P.1 

OAR Box 1338 

Prepped by Ollie Stewart 

Document Number: 

52) F. R February 13, 1991 

Docket Number: 

A-89-11 

Printed 6/17/2008 1:48:08 PM Sheet 52 of 105 
P.2 

"* 5$%8> Federal Register / Vol.'56, No.J 30v/-Wediesday;'Feb'ruaryt 13, )1991J/ Rules arid;Regulations 

delayed, timely notice will be published 

in the Federal Register. 

ADDRESSES: Copies of the state 

submittal for this action are available 

for public inspection during normal 

business hours at: the Environmental 

Protection Agency, Region VII, Air 

Branch, 726 Minnesota Avenue, Kansas 

City, Kansas 66101; Public Information 

Reference Unit, Environmental 

Protection Agency* 401 M Street SW., 

Washington, DC 20460; Environmental 

Protection Division, Iowa Department of 

Natural Resources, Wallace State Office 

Building, 900 East Grand, Des Moines, 

Iowa 50319. 

FOR FURTHER INFORMATION CONTACT: 

Wayne Kaiser at (913) 551-7603 (FTS 

276-7603). 

SUPPLEMENTARY INFORMATION: On 

October 17,1988, EPA revised the 

prevention of significant deterioration 

(PSD) regulations at 40 CFR 52.21 (see 53 

FR 40656) for nitrogen oxides. These 

regulations establish the maximum 

increase in ambient nitrogen dioxide 

concentrations allowed in an area above 

the baseline concentration; these 

maximum allowable increases are 

called increments. The intended effect of 

these regulations is to require all 

applicants for major new stationary 

sources and major modifications 

emitting nitrogen oxides to account for 

and, if necessary, restrict emissions so 

as not to cause or contribute to 

exceedances of the increment. 

On November 20,1990, the IDNR 

submitted an amendment to chapter 

22.4(455B), "Special Requirements for 

Major Stationary Sources Located in 

Areas Designated Attainment or 

Unclassified (PSD)," which incorporates 

by reference the revisions to 40 CFR part 

52.21, effective October 17,1988. The 

state rule was effective November 21-

1990. The state also provided a 

demonstration that it meets the . 

conditions for approval of adoption of 

the NO2 increment program as detailed 

in the EPA guidance memorandum on 

the subject dated August 17,1990. 

The above memorandum described 

specific conditions for EPA approval of 

a state's adoption of the NOx increment 

rule. Those conditions pertained to 

regulatory language; increment 

consumption analysis, increment 

consumption for the transition period, 

and legal authority. EPA has evaluated 

the state's submittal in accordance with 

the August 17,1990, guidance and finds 

that the state submittal is acceptable. 

EPA is publishing this action without 

prior proposal because the Agency 

views this as a noncontroversial 

amendment and anticipates no adverse 

comments. This action will be effective 

April 15,1991, unless, within 30 days of 

its publication, notice is received that 

adverse or critical comments will be 

submitted. 

If such notice is received, this action 

will be withdrawn before the effective 

date by publishing two subsequent 

notices. One notice will withdraw the 

final action and another will begin a 

new rulemaking by announcing a 

proposal of the action and establishing a 

comment period. If no such comments 

are received, the public is advised that 

this action will be effective April 15, 

1991. 

EPA Action: EPA is taking final action 

to approve a revision to Iowa rule 567-

22.4(455B) which, adopts by reference the 

PSD NOx requirements of 40 CFR 52.21 

at 53 FR 40656 (October 17,1988). 

Nothing in this action should be 

construed as permitting or allowing or 

establishing a precedent for any future 

request for revision to any SIP. Each 

request for revision to the SIP shall be 

considered separately in light of specific 

technical, economic, and environmental 

factors and in relation to relevant 

statutory and regulatory requirements. 

Under 5 U.S.C: 605(b), I certify that this 

SIP revision will not have a significant 

economic impact on a substantial 

number of small entities (See 46 FR 

8709). 

This action has been classified as a 

Table 3 action by the Regional 

Administrator under the procedures 

published in the Federal Register on 

January 19,1989 (54 FR 2214-2225). On 

January 6,1989, the Office of 

Management and Budget waived Tables 

2 and 3 SIP revisions (54 FR 2222) from 

' the requirements of Section 3 of 

Executive Order 12291 until April 1991. 

Under section 307(b)(1) of the Act, 

petitions for judicial review of this 

action must be filed in the U.S. Court of 

Appeals for the appropriate circuit by 

April 15,1991. This action may not be . 

challenged later in proceedings to 

enforce its requirements. (See section 

307(b)(2).) 

The Agency has reviewed this request 

for revision of the federally approved 

SIP for conformance with the provisions 

of the 1990 Amendments enacted on 

November 15,1990. The Agency has 

determined that this action conforms 

with those requirements irrespective of 

the fact that the adoption of the revision 

by the state preceded the date of 

enactment. 

List of Subjects in 40 CFR Part 52 

Air pollution control, Incorporation by 

reference, Intergovernmental relations, 

Nitrogen dioxide, Particulate matter, 

Sulfur oxides. 

Dated: January 28,1991. 

Morris Kay, 

Regional Administrator. 

40 CFR part 52, subpart Q, is amended 

as follows: 

PART 52—[AMENDED) 

1. The authority citation for part 52 

continues to read as follows: 

Authority: 42 U.S.C. 7401-7642. 

2. Section 52.820 is amended by 

adding paragraph (c)(53) to read as 

follows: 

§ 52.820 Identification of plan. 

**** * 

.'(c)* * * 

, (53) Revised chapter 22, rule 

22.4(455B), submitted on November 8, 

1990, incorporates by reference revised 

EPA PSD rules pertaining to NOx 

increments, 

(i) Incorporation by reference 

(A) Amendment to chapter 22, 

"Controlling Pollution," Iowa 

Administrative Code, subrule 22.4, 

adopted by the Environmental 

Protection Commission on October 17, 

1990, effective November 21,1990. 

(ii) Additional material 

(A) Letter from the state dated 

November 8,1990, pertaining to NO„ 

rules and analysis which certifies the 

material was adopted by the state on 

October 17,1990. 

[FR Doc. 91-3451 Filed 2-12-91; 8:45 am] 

BILLING. CODE 6560-50-M 

40 CFR Part 60 

[AD-FRL-3867-1] 

>/ 

Standards of Performance for New 

Stationary Sources; Addition of 

Methods for Measurement of 

Polychlorinated Dibenzo-p-Dioxins, 

Polychlorinated Dibenzofurans, and 

Hydrogen Chloride Emissions From 

Stationary Sources 

AGENCY: Environmental Protection 

Agency (EPA). 

ACTION: Final rule. 

SUMMARY: The purpose of this action is 

to add Method 23, "Determination to 

Polychlorinated Dibenzo-p-Dioxins 

(PCDD's) and Polychlorinated 

Dibenzofurans (PCDF's) from Stationary 

Sources," and Method 26, 

"Determination of Hydrogen Chloride 

Emissions from Stationary Sources" to 

appendix A of 40 CFR part 60. These 

methods are being promulgated to 

determine compliance with subparts Ca 

and Ea of part 60. 
P.4 

Federal Register / Vol. 56,!• No. '30 7 Wednesday, February 13.. 1991 / Rules and Regulatipns 5759 

DATES: Effective Date: February 13, 

1991. 

Judicial Review: Under section 

307(b)(1) of the Clean Air Act, judicial 

review of the actions taken by this 

notice is available only by 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 Clean Air Act, the 

requirements that are the subject of 

today's notice may not be challenged 

later in civil or criminal proceedings 

brought by EPA to enforce these • 

requirements. 

ADDRESSES: Background Information 

Document. The Background Information 

Document for the promulgated test 

methods may be obtained from Gary 

McAlister or Roger Shigehara, MD-19, 

U.S. EPA, Research Triangle Park. North 

Carolina 27711, telephone number (919) 

541-1062. Please refer to "Summary of 

Comments and Responses for Methods 

23 and 26." 

Docket Docket Number A-89-11, 

containing material relevant to this 

rulemaking, is available for public 

inspection and copying between 8:30 

a.m. and 3:30 p.m. Monday through 

Friday, at EPA's Air Docket Section, 

room M-1500,1st Floor, Waterside Mall, 

401M Street SW., Washington, DC 

20460. A reasonable fee may be charged 

for copying. 

FOR FURTHER INFORMATION CONTACT: 

Gary McAlister or Roger Shigehara, 

Emission Measurement Branch (MD-19), 

Technical Support Division, U.S. 

Environmental Protection Agency, 

ResearchTriangle Park, North Carolina 

27711, telephone number (919) 541-1062. 

SUPPLEMENTARY INFORMATION: 

I. The Rulemaking 

Under Subparts Ca and Ea, the EPA is 

regulating emissions from municipal 

waste combustors (MWC's) including 

setting emission limits for 

polychlorinated dibenzo-p-dioxins 

(PCDD's), polychlorinated 

dibenzofurans (PCDF's), and 

hydrochloric acid (HCl). There are 

presently no methods published in 40 

CFR part 60, appendix A, to measure 

any of these pollutants. This action 

would promulgate one method to 

measure the PCDD's and PCDF's and 

another method to measure the HCl. 

Summary of Reference Methods 

Method 23 is used to measure the 

emission of PCDD's and PCDF's from 

MWC's. A sample is withdrawn 

isokinetically from the stack through a 

probe, a filter, and a trap packed with a 

solid adsorbent. The PCDD's and 

PCDF's are collected in the probe, on the 

filter, and on the solid adsorbent. The 

PCDD's and PCDF's are extracted from 

the particulate matter and the adsorbent 

with a hot organic solvent. The 

extracted PCDD's and PCDF's are 

separated by capillary gas 

chromatography, and then, each isomer 

is identified and measured with mass 

spectrometry (GC/MS). The total 

PCDD's and PCDF's are the sum of the 

individual isomers. Toxicity factors are 

not used in the calculation. 

Method 26 is used to measure the 

emission of HCl from MWC's. A sample 

is withdrawn at a constant rate from the 

stack through a probe and impingers 

filled with a dilute acid. The HCl is 

collected in the implinger solution. The 

chloride ion is separated by ion 

chromatography and measured by a 

conductivity detector. 

Background 

In 1983, the American Society of 

Mechanical Engineers (ASME) 

recognized that the testing for PCDD's 

and PCDF's needed to be standardized. 

In February of 1984, the ASME convened 

a committee of government 

representatives, testing consultants, 

equipment manufacturers, and 

. incinerator operators to write a 

standard test procedure for PCDD's and 

PCDFs. This was eventually distributed 

as a draft ASME protocol in December 

of 1984. The procedure that we are 

promulgating was derived from this 

draft ASME protocol. There are some 

changes in the quality assurance (QA) 

requirements and the solvents used to 

recover the sample in the promulgated 

method. Because more labeled 

compounds are available, the method 

will require additional labeled internal 

standards and surrogate compounds 

which will provide better representation 

of the entire range of PCDD's and 

PCDF's. The filter and solid adsorbent 

are extracted in the laboratory with 

toluene to assure a high PCDD and 

PCDF recovery efficiency. Additionally 

the proposed sample recovery solvents 

used for rinsing the sample train 

glassware in the field would be acetone 

followed by methylene chloride with a 

final quality assurance rinse using 

toluene. However, the results from the 

toluene rinse are not used in calculating 

the total PCDD and PCDF emissions. 

EPA will continue to review the toluene 

field rinse quality assurance results and 

continue to evaluate the desirability of 

replacing methylene chloride with 

toluene for field rinsing sample 

glassware. 

II. Public Participation 

The opportunity to hold a public 

hearing at 10 a.m. on February 7,1990 

was presented, but no one requested a 

hearing. The public comment period was 

from December 20,1989 to March 5, 

1990. 

III. Significant Comments and Changes 

to the Proposed Rulemaking 

Thirteen comment letters were 

received on the proposed test methods. 

These comments have been carefully 

considered and, where deemed 

appropriate by the Administrator, 

changes have been made in the 

proposed test methods. A detailed 

discussion of these comments is 

contained in the background document 

entitled, "Summary of Comments and 

Responses for Methods 23 and 26" 

which is referred to in the ADDRESSES 

section of this preamble. 

Several commenters thought that, 

there were not enough stack sampling 

organizations that were experienced 

with Method 23 to avoid major delays in 

securing sampling and analysis 

contractors. Many of these commenters 

also thought that there would not be an 

adequate supply of calibration 

standards and audit samples. We 

believe that the number of tests required 

immediately after promulgation of the 

regulation will not exceed the 

capabilities of the available sampling 

and analytical laboratories and that 

there will be an adequate supply of 

labeled standards and audit samples. 

The full effect of the testing 

requirements for the new and existing 

sources will not be felt for about five 

years. We believe that this is adequate 

time to allow for the necessary 

expansion of testing capabilities. 

Some commenters requested 

alternative procedures or methods to 

Method 23. While testers always have 

the option of requesting alternative 

methods, requests should be submitted 

after the method becomes final. Any 

request should be in writing and should 

be accompanied by any supporting data. 

Many commenters thought that the 

gas chromatography columns specified 

in Method 23 were not the most 

appropriate choice. The column 

requirements in the method have been 

revised to allow the tester to use any 

column system provided that the tester 

can demonstrate through calibration and 

perfonnance checks that the columns 

provide the necessary isomer 

separation. 

One commenter thought that Method 

26 should be modified to allow 

isokinetic sampling so that it could be 
P.5 

5760, , Federal Register / Vol. 56, .No. 30. /, Wedngs-day, .-February* 13,, 199^ / Rule3* ftjidj Regulations 

applied to sources where hydrochloric 

acid aerosols are present. We agree that 

isokinetic sampling; may be important at 

sources other than MWC's. We have 

compared Method 26 and an isokinetic 

sampling train and found that they 

generally give similar results at stack 

concentrations above 20 PPM. At lower 

concentrations the isokinetic sampling 

train seems to have a negative bias. We 

are continuing to investigate this 

problem, and may be able to approve an 

alternative method using isokinetic 

sampling for future use. 

Another commenter wanted EPA to 

develop a QA audit sample for Method 

26. An audit sample is being developed 

and will be available for validating the 

results of compliance tests. 

IV. Administrative 

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)). 

Under Executive Order 12291, EPA 

must judge whether a regulation is 

"major" and, therefore, subject to the 

requirement of a regulatory impact 

analysis. The Agency has determined 

that this rulemaking would not result in 

any of the adverse economic effects set 

forth in Section 1 of the Order as 

grounds for finding a "major rule;" The 

Agency has, therefore, concluded that 

this regulation is not a "major rule" 

under Executive Order 12291. 

The Regulatory Flexibility Act (RFA) 

of 1980 requires the identification of . 

potentially adverse impacts of Federal 

regulations upon small business entities. 

The Act specifically requires the 

completion of an RFA analysis in those 

.instances where small business impacts 

are possible. Because this rulemaking, 

imposes no adverse economic impacts, 

an analysis has not been conducted. 

Pursuant to the provisions of 5 U.S.C. 

605(b), I hereby certify that this 

promulgated rule will not have an 

economic impact on small entities 

because no additional costs will be 

incurred from this action. 

This rule does not contain any 

information collection requirements 

currently approved by OMB review 

under the Paperwork Reduction Act of 

1980, 44 U.S.C. 3501 et seq. 

List of Subjects in 40 CFR Part 60 

Air pollution control, Municipal waste 

combustors, Polychlorinated dibenzo-pdioxins, Polychlorinated dibenzofurans, 

Hydrogen chloride. 

Dated: January 11,1991. 

F. Henry Habicht, 

Acting Administrator. 

Title 40, part 60 of the Code of Federal 

Regulations is amended as follows: 

PART 60—[AMENDED] 

1. The authority citation for part 60 

continues to read as follows: 

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

and 7601. 

2. By adding in numerical order 

Methods 23 and 26 to appendix A as 

follows: 

Appendix A—Reference Methods 

Method 23—Determination of Polychlorinated 

Dibenzo-p-Dioxins and Polychlorinated 

Dibenzofurans From Stationary Sources 

1. Applicability, and Principle 

1.1 Applicability. This method is 

applicable to the determination of 

polychlorinated dibenzo-p-dioxins (PCDD's) 

and polychlorinated dibenzofurans (PCDF's) 

from stationary sources. 

1.2 Principle. A sample is withdrawn from 

the gas stream isokinetically and collected'in 

the sample probe, on a glass fiber filter, and 

on a packed column of adsorbent material. 

The sample cannot be separated into a 

particle vapor fraction.The PCDD's and 

PCDF's are extracted from the. sample, 

separated by high resolution gas 

chromatography, and measured by high 

resolution mass spectrometry. 

2. Apparatus 

2.1 Sampling. A schematic of the sampling 

train used in this method, is shown in Figure 

23-1. Sealing greases may not be used in 

assembling the train. The train is identical, to 

that described in section 2.1 of Method 5 of' 

this appendix* with the following additions: 

BILLING. CODE 6560-50-12 
tv*w — "" T ' 

t 

Gas 

Flow 

^ Stack Wall 

\ Heated Glass Liner 

\ 

s -s"Type 

^ Pitot Tube 

Temperature 

Sensor 

Condenser 

Temperature 

Sensor 

Inclined 

Manometer 

Recirculation 

Pump 

Empty 

Dry Gas 

Meter 

r Calibrated 

Gas -1 Orifice _ 

Exit V *? 

Inclined ^i 

Manometer 

Figure 23.1 Sampling train 

BILLING CODE 6560-5IM 
5762 Federal Register / Vol. 56, No. 30 / Wednesday, February 13, 1991' / Rules and-Regulations 

P.7 77H 

2.1.1 Nozzle. The nozzle shall be made of 

nickel, nickel-plated stainless steel, quartz, or 

borosilicate glass. 

2.1.2 Sample Transfer Lines. The sample 

transfer lines, if needed, shall be heat traced, 

heavy walled TFE (% in. OD with Vfe in. wall) 

with connecting fittings that are capable of 

forming leak-free, vacuum-tight connections 

without using sealing greases. The line shall 

be as short as possible and must be 

maintained at 120 °C 

2.1.1 Filter Support. Teflon or Tefloncoated wire. 

2.1.2 Condenser. Glass, coil type with 

compatible fittings. A schematic diagram is 

shown in Figure 23-2. 

2.1.3 Water Bath. Thermostatically 

controlled to maintain the gas temperature 

exiting the condenser at <20 °C (68 °F). 

2.1.4 Adsorbent Module. Glass container 

to hold the solid adsorbent. A shematic 

diagram is shown in Figure 23-2. Other 

physical configurations of the: resin trap/ 

condenser assembly are acceptable. The 

connecting fittings shall form leak-free, 

vacuum tight seals. No sealant greases shall 

be used in the sampling; train. A coarse glass 

frit is included to retain- the adsorbent. 

2.2 Sample Recovery. 

2.2.1 Fitting Caps. Ground glass, Teflon 

tape, or aluminum foil (Section 2.2.6) to cap 

off the. sample exposed sections of the train. 

2.2.2 Wash Bottles. Teflon, 500-ml. 

2.2.3 Probe-Liner Probe-Nozzle, and FilterHolder Brushes. Inert bristle brushes with 

precleaned stainless steel or Teflon handles. 

The probe brush shall have extensions of 

stainless steel or Teflon, at least as long Ss 

the probe.. The:brushes shall be properly 

sized and shaped to brush out the nozzle, 

probe liner, and transfer line, if used. 

BILLING CODE 6560-50-M 
W* -» ' 

I i p ,m II.. . i» | f i ^, < •*ir—^^^^F - T " • •»' W "CH w -cm 

Condenser Sorbent Trap 

Flue Gas Flow * 

$20/1 6 

Water Jacket Cooling Coil Glass Wool Plug Water Jacket XAD - 2 G

Figure 23.2. Condenser and adsorbent trap 

BILUNQ CODE 6560-SO-C 
P.9 

5764 Federal Register / Vol. 56, No. 30 / Wednesday, February 13, 1991 / Rules and Regulations 

2.2.4 Filter Storage Container. Sealed 

filter holder, wide-mouth amber glass jar with 

Teflon-lined cap, or glass petri dish. 

2.2.5 Balance. Triple beam. 

2.2.8 Aluminum Foil. Heavy duty, hexanerinsed. 

2.2.7 Metal Storage Container. Air tight 

container to store silica gel. 

2.2.8 Graduated Cylinder. Glass, 250-ml 

with 2-ml graduation. 

2.2.9 Glass Sample Storage Container. 

Amber glass bottle for sample glassware 

washes, 500- or 1000-ml, with leak free 

Teflon-lined caps. 

2.3 Analysis. 

2.3.1 Sample Container. 125- and 250-ml 

flint glass bottles with Teflon-lined caps. 

2.3.2 Test Tube. Glass. 

2.3.3 Soxhlet Extraction Apparatus. 

Capable of holding 43 x 123 mm extraction 

thimbles. 

2.3.4 Extraction Thimble. Glass, 

precleaned cellulosic, or glass fiber. 

2.3.5 Pasteur Pipettes. For preparing liquid 

chromatographic columns. 

2.3.6 Reacti-viais. Amber glass, 2-ml, 

silanized prior to use. 

2.3.7 Rotary Evaporator. Buchi/Brinkman 

RF-121 or equivalent. 

2.3.8 Nitrogen Evaporative Concentrator. 

N-Evap Analytical Evaporator Model III or 

equivalent. 

2.3.9 Separatory Funnels. Glass, 2-liter. 

2.3.10 Gas Chromatograph. Consisting of 

the following components: 

2.3.10.1 Oven. Capable of maintaining the 

separation column at the proper operating 

temperature ± °C and performing 

programmed increases in temperature at 

rates of at least 40 °C/min. 

2.3.10.2 Temperature Gauge. To monitor 

column oven, detector, and exhaust 

temperatures ± 1 °C. 

2.3.10.3 Flow System. Gas metering 

system to measure sample, fuel, combustion 

gas, and carrier gas flows. 

2.3.10.4 Capillary Columns. A fused silica 

column, 60 X 0.25 mm inside diameter (ID), 

coated with DB-5 and a fused silica column, 

30 m X 0.25 mm ID coated with DB-225. 

Other column systems may be used provided 

that the user is able to demonstrate using 

calibration and performance checks that the 

column system is able to meet the 

specifications of section 6.1.2.2. 

2.3.11. Mass Spectrometer. Capable of 

routine operation at a resolution of 1:10000 

with a stability of ± 5 ppm. 

2.3.12 Data System. Compatible with the 

mass spectrometer and capable of monitoring 

at least five groups of 25 ions. 

2.3.13 Analytical Balance. To measure 

within 0.1 mg. 

3. Reagents 

3.1 Sampling. 

3.1.1 Filters. Glass fiber filters, without 

organic binder, exhibiting at least 99.95 

percent efficiency (<0.05 percent 

penetration) on 0.3-micron dioctyl phthalate 

smoke particles. The filter efficiency test 

shall be conducted in accordance with ASTM 

Standard Method D 2986-71 (Reapproved 

1978) (incorporated by reference—see 

* 60.17). 

3.1.1.1 Precleaning. All filters shall be 

cleaned before their initial use. Place a glass 

extraction thimble and 1 g of silica gel and a 

plug of glass wool into a Soxhlet apparatus, 

charge the apparatus with toluene, and reflux 

for a minimum of 3 hours. Remove the toluene 

and discard it, but retain the silica gel. Place 

no more than 50 filters in the thimble onto the 

silica gel bed and top with the cleaned glass 

wool. Charge the Soxhlet with toluene and 

reflux for 18 hours. After extraction, allow 

the Soxhlet to cool, remove the filters, and 

dry them under a clean N2 stream. Store the 

filters in a glass petri dish sealed with Teflon 

tape. 

3.1.2 Adsorbent Resin. Amberlite XAD-2 

resin. Thoroughly cleaned before initial use. 

3.1.2.1 Cleaning Procedure. This 

procedure may be carried out in a giant 

Soxhlet extractor. An all-glass filter thimble 

containing an extra-course frit is used for 

extraction of XAD-2. The frit is recessed 10-

15 mm above a crenelated ring at the bottom 

of the thimble to facilitate drainage. The resin 

must be carefully retained in the extractor 

cup with a glass wool plug and a stainless 

steel ring because it floats on methylene 

chloride. This process involves sequential 

extraction in the following order. 

Solvent 

Water 

Water 

Methanol 

Methylene Chloride 

Procedure 

in a beaker, rinse once 

with water, and 

discard. Fill with water 

a second time, let 

stand overnight, and 

discard. 

Extract with water for 8 

hours. 

3.1.2.2 Drying. 

3.1.2.2.1 Drying Column. Pyrex pipe, 10.2 

cm ID by 0.6 m long, with suitable retainers. 

3.1.2.2.2 Procedure. The adsorbent must 

be dried with clean inert gas. Liquid nitrogen 

from a standard commercial liquid nitrogen 

cylinder has proven to be a reliable source of 

large volumes of gas free from organic 

contaminants. Connect the liquid nitrogen 

cylinder to the column by a length of cleaned 

copper tubing, 0.95 cm ID, coiled to pass 

through a heat source. A convenient heat 

source is a water-bath heated from a steam 

line. The final nitrogen temperature should 

only be warm to the touch and not over 40 °C. 

Continue flowing nitrogen through the 

adsorbent until all the residual solvent is 

removed. The flow rate should be sufficient 

to gently agitate the particles but not so 

excessive as the cause the particles to 

fracture. 

3.1.2.3 Quality Control Check. The 

adsorbent must be checked for residual 

toluene. 

3.1.2.3.1 Extraction. Weigh 1.0 g sample of 

dried resin into a small vial, add 3 ml of 

toluene, cap the vial, and shake it well. 

3.1.2.3.2 Analysis. Inject a 2 fil sample of 

the extract into a gas chromatograph 

operated under the following conditions: 

Column: 6 ft X Vs in stainless steel 

containing 10 percent OV-101 on 100/120 

Supelcoport. 

Carrier Gas: Helium at a rate of 30 ml/min. 

Detector: Flame ionization detector 

operated at a sensitivity of 4 X 10— " A/ 

mV. 

Injection Port Temperature: 250 °C. 

Detector Temperature: 305 °C. 

Oven Temperature: 30 °C for 4 min; 

programmed to rise at 40 °C/min until it 

reaches 250 °C; return to 30 °C after 17 

minutes. 

Compare the results of the analysis to the 

results from the reference solution. Prepare 

the reference solution by injection 2.5 /il of 

methylene chloride into 100 ml of toluene. 

This corresponds to 100 jtg of methylene 

chloride per g of adsorbent. The maximum 

acceptable concentration is 1000 fig/g of 

adsorbent. If the adsorbent exceeds this 

level, drying must be continued until the 

excess methylene chloride is removed. 

3.1.2.4 Storage. The adsorbent must be 

used within 4 weeks of cleaning. After 

cleaning, it may be stored in a wide mouth 

amber glass container with a Teflon-lined cap 

or placed in one of the glass adsorbent 

modules tightly sealed with glass stoppers. If 

precleaned adsorbent is purchased in sealed 

containers, it must be used within 4 weeks 

after the seal is broken. 

3.1.3 Glass Wool. Cleaned by sequential 

immersion in three aliquots of methylene 

chloride, dried in a 110 °C oven, and stored in 

a methylene chloride-washed glass jar with a 

Teflon-lined screw cap. 

3.1.4 Water. Deionized distilled and 

stored in a methylene chloride-rinsed glass 

container with a Teflon-lined screw cap. 

3.1.5 Silica Gel. Indicating type, 6 to 16 

mesh. If previously used, dry at 175 °C (350 

°F) for two hours. New silica gel may be used 

as received. Alternately other types of 

desiccants (equivalent or better) may be 

used, subject to the approval of the 

Administrator. 

3.1.6 Chromic Acid Cleaning Solution. 

Dissolve 20 g of sodium dichromate in 15 ml 

of water, and then carefully add 400 ml of 

concentrated sulfuric acid. 

3.2 Sample Recovery. 

3.2.2 Acetone. Pesticide quality. 

3.2.2 Methylene Chloride. Pesticide 

qualtity. 

3.2.3 Toluene. Pesticide quality. 

3.3 Analysis. 

3.3.1 Potassium Hydroxide. ACS grade, 2-

percent (weight/volume) in water. 

3.3.2 Sodium Sulfate. Granulated, reagent 

grade. Purify prior to use by rinsing with 

methylene chloride and oven drying. Store 

the cleaned material in a glass container with 

a Teflon-lined screw cap. 

3.3.3 Sulfuric Acid. Reagent grade. 

3.3.4 Sodium Hydroxide. 1.0 N. Weigh 40 g 

of sodium hydroxide into a 1-liter volumetric 

flask. Dilute to 1 liter with water. 

3.3.5 Hexane. Pesticide grade. 

3.3.6 Methylene Chloride. Pesticide grade. 

3.3.7 Benzene. Pesticide Grade. 

3.3.8 Ethyl Acetate. 

3.3.9 Methanol. Pesticide Grade. 

3.3.10 Toluene. Pesticide Grade. 

3.3.11 Nonane. Pesticide Grade. 

3.3.12 Cyclohexane. Pesticide Grade. 

3.3.13 Basic Alumina. Activity grade 1, 

100-200 mesh. Prior to use, activate the 

alumina by heating for 16 hours at 130 °C 
P.10 

Federal Register /'Vol. 56, No. 30 /Wednesday, February 13, 1991 /: Rules and Regulations 5765 

before use. Store in a desiccator. Preactivated alumina may be purchased from a 

supplier and may be used as received. 

3.3.14 Silica Gel. Bio-Sil A 100-200 mesh. 

Prior to use, activate the silica gel by heating 

for at least 30 minutes at 180 °C. After 

cooling, rinse the silica gel sequentially with 

methanol and methylene chloride. Heat the 

rinsed silica gel at 50 °C for 10 minutes, then 

increase the temperature gradually to 180 °C 

over 25 minutes and maintain it at this 

temperature for 90 minutes. Cool at room 

temperature and store in a glass container 

with a Teflon-lined screw cap. 

3.3.15 Silica Gel Impregnated with . 

Sulfuric Acid. Combine 100 g of silica gel with 

44 g of concentrated sulfuric acid in a screw 

capped glass bottle and agitate thoroughly. 

Disperse the solids with a stirring rod until a 

uniform mixture is obtained. Store the 

mixture in a glas3 container with a Teflonlined screw cap. 

3.3.18 Silica Gel Impregnated with 

Sodium Hydroxide. Combine 39 g of 1 N , 

sodium hydroxide with 100 g of silica gel in a 

screw capped glass bottle and agitate 

thoroughly. Disperse solids with a stirring rod 

until a uniform mixture is obtained. Store the 

mixture .in glass container with a Teflon-lined 

screw cap. 

3.3.17 Carbon/Celite. Combine 10.7 g of 

AX-21 carbon with 124 g of Celite 545 in a 

250-ml glass bottle with a Teflon-lined screw 

cap. Agitate the mixture thoroughly until a 

uniform mixture is obtained. Store in the 

glass container. 

3.3.18 Nitrogen. Ultra high purity. 

3.3.19 Hydrogen. Ultra high purity. 

3.3.20 Internal Standard Solution. Prepare 

a stock standard solution containing the 

isotopically labelled PCDD's and PCDF's at 

the concentrations shown in Table 1 under 

the heading "Internal'Standards" in 10 ml of 

nonane. 

3.3.21 Surrogate Standard Solution. 

Prepare a stock standard solution containing 

the isotopically labelled PCDD's and PCDFs 

at Ihe concentrations shown in Table 1 under 

Ihe heading "Surrogate Standards" in 10 ml of 

nonane. 

3.3.22 Recovery Standard Solution. 

Prepare a stock standard solution containing 

the isotopically labelled PCDD's and PCDF's 

at the concentrations shown in Table 1 under 

the heading "Recovery Standards" in 10 .ml of 

nonane. 

4. Procedure 

4.1 .Sampling. The complexity of this 

method is such that,,in order to obtain 

reliable results, testers should be trained and 

experienced with the test procedures. 

4.1.1 Pretest Preparation. 

4.1.1.1 Cleaning Glassware. All glass 

components *of the train upstream of and 

including the adsorbent .module, shall be 

cleaned as described in section 3A of the 

"Manual of Analytical Methods for the 

Analysis of Pesticides in Human and 

Environmental Samples." Special care shall 

be devoted to the removal of residual silicone 

grease sealants on ground glass connections 

of used glassware. Any residue shall be 

removed t y soaking the glassware for several 

hours in a chromic acid cleaning .solution 

prior to cleaning as described above. 

4.1.1.2 Adsorbent Trap. The traps must be 

loaded in a clean area to avoid 

contamination. They may not be loaded in 

the field. Fill a trap with 20 to 40 g of XAD-2. 

Follow the XAD-2 with glass wool and 

tightly cap both ends of the trap. Add 100 /il 

of the surrogate standard solution (section 

3.3.21} to each trap. 

4.1.1.3 Sample Train. It is suggested that 

all components be maintained according to 

the procedure described in APTD-0578. 

4.1.1.4 Silica Gel. Weigh several 200 to 300 

g portions of silica gel in an air tight 

container to the nearest 0.5 g. Record the 

total weight of the silica gel plus container, 

on each container. As an alternative, the 

silica gel may be weighed directly in its 

impinger or sampling holder just prior to 

sampling. 

4.1.1.5 Filter. Check each filter against 

light for irregularities and flaws or pinhole 

leaks. Pack the filters flat in a clean glass 

container. 

4.1.2 Preliminary Determinations. Same as 

section 4.1.2 of Method 5. 

4.1.3 Preparation of Collection Train. 

4.1.3.1 During preparation and assembly 

of the sampling train, keep all train openings 

where contamination can enter, sealed until 

just prior to assembly or until sampling is 

about"to begin. 

Note: Do not use sealant grease in 

assembling the train. 

4.1.3.2 Place approximately 100 ml of 

water in the second and third impingers, 

leave the first and fourth impingers empty, 

and transfer approximately 200 to 300 g of 

preweighed silica gel irom its container to the 

fifth impinger. 

4.1.3.3 Place the silica gel container in a 

clean place for later use in the sample 

recovery. Alternatively, the weight of the 

silica gel plus impinger may be determined to 

the nearest 0.5 g and recorded. 

4.1.3.4 Assemble the train as shown in 

Figure 23-1. 

4.1.3.5 Turn on the adsorbent module and 

condenser coil recirculating pump and begin 

monitoring the adsorbent module .gas entry 

temperature. Ensure proper sorbent 

temperature gas entry temperature before 

proceeding and before sampling is initiated. It 

is extremely important that the'Xu\D-2 

adsorbent resin temperature never exceed 50 

°C .because thermal decomposition will occur. 

During testing, the XAD-2 temperature must 

not exceed 20 °C for efficient capture of the 

PCDD's and PCDFs. 

.4.1.4 Leak-Check Procedure. Same as 

Method 5, section 4.1.4. 

4.1.5 Sample Train Operation. Same as 

Method 5, section 4.1.5. 

4.2 Sample Recovery. Proper cleanup 

procedure begins as soon as the probe is 

removed from the stack at the end of the 

sampling period. Seal the nozzle end of the 

sampling prohe with Teflon tape or aluminum 

foil. 

When the probe can be safely handled, 

wipe off all external particulate matter near 

the tip of the probe. Remove the probe from 

the train and close off both ends with 

aluminum foiL Seal off the inlet to the train 

with Teflon tape, aground glass cap, or 

aluminum foil. 

Transfer the probe and impinger assembly 

to the cleanup area. This area shall be clean 

and enclosed so that the chances of losing or 

contaminating the sample are minimized. 

Smoking, which could contaminate the 

sample, shall not be allowed in the cleanup 

area. 

Inspect the train prior to and during 

disassembly and note any abnormal 

conditions, e.g., broken filters, colored 

impinger liquid, etc. Treat the samples as 

follows: 

4.2.1 Container No. 1. Either seal the filter 

holder or carefully remove the filter from the 

filter holder and place it in its identified 

container. Use a pair of cleaned tweezers to 

handle the filter. If it is necessary to fold the 

filter, do so such that the particulate cake is 

inside the fold. Carefully transfer to the 

container any particulate matter and filter 

fibers which adhere to the filter holder 

gasket, by using a dry inert bristle brush and 

a sharp-edged blade. Seal the container. 

4.2.2 Adsorbent Module. Remove the 

module from the train, tightly cop both ends, 

label it, cover with aluminum foil, and store it 

on ice for transport to the laboratory. 

4.2.3 Container No. 2. Quantitatively 

recover material deposited in the nozzle, 

probe transfer lines, the front half of the filter 

holder, and the cyclone, if used, first, by 

brushing while rinsing three times each with 

acetone and then, by rinsing the probe thres 

times with methylene chloride. Collect all the 

rinses in Container No. 2. 

Rinse the beck half of the filter holder three 

times with acetone. Rinse the connecting line 

between the filter and the condenser three 

times with acetone. Soak the connecting line 

with three separate portions Of methylene 

chloride for 5 minutes each. If using a 

separate condenser and adsorbent trap, rinse 

the condenser in the same manner as the 

connecting line. Collect all the rinses in 

Container No. 2 and mark the level of the 

liquid on the container. 

4.2.4 Container No. 8. Repeat the 

methylene chloride-Tinsing described in 

Section4.2.3 using toluene as the rinse 

solvent. Collect the rinses in Container No. 3 

and mark the level of the liquid on-the 

container. 

4.2.5 Impinger Water. Measure the liquid 

in the first three impingers to within .±1 ml 

by using a graduated cylinder or by weighing 

it to within ±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. 

Discard the liquid after measuring and 

recording the volume or weight. 

4:2.7 Silica Gel. Note the color of the 

indicating silica gel to determine if it has 

been completely spent and make a mention 

of its condition. Transfer the silica gel from 

the fifth impinger to its original container and 

seal. 

5. Analysis 

All,glassware shall be cleaned as 

described in section 3A of the "Manuel of 

Analytical Methods for the Analysis of 

Pesticides in Human and Environmental 

Samples." All samples must be extracted 
P.11 

5768 Federal Register /Vol. 56, No. 30 / Wednesday,-. February 13, 199,1;/ Rules and: Regulations 

within 30 days of collection and analyzed 

within 45 days of extraction. 

5.1 Sample Extraction. 

5.1.1 Extraction System. Place an 

extraction thimble (section 2.3.4), 1 g of silica 

gel, and a plug of glass wool into the Soxhlet 

apparatus, charge the apparatus with toluene, 

and reflux for a minimum of 3 hours. Remove 

the toluene and discard it, but retain the 

silica gel. Remove the extraction thimble 

from the extraction system and place it in a 

glass beaker to catch the solvent rinses. 

5.1.2 Container No. 1 (Filter). Transfer the 

contents directly to the glass thimble of the 

extraction system and extract them 

simultaneously with the XAD-2 resin. 

5.1.3 Adsorbent Cartridge. Suspend the 

adsorbent module directly over the extraction 

thimble in the beaker (See section 5.1.1). The 

glass frit of the module should be in the up 

position. Using a Teflon squeeze bottle 

containing toluene, flush the XAD-2 into the 

thimble onto the bed of cleaned silica gel. 

Thoroughly rinse the glass module catching 

the rinsings in the beaker containing the 

thimble. If the resin is wet, effective 

extraction can be accomplished by loosely 

packing the resin in the thimble. Add the 

XAD-2 glass wool plug into the thimble. 

5.1.4 Container No. 2 (Acetone and 

Methylene Chloride). Concentrate the sample 

to a volume of about 1-5 ml using the rotary 

evaporator apparatus, at a temperature of 

less than 37 °C. Rinse the sample container 

three times with small portions of methylene 

chloride and add these to the concentrated 

solution and concentrate further to near 

dryness. This residue contains particulate 

matter removed in the rinse of the train probe 

and nozzle. Add the concentrate to the filter 

and the XAD-2 resin in the Soxhlet apparatus 

described in section 5.1.1. ' 

5.1.5 Extraction. Add 100 jil of the 

internal standard solution (Section 3.3.20) to 

the extraction thimble containing the 

contents of the adsorbent cartridge, the 

contents of Container No. 1, and the 

concentrate from section 5.1.4. Cover the 

contents of the extraction thimble with the 

cleaned glass wool plug to prevent the XAD2 resin from floating into the solvent reservoir 

of the extractor. Place the thimble in the 

extractor, and add the toluene contained in 

the beaker to the solvent reservoir. Pour 

additional toluene to fill the reservoir 

approximately 2/3 full. Add Teflon boiling 

chips and assemble the apparatus. Adjust the 

heat source to cause the extractor to cycle 

three times per hour. Extract the sample for 

16 hours. After extraction, allow the Soxhlet 

to cool. Transfer the toluene extract and 

three 10-ml rinses to the rotary evaporator. 

Concentrate the extract to approximately 10 

ml. At this point the analyst may choose to 

split the sample in half. If so, split the sample, 

store one half for future use, and analyze the 

other according to the procedures in sections 

5.2 and 5.3. In either case, use a nitrogen 

evaporative concentrator to reduce the 

volume of the sample being analyzed to near 

dryness. Dissolve the residue in 5 ml of 

hexane. 

5.1.6 Container No. 3 (Toluene Rinse). 

Add 100 fil of the Internal Standard solution 

(section 3.3.2] to the contents of the 

container. Concentrate the sample to a 

volume of about 1-5 ml using the rotary 

evaporator apparatus at a temperature of less 

than 37 °C. Rinse the sample container 

apparatus at a temperature of less than 37 °C. 

Rinse the sample container three times with 

small portions of toluene and add these to the 

concentrated solution and concentrate further 

to near dryness. Analyze the extract 

separately according to the procedures in 

sections 5.2 and 5.3, but concentrate the 

solution in a rotary evaporator apparatus 

rather than a nitrogen evaporative 

concentrator. 

5.2 Sample Cleanup and Fractionation. 

5.2.1 Silica Gel Column. Pack one end of a 

glass column, 20 mm x 230 mm, with glass 

wool. Add in sequence, 1 g silica gel, 2 g of 

sodium hydroxide impregnated silica gel, 1 g 

silica gel, 4 g of acid-modified silica gel, and 1 

g of silica gel. Wash the column with 30 ml of 

hexane and discard it. Add the sample 

extract dissolved in 5 ml of hexane to the 

column with two additional 5-ml rinses. Elute 

the column with an additional 90 ml of 

hexane and retain the entire eluate. 

Concentrate this solution to a volume of 

about 1 ml using the nitrogen evaporative 

concentrator (section 2.3.7). 

5.2.2 Basic Alumina Column. Shorten a 

25-ml disposable Pasteur pipette to about 16 

ml. Pack the lower section with glass wool 

and 12 g of basic alumina. Transfer the 

concentrated extract from the silica gel 

column to the top of the basic alumina 

column and elute the column sequentially 

with 120 ml of 0.5 percent methylene chloride 

in hexane followed by 120 ml of 35 percent 

methylene chloride in hexane. Discard the 

first 120 ml of eluate. Collect the second 120 

ml of eluate and concentrate it to about 0.5 ml 

using the nitrogen evaporative concentrator. 

5.2.3 AX-21 Carbon/Celite 545 Column. 

Remove the botton 0.5 in. from the tip of a 9-

ml disposable Pasteur pipette. Insert a glass 

fiber filter disk in the top of the pipette 2.5 cm 

from the constriction. Add sufficient carbon/ 

celite mixture to form a 2 cm column. Top 

with a glass wool plug. In some cases AX-21. 

carbon fines may wash through the glass 

wool plug and enter the sample. This may be 

prevented by adding a celite plug to the exit 

end of the column. Rinse the column in 

sequence with 2 ml of 50 percent benzene in 

ethyl acetate, 1 ml of 50 percent methylene 

chloride in cyclohexane, and 2 ml of hexane. 

Discard these rinses. Transfer the 

concentrate in 1 ml of hexane from the basic 

alumina column to the carbon/celite column 

along with 1 ml of hexane rinse. Elute the 

column sequentially with 2 ml of 50 percent 

methylene chloride in hexane and 2 ml of 50 

percent benzene in ethyl acetate and discard 

these eluates. Invert the column and elute in 

the reverse direction with 13 ml of toluene. 

Collect this eluate. Concentrate the eluate in 

a rotary evaporator at 50 °C to about 1 ml. 

Transfer the concentrate to a Reacti-vial 

using a toluene rinse and concentrate to a 

volume of 200 fil using a stream of Na. Store 

extracts at room temperature, shielded from 

light, until the analysis is performed. 

5.3 Analysis. Analyze the sample with a 

gas chromatograph coupled to a mass 

spectrometer (GC/MS) using the instrumental 

parameters in sections 5.3.1 and 5.3.2. 

Immediately prior to analysis, add a 20 *xl 

aliquot of the Recovery Standard solution 

from Table 1 to each sample. A 2 -il aliquot of 

the extract is injected into the GC. Sample 

extracts are first analyzed using the DB-5 

capillary column to determine the 

concentration of each isomer of PCDD's and 

PCDF's (tetra-through octa-). If tetrachlorinated dibenzofurans are detected in 

this analysis, then analyze another aliquot of 

' the sample in a separate run, using the DB225 column to measure the 2,3,7,8 tetra-chloro 

dibenzofuran isomer. Other column systems 

may be used, provided that the user is able to 

demonstrate using calibration and 

performance checks that the column system 

is able to meet the specifications of section 

6.1.2.2. 

5.3.1 Gas Chromatograph Operating 

Conditions. 

5.3.1.1 Injector. Configured for capillary 

column, splitless, 250°C. 

5.3.1.2 Carrier Gas. Helium, 1-2 ml/min. 

5.3.1.3 Oven. Initially at 150°C. Raise by 

at least 40°C/min to 190°C and then at 3"C/ 

min up to 300°C. 

5.3.2 High Resolution Mass Spectrometer. 

5.3.2.1 Resolution. 10000 m/e. 

5.3.2.2 Ionization Mode. Electron impact. 

5.3.2.3 Source Temperature 250°C. 

5.3.2.4 Monitoring Mode. Selected ion 

monitoring. A list of the various ions to be 

monitored is summarized in Table 3. 

5.3.2.5 Identification Criteria. The 

following identification criteria shall be used 

for the characterization of polychlorinated 

dibenzodioxins and dibenzofurans. 

1. The integrated ion-abundance ratio (M/ 

M+2 or M+2/M+4) shall be within 15 

percent of the theoretical value. The 

acceptable ion-abundance ratio ranges for 

the identification of chlorine-containing 

compounds are given in Table 4. 

2. The retention time for the analytes must 

be within 3 seconds of the corresponding 

13

 C-labeled internal standard, surrogate or 

alternate standard. 

3. The monitored ions, shown in Table 3 for 

a given analyte, shall reach their maximum 

within 2 seconds of each other. 

4. The identification of specific isomers 

that do not have corresponding

 13

 C-labeled 

standards is done by comparison of the 

relative retention time (RRT) of the analyte to 

the nearest internal standard retention time 

with reference (i.e., within 0.005 RRT units) to 

the comparable RRTs found in the continuing 

calibration. 

5. The signal to noise ratio for all 

monitored ions must be greater than 2.5. 

6. The confirmation of 2, 3, 7, 8-TCDD and 

2, 3, 7, 8-TCDF shall satisfy all of the above 

identification criteria. 

7. For the identification of PCDFs, no 

signal may be found in the corresponding 

PCDPE channels. 

5.3.2.8 Quantification. The peak areas for 

the two ions monitored for each analyte are 

summed to yield the total response for each 

analyte. Each internal standard is used to 

quantify the indigenous PCDD's or PCDF's in 

its homologous series. For example, the 

13

 C u-2,3,7,8-tetra chlorinated dibenzodioxin 

is used to calculate the concentrations of all 

other tetra chlorinated isomers. Recoveries of 

the tetra- and penta- internal standards are 
P.12 

""*-. Ffederal Register */- Vdl. \56,! No. 30'. / • Wednesday; •'February- J13,1991' / Rifles arid;Regulations 3767 

calculated using the

 13

 C i2-l,2,3,4-TCDD. 

Recoveries of the hexa- through octa- internal 

standards are calculated using

 a C i2— 

1,2,3,7,8,9-HxCDD. Recoveries of the 

surrogate standards are calculated using the 

corresponding homolog from the internal 

standard. 

ft Calibration 

Same as Method 5 with the following 

additions. 

6.1 GC/MS System. 

6.1.1 Initial Calibration. Calibrate the GC/ 

MS system using the set of five standards 

shown in Table 2. The relative standard 

deviation for the mean response factor from 

each of the unlabeled analytes (Table 2) and 

of the internal, surrogate, and alternate 

standards shall be less than or equal to the 

values in Table 5. The signal to noise ratio for 

the GC signal present in every selected ion 

current profile shall be greater than or equal 

to 2.5. The ion abundance ratios shall be 

within the control limits in Table 4. 

6.1.2 Daily Performance Check. 

6.1.2.1 Calibration Check. Inject on fil.of 

solution Number 3 from Table 2. Calculate 

the relative response factor (RRF) for each 

compound and compare each RRF to the 

corresponding mean RRF obtained during the 

initial calibration. The analyzer performance 

is acceptable if the measured RRF's for the 

labeled and unlabeled compounds for the 

daily run are within the limits of the mean 

values shown in Table 5. In addition, the ion- . 

abundance ratios shall be within the 

allowable control limits shown in Table 4. 

6.1.2.2 Column Separation Check. Inject a 

solution of a mixture of PCDD's and PCDF's 

that documents resolution between 2,3,7,8-

TCDD and other TCDD isomers. Resolution is 

defined as a valley between peaks that is less 

than 25 percent of the lower of the two peaks. 

Identify and record the retention time 

windows for each homologous series. 

Perform a similar resolution check on the 

confirmation column to document the 

resolution between 2,3,7,8 TCDF and other 

TCDF isomers. 

6.2 Lock Channels. Set mass spectrometer 

lock channels as specified in Table 3. Monitor 

the quality control check channels specified 

in Table 3 to verify instrument stability 

during the analysis. 

7. Quality Control 

7.1 Sampling Train Collection Efficiency 

Check. Add 100 fil of the surrogate standards 

in Table 1 to the absorbent cartridge of each 

train before collecting the field samples. 

7.2 Internal Standard Percent Recoveries. 

A group of nine carbon labeled PCDD's and 

PCDF's representing, the terra-through 

octachlorinated homologues, is added to 

every sample prior to extraction. The role of 

the internal standards is to quantify the 

native PCDD's and PCDF's present in the 

sample as well as to determine the overall 

method efficiency. Recoveries of the internal 

standards must be between 40 to 130 percent 

for the tetra-through hexachlorinated 

compounds while the range is 25 to 130 

percent for the higher hepta- and 

octachlorinated homologues. 

7.3 Surrogate Recoveries. The five 

surrogate compounds in Table 2 are added to 

the resin in the adsorbent sampling cartridge 

before the sample is collected. The surrogate 

recoveries are measured relative to the 

internal standards and are a measure of 

collection efficiency. They are not used to 

measure native PCDD's and PCDFs. All 

recoveries shall be between 70 and 130 

percent. Poor recoveries for all the surrogates 

may be an indication of breakthrough in the 

sampling train. If the recovery of all 

standards is below 70 percent, the sampling 

runs must be repeated. As an alternative, the 

sampling runs do not have to be repeated if 

the final results are divided by the fraction of 

surrogate recovery. Poor recoveries of 

isolated surrogate compounds should not be 

grounds for rejecting an entire set of the 

samples. 

7.4 Toluene QA Rinse. Report the results 

of the toluene QA rinse separately from the 

total sample catch. Do not add it to the total 

sample. 

8. Quality Assurance 

8.1 Applicability. When the method is 

used to analyze samples to demonstrate 

compliance with a source emission -

regulation, an audit sample must be analyzed, 

subject to availability. 

8.2 Audit Procedure. Analyze an audit 

sample with each set of compliance samples. 

The audit sample contains tetra through octa 

isomers of PCDD and PCDF. 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 the compliance 

samples and the EPA audit sample. 

8.3 Audit Sample Availability. Audit 

samples will be supplied only to enforcement 

agencies for compliance tests. The 

availability of audit samples may be obtained 

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. 

8.4 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. 

9. Calculations 

Same as Method 5, section 6 with the 

following additions. 

9.1 Nomenclature. 

Aai=Integrated ion current of the noise at 

the retention time of the analyte. 

A*cl=Integrated ion current of the two ions 

characteristic of the internal standard i 

in the calibration standard. 

AcU = Integrated ion current of the two ions 

characteristic of compound i in the jth 

calibration standard. 

A*dj=Integrated ion current of the two 

ions characteristic of the internal 

standard i in the jth calibration standard. 

Aci=Integrated ion current of the two ions 

characteristic of surrogate compound i in 

the calibration standard. 

A,=Integrated ion current of the two ions 

characteristic of compound i in the 

sample. 

A*i=Integrated ion current of the two ions 

characteristic of internal standard i in 

the sample. 

Are=Integrated ion current of the two ions 

characteristic of the recovery standard. 

A,i=Integrated ion current of the two ions 

characteristic of surrogate compound i in 

the sample. 

C,=Concentration of PCDD or PCDF i in 

the sample, pg/M

 3

. 

CT=Total concentration of PCDD's or 

PCDF's in the sample, pg/M

 3

. 

mc)=Mass of compound i in the calibration 

standard injected into the analyzer, pg. 

m„=Mass of recovery standard in the 

calibration standard injected into the 

analyzer, pg. 

m,i=Mass of surrogate compound i in the 

calibration standard, pg. 

RRFi=Relative response factor. 

RRF„=Recovery standard response factor. 

RRF,=Surrogate compound response 

factor. 

9.2 Average Relative Response Factor. 

1 n Adj m*d 

RRF,= — 2 

n j= l A*d, md 

Eq. 23-1 

9.3 Concentration of the PCDD's and 

PCDFs. 

m / A, 

Eq. 23-2 

A|* RRFi VmBtd 

9.4 Recovery Standard Response Factor. 

Aci*m„ 

RRF„= Eq. 23-3 

A„ md* 

9.5 Recovery of Internal Standards (R*). 

A,* m„ 

A„ RF„ m,* 

Eq. 

23- 4 

9.6 Surrogate Compound Response 

Factor. 
P.13 

S|^88 Federal tRpgistei /^Voi 56,, No. 30 / ,Wednesdayt ffetaujaiy -1.3, .1-951J Rules gnd Regulations 

RRF„= 

Ad* m. 

Atunva* 

Eq. 

23- 5 

9.7 Recovery of Surrogate Compounds 

(R»)-

A„m,* 

A,* RRF, m, 

X100% Eq. 

23- 6 

9.8 Minimum Detectable Limit (MDL). 

MDL= 

2.5 A,! m!* 

Ad* RRF, 

Eq. 

23- 7 

9.9 Total Concentration of PCDD's and 

PCDF's in the Sample. 

n 

VuXr ~ •— luj 

i = l 

Eq. 

23- 8 

Agency. Washington DC. December 1984. 25 

P2. American Society of Mechanical 

Engineers. Analytical Procedures to Assay 

Stack Effluent Samples and Residual 

Combustion Products for Polychlorinated 

Dibenzo-p-Dioxins (PCDD) and 

Polychlorinated Dibenzofurans (PCDF). 

Prepared for the U.S. Department of Energy 

and U.S. Environmental Protection Agency. 

Washington, DC. December 1984. 23 p. 

3. Thompson, J. R. (ed.). Analysis of 

Pesticide Residues in Human and 

Environmental Samples. U.S. Environmental 

Protection Agency. Research Triangle Park, 

NG 1974. 

4. Triangle Laboratories. Case Study: 

Analysis of Samples for the Presence of Tetra 

Through Octachloro-p-Dibenzodioxins and 

Dibenzofurans. Research Triangle Park, NC. 

1988. 26 p. 

5. U.S. Environmental Protection Agency. i 

Method 8290—The Analysis of 

Polychlorinated Dibenzo-p-dioxin and 

Polychlorinated Dibenzofurans by HighResolution Gas Chromotography/HighResolution Mass Spectrometry. In: Test 

Methods for Evaluating Solid Waste. 

Washington, DC. SW-846. 

TABLE 1.—COMPOSITION OF THE SAMPLE 

FORTIFICATION AND RECOVERY STANDARDS SOLUTIONS 

Any PCDD's or PCDFs that are reported as 

nondetected (below the MDL) shall be 

counted as zero for the purpose of calculating 

the total concentration of PCDD's and PCDF's 

in the sample. 

10. Bibliography 

1. American Society of Mechanical 

Engineers. Sampling for the Determination of 

Chlorinated Organic Compounds in Stack 

Emissions. Prepared for U.S. Department of 

Energy and U.S. Environmental Protection 

. TABLE 3.—ELEMENTAL COMPOSITIONS AND EXACT MASSES OF THE IONS MONITORED BY HIGH RESOLUTION MASS SPECTROMETRY 

FOR PCDD'S AND PCDF S 

Analyte 

Internal Standards: 

1:Cls-2,3,7,8-TCDD 

l!C,2-1,2,3,7,8-PeCDD 

"Cl2-1,2,3,6,7,8-HxCDD 

"C»-1,2,3,4,6,7,8-HpCDD 

•*C12-OCDD '. 

Concentration (pg/|il) 

• 100 

100 

100 

100 

100 

TABLE 1 .—COMPOSITION OF THE SAMPLE 

FORTIFICATION AND RECOVERY STANDARDS SOLUTIONS—Continued 

Analyte 

I:C,2-2,3,7,8-TCDF -

"C„-1,2,3,7,8-PeCDF „ 

•'Cii-1,2,3,6,7,8-HxCDF 

"Ci2-1,2,3,4,6,7,8-HpCDF 

Surrogate Standards: 

slCl4-2,3,7,8-TCDD 

"Ci2-1,2,3,4,7,8-HxCDD.., 

laCi2-2,3,4,7,8-PeCDF 

•-Cia-1,2,3,4,7,8-HxCDF 

l

'Ci2-1,2,3,4,7,8,9-HpCDF 

Recovery Standards:. 

"Cla-1,2,3,4-TCDD 

"C,2-1,2,3,7,8,9-HxCDD 

Concentration (pg/jd) 

100 

100 

100 

100 

100 

100 

100 

100 

100 

500 

500 

TABLE 2.—COMPOSITION OF THE INITIAL 

CALIBRATION SOLUTIONS 

Compound 

Alternate 

Standard: 

•*C,2-

1,2,3,7,8,9-

HxCDF„ 

Recovery 

Standards: 

"Cl3-1,2,3,4-

TCDD 

•-C.2-

1,2,3,7,8,9-

HxCDD 

Concentrations (pg/jiL) 

Solution No. 

1 

2.5 

100 

100 

2 

5 

100 

100 

3 

25 

100 

100 

4 

250 

100 

100 

5 

500 

100 

100 

Descriptor No. 

2 

3 

Accurate mass 

292.9825 

303.9016 

305.8987 

315.9419 

317.9389 

319.8965 

321.8936 

327.8847 

330.9792 

331.9368 

333.9339 

339.8597 

341.8567 

351.9000 

353.8970 

355.8546 

357.8516 

367.8949 

369.8919 

375.8364 

409.7974 

373.8208 

375.8178 

383.8639 

385.8610 

389.8157 

391.8127 

392.9760 

Ion type 

LOCK 

M 

M+2 

M 

M+2 

M 

M+2 

M 

QC 

M 

M+2 

M+2 

M+4 

M+2 

M+4 

M+2 

M+4 

M+2 

M+4 

M+2 

M+2 

M+2 

M+4 

M 

M+2 

M+2 

M+4 

LOCK 

. Elemental composition 

CF„ 

Ci2Hu?5CluO 

C,2m*CTO 

-

aC,2H4"Ct10 

1

'C,sH4MCl3,1CIO 

C,2H4*CIO, 

Ci,H4

MCI.3,a02 

C,2H<"CUO. 

CFw 

*-C12H.MClu.02 

"CsHuaCTCIOj 

Ci2H3

MCU,7CIO 

CaHs^Cla^CljO 

"C,zH3'K,U"C\0 

1

^C12H>«CI3M1CI20 

C1IH,MCls37a02 

C,2H,MCI,lrCl202 

"CuHjaCU'lCIO* 

"CHjKVWl * 

c„H,3:ek*"cio 

C,2HsMCl6S7CIO 

C12H235CI5

3,CIO 

c1 2H2

M

cius ,ei2o iaC,2H!31CI«0 

1JCi2H2»weio 

Cl 2H2

3WC!02 

CnHa'WCI-.a 

C,F„ 

Analyte 

PFK 

TCDF 

TCDF 

TCDF (S) 

TCDF (S) 

TCDD 

TCDD 

TCDD (S) 

PFK 

TCDD (S) 

TCDD (S) 

PECDF 

PeCDF 

PeCDF (S) 

PeCDF (S) 

PeCDD 

PeCDD 

PeCDD (S) 

PeCDD (S) 

HxCDPE 

HpCPDE 

HxCDF 

HxCDF 

HxCDF (S) 

HxCDF (S) 

HxCDD 

HxCDD 

PFK 
P.14 

• Federal Register / Vol. 56, No. 30 / Wednesday, February 13, 1991 / Rules and Regulations 5769 

TABLE 3.—ELEMENTAL COMPOSITIONS AND EXACT MASSES OF THE IONS MONITORED BY HIGH RESOLUTION MASS SPECTROMETRY 

FOR PCDD'S AND PCDF's—Continued 

Descriptor No. 

4 

Accurate mass 

401.8559 

403.8529 

445.7555 

430.9729 

407.7818 

409.7789 

417.8253 

419.8220 

423.7766 

425.7737 

435.8169 

437.8140 

479.7165 

430.9729 

441.7428 

443.7399 

457.7377 

459.7348 

469.7779 

471.7750 

513.6775 

442.9728 

Ion type 

M+2 

M+4 

M+4 

QC 

M+2 

M+4 

M 

M+2 

M+2 

M+4 

M+2 

M+4 

M+4 

LOCK 

M+2 

M+4 

M+2 

M+4 

M+2 

M+4 

M+4 -

QC 

Elemental composition 

'

aC,2H2MCtl',1CI02 

"CuHj'WCfeO 

c-jH-^wao C F „ 

CJH^WCI O 

C12H

:wCI»slCl20 

'•CSH-^CITO 

"CuH'WCI O 

CIH^CIG'KJIOJ 

CJH"CUS ,CI 2 0 2 

"CKH'WCIO: . 

"CnH'WCfeQ, 

CuH^WW ) 

CF,, 

C1J

S5CI,slCIO 

Cu'WCWD 

Cia'WCIO-! 

Ci^le^CliOj 

'-WWCIO * 

•-WWCkQ . 

C,2MCI,;"CI202 

CloF] 7 

Analyte 

HxCDD (S) 

HxCDD (S) 

OCDPE 

PFK 

HpCDF 

HpCDF 

HpCDF (S) 

HpCDF (S) 

HpCDD 

HpCDD 

HpCDD (S) 

HpCDD (S) 

NCPDE 

PFK 

OCDF 

OCDF 

OCDD 

OCDD 

OCDD (S) 

OCDD (S) 

DCDPE 

PFK 

(a) The following nuclidic masses were used: 

H = 1.007825 

C = 12.000000 

"C = 13.003355 

F = 18.9984 

O = 15.994915 

"Cl = 34.968853 

"TO = 36.965903 

S — Labeled Standard 

QC = Ion selected for monitoring instrument stability during the GC/MS analysis. 

TABLE 4.—ACCEPTABLE RANGES FOR IONABUNDANCE RATIOS OF PCDD'S AND 

PCDF'S 

NO. Of 

chlorine 

atoms 

4 

5 

6 

6" 

7" 

7 

8 

Ion type 

M/M+2 

M+2/ 

. M+4 

M+2 / 

M+4 

M/M+2 

M/M+2 

M+2/ 

M+4 

M+2/ 

M+4 

Theoretical 

ratio 

0.77 

1.55 

1.24 

0.51 

0.44 

1.04 

0.89 

Control limits 

Lower 

0.65 

1.32 

• 

1.05 

0.43 

0.37 

0.88 

0.76 

Upper 

0.89 

1.78 

1.43 

0.59 

0.51 

1.20 

1.02 

•Used only for "C-HxCDF. 

" Used only for

 13C-HpCDF. 

TABLE 5.—MINIMUM REQUIREMENTS FOR 

INITIAL AND DAILY CALIBRATION RESPONSE FACTORS 

Compound 

Unlabeled 

Analytes: 

2,3,7,8-TCDD 

2,3,7,8-TCDF 

1,2,3,7,8-

PeCDD 

1,2,3,7,8-

PeCDF 

Relative response factors 

Initial 

calibration 

RSD 

25 

25 

25 

?5 

Daily 

calibration % 

difference 

25 

25 

25 

25 

TABLE 5.—MINIMUM REQUIREMENTS FOR 

INITIAL AND DAILY CALIBRATION RESPONSE FACTORS—Continued 

Compound 

2,3,4,7,8-

PeCDF 

1,2,4,5,7,8-

HxCDD 

1,2,3,6,7,8-

HxCDD 

1,2,3,7,8,9-

HxCDD 

1,2,3,4,7,8-

HxCDF 

1,2,3,6,7,8-

HxCDF 

1,2,3,7,8,9-

. HxCDF 

2,3,4,6,7,8-

HxCDF 

1,2,3,4,6,7,8-

HpCDD 

1,2,3,4,6,7,8-

HpCDF 

OCDD 

OCDF 

Internal 

Standards: 

•

3C12-2,3,7,8-

TCDD 

,3C,2-1,2,3,7,8-

PeCDD 

13Cl2-

1,2,3,6,7,8-

HxCDD 

Relative response factors 

Initial 

calibration 

RSD 

25 

25 

25 

25 

25 

25 

25 

25 

25 

25 

25 

30 

25 

30 

25 

Daily 

calibration % 

difference 

25 

25 

25 

25 

25 

25 

25 

25 

25 

25 

25 

30 

25 

30 

25 

TABLE 5.—MINIMUM REQUIREMENTS FOR 

INITIAL AND . DAILY CALIBRATION RESPONSE FACTORS—Continued 

Compound 

13C,2-

1,2,3,4,6,7,8-

HpCDD 

>

3C12-OCDD 

13C12-2,3,7,8-

TCDF 

13C,2-1,2,3,7,8-

PeCDF 

•**C,2-

1,2,3,6,7,8-

HxCDF 

"Cn1,2.3,4,6,7,8-

HpCDF 

Surrogate 

Standards: 

37CU-2,3,7,8-

TCDD 

13C,2-2,3,4,7,8-

PeCDF 

*

3C12-

1,2,3,4,7,8-

HxCDD 

13C,2-

1,2,3,4,7,8-

HxCDF 

•

3C12-

1,2,3,4,7,8,9-

HpCDF 

Relative response factors 

Initial 

calibration 

RSD 

30 

30 

30 

30 

30 

30 

25 

25 

25 

25 

25 

Daily 

calibration % 

difference 

30 

30 

30 

30 

30 

30 

25 

25 

25 

25 

25 
5770 Federal Register / Vol. 56, No. 30 / Wednesday, February 13, 1991 / Rules and Regulations 

TABLE 5.—MINIMUM REQUIREMENTS FOR 

INITIAL AND DAILY CALIBRATION RESPONSE FACTORS—Continued 

Compound 

Alternate 

Standard 

,3C12-

1,2,3,7,8.9-

HxCDF 

Relative response factors 

Initial 

calibration 

RSD 

25 

Daily 

calibration % 

difference 

25 

Method 28—Determination of Hydrogen 

Chloride Emissions From Stationary Sources 

1. Applicability, Principle, Interferences, 

Precision, Bias, and Stability 

1.1 Applicability. This method is 

applicable for determining hydrogen chloride 

(HCl) emissions from stationary sources. 

1.2 Principle. An integrated sample is 

extracted from the stack and passed through 

dilute sulfuric acid. In the dilute acid, the 

HCl gas is dissolved and forms chloride 

(Cl") ions. The Cl" is analyzed by ion 

chromatography (IC). 

1.3 Interferences. Volatile materials 

which produce chloride ions upon dissolution 

during sampling are obvious interferences. 

Another likely interferent is diatomic chlorine 

(Cl2) gas which reacts to form HCl and 

hypochlordus acid (HOCl) upon dissolving in 

water. However, CI2 gas exhibits a low 

solubility in water and the use of acidic, 

rather than neutral or basic collection 

solutions, greatly reduces the chance of 

dissolving any chlorine present. This method 

does not experience a significant bias when 

sampling a 400 ppm HCl gas stream 

containing 50 ppm Cl2. Sampling a 220 ppm 

HCl gas stream containing 180 ppm CI2 ' 

results in a positive bias of 3.4 percent in the 

HCl measurement. 

1.4 Precision and Bias. The withinlaboratory relative standard deviations are 

6.2 and 3.2 percent at HCl concentrations of 

3.9 and 15.3 ppm, respectively. The method 

does not exhibit a bias to CI2 when sampling 

at concentrations less than 50 ppm. 

1.5 Stability. The collected samples can 

be stored for up to 4 weeks before analysis. 

1.6 Detection Limit. The analytical 

detection limit of the method is 0.1 •xg/ml. 

2. Apparatus 

2.1 Sampling. The sampling train is shown 

in Figure 26-1, and component parts are 

discussed below. 

2.1.1 Probe. Borosilicate glass, 

approximately %-in. (9-mm) I.D. with a 

heating system to prevent moisture 

condensation. A %-in I.D. Teflon elbow 

should be attached to the inlet of the probe 

and a 1-in. (25-mm) length of %-in. I.D. Teflon 

tubing should be attached to the open end of 

the elbow to permit the opening of the probe 

to be turned away from the gas stream. This 

reduces the amount of particulate entering 

the train. This probe configuration should be 

used when the concentration of particulate 

matter in the emissions is high. When high 

concentrations are not present, the Teflon 

elbow is not necessary, and the probe inlet 

may be perpendicular to the gas stream. A 

glass wool plug should not be used to remove 

particulate matter since a negative bias in the 

data could result. Instead, a Teflon filter (see 

Section 2.1.5] should be installed at the inlet 

(for stack temperatures 00 0 °F) or outlet (for 

stack temperatures >300 °F) of the probe. 

2.1.2 Three-way Stopcock. A borosilicate, 

three-way glass stopcock with a heating 

system to prevent moisture condensation. 

The heated stopcock should connect directly 

to the outlet of the probe and the inlet of the 

first impinger. The heating system should be 

capable of preventing condensation up to the 

inlet of the first impinger. Silicone grease may 

be used, if necessary, to prevent leakage. 

BILLING CODE 6560-50-M 
P.16 

Federal Register / Vol. 56, No. 30 / Wednesday, February 13,1991 / Rules and Regulations 5771 

ZZZZZZZZZZ2 

g 

£ 

co 

co 

CM 

t 
5772 Federal Register / Vol. 56, No. 30 / Wednesday, February 13, 1991 / Rules and Regulations 

2.1.3 Impingers. Four 30-ml midget 

impingers with leak-free glass connectors. 

Silicone grease may be used, if necessary, to 

prevent leakage. For sampling at high 

moisture sources or for sampling times 

greater than 1 hour, a midget impinger with a 

shortened stem (such that the gas sample 

does not bubble through the collected 

condensate) should be used in front of the 

first impinger. 

2.1.4 Drying Tube or Impinger. Tube or 

impinger, of Mae West design, filled with 6-

to 16-mesh indicating type silica gel, or 

equivalent, to dry the gas sample and to 

protect the dry gas meter and pump. If the 

silica gel has been used previously, dry at 175 

°C (350 °F) for 2 hours. New silica gel may be 

used as received. Alternatively, other types 

of desiccants (equivalent or better) may be 

used. 

2.1.5 Filter. A 25-mm Teflon mat, Pallflex 

TX40H175 or equivalent. Locate between the 

probe liner and Teflon elbow in a glass or 

quartz filter holder in a filter box heated to 

250 °F. 

2.1.6 Sample Line. Leak-free, with 

compatible fittings to connect the last 

impinger to the needle valve. 

2.1.7 Rate Meter. Rotameter, or 

equivalent, capable of measuring flow rate to 

within 2 percent of the selected flow rate of 2 

liters/min. 

2.1.8 Purge Pump, Purge Line, Drying 

Tube, Needle Valve, and Rate Meter. Pump 

capable of purging the sampling probe at 2 

liters/min, with drying tube, filled with silica 

gel or equivalent, to protect pump, and a rate 

meter capable of measuring 0 to 5 liters/min. 

2.15 Stopcock Grease, Valve, Pump, 

Volume Meter, Barometer, and Vacuum 

Gauge. Same as in Method 6, Sections 2.1.4, 

2.1.7, 2.1.8, 2.1.10, 2.1.11, and 2.1.12. 

2.2 Sample Recovery. 

2.2.1 Wash Bottles. Polyethylene or glass, 

500-ml or larger, two. 

2.2.2 Storage Bottles. 100-ml glass, with 

Teflon-lined lids, to store impinger samples 

(two per sampling run). During clean-up, the 

two front impinger contents (0.1 N H2SO4) 

should be combined. The contents of the two 

rear impinger (0.1 N NaOH) may be 

discarded, as these solutions are included 

only to absorb Cl2, and thus protect the 

pump. 

2.3 Sample Preparation and Analysis. The 

materials required for volumetric dilution and 

chromatographic analysis of samples are 

described below. 

2.3.1 Volumetric Flasks. Class A, 100-ml 

size. 

2.3.2 Volumetric Pipets. Class A. 

assortment To dilute samples into the 

calibration range of the instrument 

2.3.3 Ion Chromatograph. Suppressed or 

nonsuppressed, with a conductivity detector 

and electronic integrator operating in the 

peak area mode. Other detectors, strip chart 

recorders, and peak height measurements 

may be used provided the 5 percent 

repeatability criteria for sample analysis and 

the linearity criteria for the calibration curve 

can be met. 

3. Reagents 

Unless otherwise indicated, all reagents 

must conform to the specifications 

established by 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 ASTM Specification D1193-

77, Type 3. 

3.1.2 Absorbing solution, 0.1 N Sulfuric 

Acid (H2SO4). To prepare 100 ml of the 

absorbing solution for the front impinger pair, 

slowly add 0.28 ml of concentrated H2SO4 to 

about 90 ml of water while stirring, and 

adjust the final volume to 100 ml using 

additional water. Shake well to mix the 

solution. 

3.1.3. Chlorine Scrubber Solution, 0.1 N 

Sodium Hydroxide (NaOH). To prepare 100 

ml of the scrubber solution for the back pair 

-of impingers, dissolve 0.40 g of solid NaOH in 

about 90 ml of water, and adjust the final 

solution volume to 100 ml using additional 

water. Shake well to mix the solution. 

3.2 Sample Preparation and Analysis. 

3.2.1 Water. Same as in Section 3.1.1. 

3.2.2 Blank Solution. A separate blank 

solution of the absorbing reagent should be 

prepared for analysis with the field samples. 

Dilute 30 ml of absorbing solution to 100 ml 

with water in a separate volumetric flask. 

3.2.3 Sodium Chloride (NaCI) Stock 

Standard Solution. Solutions containing a 

nominal certified concentration of 1000 mg/1 

are commercially available as convenient 

stock solutions from which working 

standards can be made by appropriate 

volumetric dilution. Alternately, concentrated 

stock solutions may be produced from 

reagent grade NaCI. The NaCI should be 

dried at 100 °C for 2 or more hours and cooled 

to room temperature in a desiccator 

immediately before weighing. Accurately 

weigh 1.8 to 1.7 g of the dried NaCI to within 

0.1 mg, dissolve in water, and dilute to 1 liter. 

The exact Cl concentration can be calculated 

using Eq. 26-1. 

jig Cl"/ml = g of NaClX10sX35.453/58.44 

Eq. 26-1 

Refrigerate the stock standard solution and 

store no longer than 1 month. 

3.2.4 Chromatographic Eluent Effective 

eluents for nonsuppressed IC using a resin- or 

silica-based weak ion exchange column are a 

4 mM potassium hydrogen phthalate solution, 

adjusted to pH 4.0 using a saturated sodium 

borate solution, and a 4 mM 4-hydroxy 

benzoate solution, adjusted to pH 8.6 using 1 

N NaOH. An effective eluent for suppressed 

ion chromatography is a solution containing 3 

mM sodium bicarbonate and 2.4 mM sodium 

carbonate. Other dilute solutions buffered to 

a similar pH and containing no interfering 

ions may be used. When using suppressed 

ion chromatography, if the "water dip" 

resulting from sample injection interferes 

with the chloride peak, use a 2 mM NaOH/2.4 

mM sodium bicarbonate eluent. 

4. Procedure 

4.1 Sampling. 

4.1.1 Preparation of Collection Train. 

Prepare the sampling train as follows: Pour 15 

ml of the absorbing solution into each of the 

first two impingers, and add 15 ml of 

scrubber solution to the third and fourth 

impingers. Connect the impingers in series 

with the knockout impinger first, followed by 

the two impingers containing absorbing 

solution and the two containing the scrubber 

solution. Place a fresh charge of silica gel, or 

equivalent in the drying tube or Mae West 

impinger. 

4.1.2 Leak-Check Procedures. Leak-check 

the probe and three-way stopcock before 

inserting the probe into the stack. Connect 

the stopcock to the. outlet of the probe, and 

connect the sample line to the needle valve. 

Plug the probe inlet, turn on the sample pump, 

and pull a vacuum of at least 250 mm Hg (10 

in. Hg). Turn off the needle valve, and note 

the vacuum gauge reading. The vacuum 

should remain stable for at least 30 seconds. 

Place the probe in the stack at the sampling 

location, and adjust the probe and stopcock: 

WCt g of NaCI XWX35A53 

ml 58.44 

Eq. 26-1 

Refrigerate the stock standard solution and 

store no longer than 1 month. 

3.2.4 Chromatographic Eluent. Effective 

eluents for nonsuppressed IC using a resin- or 

silica-based weak ion exchange column are a 

4 mM potassium hydrogen phthalate solution, 

adjusted to pH 4.0 using a saturated sodium 

borate solution, and a 4 mM 4-hydroxy 

benzoate solution, adjusted to pH 8.6 using 1 

N NaOH. An effective eluent for suppressed 

ion chromatography is a solution containing 3 

mM sodium bicarbonate and 2.4 mM sodium 
P.18 

Federal Register / Vol. 56, No. 30 / Wednesday, February 13, 1991 / Rules and Regulations 5773 

carbonate. Other dilute solutions buffered to 

a similar pH and containing no interfering 

ions may be used. When using suppressed 

ion chromatography, if the "water dip" 

resulting from sample injection interferes 

with the chloride peak, use a 2 mM NaOH/2.4 

mM sodium bicarbonate eluent. 

4. Procedure 

4.1 Sampling. 

4.1.1 Preparation of Collection Train. 

Prepare the sampling train as follows: Pour 15 

ml of the aborting solution into each of the 

first two impingers, and add 15 ml of 

scrubber solution to the third and fourth 

impingers. Connect the impingers in series 

with the knockout impinger first, followed by 

the two impingers containing absorbing 

solution and the two containing the scrubber 

solution. Place a fresh charge of silica gel, or 

equivalent, in the drying tube or Mae West 

impinger. 

4.1.2 Leak-Check Procedures. Leak-check 

the probe and three-way stopcock before 

inserting the probe into the stack. Connect 

the stopcock to the outlet of the probe, and 

connect the sample line to the needle valve. 

Plug the probe inlet, turn on the sample pump, 

and pull a vacuum of at least 250 mm Hg (10 

in. Hg). Turn off the needle valve, and note 

the vacuum gauge reading. The vacuum 

should remain stable for at least 30 seconds. 

Place the probe in the stack at the sampling 

location, and adjust the probe and stopcock 

heating system to a temperature sufficient to 

prevent water condensation. Connect the first 

impinger to the stopcock, and connect the 

sample line to the last impinger and the 

needle valve. Upon completion of a sampling 

run, remove the probe from the stack and 

leak-check as described above. If a leak has 

occurred, the sampling run must be voided. 

Alternately, the portion of the train behind 

the probe may be leak-checked between 

multiple runs at the same site as follows: 

Close the stopcock to the first impinger (see 

Figure 1A of Figure 26-1), and turn on the 

sampling pump. Pull a vacuum of at least 250 

mm Hg, turn off the needle valve, and note 

the vacuum gauge reading. The vacuum 

should remain stable for at least 30 seconds. 

Release the vacuum on the impinger train by 

turning the stopcock to the vent position to 

permit ambient air to enter (see Figure IB of 

Figure 26-2). If this procedure is used, the full 

train leak-check described above must be 

conducted following the final run, and all 

preceding sampling runs must be voided if a 

leak has occurred. 

4.1.3 Purge Procedure. Immediately before 

sampling, connect the purge line to the 

stopcock, and turn the stopcock to permit the 

purge pump to purge the probe (see Figure IA 

of Figure 26-1). Turn on the purge pump, and 

adjust the purge rate to 2 liters/min. Purge for 

at least 5 minutes before sampling. 

4.1.4 Sample Collection. Turn on the 

sampling pump, pull a slight vacuum of 

approximately 25 mm Hg (1 in. Hg) on the 

impinger train, and turn the stopcock to 

permit stack gas to be pulled through the 

impinger train (see Figure lC of Figure 26-3). 

Adjust the sampling rate to 2 liters/min, as 

indicated by the rate meter, and maintain this 

rate to within 10 percent during the entire 

sampling run. Take readings of the dry gas 

meter volume and temperature, rate meter, 

and vacuum gauge at least once every 5 

minutes during the run. A sampling time of 1 

hour is recommended. Shorter sampling times 

may introduce a significant negative bias in 

the HCl concentration. At the conclusion of 

the sampling run, remove the train from the 

stack, cool, and perform a leak-check as 

described in section 4.1.2. 

4.2 Sample Recovery. Disconnect the 

impingers after sampling. Quantitatively 

transfer the contents of the first three 

impingers (the knockout impinger and the 

two absorbing solution impingers) to a leakfree storage bottle. Add the water rinses of 

each of these impingers and connecting 

glassware to the storage bottle. The contents 

of the scrubber impingers and connecting 

glassware rinses may be discarded. The 

sample bottle should be sealed, shaken to 

mix, and labeled. 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. 

4.3 Sample Preparation for Analysis. 

Check the liquid level in each sample, and 

determine if any sample was lost during 

shipment. If a noticeable amount of leakage 

has occurred, the volume lost can be 

determined from the difference between the 

initial and final solution levels, and this value 

can be used to correct the analytical results. 

Quantitatively transfer the sample solution to 

a 100-ml volumetric flask, and dilute the 

solution to 100 ml with water. 

4.4 Sample Analysis. 

4.4.1 The IC conditions will depend upon 

analytical column type and whether 

suppressed or nonsuppressed IC is used. An 

example chromatogram from a 

nonsuppressed system using a 150-mm 

Hamilton PRP-X100 anion column, a * * *. 2 

l/min flow rate of a 4 mM 4-hydroxy 

benzoate solution adjusted to a pH of 8.6 

using 1 N NaOH, a 50 -il sample loop, and a 

conductivity detector set on 1.0 jiS full scale 

is shown in Figure 26-2. 

4.4.2 Before sample analysis, establish a 

stable baseline. Next inject a sample of 

water, and determine if any Cl" appears in 

the chromatogram. If Cl" is present repeat 

the load/injection procedure until no Cl" is 

present. At this point, the instrument is ready 

for use. 

4.4.3 First inject the calibration standards 

covering an appropriate concentration range, 

starting with the lowest concentration 

standard. Next inject in duplicate, a QC 

sample followed by a water blank and the 

field samples. Finally, repeat the injection of 

calibration standards to allow compensation 

for any drift in the instrument during analysis 

of the field samples. Measure the Cl" peak 

areas or heights of the samples. Use the 

average response from the duplicate 

injections to determine the field sample 

concentrations using a linear calibration 

curve generated from the standards. 

4.5 Audit Analysis. An audit sample must 

be analyzed, subject to availability. 

0.799 

0.944 

1.957 

Chloride 

Figure 26-2. Example Chromatogram 

5. Calibration 

5.1 Dry Gas Metering System, 

Thermometers, Rate Meter, and Barometer. 

Same as in Method 6, sections 5.1, 5.2, 5.3, 

and 5.4. 

5.2 Calibration Curve for Ion 

Chromatograph. To prepare calibration 

standards, dilute given volumes (1.0 ml or 

greater) of the stock standard solution, with 

0.1 N H2SO4 (section 3.1.2) to convenient 

volumes. Prepare at least four standards that 

are within the linear range of the instrument 

and which cover the expected concentration 

range of the field samples. Analyze the 

standards as instructed in section 4.4.3, 

beginning with the lowest concentration 

standard. Determine the peak measurements, 

and plot individual values versus Cl' 

concentration in fig/ml. Draw a smooth curve 

through the points. Use linear regression to 
P.19 

5774 Federal Register / Vol. 56,. No. 30 / Wednesday,. February 13, 1991*/ Rules andiRegulatiGhs 

calculate a formula describing the resulting 

linear curve. 

ft Quality Assurance 

6.1 Applicability. When the method is 

used to analyze samples to demonstrate 

compliance with a source emission 

regulation, a set of two audit samples must be 

analyzed. 

6.2 Audit Procedure. The audit sample 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 EPA 

audit samples. If this condition is met, 

auditing the 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. 

6.3 Audit Sample Availability. The audit 

samples may be obtained by writing or 

calling the EPA Regional Office or the 

appropriate enforcement agency. The request 

for the audit samples must be made at least 

30 days prior to the scheduled compliance 

sample analyses. 

' 6.4 Audit Results. Calculate the 

concentrations in mg/dscm using the 

specified sample volume in the audit 

instructions. 

Nots* Indication of acceptable results may 

be obtained immediately by reporting the 

audit results in mg/dscm and compliance 

results in total fig HCl/ sample to the 

responsible enforcement agency. 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. Include this information 

with subsequent analyses for the same 

enforcement agency during the 30-day period. 

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. However, if the audit results do 

Inot affect the compliance or noncompliance 

status of the affected facility, the 

Administrator may waive the reanalysis 

requirement further audits, or retests and 

accept the results of the compliance test. 

While steps are being taken to resolve audit 

analysis problems, the Administrator may 

also choose to use the data to determine the 

compliance or noncompliance status of the 

affected facility. 

7. 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. 

7.1 Sample Volume, Dry Basis, Corrected 

to Standard Conditions. Calculate the sample 

volume using Eq. 6-1 of Method 6. 

7.2 Total fig HCl Per Sample. 

(S-fl)(100)(36.46) 

(35.453) 

= (102.84)(S-5) 

Eq. 26-2 

where: 

m = Mass of Hcl in sample, fig. 

S = Concentration of sample, fig Cl'/ml. 

*B = Concentration of blank, fig Cl'/mL 

100 = Volume of filtered and diluted sample, 

ml. 

36.46 -= Molecular weight of HCl, fig/figmole. 

35.453 = Atomic weight of Cl, fig/fig-mole. 

7.3 Concentration of HCl in the Flue Gas. 

Km 

VmUld) 

Eq. 26-3 

where: 

C = Concentration of HCl, dry basis, mg/ 

dscm. 

K = 10'mg/fig. 

m = Mass of HCl in sample, fig. 

Vm(rtd) = Dry gas volume measured by the 

dry gas meter, corrected to standard 

conditions, dscm. 

ft 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. Report No. 

, 1989. 

2. State of California, Air Resources Board. 

Method 421. "Determination of Hydrochloric 

Acid Emissions from Stationary Sources." 

March 18,1987. 

3. Entropy Environmentalists Inc. 

"Laboratory Evaluation of a Sampling and 

Analysis Method for Hydrogen Chloride 

Emissions from Stationary Sources: Interim 

Report." EPA Contract No. 68-02-4442. 

Research Triangle Park, North Carolina. 

January 22,1988. 

Appendix A [Amended] 

3. Method 19 of appendix A part 60 is 

amended by adding paragraphs 4.3 and 5.4 as 

follows: Method 19—Determination of Sulfur 

Dioxide Removal Efficiency and Particulate 

Matter, Sulfur Dioxide, and Nitrogen Oxides 

Emission Rates 

**** * 

4.3 Daily Geometric Average Pollutant 

Rates from Hourly Values. The geometric 

average pollutant rate (Em) is computed using 

the following equation: 

E«. = EXP [(1/n) 2 [lnfEJ]] 

1=1 

Eq. 19-

20a 

where: 

Era = daily geometric average pollutant rate, 

ng/J (lbs/million Btu) or ppm corrected to 

7 percent O2. 

Ehj = hourly arithmetic average pollutant rate 

for hour "j," ng/J (lb/million Btu) or ppm 

corrected to 7 percent O2. 

n = total number of hourly averages for 

which pollutant rates are available 

within the 24 hr midnight to midnight 

daily period. 

In = natural log of indicated value. 

EXP = the natural logarithmic base (2.718) 

raised to the value enclosed by brackets. 

• * * * * 

5.4 Daily Geometric Average Percent 

Reduction from Hourly Values. The geometric 

average percent reduction (%R„) is computed 

using the following equation: 

: 

! 
P.20 

Federa l Riegister. / £ Vol. "56* 'No. "30 >/' We'dries'day, - February 13, 1991 7 Rules and ReguMtoris 5775: 

%R„ = 100 1-EXP [(1/n) 2 In (Ej0/EM)] 

1

 j=l ' 

Eq. 19-

24a 

where: 

%R„ = daily geometric average percent . 

reduction. 

Ejo, EM = matched pair hourly arithmetic 

average pollutant rate, outlet and inlet, 

respectively, ng/J (lb/million Btu) or ppm 

corrected to 7 percent 02. 

n = total number of hourly averages for 

which paired inlet and outlet pollutant 

rates are available within the 24-hr 

midnight to midnight daily period. 

In=natural log of indicated value. 

EXP = the natural logarithmic base (2.718) 

raised to the value enclosed by brackets. 

Note: The calculation includes only paired 

data sets (hourly average) for the inlet and 

outlet pollutant measurements. 

* * ' * * * 

[FR Doc. 91-1399 Filed 2-12-91; 8:45 am] 

BILLING CODE 6560-50-M 

DEPARTMENT OF COMMERCE 

National Oceanic and Atmospheric 

Administration 

50 CFR Parts 672 and 675 

[Docket No. 90899-1019] 

Groundfish of the Guif of Alaska; 

Groundfish of the Bering Sea and 

Aleutian Islands 

AGENCY: National Marine Fisheries 

Service (NMFS), NOAA, Commerce. 

ACTION: Final rule, technical 

amendment. 

SUMMARY: The Secretary of Commerce 

issues this final rule implementing a 

technical amendment to reinstate 

regulatory language that was 

unintentionally deleted by regulations 

implementing Amendment 13 to the 

Fishery Management Plan for the Bering 

Sea/Aleutian Islands Groundfish 

(Bering FMP) and Amendment 18 to the 

Fishery Management Plan for the Gulf of 

Alaska Groundfish Fishery (Gulf FMP) 

(54 FR 50386, December 6,1989). 

EFFECTIVE DATE: February 8,1991. 

FOR FURTHER INFORMATION CONTACT: 

Patricia Peacock (Fishery Management 

Specialist), NMFS, Plans and 

Regulations Division, 1335 East-West 

Highway, Silver Spring, Maryland 20910, 

telephone 301-427-2343. 

SUPPLEMENTARY INFORMATION: 

Groundfish fisheries in the Exclusive 

Economic Zone off Alaska are governed 

by Federal regulations at 50 CFR parts 

611, 620, 672, and 675 that implement the 

Bering and the Gulf FMPs. These FMPs 

were prepared by the North Pacific 

Fishery Management Council and 

approved by the Secretary of Commerce 

(Secretary) under provisions of the 

Magnuson Fishery Conservation and 

Management Act. 

This final rule implements a technical 

amendment that (1) reinstates language 

unintentionally deleted by amendatory 

language in 54 FR 50383 (December 6, 

1989) and (2) retains the amendatory 

language of 56 FR 492 (January 7,1991). 

On December 6,1989, a final rule was 

published in the Federal Register (54 FR 

50386) that was intended only to amend 

the introductory language of 

§§ 672.20(a)(2) and 675.20(a)(2). Item 11 

of this amendatory language states that 

* * * paragraphs (a)(2) and (f)(1) are 

revised * * *; item 20 states that 

* * * paragraph (a)(2) is revised * * *. 

This amendatory language revised the 

introductory text of paragraph (a)(2) in 

these sections but deleted the remainder 

of the regulatory language in 

§§ 672.20(a)(2) and 675.20(a)(2). 

Paragraphs in § 672.20 that were 

unintentionally deleted were (a)(2)(i), 

(a)(2)(H), (a)(2)(ii)(A), and (a)(2)(ii)(B). 

Table 1 in § 672.20 also was 

unintentionally deleted. Paragraphs that 

were unintentionally deleted in § 675.20 

were as follows: (a)(2)(i), (a)(2)(i)(A), 

and (a)(2)(i)(B). 

On January 1,1991, final rules' 

implementing Amendment 14 to the 

Bering FMP and Amendment 19 to the 

Gulf FMP also revised text in 

§§ 672.20(a)(2) and 675.20(a)(2) (56 FR 

492, January 7,1991). This rule retains 

the changes to these sections resulting 

from Amendments 14 and 19. 

The Gulf and Bering FMPs were 

implemented using procedures specified 

by the Magnuson Act and the 

Administrative Procedure Act. However, 

as explained above, the language 

currently in §§ 672.20(a) and 675.20(a) 

does not correctly reflect the Gulf or 

Bering FMPs and subsequent 

amendments. 

This final rule, technical amendment, 

is reinstating regulatory language 

needed to implement correctly the 

Bering and Gulf FMPs as amended. 

Classification 

This final rule, technical amendment, 

is issued under parts 672 and 675. 

Because this rule reinstates regulatory 

text that was inadvertently deleted 

during an earlier rulemaking proceeding 

and makes no substantive changes other 

than changes determined in rulemaking 

for Amendments 14 and 19, it is 

unnecessary under 5 U.S.C. 553(b)(B) to 

provide for prior public comment and 

there is good cause under 5 U.S.C. 553(d) 

not to delay for 30 days its effective 

date. 

Because this rule is being issued 

without prior comment, a regulatory 

flexibility analysis is not required under 

the Regulatory Flexibility Act and none 

has been prepared. 

This rule reinstates language that has 

been determined not to be a major rule 

under Executive Order 12291, does not 

contain policies with federalism 

implications sufficient to warrant 

preparation of a federalism assessment 

under E.0.12612, and does not contain a 

collection-of-information requirement 

for the purposes of the Paperwork 

Reduction Act. There is no change in the 

regulatory impacts previously reviewed 

and analyzed. 

List of Subjects in 50 CFR Parts 672 and 

675 

Fisheries, General limitations. 

Dated: February 7,1991. 

Michael F. Tillman, 

Acting Assistant Administrator for Fisheries, 

National Marine Fisheries Service. 

For reasons set out in the preamble, 50 

CFR parts 672 and 675 are amended as 

follows: 

PART 672—GROUNDFISH OF THE 

GULF OF ALASKA 

1. The authority citation for part 672 

continues to read as follows: 

Authority: 16 U.S.C. 1801 et seq. 

2. Section 672.20(a)(2) is revised and 

Table 1 is added to the section to read 

as follows: