there are no environmental, economic, or energy impacts

associated with the promulgated methods. Thus, this action is not

considered a ``significant'' regulatory action within the meaning of

Executive Order 12866.

D. Regulatory Flexibility Act Compliance

The Regulatory Flexibility Act (5 U.S.C. 601 et seq.) requires the

EPA to consider potential impacts of Federal regulations on small

business entities. Because these test methods impose no impacts, a

Regulatory Flexibility analysis has not been conducted.

Pursuant to the provisions of 5 U.S.C. 605(b), I hereby certify

that this rule will not have an economic impact on small entities

because no additional costs will be incurred.

List of Subjects in 40 CFR Part 60

Environmental Protection, Air pollution control, Incorporation by

reference, Intergovernmental relations, Reporting and recordkeeping

requirements, Synthetic organic chemical manufacturing, Test method,

Vapor-phase organic concentration, Volatile organic concentration,

Waste, Waste testing.

Dated: February 28, 1994.

Carol M. Browner,

The Administrator.

For the reasons set out in the preamble, title 40, chapter I, part

60 of the Code of Federal Regulations is amended as follows:

PART 60--[AMENDED]

1. The authority of citation for part 60 continues to read as

follows:

Authority: 42 U.S.C. 7401, 7411, 7414, 7416, 7601.

2. Section 60.17 is amended by revising paragraph (a)(22) to read

as follows:

Sec. 60.17 Incorporation by reference.

* * * * *

(a) * * *

(22) ASTM D 1193-77, Standard Specification for Reagent Water, for

appendix A to part 60, Method 6, par. 3.1.1; Method 7, par. 3.2.2;

Method 7C, par. 3.1.1; Method 7D, par. 3.1.1; Method 8, par. 3.1.3;

Method 12, par. 4.1.3; Method 25D, par. 3.2.2.4; Method 26A, par.

3.1.1.

* * * * *

Appendix A--Test Methods [Amended]

3. In appendix A, Method 18 is amended by revising section 2.1; by

adding paragraph (c) to section 3; by revising sections 7.4.4.1 and

7.4.4.5; and adding section 7.6 to read as follows:

Method 18--Measurement of Gaseous Organic Compound Emissions by Gas

Chromatography

* * * * *

2.1 Range. The lower range of this method is determined by the

sampling system; adsorbents may be used to concentrate the sample,

thus lowering the limit of detection below the 1 part per million

(ppm) typically achievable with direct interface or bag sampling.

The upper limit is governed by GC detector saturation or column

overloading; the upper range can be extended by dilution of sample

with an inert gas or by using smaller volume gas sampling loops. The

upper limit can also be governed by condensation of higher boiling

compounds.

* * * * *

3. Precision and Accuracy

* * * * *

(c) Recovery. After developing an appropriate sampling and

analytical system for the pollutants of interest, conduct the

procedure in Section 7.6. Conduct the appropriate recovery study in

Section 7.6 at each sampling point where the method is being

applied. Submit the data and results of the recovery procedure with

the reporting of results under Section 7.5.

* * * * *

7. Final Sampling and Analysis Procedure

* * * * *

7.4.4 Quality Assurance.

7.4.4.1 Determine the recovery efficiency of the pollutants of

interest according to Section 7.6.

7.4.4.2 * * *

7.4.4.3 * * *

7.4.4.4 * * *

7.4.4.5 Calculations. All calculations can be performed

according to the respective NIOSH method. Correct all sample volumes

to standard conditions. If a sample dilution system has been used,

multiply the results by the appropriate dilution ratio. Correct all

results according to the applicable procedure in Section 7.6. Report

results as ppm by volume, dry basis.

* * * * *

7.6 Recovery Study. After conducting the presurvey and

identifying all of the pollutants of interest, conduct the

appropriate recovery study during the test based on the sampling

system chosen for the compounds of interest.

7.6.1 Recovery Study for Direct Interface or Dilution Interface

Sampling. If the procedures in Section 7.2 or 7.3 are to be used to

analyze the stack gas, conduct the calibration procedure as stated

in Section 7.2.2 or 7.3.2, as appropriate. Upon successful

completion of the appropriate calibration procedure, attach the mid-

level calibration gas for at least one target compound to the inlet

of the probe or as close as possible to the inlet of the probe, but

before the filter. Repeat the calibration procedure by sampling and

analyzing the mid-level calibration gas through the entire sampling

and analytical system until two consecutive samples are within 5

percent of their mean value. The mean of the calibration gas

response directly to the analyzer and the mean of the calibration

gas response sampled through the probe shall be within 10 percent of

each other. If the difference in the two means is greater than 10

percent, check for leaks throughout the sampling system and repeat

the analysis of the standard through the sampling system until this

criterion is met.

7.6.2 Recovery Study for Bag Sampling. Follow the procedures

for bag sampling and analysis in Section 7.1. After analyzing all

three bag samples, choose one of the bag samples and analyze twice

more (this bag will become the spiked bag). Spike the chosen bag

sample with a known mixture (gaseous or liquid) of all of the target

pollutants. Follow a procedure similar to the calibration standard

preparation procedure listed in Section 6.2, as appropriate. The

theoretical concentration, in ppm, of each spiked compound in the

bag shall be 40 to 60 percent of the average concentration measured

in the three bag samples. If a target compound was not detected in

the bag samples, the concentration of that compound to be spiked

shall be 5 times the limit of detection for that compound. Analyze

the bag three times after spiking. Calculate the average fraction

recovered (R) of each spiked target compound with the following

equation:

TR22AP94.006

where

t = measured average concentration (ppm) of target compound and

source sample (analysis results subsequent to bag spiking)

u = source sample average concentration (ppm) of target compound

in the bag (analysis results before bag spiking)

s = theoretical concentration (ppm) of spiked target compound in

the bag

For the bag sampling technique to be considered valid for a

compound, 0.70R1.30. If the R value does not

meet this criterion for a target compound, the sampling technique is

not acceptable for that compound, and therefore another sampling

technique shall be evaluated for acceptance (by repeating the

recovery study with another sampling technique). Report the R value

in the test report and correct all field measurements with the

calculated R value for that compound by using the following

equation:

TR22AP94.007

7.6.3 Recovery Study for Adsorption Tube Sampling. If following

the adsorption tube procedure in Section 7.4, conduct a recovery

study of the compounds of interest during the actual field test. Set

up two identical sampling trains. Collocate the two sampling probes

in the stack. The probes shall be placed in the same horizontal

plane, where the first probe tip is 2.5 cm from the outside edge of

the other and with a pitot tube on the outside of each probe. One of

the sampling trains shall be designated the spiked train and the

other the unspiked train. Spike all of the compounds of interest (in

gaseous or liquid form) onto the adsorbent tube(s) in the spiked

train before sampling. The mass of each spiked compound shall be 40

to 60 percent of the mass expected to be collected with the unspiked

train. Sample the stack gas into the two trains simultaneously.

Analyze the adsorbents from the two trains utilizing the same

analytical procedure and instrumentation. Determine the fraction of

spiked compound recovered (R) using the following equations.

TR22AP94.008

where

mv = mass per volume of spiked compound measured

(g/L).

ms = total mass of compound measured on adsorbent with

spiked train (g).

vs = volume of stack gas sampled with spiked train (L).

mu = total mass of compound measured on adsorbent with

unspiked train (g).

vu = volume of stack gas sampled with unspiked train (L).

TR22AP94.009

where S = theoretical mass of compound spiked onto adsorbent in

spiked train (g).

7.6.3.1 Repeat the procedure in Section 7.6.3 twice more, for a

total of three runs. In order for the adsorbent tube sampling and

analytical procedure to be acceptable for a compound,

0.70R1.30 (R in this case is the average of

three runs). If the average R value does not meet this criterion for

a target compound, the sampling technique is not acceptable for that

compound, and therefore another sampling technique shall be

evaluated for acceptance (by repeating the recovery study with

another sampling technique). Report the R value in the test report

and correct all field measurements with the calculated R value for

that compound by using the following equation:

TR22AP94.010

* * * * *

4. Method 26 of appendix A is amended by revising Sections 1.1,

1.2, 1.3, 1.5, 1.6, 2.1.5, 2.2.2, 3.2.2, 3.2.3, 4.1.1, 4.2, 4.3, 4.4.2,

4.4.3, 5.2, and 7.2; in Section 2.1, revising Figure 26A-1; in Section

3.1.2, by revising the words ``Absorbing solution'' in the first

sentence to read, ``Acidic Absorbing Solution''; in Section 3.1.3, by

revising the words ``Chlorine Scrubber Solution'' in the first sentence

to read, ``Alkaline Absorbing Solution''; adding new Sections 3.1.4,

7.3, and 7.4; and adding Citations 4 and 5 to Section 8. Bibliography;

to read as follows:

Appendix A--Test Methods

* * * * *

Method 26--Determination of Hydrogen Halide and Halogen Emissions from

Stationary Sources - Midget Impinger Method

* * * * *

1. * * *

1.1 Applicability. This method is applicable for determining

emissions of hydrogen halides (HX) [hydrogen chloride (HCl),

hydrogen bromide (HBr), and hydrogen fluoride (HF)] and halogens

(X2) [chlorine (Cl2) and bromine (Br2)] from

stationary sources. Sources, such as those controlled by wet

scrubbers, that emit acid particulate matter must be sampled using

Method 26A.

[Note: Mention of trade names or specific products does not

constitute endorsement by the Environmental Protection Agency.]

1.2 Principle. An integrated sample is extracted from the

source and passed through a prepurged heated probe and filter into

dilute sulfuric acid and dilute sodium hydroxide solutions which

collect the gaseous hydrogen halides and halogens, respectively. The

filter collects other particulate matter including halide salts. The

hydrogen halides are solubilized in the acidic solution and form

chloride (Cl-), bromide (Br-), and fluoride (F-)

ions. The halogens have a very low solubility in the acidic solution

and pass through to the alkaline solution where they are hydrolyzed

to form a proton (H+), the halide ion, and the hypohalous acid

(HClO or HBrO). Sodium thiosulfate is added in excess to the

alkaline solution to assure reaction with the hypohalous acid to

form a second halide ion such that 2 halide ions are formed for each

molecule of halogen gas. The halide ions in the separate solutions

are measured by ion chromatography (IC).

1.3 Interferences. Volatile materials, such as chlorine dioxide

(ClO2) and ammonium chloride (NH4Cl), which produce halide

ions upon dissolution during sampling are potential interferents.

Interferents for the halide measurements are the halogen gases which

disproportionate to a hydrogen halide and a hydrohalous acid upon

dissolution in water. However, the use of acidic rather than neutral

or basic solutions for collection of the hydrogen halides greatly

reduces the dissolution of any halogens passing through this

solution. The simultaneous presence of HBr and CL2 may cause a

positive bias in the HCL result with a corresponding negative bias

in the Cl2 result as well as affecting the HBr/Br2 split.

High concentrations of nitrogen oxides (NOX) may produce

sufficient nitrate (NO3-) to interfere with measurements

of very low Br- levels.

* * * * *

1.5 Sample Stability. The collected Cl- samples can be

stored for up to 4 weeks.

1.6 Detection Limit. The analytical detection limit for

Cl- is 0.1 g/ml. Detection limits for the other

analyses should be similar.

* * * * *

2. * * *

2.1 * * *

BILLING CODE 6560-50-P

TR22AP94.011

BILLING CODE 6560-50-C

2.1.5 * * *

When the stack gas temperature exceeds 210 deg.C (410 deg.F) and

the HCl concentration is greater than 20 ppm, a quartz-fiber filter

may be used.

* * * * *

2.2 * * *

2.2.2 Storage Bottles. 100- or 250-ml, high-density

polyethylene bottles with Teflon screw cap liners to store

impinger samples.

* * * * *

3. * * *

3.1.2 Acidic Absorbing Solution * * *

3.1.3 Alkaline Absorbing Solution * * *

3.1.4 Sodium Thiosulfate (Na2S2O3.5

H2O)

3.2 * * *

3.2.2 Absorbing Solution Blanks. A separate blank solution of

each absorbing reagent should be prepared for analysis with the

field samples. Dilute 30 ml of each absorbing solution to

approximately the same final volume as the field samples using the

blank sample of rinse water.

3.2.3 Halide Salt Stock Standard Solutions. Prepare

concentrated stock solutions from reagent grade sodium chloride

(NaCl), sodium bromide (NaBr), and sodium fluoride (NaF). Each must

be dried at 110 deg.C for two or more hours and then cooled to room

temperature in a desiccator immediately before weighing. Accurately

weigh 1.6 to 1.7 g of the dried NaCl to within 0.1 mg, dissolve in

water, and dilute to 1 liter. Calculate the exact Cl-

concentration using Equation 26-1.

g Cl-/ml = g of NaCl x 103 x 35.453/58.44

Eq. 26-1

In a similar manner, accurately weigh and solubilize 1.2 to 1.3

g of dried NaBr and 2.2 to 2.3 g of NaF to make 1-liter solutions.

Use Equations 26-2 and 26-3 to calculate the Br- and F-

concentrations.

g Br-/ml=g of NaBr x 10\3\ x 79.904/102.90 Eq. 26-2

g F-/ml=g of NaF x 10\3\ x 18.998/41.99

Eq. 26-3

Alternately, solutions containing a nominal certified concentration

of 1000 mg/l NaCl are commercially available as convenient stock

solutions from which standards can be made by appropriate volumetric

dilution. Refrigerate the stock standard solutions and store no

longer than one month.

* * * * *

4. * * *

4.1 * * *

4.1.1 Preparation of Collection Train. Prepare the sampling

train as follows: Pour 15 ml of the acidic absorbing solution into

each one of the first pair of impingers, and 15 ml of the alkaline

absorbing solution into each one of the second pair of impingers.

Connect the impingers in series with the knockout impinger first, if

used, followed by the two impingers containing the acidic absorbing

solution and the two impingers containing the alkaline absorbing

solution. Place a fresh charge of silica gel, or equivalent, in the

drying tube or impinger at the end of the impinger train.

* * * * *

4.2 Sample Recovery. Disconnect the impingers after sampling.

Quantitatively transfer the contents of the acid impingers and the

knockout impinger, if used, to a leak-free storage bottle. Add the

water rinses of each of these impingers and connecting glassware to

the storage bottle. Repeat this procedure for the alkaline impingers

and connecting glassware using a separate storage bottle. Add 25 mg

sodium thiosulfate per the product of ppm of halogen anticipated to

be in the stack gas times the dscm stack gas sampled. [Note: This

amount of sodium thiosulfate includes a safety factor of

approximately 5 to assure complete reaction with the hypohalous acid

to form a second Cl- ion in the alkaline solution.] Save

portions of the absorbing reagents (0.1 N H2SO4 and 0.1 N

NaOH) equivalent to the amount used in the sampling train (these are

the absorbing solution blanks described in Section 3.2.2); dilute to

the approximate volume of the corresponding samples using rinse

water directly from the wash bottle being used. Add the same amount

of sodium thiosulfate solution to the 0.1 N NaOH absorbing solution

blank. Also, save a portion of the rinse water used to rinse the

sampling train. Place each in a separate, prelabeled storage bottle.

The sample storage bottles should be sealed, shaken to mix, and

labeled. Mark the fluid level.

4.3 Sample Preparation for Analysis. Note the liquid levels in

the storage bottles and confirm on the analysis sheet whether or not

leakage occurred during transport. If a noticeable leakage has

occurred, either void the sample or use methods, subject to the

approval of the Administrator, to correct the final results.

Quantitatively transfer the sample solutions to 100-ml volumetric

flasks, and dilute to 100 ml with water.

4.4 * * *

4.4.2 Before sample analysis, establish a stable baseline.

Next, inject a sample of water, and determine if any Cl-,

Br-, or F- appears in the chromatogram. If any of these

ions are present, repeat the load/injection procedure until they are

no longer present. Analysis of the acid and alkaline absorbing

solution samples requires separate standard calibration curves;

prepare each according to Section 5.2. Ensure adequate baseline

separation of the analyses.

4.4.3 Between injections of the appropriate series of

calibration standards, inject in duplicate the reagent blanks,

quality control sample, and the field samples. Measure the areas or

heights of the Cl-, Br-, and F- peaks. Use the mean

response of the duplicate injections to determine the concentrations

of the field samples and reagent blanks using the linear calibration

curve. The values from duplicate injections should agree within 5

percent of their mean for the analysis to be valid. Dilute any

sample and the blank with equal volumes of water if the

concentration exceeds that of the highest standard.

* * * * *

5. * * *

5.2 Ion Chromatograph. To prepare the calibration standards,

dilute given amounts (1.0 ml or greater) of the stock standard

solutions to convenient volumes, using 0.1 N H2SO2 or 0.1

N NaOH, as appropriate. Prepare at least four calibration standards

for each absorbing reagent containing the appropriate stock

solutions such that they are within the linear range of the field

samples. Using one of the standards in each series, ensure adequate

baseline separation for the peaks of interest. Inject the

appropriate series of calibration standards, starting with the

lowest concentration standard first both before and after injection

of the quality control check sample, reagent blanks, and field

samples. This allows compensation for any instrument drift occurring

during sample analysis.

Determine the peak areas, or heights, for the standards and plot

individual values versus halide ion concentrations in g/ml.

Draw a smooth curve through the points. Use linear regression to

calculate a formula describing the resulting linear curve.

* * * * *

7. * * *

7.2 Total g HCl, HBr, or HF Per Sample.

mHX=K Vs (SX--BX-) Eq. 26-4

where:

BX-=Mass concentration of applicable absorbing

solution blank, g halide ion (Cl-, Br-, F-)/

ml, not to exceed 1 g/ml which is 10 times the published

analytical detection limit of 0.1 g/ml.

mHX=Mass of HCl, HBr, or HF in sample, g.

SX-=Analysis of sample, g halide ion

(Cl-, Br-, F-)/ml.

Vs=Volume of filtered and diluted sample, ml.

KHCl=1.028 (g HCl/g-mole)/(g

Cl-/g-mole).

KHBr=1.013 (g HBr/g-mole)/(g

Br-/g-mole).

KHF=1.053 (g HF/g-mole)/(g

F-/g-mole).

7.3 Total g Cl2 or Br2 Per Sample.

mX2=Vs (SX--BX-) Eq. 26-5

where:

mX2=Mass of Cl2 or Br2 in sample, g.

7.4 Concentration of Hydrogen Halide or Halogen in Flue Gas.

C=K mHX,X2/Vm(std) Eq. 26-6

where:

C=Concentration of hydrogen halide (HX) or halogen (X2),

dry basis, mg/dscm.

Vm(std)= Dry gas volume measured by the dry gas meter,

corrected to standard conditions, dscm.

K=10-3 mg/g.

8. * * *

4. Stern, D. A., B. M. Myatt, J. F. Lachowski, and K. T.

McGregor. Speciation of Halogen and Hydrogen Halide Compounds in

Gaseous Emissions. In: Incineration and Treatment of Hazardous

Waste: Proceedings of the 9th Annual Research Symposium, Cincinnati,

Ohio, May 2-4, 1983. Publication No. 600/9-84-015. July 1984.

Available from National Technical Information Service, Springfield,

VA 22161 as PB84-234525.

5. Holm, R. D. and S. A. Barksdale. Analysis of Anions in

Combustion Products. In: Ion Chromatographic Analysis of

Environmental Pollutants. E. Sawicki, J. D. Mulik, and E.

Wittgenstein (eds.). Ann Arbor, Michigan, Ann Arbor Science

Publishers. 1978. pp. 99-110.

* * * * *

5. Part 60 is amended by adding and reserving Method 25C and adding

Method 25D to Appendix A as follows:

Appendix A--Test Methods

* * * * *

Method 25D--Determination of the Volatile Organic Concentration of

Waste Samples

Introduction

Performance of this method should not be attempted by persons

unfamiliar with the operation of a flame ionization detector (FID)

or an electrolytic conductivity detector (ELCD) because knowledge

beyond the scope of this presentation is required.

1. Applicability and Principle

1.1 Applicability. This method is applicable for determining

the volatile organic (VO) concentration of a waste sample.

1.2 Principle. A sample of waste is obtained at a point which

is most representative of the unexposed waste (where the waste has

had minimum opportunity to volatilize to the atmosphere). The sample

is suspended in an organic/aqueous matrix, then heated and purged

with nitrogen for 30 min in order to separate certain organic

compounds. Part of the sample is analyzed for carbon concentration,

as methane, with an FID, and part of the sample is analyzed for

chlorine concentration, as chloride, with an ELCD. The VO

concentration is the sum of the carbon and chlorine content of the

sample.

2. Apparatus

2.1 Sampling. The following equipment is required:

2.1.1 Sampling Tube. Flexible Teflon, 0.25 in. ID.

Note: Mention of trade names or specific products does not

constitute endorsement by the Environmental Protection Agency.

2.1.2 Sample Container. Borosilicate glass, 40 mL, and a Teflon

lined screw cap capable of forming an air tight seal.

2.1.3 Cooling Coil. Fabricated from 0.25 in. ID 304 stainless

steel tubing with a thermocouple at the coil outlet.

2.2 Analysis. The following equipment is required:

2.2.1 Purging Apparatus. For separating the VO from the waste

sample. A schematic of the system is shown in Figure 25D-1. The

purging apparatus consists of the following major components.

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2.2.1.1 Purging Flask. A glass container to hold the sample

while it is heated and purged with dry nitrogen. The cap of the

purging flask is equipped with three fittings: one for a purging

lance (fitting with the #7 Ace-thread), one for the Teflon exit

tubing (side fitting, also a #7 Ace-thread), and a third (a 50-mm

Ace-thread) to attach the base of the purging flask as shown in

Figure 25D-2. The base of the purging flask is a 50-mm ID

cylindrical glass tube. One end of the tube is open while the other

end is sealed. Exact dimensions are shown in Figure 25D-2.

2.2.1.2 Purging Lance. Glass tube, 6-mm OD by 30 cm long. The

purging end of the tube is fitted with a four-arm bubbler with each

tip drawn to an opening 1 mm in diameter.

Details and exact dimensions are shown in Figure 25D-2.

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2.2.1.3 Coalescing Filter. Porous fritted disc incorporated

into a container with the same dimensions as the purging flask. The

details of the design are shown in Figure 25D-3.

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2.2.1.4 Constant Temperature Chamber. A forced draft oven

capable of maintaining a uniform temperature around the purging

flask and coalescing filter of 752 deg.C.

2.2.1.5 Three-way Valve. Manually operated, stainless steel. To

introduce calibration gas into system.

2.2.1.6 Flow Controllers. Two, adjustable. One capable of

maintaining a purge gas flow rate of 6.06 L/min. The

other capable of maintaining a calibration gas flow rate of 1-100

mL/min.

2.2.1.7 Rotameter. For monitoring the air flow through the

purging system (0-10 L/min).

2.2.1.8 Sample Splitters. Two heated flow restrictors (placed

inside oven or heated to 12010 deg.C). At a purge rate

of 6 L/min, one will supply a constant flow to the first detector

(the rest of the flow will be directed to the second sample

splitter). The second splitter will split the analytical flow

between the second detector and the flow restrictor. The approximate

flow to the FID will be 40 mL/min and to the ELCD will be 15 mL/min,

but the exact flow must be adjusted to be compatible with the

individual detector and to meet its linearity requirement. The two

sample splitters will be connected to each other by \1/8\'' OD

stainless steel tubing.

2.2.1.9 Flow Restrictor. Stainless steel tubing, \1/8\'' OD,

connecting the second sample splitter to the ice bath. Length is

determined by the resulting pressure in the purging flask (as

measured by the pressure gauge). The resulting pressure from the use

of the flow restrictor shall be 6-7 psiG.

2.2.1.10 Filter Flask. With one-hole stopper. Used to hold ice

bath. Excess purge gas is vented through the flask to prevent

condensation in the flowmeter and to trap volatile organic

compounds.

2.2.1.11 Four-way Valve. Manually operated, stainless steel.

Placed inside oven, used to bypass purging flask.

2.2.1.12 On/Off Valves. Two, stainless steel. One heat

resistant up to 130 deg.C and placed between oven and ELCD. The

other a toggle valve used to control purge gas flow.

2.2.1.13 Pressure Gauge. Range 0-40 psi. To monitor pressure in

purging flask and coalescing filter.

2.2.1.14 Sample Lines. Teflon, 1/4'' OD, used inside

the oven to carry purge gas to and from purging chamber and to and

from coalescing filter to four-way valve. Also used to carry sample

from four-way valve to first sample splitter.

2.2.1.15 Detector Tubing. Stainless steel, \1/8\'' OD, heated

to 12010 deg.C. Used to carry sample gas from each

sample splitter to a detector. Each piece of tubing must be wrapped

with heat tape and insulating tape in order to insure that no cold

spots exist. The tubing leading to the ELCD will also contain a

heat-resistant on-off valve (Section 2.2.1.12) which shall also be

wrapped with heat-tape and insulation.

2.2.2 Volatile Organic Measurement System. Consisting of an FID

to measure the carbon concentration of the sample and an ELCD to

measure the chlorine concentration.

2.2.2.1 FID. A heated FID meeting the following specifications

is required.

2.2.2.1.1 Linearity. A linear response (+ 5 percent) over the

operating range as demonstrated by the procedures established in

Section 5.1.1.

2.2.2.1.2 Range. A full scale range of 50 pg carbon/sec to 50

Kg carbon/sec. Signal attenuators shall be available to

produce a minimum signal response of 10 percent of full scale.

2.2.2.1.3 Data Recording System. A digital integration system

compatible with the FID for permanently recording the output of the

detector. The recorder shall have the capability to start and stop

integration at points selected by the operator or it shall be

capable of the ``integration by slices'' technique (this technique

involves breaking down the chromatogram into smaller increments,

integrating the area under the curve for each portion, subtracting

the background for each portion, and then adding all of the areas

together for the final area count).

2.2.2.2 ELCD. An ELCD meeting the following specifications is

required. The ELCD components shall consist of quartz reactor tubing

and 1-propanol as electrolyte. The electrolyte flow through the

conductivity cell shall be 1 to 2 mL/min.

Note: A \1/4\-in. ID quartz reactor tube is recommended to

reduce carbon buildup and the resulting detector maintenance.

2.2.2.2.1 Linearity. A linear response ( 10

)

5.1.2.

2.2.2.2.2 Range. A full scale range of 5.0 pg/sec to 500 ng/sec

chloride. Signal attenuators shall be available to produce a minimum

signal response of 10 percent of full scale.

2.2.2.2.3 Data Recording System. A digital integration system

compatible with the output voltage range of the ELCD. The recorder

must have the capability to start and stop integration at points

selected by the operator or it shall be capable of performing the

``integration by slices'' technique.

3. Reagents

3.1 Sampling.

3.1.1 Polyethylene Glycol (PEG). Ninety-eight percent pure with

an average molecular weight of 400. Before using the PEG, remove any

organic compounds that might be detected as volatile organics by

heating it to 120 deg.C and purging it with nitrogen at a flow rate

of 1 to 2 L/min for 2 hours. The cleaned PEG must be stored under a

1 to 2 L/min nitrogen purge until use. The purge apparatus is shown

in Figure 25D-4.

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3.2 Analysis.

3.2.1 Sample Separation. The following are required for the

sample purging step.

3.2.1.1 PEG. Same as Section 3.1.1.

3.2.1.2 Purge Gas. Zero grade nitrogen (N2), containing

less than 1 ppm carbon.

3.2.2 Volatile Organics Measurement. The following are required

for measuring the VO concentration.

3.2.2.1 Hydrogen (H2). Zero grade H2, 99.999 percent

pure.

3.2.2.2 Combustion Gas. Zero grade air or oxygen as required by

the FID.

3.2.2.3 Calibration Gas. Pressurized gas cylinder containing 10

percent propane and 1 percent 1,1-dichloroethylene by volume in

nitrogen.

3.2.2.4 Water. Deionized distilled water that conforms to

American Society for Testing and Materials Specification D 1193-77,

Type 3 (incorporated by reference as specified in Sec. 60.17), is

required for analysis. At the option of the analyst, the KMnO4

test for oxidizable organic matter may be omitted when high

concentrations are not expected to be present.

3.2.2.5 1-Propanol. ACS grade or better. Electrolyte Solution.

For use in the ELCD.

4. Procedure

4.1 Sampling.

4.1.1 Sampling Plan Design and Development. Use the procedures

in chapter nine of the Office of Solid Waste's publication, Test

Methods for Evaluating Solid Waste, third edition (SW-846), as

guidance in developing a sampling plan.

4.1.2 Single Phase or Well-mixed Waste. Well-mixed in the

context of this method refers to turbulent flow which results in

multiple-phase waste in effect behaving as single-phase waste due to

good mixing.

4.1.2.1 Install a sampling tap to obtain the sample at a point

which is most representative of the unexposed waste (where the waste

has had minimum opportunity to volatilize to the atmosphere).

Assemble the sampling apparatus as shown in Figure 25D-5.

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4.1.2.2 Prepare the sampling containers as follows: Pour 30 mL

of clean PEG into the container. PEG will reduce but not eliminate

the loss of organics during sample collection. Weigh the sample

container with the screw cap, the PEG, and any labels to the nearest

0.01 g and record the weight (mst). Store the containers in an

ice bath until 1 h before sampling (PEG will solidify at ice bath

temperatures; allow the containers to reach room temperature before

sampling).

4.1.2.3 Begin sampling by purging the sample lines and cooling

coil with at least four volumes of waste. Collect the purged

material in a separate container and dispose of it properly.

4.1.2.4 After purging, stop the sample flow and direct the

sampling tube to a preweighed sample container, prepared as

described in Section 4.1.2.2. Keep the tip of the tube below the

surface of the PEG during sampling to minimize contact with the

atmosphere. Sample at a flow rate such that the temperature of the

waste is less than 10 deg.C. Fill the sample container and

immediately cap it (within 5 seconds) so that a minimum headspace

exists in the container. Store immediately in a cooler and cover

with ice.

4.1.3 Multiple-phase Waste. Collect a 10 g sample of each phase

of waste generated using the procedures described in Section 4.1.2

or 4.1.5. Each phase of the waste shall be analyzed as a separate

sample. Calculate the weighted average VO concentration of the waste

using Equation 13 (Section 6.14).

4.1.4 Solid waste. Add approximately 10 g of the solid waste to

a container prepared in the manner described in Section 4.1.2.2,

minimizing headspace. Cap and chill immediately.

4.1.5 Alternative to Tap Installation. If tap installation is

impractical or impossible, fill a large, clean, empty container by

submerging the container into the waste below the surface of the

waste. Immediately fill a container prepared in the manner described

in Section 4.1.2.2 with approximately 10 g of the waste collected in

the large container. Minimize headspace, cap and chill immediately.

4.1.6 Alternative sampling techniques may be used upon the

approval of the Administrator.

4.2 Sample Recovery.

4.2.1 Assemble the purging apparatus as shown in Figures 25D-1

and 25D-2. The oven shall be heated to 75 2 deg.C. The

sampling lines leading from the oven to the detectors shall be

heated to 120 10 deg.C with no cold spots. The flame

ionization detector shall be operated with a heated block. Adjust

the purging lance so that it reaches the bottom of the chamber.

4.2.2 Remove the sample container from the cooler, and wipe the

exterior of the container to remove any extraneous ice, water, or

other debris. Reweigh the sample container to the nearest 0.01 g,

and record the weight (msf). Pour the contents of the sample

container into the purging flask, rinse the sample container three

times with a total of 20 mL of PEG (since the sample container

originally held 30 mL of PEG, the total volume of PEG added to the

purging flask will be 50 mL), transferring the rinsings to the

purging flask after each rinse. Cap purging flask between rinses.

The total volume of PEG in the purging flask shall be 50 mL. Add 50

mL of water to the purging flask.

4.3 Sample Analysis.

4.3.1 Turn on the constant temperature chamber and allow the

temperature to equilibrate at 75 2 deg.C. Turn the

four-way valve so that the purge gas bypasses the purging flask, the

purge gas flowing through the coalescing filter and to the detectors

(standby mode). Turn on the purge gas. Allow both the FID and the

ELCD to warm up until a stable baseline is achieved on each

detector. Pack the filter flask with ice. Replace ice after each run

and dispose of the waste water properly. When the temperature of the

oven reaches 752 deg.C, start both integrators and

record baseline. After 1 min, turn the four-way valve so that the

purge gas flows through the purging flask, to the coalescing filter

and to the sample splitters (purge mode). Continue recording the

response of the FID and the ELCD. Monitor the readings of the

pressure gauge and the rotameter. If the readings fall below

established setpoints, stop the purging, determine the source of the

leak, and resolve the problem before resuming. Leaks detected during

a sampling period invalidate that sample.

4.3.2 As the purging continues, monitor the output of the

detectors to make certain that the analysis is proceeding correctly

and that the results are being properly recorded. Every 10 minutes

read and record the purge flow rate, the pressure and the chamber

temperature. Continue the purging for 30 minutes.

4.3.3 For each detector output, integrate over the entire area

of the peak starting at 1 minute and continuing until the end of the

run. Subtract the established baseline area from the peak area.

Record the corrected area of the peak. See Figure 25D-6 for an

example integration.

4.4 Water Blank. A water blank shall be analyzed for each batch

of cleaned PEG prepared. Transfer about 60 mL of water into the

purging flask. Add 50 mL of the cleaned PEG to the purging flask.

Treat the blank as described in Sections 4.2 and 4.3, excluding

Section 4.2.2. Calculate the concentration of carbon and chlorine in

the blank sample (assume 10 g of waste as the mass). A VO

concentration equivalent to 10 percent of the applicable

standard may be subtracted from the measured VO concentration of the

waste samples. Include all blank results and documentation in the

test report.

5. Operational Checks and Calibration.

Maintain a record of performance of each item.

5.1 Initial Performance Check of Purging System.

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Before placing the system in operation, after a shutdown of greater

than six months, after any major modifications, and at least once

per month during continuous operation, conduct the linearity checks

described in Sections 5.1.1 and 5.1.2. Install calibration gas at

the three-way calibration gas valve. See Figure 25D-1.

5.1.1 Linearity Check Procedure. Using the calibration standard

described in Section 3.2.2.3 and by varying the injection time, it

is possible to calibrate at multiple concentration levels. Use

Equation 3 to calculate three sets of calibration gas flow rates and

run times needed to introduce a total methane mass (mco) of 1,

5, and 10 mg into the system (low, medium and high FID calibration,

respectively). Use Equation 4 to calculate three sets of calibration

gas flow rates and run times needed to introduce a total chloride

mass (mch) of 1, 5, and 10 mg into the system (low, medium and

high ELCD calibration, respectively). With the system operating in

standby mode, allow the FID and the ELCD to establish a stable

baseline. Set the secondary pressure regulator of the calibration

gas cylinder to the same pressure as the purge gas cylinder and set

the proper flow rate with the calibration flow controller (see

Figure 25D-1). The calibration gas flow rate can be measured with a

flowmeter attached to the vent position of the calibration gas

valve. Set the four-way bypass valve to standby position so that the

calibration gas flows through the coalescing filter only. Inject the

calibration gas by turning the calibration gas valve from vent

position to inject position. Continue the calibration gas flow for

the appropriate period of time before switching the calibration

valve to vent position. Continue recording the response of the FID

and the ELCD for 5 min after switching off calibration gas flow.

Make triplicate injections of all six levels of calibration.

5.1.2 Linearity Criteria. Calculate the average response factor

(Equations 5 and 6) and the relative standard deviation (RSD)

(Equation 10) at each level of the calibration curve for both

detectors. Calculate the overall mean of the three response factor

averages for each detector. The FID linearity is acceptable if each

response factor is within 5 percent of the overall mean and if the

RSD for each set of triplicate injections is less than 5 percent.

The ELCD linearity is acceptable if each response factor is within

10 percent of the overall mean and if the RSD for each set of

triplicate injections is less than 10 percent. Record the overall

mean value of the response factors for the FID and the ELCD. If the

calibration for either the FID or the ELCD does not meet the

criteria, correct the detector/system problem and repeat Sections

5.1.1 and 5.1.2.

5.2 Daily Calibrations.

5.2.1 Daily Linearity Check. Follow the procedures outlined in

Section 5.1.1 to analyze the medium level calibration for both the

FID and the ELCD in duplicate at the start of the day. Calculate the

response factors and the RSDs for each detector. For the FID, the

calibration is acceptable if the average response factor is within 5

percent of the overall mean response factor (Section 5.1.2) and if

the RSD for the duplicate injection is less than 5 percent. For the

ELCD, the calibration is acceptable if the average response factor

is within 10 percent of the overall mean response factor (Section

5.1.2) and if the RSD for the duplicate injection is less than 10

percent. If the calibration for either the FID or the ELCD does not

meet the criteria, correct the detector/system problem and repeat

Sections 5.1.1 and 5.1.2.

5.2.2 Calibration Range Check.

5.2.2.1 If the waste concentration for either detector falls

below the range of calibration for that detector, use the procedure

outlined in Section 5.1.1 to choose 2 calibration points that

bracket the new target concentration. Analyze each of these points

in triplicate (as outlined in Section 5.1.1) and use the criteria in

Section 5.1.2 to determine the linearity of the detector in this

``mini-calibration'' range.

5.2.2.2 After the initial linearity check of the

minicalibration curve, it is only necessary to test one of the

points in duplicate for the daily calibration check (in addition to

the points specified in Section 5.2.1). The average daily mini-

calibration point should fit the linearity criteria specified in

Section 5.2.1. If the calibration for either the FID or the ELCD

does not meet the criteria, correct the detector/system problem and

repeat the calibration procedure mentioned in the first paragraph of

Section 5.2.2. A mini-calibration curve for waste concentrations

above the calibration curve for either detector is optional.

5.3 Analytical Balance. Calibrate against standard weights.

5.4 Audit Procedure. Concurrently analyze the audit sample and

a set of compliance samples in the same manner to evaluate the

technique of the analyst and the standards preparation. The same

analyst, analytical reagents, and analytical system shall be used

both for compliance samples and the EPA audit sample. If this

condition is met, auditing of subsequent compliance analyses for the

same enforcement agency within 30 days is not required. An audit

sample set may not be used to validate different sets of compliance

samples under the jurisdiction of different enforcement agencies,

unless prior arrangements are made with both enforcement agencies.

5.5 Audit Samples. Audit Sample Availability. Audit samples

will be supplied only to enforcement agencies for compliance tests.

The availability of audit samples may be determined by writing:

Source Test Audit Coordinator (MD-77B), Quality Assurance Division,

Atmospheric Research and Exposure Assessment Laboratory, U.S.

Environmental Protection Agency, Research Triangle Park, NC 27711 or

by calling the Source Test Audit Coordinator (STAC) at (919) 541-

7834. The request for the audit sample must be made at least 30 days

prior to the scheduled compliance sample analysis. If audit samples

are not available, follow the quality control sample procedures in

Section 5.7.

5.6 Audit Results. Calculate the audit sample concentration

according to the calculation procedure described in the audit

instructions included with the audit sample. Fill in the audit

sample concentration and the analyst's name on the audit response

form included with the audit instructions. Send one copy to the EPA

Regional Office or the appropriate enforcement agency and a second

copy to the STAC. The EPA Regional office or the appropriate

enforcement agency will report the results of the audit to the

laboratory being audited. Include this response with the results of

the compliance samples in relevant reports to the EPA Regional

Office or the appropriate enforcement agency.

5.7 Quality Control Samples. If audit samples are not

available, prepare and analyze the two types of quality control

samples (QCS) listed in Sections 5.7.1 and 5.7.2. Before placing the

system in operation, after a shutdown of greater than six months,

and after any major modifications, analyze each QCS in triplicate.

For each detector, calculate the percent recovery by dividing

measured concentration by theoretical concentration and multiplying

by 100. Determine the mean percent recovery for each detector for

each QCS triplicate analysis. The RSD for any triplicate analysis

shall be 10 percent. For QCS 1 (methylene chloride), the

percent recovery shall be 90 percent for carbon as

methane, and 55 percent for chlorine as chloride. For QCS

2 (1,3-dichloro-2-propanol), the percent recovery shall be

15 percent for carbon as methane, and 6

percent for chlorine as chloride. If the analytical system does not

meet the above-mentioned criteria for both detectors, check the

system parameters (temperature, system pressure, purge rate, etc.),

correct the problem, and repeat the triplicate analysis of each QCS.

5.7.1 QCS 1, Methylene Chloride. Prepare a stock solution by

weighing, to the nearest 0.1 mg, 55 L of HPLC grade

methylene chloride in a tared 5 mL volumetric flask. Record the

weight in milligrams, dilute to 5 mL with cleaned PEG, and inject

100 L of the stock solution into a sample prepared as a

water blank (50 mL of cleaned PEG and 60 mL of water in the purging

flask). Analyze the QCS according to the procedures described in

Sections 4.2 and 4.3, excluding Section 4.2.2. To calculate the

theoretical carbon concentration (in mg) in QCS 1, multiply mg of

methylene chloride in the stock solution by 3.777 x 10-3. To

calculate the theoretical chlorine concentration (in mg) in QCS 1,

multiply mg of methylene chloride in the stock solution by 1.670 x

10-2.

5.7.2 QCS 2, 1,3-dichloro-2-propanol. Prepare a stock solution

by weighing, to the nearest 0.1 mg, 60 L of high purity

grade 1,3-dichloro-2-propanol in a tared 5 mL volumetric flask.

Record the weight in milligrams, dilute to 5 mL with cleaned PEG,

and inject 100 L of the stock solution into a sample

prepared as a water blank (50 mL of cleaned PEG and 60 mL of water

in the purging flask).

Analyze the QCS according to the procedures described in

Sections 4.2 and 4.3, excluding Section 4.2.2. To calculate the

theoretical carbon concentration (in mg) in QCS 2, multiply mg of

1,3-dichloro-2-propanol in the stock solution by 7.461 x

10-3. To calculate the theoretical chlorine concentration (in

mg) in QCS 2, multiply mg of 1,3-dichloro-2-propanol in the stock

solution by 1.099 x 10-2.

5.7.3 Routine QCS Analysis. For each set of compliance samples

(in this context, set is per facility, per compliance test), analyze

one QCS 1 and one QCS 2 sample. The percent recovery for each sample

for each detector shall be 13 percent of the mean

recovery established for the most recent set of QCS triplicate

analysis (Section 5.7). If the sample does not meet this criteria,

check the system components and analyze another QCS 1 and 2 until a

single set of QCS meet the 13 percent criteria.

6. Calculations

6.1 Nomenclature.

Ab=Area under the water blank response curve, counts.

Ac=Area under the calibration response curve, counts.

As=Area under the sample response curve, counts.

C=Concentration of volatile organics in the sample, ppmw.

Cc=Concentration of carbon, as methane, in the calibration gas,

mg/L.

Chh=Concentration of chloride in the calibration gas, mg/L.

Cj=VO concentration of phase j, ppmw.

DRt=Average daily response factor of the FID, mg CH4

counts.

DRth=Average daily response factor of the ELCD, mg Cl-

counts.

Fj= Weight fraction of phase j present in the waste.

mco=Mass of carbon, as methane, in a calibration run, mg.

mch=Mass of chloride in a calibration run, mg.

ms=Mass of the waste sample, g.

msc=Mass of carbon, as methane, in the sample, mg.

msf=Mass of sample container and waste sample, g.

msh=Mass of chloride in the sample, mg.

mst=Mass of sample container prior to sampling, g.

mvo=Mass of volatile organics in the sample, mg.

n=Total number of phases present in the waste.

Pp=Percent propane in calibration gas (L/L).

Pvc=Percent 1,1-dichloroethylene in calibration gas (L/L).

Qc=Flow rate of calibration gas, L/min.

tc=Length of time standard gas is delivered to the analyzer,

min.

W=Weighted average VO concentration, ppmw.

6.2 Concentration of Carbon, as Methane, in the Calibration

Gas.

Cc=(19.681 x Pp) + (13.121 x Pvc) Eq. 1

6.3 Concentration of Chloride in the Calibration Gas.

Ch=28.998 x Pvc Eq. 2

6.4 Mass of Carbon, as Methane, in a Calibration Run.

mco=Cc x Qc x tc Eq. 3

6.5 Mass of Chloride in a Calibration Run.

mch=Cch x Qc x tc Eq. 4

6.6 FID Response Factor, mg/counts.

Rt=mco/Ac Eq. 5

6.7 ELCD Response Factor, mg/counts.

Rth=mch/Ac Eq. 6

6.8 Mass of Carbon in the Sample.

msc=DRt (As-Ab) Eq. 7

6.9 Mass of Chloride in the Sample.

msh=DRth (As-Ab) Eq. 8

6.10 Mass of Volatile Organics in the Sample.

mvo=msc + msh Eq. 9

6.11 Relative Standard Deviation.

TR22AP94.019

6.12 Mass of Sample.

ms=msf-mst Eq. 11

6.13 Concentration of Volatile Organics in Waste.

C=(mvo x 1000)/ms Eq. 12

6.14 Weighted Average VO Concentration of Multi-phase Waste.

TR22AP94.020

6. 40 CFR Part 60 is amended by adding Method 26A to Appendix A

as follows:

Appendix A--Test Methods

* * * * *

Method 26A--Determination of Hydrogen Halide and Halogen Emissions from

Stationary Sources--Isokinetic Method

1. Applicability, Principle, Interferences, Precision, Bias, and

Stability

1.1 Applicability. This method is applicable for determining

emissions of hydrogen halides (HX) [hydrogen chloride (HCl),

hydrogen bromide (HBr), and hydrogen fluoride (HF)] and halogens

(X2) [chlorine (Cl2) and bromine (Br2)] from

stationary sources. This method collects the emission sample

isokinetically and is therefore particularly suited for sampling at

sources, such as those controlled by wet scrubbers, emitting acid

particulate matter (e.g., hydrogen halides dissolved in water

droplets). [Note: Mention of trade names or specific products does

not constitute endorsement by the Environmental Protection Agency.]

1.2 Principle. Gaseous and particulate pollutants are withdrawn

isokinetically from the source and collected in an optional cyclone,

on a filter, and in absorbing solutions. The cyclone collects any

liquid droplets and is not necessary if the source emissions do not

contain them; however, it is preferable to include the cyclone in

the sampling train to protect the filter from any moisture present.

The filter collects other particulate matter including halide salts.

Acidic and alkaline absorbing solutions collect the gaseous hydrogen

halides and halogens, respectively. Following sampling of emissions

containing liquid droplets, any halides/halogens dissolved in the

liquid in the cyclone and on the filter are vaporized to gas and

collected in the impingers by pulling conditioned ambient air

through the sampling train. The hydrogen halides are solubilized in

the acidic solution and form chloride (Cl-), bromide

(Br-), and fluoride (F-) ions. The halogens have a very

low solubility in the acidic solution and pass through to the

alkaline solution where they are hydrolyzed to form a proton

(H+), the halide ion, and the hypohalous acid (HClO or HBrO).

Sodium thiosulfate is added to the alkaline solution to assure

reaction with the hypohalous acid to form a second halide ion such

that 2 halide ions are formed for each molecule of halogen gas. The

halide ions in the separate solutions are measured by ion

chromatography (IC). If desired, the particulate matter recovered

from the filter and the probe is analyzed following the procedures

in Method 5. [Note: If the tester intends to use this sampling

arrangement to sample concurrently for particulate matter, the

alternative TeflonR probe liner, cyclone, and filter holder

should not be used. The TeflonR filter support must be used.

The tester must also meet the probe and filter temperature

requirements of both sampling trains.]

1.3 Interferences. Volatile materials, such as chlorine dioxide

(ClO2) and ammonium chloride (NH4Cl), which produce halide

ions upon dissolution during sampling are potential interferents.

Interferents for the halide measurements are the halogen gases which

disproportionate to a hydrogen halide and an hypohalous acid upon

dissolution in water. The use of acidic rather than neutral or basic

solutions for collection of the hydrogen halides greatly reduces the

dissolution of any halogens passing through this solution. The

simultaneous presence of both HBr and C12 may cause a positive

bias in the HCl result with a corresponding negative bias in the

C12 result as well as affecting the HBr/Br2 split. High

concentrations of nitrogen oxides (NOx) may produce sufficient

nitrate (NO3-) to interfere with measurements of very low

Br- levels.

1.4 Precision and Bias. The method has a possible measurable

negative bias below 20 ppm HCl perhaps due to reaction with small

amounts of moisture in the probe and filter. Similar bias for the

other hydrogen halides is possible.

1.5 Sample Stability. The collected Cl- samples can be

stored for up to 4 weeks for analysis for HCl and C12.

1.6 Detection Limit. The in-stack detection limit for HCl is

approximately 0.02g per liter of stack gas; the analytical

detection limit for HCl is 0.1 1g/ml. Detection limits for

the other analyses should be similar.

2. Apparatus

2.1 Sampling. The sampling train is shown in Figure 26A-1; the

apparatus is similar to the Method 5 train where noted as follows:

BILLING CODE 6560-50-P

TR22AP94.018

BILLING CODE 6560-50-C

2.1.1 Probe Nozzle. Borosilicate or quartz glass; constructed

and calibrated according to Method 5, Sections 2.1.1 and 5.1, and

coupled to the probe liner using a Teflon union; a

stainless steel nut is recommended for this union. When the stack

temperature exceeds 210 deg.C (410 deg.F), a one-piece glass

nozzle/liner assembly must be used.

2.1.2 Probe Liner. Same as Method 5, Section 2.1.2, except

metal liners shall not be used. Water-cooling of the stainless steel

sheath is recommended at temperatures exceeding 500 deg.C. Teflon

may be used in limited applications where the minimum

stack temperature exceeds 120 deg.C (250 deg.F) but never exceeds

the temperature where Teflon is estimated to become

unstable (approximately 210 deg.C).

2.1.3 Pitot Tube, Differential Pressure Gauge, Filter Heating

System, Metering System, Barometer, Gas Density Determination

Equipment. Same as Method 5, Sections 2.1.3, 2.1.4, 2.1.6, 2.1.8,

2.1.9, and 2.1.10.

2.1.4 Cyclone (Optional). Glass or PTeflon . Use of

the cyclone is required only when the sample gas stream is saturated

with moisture; however, the cyclone is recommended to protect the

filter from any moisture droplets present.

2.1.5 Filter Holder. Borosilicate or quartz glass, or

Teflon filter holder, with a Teflon filter

support and a sealing gasket. The sealing gasket shall be

constructed of Teflon or equivalent materials. The holder

design shall provide a positive seal against leakage at any point

along the filter circumference. The holder shall be attached

immediately to the outlet of the cyclone.

2.1.6 Impinger Train. The following system shall be used to

determine the stack gas moisture content and to collect the hydrogen

halides and halogens: five or six impingers connected in series with

leak-free ground glass fittings or any similar leak-free

noncontaminating fittings. The first impinger shown in Figure 26A-1

(knockout or condensate impinger) is optional and is recommended as

a water knockout trap for use under high moisture conditions. If

used, this impinger should be constructed as described below for the

alkaline impingers, but with a shortened stem, and should contain 50

ml of 0.1 N H2SO4. The following two impingers (acid

impingers which each contain 100 ml of 0.1 N H2SO4) shall

be of the Greenburg-Smith design with the standard tip (Method 5,

Section 2.1.7). The next two impingers (alkaline impingers which

each contain 100 ml of 0.1 N NaOH) and the last impinger (containing

silica gel) shall be of the modified Greenburg-Smith design (Method

5, Section 2.1.7). The condensate, acid, and alkaline impingers

shall contain known quantities of the appropriate absorbing

reagents. The last impinger shall contain a known weight of silica

gel or equivalent desiccant. Teflon impingers are an

acceptable alternative.

2.1.7 Ambient Air Conditioning Tube (Optional). Tube tightly

packed with approximately 150 g of fresh 8 to 20 mesh sodium

hydroxide-coated silica, or equivalent, (Ascarite II has

been found suitable) to dry and remove acid gases from the ambient

air used to remove moisture from the filter and cyclone, when the

cyclone is used. The inlet and outlet ends of the tube should be

packed with at least 1-cm thickness of glass wool or filter material

suitable to prevent escape of fines. Fit one end with flexible

tubing, etc. to allow connection to probe nozzle following the test

run.

2.2 Sample Recovery. The following items are needed:

2.2.1 Probe-Liner and Probe-Nozzle Brushes, Wash Bottles,

Glass Sample Storage Containers, Petri Dishes, Graduated

Cylinder or Balance, and Rubber Policeman. Same as Method 5,

Sections 2.2.1, 2.2.2, 2.2.3, 2.2.4, 2.2.5, and 2.2.7.

2.2.2 Plastic Storage Containers. Screw-cap polypropylene or

polyethylene containers to store silica gel. High-density

polyethylene bottles with Teflon screw cap liners to store impinger

reagents, 1-liter.

2.2.3 Funnels. Glass or high-density polyethylene, to aid in

sample recovery.

2.3 Analysis. For analysis, the following equipment is needed:

2.3.1 Volumetric Flasks. Class A, various sizes.

2.3.2 Volumetric Pipettes. Class A, assortment, to dilute

samples to calibration range of the ion chromatograph (IC).

2.3.3 Ion Chromatograph. Suppressed or nonsuppressed, with a

conductivity detector and electronic integrator operating in the

peak area mode. Other detectors, a strip chart recorder, and peak

heights may be used.

3. Reagents

Unless otherwise indicated, all reagents must conform to the

specifications of the Committee on Analytical Reagents of the

American Chemical Society (ACS reagent grade). When such

specifications are not available, the best available grade shall be

used.

3.1 Sampling.

3.1.1 Water. Deionized, distilled water that conforms to

American Society of Testing and Materials (ASTM) Specification D

1193-77, Type 3 (incorporated by reference as specified in

Sec. 60.17).

3.1.2 Acidic Absorbing Solution, 0.1 N Sulfuric Acid

(H2SO4). To prepare 1 L, slowly add 2.80 ml of

concentrated H2SO4 to about 900 ml of water while

stirring, and adjust the final volume to 1 L using additional water.

Shake well to mix the solution.

3.1.3 Alkaline Absorbing Solution, 0.1 N Sodium Hydroxide

(NaOH). To prepare 1 L, dissolve 4.00 g of solid NaOH in about 900

ml of water and adjust the final volume to 1 L using additional

water. Shake well to mix the solution.

3.1.4 Filter. Teflon mat (e.g., Pallflex

TX40H145) filter. When the stack gas temperature exceeds 210 deg.C

(410 deg.F) a quartz fiber filter may be used.

3.1.5 Silica Gel, Crushed Ice, and Stopcock Grease. Same as

Method 5, Sections 3.1.2, 3.1.4, and 3.1.5, respectively.

3.1.6 Sodium Thiosulfate, (Na2S2O33.5 H2O).

3.2 Sample Recovery

3.2.1 Water. Same as Section 3.1.1.

3.2.2 Acetone. Same as Method 5, Section 3.2.

3.3 Sample Analysis.

3.3.1 Water. Same as Section 3.1.1.

3.3.2 Reagent Blanks. A separate blank solution of each

absorbing reagent should be prepared for analysis with the field

samples. Dilute 200 ml of each absorbing solution (250 ml of the

acidic absorbing solution, if a condensate impinger is used) to the

same final volume as the field samples using the blank sample of

rinse water. If a particulate determination is conducted, collect a

blank sample of acetone.

3.3.3 Halide Salt Stock Standard Solutions. Prepare

concentrated stock solutions from reagent grade sodium chloride

(NaCl), sodium bromide (NaBr), and sodium fluoride (NaF). Each must

be dried at 110 deg.C for 2 or more hours and then cooled to room

temperature in a desiccator immediately before weighing. Accurately

weigh 1.6 to 1.7 g of the dried NaCl to within 0.1 mg, dissolve in

water, and dilute to 1 liter. Calculate the exact

Cl-concentration using Equation 26A-1.

g Cl-/ml=g of NaCl x 103 x 35.453/58.44 Eq.

26A-1

In a similar manner, accurately weigh and solubilize 1.2 to 1.3

g of dried NaBr and 2.2 to 2.3 g of NaF to make 1-liter solutions.

Use Equations 26A-2 and 26A-3 to calculate the Br- and F-

concentrations.

g Br-/ml=g of NaBr x 103 x 79.904/102.90 Eq.

26A-2

g F-/ml=g of NaF x 103 x 18.998/41.99 Eq.

26A-3

Alternately, solutions containing a nominal certified

concentration of 1000 mg/L NaCl are commercially available as

convenient stock solutions from which standards can be made by

appropriate volumetric dilution. Refrigerate the stock standard

solutions and store no longer than 1 month.

3.3.4 Chromatographic Eluent. Same as Method 26, Section 3.2.4.

4. Procedure

Because of the complexity of this method, testers and analysts

should be trained and experienced with the procedures to ensure

reliable results.

4.1 Sampling.

4.1.1 Pretest Preparation. Follow the general procedure given

in Method 5, Section 4.1.1, except the filter need only be

desiccated and weighed if a particulate determination will be

conducted.

4.1.2 Preliminary Determinations. Same as Method 5, Section

4.1.2.

4.1.3 Preparation of Sampling Train. Follow the general

procedure given in Method 5, Section 4.1.3, except for the following

variations:

Add 50 ml of 0.1 N H2SO4 to the condensate impinger,

if used. Place 100 ml of 0.1 N H2SO4 in each of the next

two impingers. Place 100 ml of 0.1 N NaOH in each of the following

two impingers. Finally, transfer approximately 200-300 g of

preweighed silica gel from its container to the last impinger. Set

up the train as in Figure 26A-1. When used, the optional cyclone is

inserted between the probe liner and filter holder and located in

the heated filter box.

4.1.4 Leak-Check Procedures. Follow the leak-check procedures

given in Method 5, Sections 4.4.1 (Pretest Leak-Check), 4.1.4.2

(Leak-Checks During the Sample Run), and 4.1.4.3 (Post-Test Leak-

Check).

4.1.5 Train Operation. Follow the general procedure given in

Method 5, Section 4.1.5. Maintain a temperature around the filter

and (cyclone, if used) of greater than 120 deg.C (248 deg.F).

For each run, record the data required on a data sheet such as

the one shown in Method 5, Figure 5-2. If the condensate impinger

becomes too full, it may be emptied, recharged with 50 ml of 0.1 N

H2SO4, and replaced during the sample run. The condensate

emptied must be saved and included in the measurement of the volume

of moisture collected and included in the sample for analysis. The

additional 50 ml of absorbing reagent must also be considered in

calculating the moisture. After the impinger is reinstalled in the

train, conduct a leak-check as described in Method 5, Section

4.1.4.2.

4.1.6 Post-Test Moisture Removal (Optional). When the optional

cyclone is included in the sampling train or when moisture is

visible on the filter at the end of a sample run even in the absence

of a cyclone, perform the following procedure. Upon completion of

the test run, connect the ambient air conditioning tube at the probe

inlet and operate the train with the filter heating system at least

120 deg.C (248 deg.F) at a low flow rate (e.g., H=1 in.

H2O) to vaporize any liquid and hydrogen halides in the cyclone

or on the filter and pull them through the train into the impingers.

After 30 minutes, turn off the flow, remove the conditioning tube,

and examine the cyclone and filter for any visible moisture. If

moisture is visible, repeat this step for 15 minutes and observe

again. Keep repeating until the cyclone is dry. [Note: It is

critical that this is repeated until the cyclone is completely dry.]

4.2 Sample Recovery. Allow the probe to cool. When the probe

can be handled safely, wipe off all the external surfaces of the tip

of the probe nozzle and place a cap loosely over the tip. Do not cap

the probe tip tightly while the sampling train is cooling down

because this will create a vacuum in the filter holder, drawing

water from the impingers into the holder. Before moving the sampling

train to the cleanup site, remove the probe, wipe off any silicone

grease, and cap the open outlet of the impinger train, being careful

not to lose any condensate that might be present. Wipe off any

silicone grease and cap the filter or cyclone inlet. Remove the

umbilical cord from the last impinger and cap the impinger. If a

flexible line is used between the first impinger and the filter

holder, disconnect it at the filter holder and let any condensed

water drain into the first impinger. Wipe off any silicone grease

and cap the filter holder outlet and the impinger inlet. Ground

glass stoppers, plastic caps, serum caps, Teflon tape,

Parafilm, or aluminum foil may be used to close these

openings. Transfer the probe and filter/impinger assembly to the

cleanup area. This area should be clean and protected from the

weather to minimize sample contamination or loss. Inspect the train

prior to and during disassembly and note any abnormal conditions.

Treat samples as follows:

4.2.1 Container No. 1 (Optional; Filter Catch for Particulate

Determination). Same as Method 5, Section 4.2, Container No. 1.

4.2.2 Container No. 2 (Optional; Front-Half Rinse for

Particulate Determination). Same as Method 5, Section 4.2, Container

No. 2.

4.2.3 Container No. 3 (Knockout and Acid Impinger Catch for

Moisture and Hydrogen Halide Determination). Disconnect the

impingers. Measure the liquid in the acid and knockout impingers to

1 ml by using a graduated cylinder or by weighing it to

0.5 g by using a balance. Record the volume or weight of

liquid present. This information is required to calculate the

moisture content of the effluent gas. Quantitatively transfer this

liquid to a leak-free sample storage container. Rinse these

impingers and connecting glassware including the back portion of the

filter holder (and flexible tubing, if used) with water and add

these rinses to the storage container. Seal the container, shake to

mix, and label. The fluid level should be marked so that if any

sample is lost during transport, a correction proportional to the

lost volume can be applied. Retain rinse water and acidic absorbing

solution blanks and analyze with the samples.

4.2.4 Container No. 4 (Alkaline Impinger Catch for Halogen and

Moisture Determination). Measure and record the liquid in the

alkaline impingers as described in Section 4.2.3. Quantitatively

transfer this liquid to a leak-free sample storage container. Rinse

these two impingers and connecting glassware with water and add

these rinses to the container. Add 25 mg of sodium thiosulfate per

ppm halogen-dscm of stack gas sampled. [Note: This amount of sodium

thiosulfate includes a safety factor of approximately 5 to assure

complete reaction with the hypohalous acid to form a second Cl-

ion in the alkaline solution.] Seal the container, shake to mix, and

label; mark the fluid level. Retain alkaline absorbing solution

blank and analyze with the samples.

4.2.5 Container No. 5 (Silica Gel for Moisture Determination).

Same as Method 5, Section 4.2, Container No. 3.

4.2.6 Container Nos. 6 through 9 (Reagent Blanks). Save

portions of the absorbing reagents (0.1 N H2SO4 and 0.1 N

NaOH) equivalent to the amount used in the sampling train; dilute to

the approximate volume of the corresponding samples using rinse

water directly from the wash bottle being used. Add the same ratio

of sodium thiosulfate solution used in container No. 4 to the 0.1 N

NaOH absorbing reagent blank. Also, save a portion of the rinse

water alone and a portion of the acetone equivalent to the amount

used to rinse the front half of the sampling train. Place each in a

separate, prelabeled sample container.

4.2.7 Prior to shipment, recheck all sample containers to

ensure that the caps are well-secured. Seal the lids of all

containers around the circumference with Teflon tape. Ship

all liquid samples upright and all particulate filters with the

particulate catch facing upward.

4.3 Sample Preparation and Analysis. Note the liquid levels in

the sample containers and confirm on the analysis sheet whether or

not leakage occurred during transport. If a noticeable leakage has

occurred, either void the sample or use methods, subject to the

approval of the Administrator, to correct the final results.

4.3.1 Container Nos. 1 and 2 and Acetone Blank (Optional;

Particulate Determination). Same as Method 5, Section 4.3.

4.3.2 Container No. 5. Same as Method 5, Section 4.3 for silica

gel.

4.3.3 Container Nos. 3 and 4 and Absorbing Solution and Water

Blanks. Quantitatively transfer each sample to a volumetric flask or

graduated cylinder and dilute with water to a final volume within 50

ml of the largest sample.

4.3.3.1 The IC conditions will depend upon analytical column

type and whether suppressed or nonsuppressed IC is used. Prior to

calibration and sample analysis, establish a stable baseline. Next,

inject a sample of water, and determine if any Cl-, Br-,

or F- appears in the chromatogram. If any of these ions are

present, repeat the load/injection procedure until they are no

longer present. Analysis of the acid and alkaline absorbing solution

samples requires separate standard calibration curves; prepare each

according to Section 5.2. Ensure adequate baseline separation of the

analyses.

4.3.3.2 Between injections of the appropriate series of

calibration standards, inject in duplicate the reagent blanks and

the field samples. Measure the areas or heights of the Cl-,

Br-, and F- peaks. Use the average response to determine

the concentrations of the field samples and reagent blanks using the

linear calibration curve. If the values from duplicate injections

are not within 5 percent of their mean, the duplicate injection

shall be repeated and all four values used to determine the average

response. Dilute any sample and the blank with equal volumes of

water if the concentration exceeds that of the highest standard.

4.4 Audit Sample Analysis. Audit samples must be analyzed

subject to availability.

5. Calibration

Maintain a laboratory log of all calibrations.

5.1 Probe Nozzle, Pitot Tube, Dry Gas Metering System, Probe

Heater, Temperature Gauges, Leak-Check of Metering System, and

Barometer. Same as Method 5, Sections 5.1, 5.2, 5.3, 5.4, 5.5, 5.6,

and 5.7, respectively.

5.2 Ion Chromatograph. To prepare the calibration standards,

dilute given amounts (1.0 ml or greater) of the stock standard

solutions to convenient volumes, using 0.1 N H2SO4 or 0.1

N NaOH, as appropriate. Prepare at least four calibration standards

for each absorbing reagent containing the three stock solutions such

that they are within the linear range of the field samples. Using

one of the standards in each series, ensure adequate baseline

separation for the peaks of interest. Inject the appropriate series

of calibration standards, starting with the lowest concentration

standard first both before and after injection of the quality

control check sample, reagent blanks, and field samples. This allows

compensation for any instrument drift occurring during sample

analysis. Determine the peak areas, or height, of the standards and

plot individual values versus halide ion concentrations in

g/ml. Draw a smooth curve through the points. Use linear

regression to calculate a formula describing the resulting linear

curve.

6. Quality Control

Same as Method 5, Section 4.4.

7. Quality Assurance

7.1 Applicability. When the method is used to demonstrate

compliance with a regulation, a set of two audit samples shall be

analyzed.

7.2 Audit Procedure. The currently available audit samples are

chloride solutions. Concurrently analyze the two audit samples and a

set of compliance samples in the same manner to evaluate the

technique of the analyst and the standards preparation. The same

analyst, analytical reagents, and analytical system shall be used

both for compliance samples and the Environmental Protection Agency

(EPA) audit samples.

7.3 Audit Sample Availability. Audit samples will be supplied

only to enforcement agencies for compliance tests. Audit samples may

be obtained by writing the Source Test Audit Coordinator (MD-77B),

Quality Assurance Division, Atmospheric Research and Exposure

Assessment Laboratory, U.S. Environmental Protection Laboratory,

Research Triangle Park, NC 27711 or by calling the Source Test Audit

Coordinator (STAC) at (919) 541-7834. The request for the audit

samples should be made at least 30 days prior to the scheduled

compliance sample analysis.

7.4 Audit Results. Calculate the concentrations in mg/dscm

using the specified sample volume in the audit instructions. Include

the results of both audit samples, their identification numbers, and

the analyst's name with the results of the compliance determination

samples in appropriate reports to the EPA regional office or the

appropriate enforcement agency. (NOTE: Acceptability of results may

be obtained immediately by reporting the audit results in mg/dscm

and compliance results in total g HCl/sample to the

responsible enforcement agency.) The concentrations of the audit

samples obtained by the analyst shall agree within 10 percent of the

actual concentrations. If the 10 percent specification is not met,

reanalyze the compliance samples and audit samples, and include

initial and reanalysis values in the test report. Failure to meet

the 10 percent specification may require retests until the audit

problems are resolved.

8. Calculations

Retain at least one extra decimal figure beyond those contained

in the available data in intermediate calculations, and round off

only the final answer appropriately.

8.1 Nomenclature. Same as Method 5, Section 6.1. In addition:

1 BX-=Mass concentration of applicable absorbing solution

blank, g halide ion (Cl-, Br-, F-)/ml, not

to exceed 1 g/ml which is 10 times the published analytical

detection limit of 0.1 g/ml. (It is also approximately 5

percent of the mass concentration anticipated to result from a one

hour sample at 10 ppmv HCl.)

C=Concentration of hydrogen halide (HX) or halogen (X2), dry

basis, mg/dscm.

mHX=Mass of HCl, HBr, or HF in sample, g.

mX2=Mass of Cl2 or Br2 in sample, g.

SX--=Analysis of sample, g halide ion (Cl-,

Br-, F-)/ml.

VS=Volume of filtered and diluted sample, ml.

8.2 Average Dry Gas Meter Temperature and Average Orifice

Pressure Drop. See data sheet (Figure 5-2 of Method 5).

8.3 Dry Gas Volume. Calculate Vm(std) and adjust for

leakage, if necessary, using the equation in Section 6.3 of Method

5.

8.4 Volume of Water Vapor and Moisture Content. Calculate the

volume of water vapor Vw(std) and moisture content Bws

from the data obtained in this method (Figure 5-2 of Method 5); use

Equations 5-2 and 5-3 of Method 5.

8.5 Isokinetic Variation and Acceptable Results. Use Method 5,

Sections 6.11 and 6.12.

8.6 Acetone Blank Concentration, Acetone Wash Blank Residue

Weight, Particulate Weight, and Particulate Concentration. For

particulate determination.

8.7 Total g HCl, HBr, or HF Per Sample.

mHX=K Vs (SX--BX-) Eq. 26A-4

where:

KHC1 = 1.028 (g HCl/g-mole)/(g

Cl-/g-mole).

KHBr=1.013 (g HBr/g-mole)/(g

Br-/g-mole).

KHF=1.053 (g HF/g-mole)/(g

F-/g-mole).

8.8 Total g Cl2 or Br2 Per Sample.

mX2= Vs (SX--BX-) Eq. 26A-5

8.9 Concentration of Hydrogen Halide or Halogen in Flue Gas.

C=K mHX,X2/Vm(std) Eq. 26A-6

where: K=1010- mg/g

8.10 Stack Gas Velocity and Volumetric Flow Rate. Calculate the

average stack gas velocity and volumetric flow rate, if needed,

using data obtained in this method and the equations in Sections 5.2

and 5.3 of Method 2.

9. Bibliography

1. Steinsberger, S. C. and J. H. Margeson. Laboratory and Field

Evaluation of a Methodology for Determination of Hydrogen Chloride

Emissions from Municipal and Hazardous Waste Incinerators. U.S.

Environmental Protection Agency, Office of Research and Development.

Publication No. 600/3-89/064. April 1989. Available from National

Technical Information Service, Springfield, VA 22161 as PB89220586/

AS.

2. State of California Air Resources Board. Method 421--

Determination of Hydrochloric Acid Emissions from Stationary

Sources. March 18, 1987.

3. Cheney, J.L. and C.R. Fortune. Improvements in the

Methodology for Measuring Hydrochloric Acid in Combustion Source

Emissions. J. Environ. Sci. Health. A19(3): 337-350. 1984.

4. Stern, D.A., B.M. Myatt, J.F. Lachowski, and K.T. McGregor.

Speciation of Halogen and Hydrogen Halide Compounds in Gaseous

Emissions. In: Incineration and Treatment of Hazardous Waste:

Proceedings of the 9th Annual Research Symposium, Cincinnati, Ohio,

May 2-4, 1983. Publication No. 600/9-84-015. July 1984. Available

from National Technical Information Service, Springfield, VA 22161

as PB84-234525.

5. Holm, R.D. and S.A. Barksdale. Analysis of Anions in

Combustion Products. In: Ion Chromatographic Analysis of

Environmental Pollutants, E. Sawicki, J.D. Mulik, and E.

Wittgenstein (eds.). Ann Arbor, Michigan, Ann Arbor Science

Publishers. 1978. pp. 99-110.

[FR Doc. 94-9574 Filed 4-21-94; 8:45 am]

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