- r

ENVIRONMENTAL

PROTECTION

AGENCY

KRAFT PULP MILLS

Standards of Performance for

New Stationary Sources and

Availability of Draft Guideline

Document

THURSDAY, FEBRUARY 23, 1978

PART V

ES

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7568 RubLES7' AI~i kREdIJrATdhV

[6560-01]

Title 40-Protection of the Environment

CHAPTER I-ENVIRONMENTAL PROTECTION

AGENCY

SUBCHAPTER C-AIR PROGRAMS

EFRL 833-1]

PART 60-STANDARDS OF PERFORMANCE

FOR NEW STATIONARY SOURCES

Kraft Pulp Mills

AGENCY: Environmental Protection

Agency.

ACTION: Final rule.

SUMMARY: The standards limit emissions of total reduced sulfur (TRS)

and particulate matter from new,

modified, and reconstructed kraft pulp

mills. The standards implement the

Clean Air Act and are based on the

Administrator's determination that

emissions from kraft pulp mills con- tribute significantly to air pollution.

The intended effect of these standards

is to require new, modified, and recon- structed kraft pulp mills to use the

best demonstrated system of continu- ous emission reduction.

EFFECTIVE DATE: February 23,

1978.

ADDRESSES: The Standards Support

and Environmental Impact Statement

(SSEIS) may be obtained from the

U.S. EPA Library (MD-35), Research

Triangle Park, N.C. 27711 (specify

"Standards Support and Environmental Impact Statement, Volume 2: Promulgated Standards of Performance

for Kraft Pulp Mills" (EPA-450/2-76-

014b)). Copies of all comment letters

received from interested persons participating in this rulemaking are available for inspection and copying during

normal business hours at EPA's Public

Information Reference Unit, Room

2922 (EPA Library), 401 M Street SW.,

Washington, D.C.

FOR FURTHER INFORMATION

CONTACT:

Don R. Goodwin, Emission Standards and Engineering Division, Environmental Protection Agency, Research Triangle Park, N.C. 27711,

telephone No. 919-541-5271.

SUPPLEMENTARY INFORMATION:

On September 24, 1976 (41 FR 42012),

standards of performance were proposed for new, modified, and recon- structed kraft pulp mills under section'

111 of the Clean Air Act, as amended.

The significant comments that were received during the public comment

period have been carefully reviewed

and considered and, where determined

by the Administrator to be appropriate, changes have been included in

this notice-of final rulemaking.

THE STANDARDs

The standards limit emissions of particulate matter from three affected facilities at kraft pulp mills. The limits are: 0.10 gram per dry standard cubic

meter (g/dscm) at 8 percent oxygen

for recovery furnaces, 0.10 gram per

kilogram of black liquor solids (dry

weight) (g/kg BLS) for smelt dissolving tanks, 0.15 g/dscm at 10 percent

oxygen for lime kilns when burning

gas, and 0.30 g/dscm at 10 percent

oxygen for lime kilns when burning

oil. Visible emissions from recovery

furnaces are limited to 35 percent

opacity.

The standards also limit emissions of

TRS. from eight affected facilities at

kraft pulp mills. The limits are: 5 parts

.per million (ppm) by volume at 10 percent oxygen from the digester systems, multiple-effect evaporator systems, brown stock, washer' systems,

black liquor oxidation systems, and

condensate stripper systems; 5 ppm by

volume at 8 percent oxygen from

straight kraft recovery furnaces, 8

ppm by volume at 10 percent oxygen

from lime kilns; and 25 ppm by volume

at 8 percent oxygen from cross recov- ery furnaces, which are defined as fur- naces burning at least 7 percent neu- tral sulfite semi-chemidal (NSSC)

liquor and having a green liquor sulfidity of at least 28 percent. In addition,

TRS emissions from smelt dissolving

tanks are limited to 0.0034 g/kg BIS.

The proposed TRS standard for the

lime kiln has been changed, a separate

TRS standard for cross recovery fur- naces has been developed, and the proposed format of the standards for

smelt dissolving tanks, digesters, multiple-effect evaporators, brown stock

washers, black liquor oxidation and

condensate strippers have been

changed. The TRS, particulate matter

and opacity standards for the other facilities, however, are essentially the same as those proposed.

It should be noted that standards of

performance for new sources established under section 111 of the Clean

Air Act reflect emission limits achievable with the best adequately demonstrated technological system of con- tinuous emission reduction considering the cost of achieving such emission re- ductions and any nonair quality

health, environmental, and energy impacts. State implementation plans

(SIP's) approved or promulgated

under section 110 of the Act, on the

other hand, must provide for the attainment and maintenance of national

ambient air quality standards

(NAAQS) designed to protect public health and welfare. For that purpose

SIP's must in some cases require

greater emission reductions than those

required by standards of performance

for new sources. Section 173(2) of the

Clean Air Act, as amended in 1977, re- quires, among other things, that a new

or modified source constructed In an area which exceeds the NAAQS must

reduce emissions to the level which re- flects the "lowest achievable emission

rate" for such category of source,

unless the owner or operator demon

strates that the source cannot achieve

such an emission rate. In no event can the emission rate exceed any applicable standard of performance.

A similar situation may arise when a major emitting facility is to be con- structed in a geographic area which

falls under the prevention of significant deterioration of air quality provisions of the Act (Part C). These provisions require, among other things,

that major emitting facilities to be

constructed in such areas are to be

subject to best available control technology. The term "best available con- trol technology" (BACT) means "an

emission limitation based on the maxi- mum degree of reduction of each pollutant subject to regulation under this

Act emitted from or which results

from any major emitting facility,

which the permitting authority, on a case-by-case basis, taking into account

energy, environmental, and economic

impacts and other costs, determines It

achievable for such facility through

application of production processes

and available methods, systems, and

techniques, including fuel cleaning or treatment or innovative fuel combustion techniques for control of each

such pollutant. In no event shall application of 'best available control technology' result in emissions of any pollutants which will exceed the emissions allowed by any applicable standard established pursuant to section

111 or 112 of this Act."

Standards of performance 'should

not be viewed as the ultimate in

achievable emission control and

should not preclude the imposition of a more stringent emission standard,

where appropriate. For example, cost

of achivement may be an important

factor in determining standards of performance applicable to all areas of the

country (clean as well as dirty). Costs

must be accorded far less weight in determining the "lowest achievable emission rate" for new or modified sources locating in areas violating statutorilymandated health and welfare standards. Although there may be emission control technology available that can reduce emissions below those

levels required to comply with standards of performance, this technology

might not be selected as the basis of

standards of performance due to costs

associated with its use. This in no way

should preclude its use in situations

where cost is a lesser consideration,

such as determination of the "lowest

achievable emissioli rate."

In addition, States are free under

section 116 of the Act to establish even more stringent emission limits than

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RULES AND REGULATIONS

those established under section 111 or those necessary to attain or maintain

the NAAQS under section 110. Thus, new sources may in some cases be subject to limitations more stringent than

standards of performance under sec- tion 111, and prospective owners and

operators of new sources should be aware of this possibility in planning

for such facilities.

ENVIRONMrrAL AND ECONOMIC IMPACT

The promulgated standards will

reduce particulate emissions about 50

percent below requirements of the

average existing State regulations.

TRS emissions will be reduced by

about 80 percent below requirements

of the average existing State regulations, and this reduction will prevent

odor problems from arising at most new kraft pulp mills. The secondary

environmental impacts of the promulgated standard will be slight increases

in water demand and wastewater

treatment requirements. The energy

impact of the promulgated standards

will be small, increasing national

-energy consumption in -1980 by the

equivalent of only 14 million barrels

per year of No. 6 oil. The economic

impact will be small with fifth-year

annualized costs being estimated at

$33 million.

PUBLIC PARTICIPATION

Prior to proposal of the Standards,

interested parties were advised by

public notice in the FEDERAL REGISTER

of a meeting of the-National Air Pollution Control Techniques Advisory

Committee. In addition, copies of the

proposed standards and the Standards

Support and Environmental- Impact

Statement (SSEIS) were distrubited to

members of the kraft pulp industry

and several environmental groups at

the time of proposal. The public com- ment period extended from September

24, 1976, to March 14, 1977, and resulted in 42 comment letters with 28 of

these letters coming from the industry, 12 from various regulatory agencies, and two from U.S. citizens. Several comments resulted in changes to

the proposed standards. A detailed discussion of the comments and changes

which resulted is presented in Volume

2 of the SSEIS. A summary is presented here.

SIGNIFIcATr COMM=S AND CHANGES

MADE IN THE PROPOSED REGULATIONS

Most of the comment letters re- ceived contained multiple comments.

The most significant comments and

changes made to the proposed regulations are discussed below.

IMPACTS OF THE PROPOSED STANDARDS

Several commenters expressed con- cern about the increased energy con- sumption which would result from

compliance with proposed standards.

These commenters felt that this would

conflict with the Department of Energy's goal to reduce total energy con- sumption in the pulp and paper industry by 14 percent. This factor was con- sidered in the analysis of the energy impact associated with the standards

and is discussed in the SSEIS. Although the standards will increase the

difficulty of attaining this energy re- duction goal, the 4.3 percent increase

in energy usage that will be required

by new, modified, or reconstructed by kraft pulp mills to comply with the

standards is considered reasonable in

comparison to the benefits which will

result from the corresponding reduction in TRS and particulate matter

emissions.

EMISSION CONTROL TECHNOLOGY

Most of the comments received re- garding emission control technology

concerned the application of this technology to either lime kilns or recovery

furnaces. A few comments, however,

expressed concern with the use of the

oxygen correction factor included in

the proposed standards for both lime

kilns and recovery furnaces. These

commenters pointed out that adjusting the concentration of particulate

.matter and TRS emissions to 10 percent oxygen for lime kilns and 8 percent oxygen for recovery furnaces

only when the oxygen concentration

exceeded these values effectively

placed more stringent standards on the most energy-efficient operators.

To ensure that the standard Is equitable for all operators, these coinmenters 'suggested that the measured

particulate matter and TRS concen- trations should always be adjusted to

10 percent oxygen for the lime kiln

and 8 percent oxygen for the recovery

furnace.

These comments are valid. Requiring a lime kiln or recovery furnace

with a low oxygen concentration to

meet the same emission concentration as a lime kiln or recovery furnace with a high oxygen concentration would effectively place a more stringent emission limit on the kiln or furnace with

the low oxygen concentration. Consequently, the promulgated standards

require correction of particulate

matter and TRS concentrations to 10

percent or 8 percent oxygen, as appropriate, in all cases. Lime Kans. Numerous comments were received on the emission control

technology for lime kIns. The main

points, questioned by the commenters were: (a) Whether caustic scrubbing is

effective in reducing TRS emissions

from lime kilns; (b) whether an over- design of the mud washing facilities at

lime kiln E was responsible for the

lower TRS emissions observed at this

lime kiln; and (c) the adequacy of the

data base used in developing the TRS

standard.

The effectiveness of caustic scrubbing is substantiated by comparison of

TRS emissions during brief periods

when caustic was not being added to

the scrubber at lime kiln E, with TRS

emissions during normal operation at

lime kiln E when caustic is being

added to the scrubber. These observations clearly indicate that TRS emissions would be higher if caustic was not used In the scrubber. The ability

of caustic scrubbing to reduce TRS

emissions is also substantiated by the

experience at another kraft pulp mill

which was able to reduce TRS emisslons from Its lime kiln -rom 40-50

ppm to about 20 ppm merely by

adding caustic to the scrubber. These

factors, coupled with the emission

data showing higher TRS emissions

from those lime kilns which employed

only efficient mud washing and-good

lime kiln process control, clearly show

that, caustic scrubbing reduces TRS

emissions.

The mud washing facilities at lime

kiln E are larger than those at other

kraft pulp mills of equivalent pulp ca- pacity. This "overdesign'" resulted

from initial plans of the company to

process lime mud from waste water

treatment. These waste water treatment plans were later abandoned.

Since the quality or efficiency of mud

washing has been shown to be a significant factor In reducing TRS emissions from lime kilns, the larger mud

washing facilities at lime kiln E un- doubtedly contributed to the low TRS

emissions observed at this kiln. With

the data available, however, It is not

possible to separate the relative contribution of these mud washing facilities

to the low TRS emissions observed

from the relative contributions of

good process operation of the lime kiln

and caustic scrubbing.

Comments questioning the adequacy

of the data base used in developing

the standards for lime kilns were mainly directed toward the following

points: the TRS standard was based on only one lime kiln; sampling losses

which may have occurred during testing were not taken into account; and no lime kiln met both the TRS standard and the particulate standard. . As mentioned above, the TRS standard is based upon the emission con- trol system installed at lime kiln E

(i.e., efficient mud washing, good lime

kiln process operation, and caustic

scrubbing). While it Is true that no other lime kiln in the United States is

currently achieving the TRS emission

levels observed at lime kiln E, there is no other lime kiln in the United States

which is using the same-emission con- trol system that is employed at this facility. As discussed In the SSEIS, an analysis of the various parameters Influencing TRS emissions from lime

kilns indicates that this system of

emission reduction could be applied to

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RULES AND REGULATIONS

all new, modified, or reconstructed

lime kilns and achieve the same reduction in emissions as observed at lime

kiln E. Section 111 of the Clean Air

Act requires that "standards of perfor- mance reflect the degree of emission

reduction achievable through the application of the best system of con- tinuous emission reduction which

(taking into consideration the cost of

achieving such emission reduction, and

any nonair quality health and environmental impact and energy requirements) the Administrator determines

has been adequately demonstrated for

that category of sources." Litigation of

standards of performance has resulted

in clarification of the term "adequately demonstrated." In Portland Cement

Association v. Ruckelshaus (486 F. 2d

375, D.C. Circuit, 1973), the standards

of performance were viewed by the

Court as "technology-forcing." Thus,

while a system of emission reduction

must be available for use to be considered adequately demonstrated, it does

not have to be in routine use. However, in order to ensure that the numerical emission limit selected was consistent with proper operation and maintenance of the emission control system on lime kiln E, continuous monitoring

data was examined. This analysis indicated that an emission source test of

lime kiln E would have found TRS

emission above 5 ppm greater than 5

percent of the time. This analysis also

indicated, however, that it was very

unlikely that an emission source test

of lime kiln E would have found TRS

emissions above 8 ppm. Thus, it appeared that the 5 ppm TRS numerical

emission limit included in the proposed standard for lime kilns was too

stringent. Accordingly, the numerical

emission limit included in the promulgated TRS standard for lime kilns has

been revised to 8 ppm. As discussed

later in this preamble, consistent with

this change in the numerical emission

limit, the excess emissions allowance

included within the emission monitoring requirements has been eliminated.

This does not reflect a change in the

basis for the standard. The standard is

still based on the best system of emission reduction, considering costs, for

controlling TRS emissions from lime

kilns (i.e., efficient mud washing, good

lime kiln process operation, and caustic scrubbing). This system, or one equivalent to it, will still be required

to comply with the standard. .Since proposal of the standards,

sample losses of up to 20 percent

during emission source testing have

been confirmed. Although these losses were not considered in selecting the

numerical emission limit included in

the proposed TRS emission standard,

they have been considered iri selecting

the numerical emission limit included

in the promulgated standard. Also,

since the amount of sample loss that

occurs within the TRS emission measurement system during source testing can be determined, procedures have

been added to Reference Method 16

requiring determination of these losses

during each source test and adjustment of the emission data obtained to

take these losses into account.

With regard to the ability of a lime

kiln to comply with both the TRS

emission standard and the particulate

emission standard simultaneously,

caustic scrubbing will tend to increase

particulate emissions due to release of

-sodium fume from the scrubbing

liquor. Compared to the concentration

of particulate matter permitted in the

gases discharged to the atmosphere,

however, the potential contribution of

sodium fume from caustic scrubbing is

quite small. Consequently, with proper

operation and maintenance, sodium

fume due to caustic scrubbing will not cause particulate emissions from a

lime kiln to exceed the numerical

emission limit included in the promulgated standard.

Recovery Furnace. A number of com- ments were received regarding both

the proposed TRS emission standard

and the proposed particulate emission

standard for recovery furnaces. Basically, the major issue was whether a cross recovery furnace could comply

with the 5 ppm TRS standard or whether a separate standard was nec- essary.

- Review of the data and information

submitted N'ith these comments indicates that the operation of cross recov- ery furnaces is substantially different

from that of straight kraft recovery

furnaces. The sulfidity of the black

liquor burned in cross recovery fur- naces and the heat content of the

liquor, both of which are significant

factors influencing TRS emissions, are considerably different from the levels

found in straight kraft recovery furnaces.

Analysis of the data indicated that

TRS emissions were generally less

than 25 ppm, with only occasional ex- cursions exceeding this level. Consequently, the promulgated TRS emission standard has been revised to Include a separate TRS numerical emission limit of 25 ppm for cross recovery

furnaces.

Smelt Dissolving Tank Numerous

comments were received concerning

the format of the proposed TRS and

particulate emission standards for

smelt dissolving tanks. These. com- ments pointed out that standards in

terms of emissions per unit of air-dried

pulp were inequitable for kraft pulp

mill which produced low-yield pulps

since both TRS and particulate emissions from the smelt dissolving tanks are proportional to the tons of black

liquor solids fed into the tanks. The

black liquor solids produced per ton of

air-dried pulp, however, can vary substantially from mill to mill. A standard

in terms of emissions per unit of airdried pulp, therefore, requires greater

control of emissions at kraft pulp mills

which use low-yield pulps (higher

solids-to-pulp ratio).

Review of these comments does

indeed indicate that the format of the

proposed standards was inequitable,

The format of the promulgated standards, therefore, has been revised to

emissions per unit of black liquor

solids fed to the smelt dissolving

tanks. Since the percent solids and

black liquor flow rate to the recovery

furnace is routinely monitored at kraft

pulp mills, the weight of black liquor

solids corresponding to a particular

emissions period will be easy to determine.

Brown Stock Washers. Several comments expressed concern about com- bustion of the high volume-low TRS

concentration gases discharged from

brown stock washers and black liquor

oxidation facilities in recovery fur- naces without facing a serious risk of

explosions. As discussed In the SSEIS,

information obtained from two kraft

pulp mill operators indicates that this

practice is both safe and reliable when

it is accompanied by careful engineering and operating practices. Danger of an explosion occurring is essentially

eliminated by introducing the gases

high in the furnace. Since some older

furnaces do not have the capability to

.accept large volumes of gases at

higher combustion ports, this practice

may not be safe for some existing fur- naces. In addition, the costs associated

with altering these furnaces to accept

these gases are frequently prohibitive.

Consequently, the promulgated standards include an exemption for new,

modified, or reconstructed brown

stock washers and black liquor oxida.

tion facilities within existing kraft

pulp mills where combustion of these

gases in an existing facility is not feasible from a safety or economic standpoint.

CONTINUOUS MONITORING

Numerous comments were received

concerning the proposed continuous

monitoring requirements. Generally,

these comments questioned the re- quirement to install TRS monitors in

light of the absence of performance

specifications for these monitors.

At the time of proposal of the standards, both EPA and the kraft pulp

mill industry were engaged in developing performance specifications for

TRS continuous emission monitoring

systems. It was expected that 'this

work would lead to performance specifications for these monitoring systems

.by the time the standards of perfor- mance were promulgated. Unfortunately, this is not the case. In a joint

EPA/industry effort, the compatibility

of various TRS emission monitoring

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methods with Reference Method 16,

which is the performance test method

to determine TRAS emissions, is still

under study. There is little doubt but

that these TRS emission -monitoring

systems will be shown to be compatible -with Reference Method 16, and

that performance -specifications for

these systems will be developed. Consequently, the promulgated standards

include TRS continuous emission-monitoring requirements. These requirements, however, willnot become effective until performance specifications

for TRS continuous emission monitoring systems have been developed. To

accommodate this situation, not only

for the promulgated standards for

kraft pulp mills, but also for standards

of performance that may be developed

in the future that may also face this

situation, section 60.13 of the General

Provisions for subpart 60 is amended

to brovide that continuous monitoring

systems need not be installed until

performance specifications for these

systems are promulgated under Appendix B to subpart 60. This will ensure that all facilities which are covered-by standards of performance will

eventually install continuous emission

monitoring systems where required.

EXCESS E1 ISSIONS

Numerous comments were received

which were concerned with the excess emission allowances and the reporting

requirements for excess emissions. In

general, these comments reflected a lack of understanding with regard to

the concept of excess emissions. Consequently, a brief xeview of tjiis con- cept is appropriate.

Standards of performance have two

major objectives. The first is installation of the best system of emission re- duction, considering costs; and the

second is continued proper operation

and maintenance of the system

throughout its useful life. Since the

numerical emission limit included in

standards of performance is selected

to reflect the performance of the best

system of emission reduction under

conditions of proper operation and

maintenance, the performance test,

under 40 CFR 60.8 rejpresents the ability of the source to meet these objectives. Performance tests, however, are often time consuming and complex. As

a-result, -while the performance test is an excellent mechanism for achieving

these objectives, it is rather cumbersome and inconvenient for routinely

achieving these objectives. Therefore,

the Agency believes that continuous

monitors must play an important role

in meeting these objectives.

Excess emissions-are defined-as emissions exceeding the miumerical emission limit included in a standard of

performance. Continuous emission

monitoring, therefore, identifies periods of excess emissions and when combined with the requirement that these

periods be reported to EPA. It provides

the Agency with a useful mechanism

for achieving the previously men- tioned objectives.

Continuous emlIon monitoring,

however, will identify all periods of excess emissions, including those

which are not the result of improper

operation and maintenance. Excess

emissions due to start-ups, shutdowns,

and malfunctions, for example, are un- avoidable or beyond the control of an owner or operator and cannot be attributed to Improper operation and

maintenance. Similarly, excess emissions as a result of some inherent var- ability or fluctation within a process

which influences emissions cannot be

attributed to Improper operation and

maintenance, unless these fluctations

could be controlled by more carefully

attending to those process operating

parameters during routine operation

which have little effect on operation

of the process, but which may have a significant effect on emissions.

To quantify the potential for excess emissions due to Inherent variability

in a process, continuous monitoring

data are used whenever possible to calculate an excess emission allowance.

For TRS emissions at kraft pulp mills,

this allowance Is defined as follows. If a calendar quarter is divided into dlscrete contiguous 12-hour time periods,

the excess emission allowance is expressed as the percentage of these

time periods. Excess emissions may occur as the result of unavoidable variability within the kraft pulping process. Thus, the excess emlssions

allowance represents the potential for excess emissions under conditions of

proper operation and maintenance in

the absence of start-ups, shutdowns

and malfunctions, and Is used as a guideline or screening mechanism for

interpreting the data generated by the excess emission reporting requirements.

Although the excess emission reporting requirements provide a mechanism

for achieving the objective of proper

operation and maintenance of the best

system of emission reduction, this

mechanism Is not necessarily a direct

indicator of improper operation and

maintenance. Consequently, excess emission reports must be reviewed and

interpreted for proper decislonmaking.

In general, the comments received

concerning the excess emission reporting requirements questioned: (1) The

adequacy of the TRS excess emission

allowance for lime kilns and (2) the

lack of a TRS excess emission

allowance for recovery furnaces.

With regard to the adequacy of the

TRS excess emissions allowance for

lime kilns, a reevaluation of the TRS

emission data from lime kiln E led the

Agency to the conclusion that, for a TRS emission limit of 5 ppm, an

excem emission allowance of 6 percent was appropriate. However, a simil

analysis also indicates that an excess

emission allowance is not appropriate

at a TRS emission level of 8 ppm. Accordingly, the excess emission reportIng iequirements included in the promulgated standard for lime kilns con- tains no excess emission allowance.

This does not represent a change in

the basis of the standard. The standard will still require installation of the

best system of emission reduction, con- sidering costs (Le., efficient mud washing, good lime kiln process operation,

and caustic scrubbing; or an alternative system equivalent to the perfor- mance of this system).

With regard to the lack of a TRS excess emission allowance for recovery

furnaces, at the time of proposal of

the standards, no TRS continuous

emission monitoring data were available from a well-controlled and well

operated recovery furnace which could

be used to determine an excess emission allowance. Several months of

TRS continuous emission monitoring

data, however, were submitted with

the comments received from the operator of recovery furnaceD concerning

this point.

A review of the data indicates that,

while some of the excursions of TRS

emissions above 5 ppm reflected either

Improper operation and maintenance, or start-ups, shutdowns, or malfunctions, most of these excursions reflected unavoidable normal variability in

the operation of a kraft-pulp mill re- covery furnace. Discounting those ex- cursions in emissions from the data

which were due to iniproper operation

and maintenance, or start-ups, shutdowns, or malfunctions indicates that an excess emission allowance of 1 percent Is appropriate for all recovery

furnaces.

Including an excess emissions

allowance in the promulgated standards for recovery furnaces, but not

for lime kilns, is a reversal of the proposed requirements. Including such an allowance for recovery furnaces but

not for lime kilns, however, is consistent with the nature of the different

emission control systems which were selected as the bases for these standards. The emission control system

upon whlch-Jhe TRS standard for re- covery furnaces is. based consists of

black liquor oxidation and good pro- cess operation of the recovery furnace

for direct recovery furnaces, and good

process operation alone for indirect re- covery furnaces. Neither of these emission control systems are particularly

well suited to controlling fluctuations

in the rlaaft pulping process. Thus,

fluctuations in the process tend to

pass through the emission control

system and show up as fluctuations in

TRS emissions.

The emission control system upon

which the TRS standard for lime kilns

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is based consists of efficient mud*

washing, good process operation of the

lime kiln, and caustic scrubbing of the

gases discharged from the lime kiln.

As with the emission control system

upon which the standard for recovery furnaces is based, the first two emission control techniques (i.e., mud

washing and good process operation)

are not particularly well suited to controlling fluctuations in the kraft pulping process. The third emission control

technique, however, caustic scrubbing,

is an "add-on" emission control technique that can be designed to accommodate fluctuations in TRS emissions

and minimize or essentially eliminate

these fluctuations.

EMISSION TESTING

A few comments were received

which questioned the validity of the

results obtained by Reference Method

16, due to sample losses and sulfur

dioxide (SO2) interference.

With regard to the validity of the results obtained by Reference Method

16, as mentioned earlier, during the

emission testing program, it was not

widely known that sample losses could

occur within the TRS emission measurement system. Since proposal of

the standards, however, sample losses

of up to 20 percent during emission

source testing have been confirmed.

Although these losses were not considered in selecting the numerical emission limits included in the proposed TRS emission standards, they have

been considered in selecting the nu-.

merical emission limit included in the

promulgated standards. Also, since the

amount of sample loss that occurs

within the TRS emission measurement system during source testing can

be determined, procedures have been

added to Reference Method 16 requir- ing determination of these losses

-during each source test and adjustment of the emission data obtained to

take these losses into account. This

will ensure that the TRS emission

data obtained during a performance

test are accurate.

It has also been confirmed that high

concentrations of SO2 will interfere

with the determination of TRS emissions to some extent. At this point,

however, it is not known what SO2

concentration levels will result in a sig- nificant loss of accuracy in determining TRS emissions. The ability of a citrate scrubber to selectively remove

S02 prior to measurement of TRS

emissions is now being tested. In addition, various chromatographic columns might exist which would effectively resolve this problem. As soon as

an appropriate technique is developed

to overcome this problem, Reference

Method 16 will be amended.

This problem of S02 interference

will not present major difficulties to

the use of Reference Method 16. RelaRULES AND REGULATIONS

tively high S02 concentration levels

were observed in only one EPA emission source test. Accordingly, high SO2

concentration levels are probably not

a frequent occurrence within kraft

pulp mills. More importantly, however, high S02 concentrations only interfere with the determination of methyl

mercaptan in the emission measurement system outlined in Reference

Method 16. Since methyl mercaptan is

usually only a small contributor to

total TRS emissions, neglecting

methyl mercaptan where this interfer- ence occurs should not seriously affect

the determination of TRS emissions.

Consequently, Reference Method 16 can be used to enforce the promulgated standards without major difficulties.

Miscellaneous: The effective date of

this regulation is February 24, 1976.

Section 111(b)(1)(B) of the Clean Air

Act provides that standards of perfor- mance or revisions of them become effective upon promulgation and apply

to affected facilities, construction or modification of which was commended

after the date of proposal (September

24, 1976).

Nor.-An economic assessment has been

prepared as required under section 317 of

the Act. This also satisfies the requirements of Executive Orders 11821 and OMB Circular A-107.

Dated: February 10, 1978.

BARBARA BLUm,

Acting Administrator.

Part 60 of Chapter I, Title 40 of the

Code of Federal Regulations is amended as follows:

Subpart A-General Provisions

1. Section 60.13 is amended to clarify

the provisions in paragraph (a) by revising paragraph (a) to read as follows:

§ 60.13 Monitoring requirements.

(a) For the purposes of this section,

all continuous monitoring systems re- quired under applicable subparts shall

be subject to the provisions of this sec- tion upon promulgation of perfor- mance specifications for continuous

monitoring system under Appendix B

to this part, unless:

(1) The continuous monitoring

system is subject to the provisions of

paragraphs (c)(2) and (c)(3) of this

section, or (2) otherwise specified in an applicable subpart or by the Administrator.

* * * * S

2. Part 60 is amended by adding subpart BB as follows:

Subpart BB-Standards of Performanc, for Kraft Pulp -

Mills

Sec. " 60.280 Applicability and designation bf affected facility. 60.281 Definitions.

60.282 Standard for particulate matter,

60.283 Standard for total reduced sulfur

(TRS). 60.284 Monitoring of emissions and operations.

60.285 Test methods and procedures.

AuTHmoiTy: Sees. 111, 301(a) of the Clean

Air Act, as amended [42 U.S.C. '7411,

7601(a)], and additional authority as noted

below.

Subpart BD--Standards of Performance for

Kraft Pulp Mills

60.280 Applicability and designation of affected facility.

(a) The provisions of this subpart are applicable to the following affected facilities in kraft pulp mills: digest- er system, brown stock washer system,

multiple-effect evaporator system,

black liquor oxidation system, recov- ery furnace, smelt dissolving tank,

lime kiln, and condensate stripper

system. In pulp mills where kraft

pulping is combined with neutral sulfite semichemical pulping, the provisions of this subpart are applicable

when any portion of the material

charged to an affected facility is produced by the kraft pulping operation.

(b) Any facility under paragraph (a)

of this section that commences con- struction or modification after September 24, 1976, is subject to the re- quirements of thlssubpart.

§ 60.281 Definitions.

As used in this subpart, all terms not

defined herein shall have the same

meaning given them in the Act and in

Subpart A.

(a) "Kraft pulp mill" means any stationary "source which produces pulp

from wood by cooking (digesting)

wood chips in a water solution of

sodium hydroxide and sodium sulfide

(white liquor) at high temperature

and pressure. Regeneration of the

cooking chemicals through a recovery

process is also considered part of the

kraft pulp mill.

(b) "Neutral sulfite semichemical

pulping operation" means any operation in which pulp is produced from

wood by cooking (digesting) wood

chips in a solution of sodium sulfite

and sodium bicarbonate, followed by

mechanical defibrating (grinding),

(c) "Total reduced sulfur (TRS)" means the sum of the sulfur com- pounds hydrogen sulfide, methyl mer- captan, dimethyl sulfide, and dimethyl

disulfide, that are released during the

kraft pulping operation and measured

by Reference Method 16.

(d) "Digester system" means each

continuous digester or each batch digester used for the cooking of wood in

white liquor, and associated flash

tank(s), below tank(s), chip steamer(s),

and condenser(s),

(e) "Brown stock washer system" means brown stock washers and associated knotters, vacuum pumps, and filFEDERAL REGISTER, VOL. 43, NO. 37-THURSDAY, FEBRUARY 23, 1978

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RULES AND REGULATIONS

trate tanks used to wash the pulp following the digester system. (f) "Multiple-effect evaporator

system" means the multiple-effect

evaporators and associated

condenser(s) and hotwell(s) used to

concentrate the spent cooking liquid

that is- separated from-the pulp -(black

liquor).

(g) 'Black liquor oxidation system" means the vessels used to oxidize, with

air or oxygen, the black liquor, and as- sociated -storage tank(s). (h) "Recovery furnace" means either a straight kraft : recovery furnace or a cross recovery furnace, -and includes

the direct-contact cvaporator for a direct-contact furnace.

(i) "Straight kraft recovery furnace" means- a furnace used to recover chemicals consisting primarily of

sodium and sulfur compounds by

burning black liquor which on a quarterly basis contains 7 weight percent or less of the total pulp solids from

the neutral sulfite semichemical process or has green liquor sulfidity of 28

percent or less.

C) "Cross recovery furnace" means a furnace used to recover chemicals con- sisting primarily of sodium and sulfur

compounds by burning black liquor

which on a quarterly basis contains more than 7 weight percent of the

total pulp solids from the neutral sulfite seemichemical process and has a green liquor sulfidity of -more than 28

percent.

,(k) "Black liquor solids" means the

dry weight of the solids which enter

the recovery furnace in the black

liquor.

(1) "Green liquor sulfidity" means the sulfidity of the liquor which leaves

the smelt dissolving tank.

(m) "Smelt dissolving tank" means a vessel used for dissolving the smelt

collected from the recovery furnace.

(n) 'ULme kiln" means a unit used to

calcie lime mud, which consists pri- marily of calcium carbonate, into

Quicklime, which is calcium oxide.

(o) "Condensate stripper system" means a column, and associated con- densers, used -to strip, with air or steam, TRS compounds from condensate streams from various .processes

within a kraft pulp mill.

§ 60.282 Standard for particulate matter.

Ca) On and after the date on which

the performance test required to be

conducted 'by §60.8 is completed, no owner or operator subjectto the provi--

sions of this subpart shall cause to be

discharged into the atmosphere:-

(1) From any recovery furnace any

gases which:

(i) Contain particulate matter in excess of 0.10 g/dscm (0.044 gr/dscf)

corrected to 8 percent-oxygen.

(ii) Exhibit 35 percent opacity or greater.

(2) From any smelt dissolving tank

any gases which -contain particulate

matter in excess of 0.1 g/kg black

liquor solids (dry weight)[0.2 lb/ton

black liquor solids (dry weight)].

(3) From any lime kiln any gases

which contain particulate matter in excess of:

(C) 0.15 g/dscm (0.067 gr/dscf) cor- rected to 10 percent oxygen, when gaseous fossil fuel is burned.

(ii) 0.30 g/dscm (0.13 gr/dscf) cor- rected to 10 percent oxygen, when

liquid fossil fuel is burned.

§60.283 Standard for total reduced sulfur

(TRS).

(a) On and after the date on which

the performance test required to be

conducted by §60.8 is completed, no owner or operator subject to the provi-'

sions of this subpart shall cause to be

discharged into the atmosphere:

(1) From any digester system, brown

stock washer system, multiple-effect

evaporator system, black liquor oxidation system, or condensate stripper

system any gases which contain TRS

In excess of 5 ppm by volume on a dry

basis, corrected to 10 percent oxygen,

unless the following conditions are met:

(1) The gases -are combusted in a lime

kiln subject to the provisions of paragraph (a)(5) of this section; or (i) The gases are combusted in a re- covery furnace subject to the provisions of paragraphs (a)(2) or (a)(3) of

this section; or (W) The gases are combusted with

other waste gases in an Incinerator or

other device, or combusted in a lime

kiln or recovery furnace not subject to

the provisions of this subpart, and are subjected to a minimum temperature

of 1200' F. for at least 0.5 second; or (iv) It has been demonstrated to the

Adijujistrator's satisfaction by the owner or operator that incinerating

the exhaust gases from a new, modified, or reconstructed black liquor oxidation system or brown stock washer

system in an existing facility is technologically or economically not feasible. Any exempt system will become

subject tb the provisions of this subpart If the facility Is changed so that

the gases can be incinerated.

(2) From any straight kraft recovery

furnace any gases which contain TRS

in excess of 5 ppm by volume on a dry

basis, corrected to 8 percent oxygen.

(3) From any cross recovery furnace

any gases which contain TRS in excess of 25 ppm by volume on a dry -basis,

corrected to 8 percent oxygen.

(4) From any smelt dissolving tank

any gases which contain TRS in excess of 0.0084 g/kg black liquor solids (dry

weight) [0.0168 lblton liquor solids

(dry weight)].

(5) From any lime kiln any gases

which contain TRS in excess of 8 ppm

by volume on a dry basis, corrected to

10 percent oxygen.

§ 60.284 Monitoring of emissions and operationL

(a) Any owner or operator subject to

the provisions of this subpart shall install, calibrate, maintain, and operate

the following continuous monitoring

systems:

(1) A continuous monitoring system

to monitor and record the opacity of

the gases discharged into the atmosphere from any recovery furnace. The

span of this system shall be set at 70

percent opacity.

(2) Continuous monitoring systems

to monitor and record the concentration of TRS emissions on a dry basis

and the percent of oxygen by volume on a dry basis in the gases discharged

into the atmosphere from any lime

kiln, recovery furnace, digester

system, brown stock washer system,

multiple-effect evaporator system,

black liquor oxidation system, or con- densate stripper system, except where

the provisions of § 60.283(a)(1) (ii) or (iv) apply. These systems sba be located downstream of the control

device(s) and the span(s) of these con- tinuous monitoring system(s) shall be

set:

(i) At a TRS concentration of 30

ppm for the TRS continuous monitoring system, except that for any cross recovery furnace the span shall be set

at 50 ppm.

(I1) At 20 percent oxygen for the

continuous oxygen monitoring system.

(b) Any owner or operator subject to

the provisions of this subpart shall install, calibrate, maintain, and operate

the following continuous monitoring

devices:

(1) A monitoring device which mea- sures the combustion temperature at

the point of incineration of effluent

gases which are emitted from any digester system, brown stock washer

system, multiple-effect evaporator

system, black liquor oxidation system, or condensate stripper system where

the provisions of § 60.283(a)(lXiii)

apply. The monitoring device is to be

certified by the manufacturer to be ac- curate within ±1 percent of the temperature being measured.

(2) For any lime kiln or smelt dissolving tank using a scrubber emission

control device:

(i) A monitoring device for the con- tinuous measurement of the pressure

loss of the gas stream through the

control equipment. The monitoring

device is to be certified by the manu- facturer to be accurate to within a gage pressure of t500 pascals (ca. ±2

inches water gage pressure). *

(WI) A monitoring device for the conitinuous measurement of the scrubbing

liquid supply pressure to the control

equipment. The monitoring device is

to be certified by the manufacturer to

be accurate within ±15 percent of

design scrubbing liquid supply pres- sure. The pressure sensor or tap is to

FEDERAL REGISTER, VOL 43, NO. 37-THURSDAY, FEBRUARY 23, 1978

7573

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RULES 'AND -REGULATIONS

be located close to the scrubber liquid

discharge point. The Administrator

may be consulted for approval of alternative locations.

(c) Any owner or operator subject to

the provisions of this subpart shall,

except where the provisions of

§ 60.283(a)(1)(iv) or § 60.283(a)(4)

apply.

(1) Calculate and record on a daily

basis 12-hour average TRS concentrations for the two consecutive periods

of each operating day. Each 12-hour

average shall be determined as the

arithmetic mean of the appropriate 12

contiguous 1-hour average total re- duced sulfur concentrations provided

by each continuous monitoring system installed, under paragraph (a)(2) of

this section.

(2) Calculate and record on a daily

basis 12-hour average oxygen concen- trations for the two consecutive periods of each operating day for the re- covery furnace and lime kiln. These

12-hour averages shall correspond to

the 12-hour average TRS concentrations under paragraph (c)(1) of this

section and shall be determined as an arithmetic mean of the appropriate 12

contiguous 1-hour average oxygen con- centrations provided by each continu- ous monitoring system installed under

paragraph (a)(2) of this section.

(3) Correct all 12-hour average TRS

concentrations to 10 volume percent

oxygen, except that all 12-hour aver- age TRS concentration from a recov- ery furnace shall be corrected to 8

volume percent using the following

equation:

where:

C.,=the concentration - corrected ' for

oxygen.

Cm,,=the concentration ,uncorrected for

oxygen. X=the volumetric oxygen concentration in

percentage to be corrected to (8 percent

for recovery furnaces and 10 percent for

lime kilns, incinerators, or other devices).

Y=the measured 12-hour average volumetric oxygen concentration.

(d) For the purpose of reports re- quired under § 60.7(c), any owner or operator subject to the provisions of

this subpart shall report periods of excess emissions as follows:

(1) For emissions from any recovery furnace periods of excess emissions are:

(i) All 12-hour averages of TRS con- centrations above 5 ppm by volume for

straight kraft recovery furnaces and

above 25 ppm by volume for cross re- covery furnaces.

(ii) All 6-minute average opacities

that exceed 35 percent. (2) For emissions from any lime kiln,

periods of excess emissions are all 12-

hour average TRS concentration

above 8 ppm by volume.

(3) For emissions from any digester

system, brown stock washer system,

multiple-effect evaporator system,

black liquor oxidation system, or con- densate stripper system- periods of excess emissions are: (i) All 12-hour average TRS concen- trations above 5 ppm by volume unless

the provisions of § 60.283(a)(1) (i), (i), or (iv) apply; or (1i) All periods in excess of 5 minutes

and their duration during which the

combustion temperature at the point

of incineration is less than -1200* F.

where , the provisions of

§ 60.283(a)(1)(ii) apply.

(e) The Administrator will not con- sider periods of excess emissions re- ported under paragraph (d) of this sec- tion to be indicative of a violation of • § 60.11(d) provided that:

(1) The percent of the total number

of possible contiguous periods of excess emissions in a quarter (excluding periods of startup, shutdown, or malfunction and periods when the facility is not operating) during which excess emissions occur does not

exceed:

(i) One percent for TRS emissions

from recovery furnaces.

(i) Six percent for average opacities

from recovery furnaces.

(2) The Administrator determines

that the affected facility, including air

pollution control equipment, is maintained and operated in a manner which is consistent with good air pollution control practice for minimizing

emissions during periods of excess emissions.

§ 60.285 Test methods and procedures.

(a) Reference methods in Appendix

A of this part, except as provided

under § 60.8(b), shall be used to determine compliance with § 60.282(a-) as follows:

(1) Method 5 for the concentration

of particulate matter and the associated moisture content,

(2) Method 1 for sample and velocity

traverses,

(3) When determining compliance

with § 60.282(a)(2), Method 2 for velocity and volumetric flow rate, . (4) Method 3 for gas analysis, and

(5) Method 9 for visible emissions.

(b) For Method 5, the sampling time

for each run shall be at least 60 minutes and the sampling rate shall be at

least 0.85 dscm/hr (0.53 dscf/min)

except that shorter sampling times,

when necessitated by process variables or other factors, may be approved by

the Administrator. Water shall be

used as the cleanup solvent instead of

acetone in the sample recovery procedure outlined in Method 5.

(c) Method 17 (in-stack filtration)

may be used as an alternate method

for Method 5 for determining compli- ance with §60.282(a)(1)(i): Provided,

That a constant value of 0.009 g/dscm

(0.004 gr/dscf) is added to the results

of Method 17 and the stack temperature Is no greater than 205' C (ca. 400

F). Water shall be used as the cleanup

solvent instead of acetone in the

sample recovery procedure outlined in

Method 17.

(d) For the purpose of determining

compliance with § 60.283(a) (1), (2),

(3), (4), and (5), the following refer- ence methods shall be used:

(1) Method 16 for the concentration

of TRS,

(2) Method 3 for gas analysis, and

(3) When determining compliance

with § 60.283(a)(4), use the results of

Method 2, Method 16, and the black

liquor solids feed rate in the following

equation to determine the TRS emission rate.

E = (C, F,s + Cm.sFu.,su + CDmsFDm9 + C

D3WsFDHDS) (Qsd)/BLS

Where:

E = mass of TRS emitted per unity of black

liquor solids (g/kg) (lb/ton) Cm= average concentration of hydrogen sulfide (H.S) during the test period, PPM.

CM.ss = average concentration of methyl

mercaptan (MeSH) during the test

period, PPM.

CDs= average concentration of dinethyl sulfide (DMS) during the test period, PPM.

CDs = average concentration of dlmethyl disulfide (DMDS) during the test period, PPM.

Fm = 0.001417 g/ms PPM for metric units = 0.08844 lb/ft' PPM for English units

Finsu = 0.00200 g/m' PPM for metric units = 0.1248 lb/fts PPM for English units Ems = 0.002583 g/m, PPM for metric units = 0.1612 lb/ft, PPM for English units

FDs = 0.003917 g/m' PPM for metric units = 0.2445 lb/fts PPM for English units

Qd = dry volumetric stack gas flow rate cor- rected to standard conditions, d&cm/hr

(dscf/hr)

BLS = black liquor solids feed rate, kg/hr (lb/hr)

(4) When determining whether a furnace is straight kraft recovery fur- nace or a cross recovery furnace,

TAPPI Method T.624 shall be used to

determine sodium sulfide, sodium hydroxide and sodium carbonate. These

determinations shall be made three

times daily from the green liquor and

the daily average values shall be converted to sodium oxide (Na 2O) and

substituted into the following equation to determine the green liquor sulfidity:

GLS = 100 CV.P/CH' + CN.,, + CN.Wo

Where:

GLS = percent green liquor sulfidity CNv = average concentration of NaIL9 ex- pressed as NaO (mg/i) CN.OH = average concentration of NaOH

expressed as NaO (mg/1)

Cx..CO. = average concentration of NaCO, expressed as AVa.O (mg/1)

(e) All concentrations of particulate

matter and TRS required to be mea- sured by this section from lime kilns or incinerators shall be corrected 10

volume percent oxygen and those con- centrations from recovery furnaces

FEDERAL REGISTER, VOL. 43, NO. 37-THURSDAY, FEBRUARY 23, 1978

7574

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PULES AN" REGULATIONS

-'shall be corrected to 8 volume percent graphs should show agreement within the

oxygen. These corrections shall be precision limits of Section 4.1.

made in the manner specified in 3.3 Particulate Matter. Particulate

§ 60.284(c)(3). * matter in gas samples can cause Interfer- ence by eventual clogging of the analytical

APPrNDix A-REmENcE METHODS system. This interference must be eliminated by use of a probe filter.

(3) Method 16 and Method 17 are 3.4 Sulfur Dioxide. SO, is not a specific

added'to Appendix A as follows: interferent but may be present in such large

amounts that it cannot be effectively separated from other compounds of interest.

The procedure must be designed to ellmlN nate this problem either by the choice of MEOD 16. SEMICONTINUOUS DETERMINATIO separation columns or by removal of SO.

OF SULFUR EMsSIONS FROM STATIONARY from the sample.

SOURCES Compliance with this section can be demIntroduction onstrated by submitting chromatographs of

calibration gases with SO, present in the

The method described below uses the same quantities expected from the emission

prineiple of gas chromatographic separation source to be tested. Acceptable systems

and flame photometric detection. Since shall show baseline separation with the am- there are many systems or sets of operating plifier attenuation set so that the reduced

conditions that represent usable methods of sulfur compound of concern Is at least 50

determining sulfur emissions, all systems percent of full scale. Base line separation is

wlich employ this principle, but differ only defined as a return to zero t percent in the

in details of equipment and operation, may interval between peaks.

be used as alternative methods, provided 4. Precision and Accuracy.

that the criteria set below are met. 4.1 GC/FPD and Dilution System Call.

1. Principle and Applicability. bration Precision. A series of three consecu- 1.1 Principle. A gas sample is extracted tive injections of the same calibration gas,

from the emission source and diluted with at any dilution, shall produce results which

.clean dry air. An aliquot of the diluted do not vary by more than ±3 percent from

sample is then analyzed for hydrogen sul- the mean of the three Injections.

fide (H-S), methyl mercaptan (MeSH), di- 4.2 GC/FPD and Dilution System Callmethyl sulfide (DMS) and dimethyl disul- bration Drift. The calibration drift deterfide (DMDS) by gas chromatographic (GC) mined from the mean of three injections

separation and flame photometric detection made at the beginning and end of any 8-

(FPD). These four compounds are known hour period shall not exceed ± percent.

collectively as total reduced sulfur (TRS). 4.3 System Calibration Accuracy. The

1.2 Applicability. This method is applica- complete system must quantitatively transble for determination of TRS compounds port and analyze with an accuracy of 20 per.

from recovery furnaces, lime kilns, and cent. A correction factor is developed to

smelt dissolving tanks at kraft pulp mills, adjust calibration accuracy to 100 percent.

2. Range and Sensitivity. 5. Apparatus (See Figure 16-1).

2.1 Range. Coupled with a gas chromato- 5.1.1 Probe. The probe must be made of

graphic system utilizing a ten milliliter inert material such as stainless steel or sample size, the maximum limit of the FPD glass. It should be designed to Incorporate a for each sulfur compound is approximately filter and to allow calibration gas to enter

I ppm. This limit is expanded by dilution of the probe at or near the sample entry point.

the sample gas before analysis. Kraft mill Any portion of the probe not exposed to the

gas samples are normally -diluted tenfold stack gas must be heated to prevent mois-

(9:1), resulting in an upper-limit.of about 10 ture condensation.

ppm for each compound. 5.1.2 Sample Line. The Sample line must

-For sources with emission levels between be made of Teflon., no greater than 1.3 cm 10 and 100 ppm, the measuring range can be (M) inside diameter. All parts from the

best extended by reducing the sample size probe to the dilution system must be ,therto 1 milliliter. mostatically heated to 120' C.

2.2 Using the sample size, the minimum 5.1.3 Sample Pump. The Sample pump

detectable concentration is approximately shall be a leakless Teflon-coated diaphragm

50 ppb. type or equivalent. If the pump Is upstream

3. Interferences. of the dilution system, the pump head must

3.1 Moisture Condensation. Moisture be heated to 120- C.

condensation in the sample delivery system, 5.2 Dilution System. The dilution system

the analytical column, or the FPD burner must be constructed such that all sample

block can cause losses or interferences. This contacts are made of inert materials (e.g..

potential is eliminated by heating the stainless steel or Teflon). It must be heated

sample line, and by conditioning the sample to 120' C. and be capable of approximately a

with dry dilution air to lower-its dew point 9:1 dilution of the sample.

below the operating temperature of the 5.3 Gas Chromatograph. The gas chroGC/FPD analytical system prior to analysis. matograph must have at least the following

3.2 Carbon Monoxide and Carbon Diox- components:

ide. CO and CO, have substantial desensitiz- 5.3.1 Oven. Capable of maintaining the

ing effect on the flame photometric detec- separation column at the proper operating

tor even after 9:1 dilution. Acceptable sys- temperature ±1" C.

tems must demonstrate that they have 5.3.2 Temperature Gauge. To monitor

eliminated this interference by some proce- column oven, detector, and exhaust temdure such as eluting these compounds perature±1' C.

before any of the compounds to be mea- 5.3.3 Flow System. Gas metering system

sured. Compliance with this requirement to measure sample, fuel, combustion gas, can be demonstrated by submitting chroma- and carrier gas flows.

tograms of calibration gases with and without CO. in the diluent gas. The CO. level 'Mention of trade names or specific prod.

should be approximately 10 percent for the ucts does not constitute endorsement by the case with CO present. The two chromato- Environmental Protection Agency.

7575

5.3.4 Flame Photometric Detector.

5.3.4.1 Electrometer. Capable of full scale

amplification of linear ranges of 10- to 10-4

amperes full scale.

5.3.4.2 Power Supply. Capable of deliverlng up to 7150 volts.

5.3.4.3 Recorder. Compatible with the

output voltage range of the electrometer.

5.4 Gas Chromatograph Columns. The

column system must be demonstrated to be

capble of resolving the four major reduced

sulfur compounds: H.S. MeSH. DMS. and

DMDS. It must also demonstrate freedom

from known interferences.

To demonstrate that adequate resolution

has been achieved, the tester must submit a chromatograph of a calibration gas containing all four of the TRS compounds in the

concentration range of the applicable standard. Adequate resolution will be defined as

base line separation of adjacent peaks when

the amplifier attenuation is set so that the

smaller peak is at least 50 percent of full

scale. Base line separation is defined in Section 3.4. Systems not meeting this criteria

may be considered alternate methods subject to the approval of the Adminstrator.

5.5. Calibration System. The calibration

system must contain the following components.

5.5.1 Tube Chamber. Chamber of glass or Teflon of sufficient dimensions to house

permeation tubes.

5.5.2 Flow System. To measure air flow over permeation tubes at ±2 percent. Each

flowmeter shall be calibrated after a com- plete test series with a wet test meter. If the

flow measuring device differs from the wet

test meter by 5 percent, the completed test

shall be discarded. Alternatively, the tester

may elect to use the flow data that would

yield the lowest flow measurement. Calibration with a wet test meter before a test Is

optional.

' 5.5.3 Constant Temperature Bath. Device

capable of maintaining the permeation

tubes at the calibration temperature within

0.1 C.

5.5.4 Temperiture Gauge. Thermometer or equivalent to monitor bath temperature

within ±r C.

6. ReagentL • 6.1 Fuel. Hydrogen (H,) prepurifled

grade or better.

6.2 Combustion Gas. Oxygen (0.) or air.

research purity or better.

6.3 Carrier Gas. Prepurifled grade or better.

6.4 Diluent. Air containing less than 50

ppb total sulfur compounds and less than 10

ppm each of moisture and total hydrocarbons. This gas must be heated prior to

mixing with the sample to avoid water con- densation at the point of contact.

6.5 Calibration Gases. Permeation tubes, one each of HS, MeSH, DMS, and DMDS,

agravimetrically calibrated and certified at some convenient operating temperature.

These tubes consist of hermetically sealed

FE? Teflon tubing in which a liquifled gas- eous substance is enclosed. The enclosed gas

permeates through the tubing wall at a con- stant rate. When the temperature is con- stant, calibration gases coverning a wide

range of known concentrations can be generated by varying and accurately measuring

the flow rate of diluent gas passing over the

tubes. These calibration gases are used to

calibrate the GC/FPD system and the dilution system.

7. Pretest Procedure& The following procedures are optional but would be helpful in

preventing any problem which might occur later and invalidate the entire test.

FEDERAL REGISTER, VOL 43, NO. 37-THURSDAY, FEBRUARY 23, 1978

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RULES -ANDr'REGULATIONS'

7.1 After the complete measurement - system has been set up at the site and

deemed to be operational, the following procedures should be completed before sam- pling is initiated.

7.1.1 Leak Test. Appropriate leak test

procedures should be employed to verify the

integrity of all components, sample lines,

and. connections. The following leak test

procedure Is suggested: For components upstream of the sample pump, attach the

probe end of the sample line to a ma- nometer or vacuum gauge, start the pump and

pull greater than 50 mm (2 in.) Hg vacuum,

close off the pump outlet, and then stop the

pump and ascertain that there is no leak for

1 minute. For components after the pump,

apply a slight positive pressure and check

for leaks by applying a liquid (detergent in

water, for example) at each joint. Bubbling

indicates the presence of a leak.

7.1.2 System Performance. Since the

complete system is calibrated following each

test, the precise calibration of each component is not critical. However, these components should be verified to be operating

properly. This verification can be performed

by observing the response of flowmeters or

of the GC output to changes in flow rates or calibration gas concentrations and ascertaining the response to be within predicted

limits. In any component, or if the complete

system fails to respond in a normal and predictable manner, the source of the discrepancy should be Identified and corrected

before proceeding. 8. Calibration. Prior to any sampling run,

calibrate the system using the following

procedures. (If more than one run is performed during any 24-hour period, a calibration need not be performed prior to the

second and any subsequent runs. The calibration must, however, be verified as prescribed in Section 10, after the last run made within the 24-hour period.) 8.1 General Considerations. This section

outlines steps to be followed for use of the

GC/FPD and the dilution system. The procedure does not include detailed instructions because the operation of these systems

is complex, and It requires a understanding

of the individual system being used. Each

system should include a written operating

manual describing in detail the operating

procedures associated with each component

in the measurement system. In addition, the

operator should be familiar with the operating principles of the components; particularly the GC/FPD. The citations in the Bibliography at the end of this method are recommended for review for this purpose.

8.2 Calibration Procedure. Insert the permeation tubes into the tube chamber.

Check the bath temperature to assure agreement with the calibration temperature

of the tubes within ±O.1 ° C. Allow 24 hours

for the tubes to equilibrate. Alternatively

equilibration may be verified by injecting

samples of calibration gas at 1-hour intervals. The permeation tubes can be assumed

to have reached equilibrium when consecu- tive hourly samples agree within the precision limits of Section 4.1.

Vary the amount of air flowing over the

tubes to produce the desired concentrations

for calibrating the analytical and dilution"

systems. The air flow across the tubes must

at all times exceed the flow requirement of

the analytical systems. The concentration in

parts per million generated by a tube con- taining a specific permeant can be calculated as follows: p

Equation 16-1

where:

C=Concentration of permeant produced in

ppm.

P,=Permeation rate of the tube in pg/min.

M=Molecular weight of the permeant (g/gmole).

L=Flow rate, 1/min, of air over permeant @

20' C, 760 mm Hg.

K=Gas constant at 20' C and 760 mm

Hg=24.04 1/g mole.

8.3 Calibration of analysis system. Generate a series of three or more known con- centrations spanning the linear range of the

FPD (approximately 0.05 to 1.0 ppm) for

each of the four major sulfur compounds.

Bypassing the dilution system, Inject these

standards into the GC/FPD analyzers and

monitor the responses. Three injects for

each concentration must yield the precision

described in Section 4.1. Failure to attain

this precision is an indication of a problem

in the calibration or analytical system. Any

such problem must be identified and cor- rected before proceeding.

8.4 Calibration Curves. Plot the GC/FPD

response in current (amperes) versus their

causative concentrations in ppm on log-log

coordinate graph paper for each sulfur compound. Alternatively, a least squares equation may be generated from the calibration

data.

8.5 Calibration of Dilution System. Generate a known concentration of hydrogen

sulfide using the permeation tube system.

Adjust the flow rate of diluent air for the

first dilution stage so that the desired level

of dilution is approximated. Inject the diluted calibration gas into the GC/FPD system

and monitor its response. Three injections

for each dilution must yield the precision

described in Section 4.1. Failure to attain

this precision in this step is an indication of

a problem in the dilution system. Any such

problem must be identified and corrected

before proceeding. Using the calibration

data for H.S (developed under 8.3) determine the diluted calibration gas concentration in ppm. Then calculate the dilution

factor as the ratio of the calibration gas

concentration before dilution to the diluted

calibration gas concentration determined

under this paragraph. Repeat this procedure for each stage of dilution required. Alternatively, the GC/FPD system may be

calibrated by generating a series of three or

more concentrations of each sulfur compound and diluting these samples before inJectinrg them into the GC/FPD system. This

data will then serve as the calibration data

for the unknown samples and a separate determination of the dilution factor will not

be necessary. However, the precision re- quirements of Section 4.1 are still applicable.

9. Sampling and Analy/sis Procedure

9.1 Sampling. Insert the sampling probe

into the test port making certain that no dilution air enters the stack. through the port.

Begin sampling and dilute the sample approximtely 9:1 using the dilution system.

Note that the precise dilution factor is that

which is determined in paragraph 8.5. Condition the entire system with sample for a minimum of' 15. minutes prior to commencing analysis.

9.2 Analysis. Aliquots of diluted sample

are injected into the QC/FPD analyzer for

analysis.

9.2.1 Sample Run. A sample run is com- posed of 16 individual analyses (injects) performed over a period of not less than 3

hours or more than 6 hours.

9.2.2 Observation for Clogging of Probe, If reductions in sample concentrations are observed during a sample run that cannot

be explained by process conditions, the sam- pling must be interrupted to determine If

the sample probe is clogged with particulate

matter. If the probe is found to be clogged,

the test must be stopped and the results up

to that point discarded. Testing may resume

after cleaning the probe or replacing It with a clean one. After each run, the sample

probe must be inspected and, if necessary,

dismantled and cleaned.

10. Post-Test Procedures.

10.1 Sample Line Loss. A known concen- tration of hydrogen sulfide at the level of

the applicable standard, :1:20 percent, must

be introduced into the sampling system at

the opening of the probe in sufficient quantities to insure that there is an excess of

sample which must be vented to the atmosphere. The sample must be transported

through the entire sampling system to the

measurement system in the normal manner. The resulting measured concentration

should be compared to the known value to

determine the sampling system loss. A sampling system loss of more than 20 percent Is

unacceptable. Sampling losses of 0-20 percent must be corrected for by dividing the

resulting sample concentration by the fraction of recovery. The known gas sample may

be generated using permeation tubes. Alternatively, cylinders of hydrogen sulfide

mixed in air may be used provided they are

traceable to permeation tubes. The optional

pretest procedures provide a good guideline

for determining if there are leaks in the

sampling system.

10.2 Recalibration. After each run, or

after a series of runs made within a 24-hour

period, perform a partial recalibration using

the procedures in Section 8. Only HS (or

other permeant) need be used to recalibrate

the GC/FPD analysis system (8.3) and the

dilution system (8.5).

10.3 Determination of Calibration Drift.

Compare the calibration curves obtained

prior to the runs, to the calibration curves

obtained under paragraph 10.1. The calibration drift should not exceed the limits set

forth in paragraph 4.2. If the drift exceeds

this limit, the intervening run or runs should be considered not valid. The tester,

however, may instead have the option of

choosing the calibration data set which

would give the highest sample values.

11. Calculations.

11,1 Determine the concentrations of

each reduced sulfur compound detected directly from the calibration curves. Alternatively, the concentrations may be calculated

using the equation for the least square line.

11.2 Calculation of TRS. Total reduced

sulfur will be determined for each anaylsis

made by summing the concentrations of

each reduced sulfur compound resolved

during a, given analysis.

TRS=Z (H.S, MeSH, DMS, 2DMDS)d

Equation 16-2

where:

TRS=Total reduced sulfur in ppm, wet

basis,

HS=Hydrogen sulfide, ppm.

MeSH=Methyl mercaptan, ppm.

DMS=Dimethyl sulfide, ppm,

DMDS=Dimethyl disulfide, ppm.

d=DIlution factor, dimensionless.

FEDERAL REGISTER, VOL 43, NO. 37-THURSDAY, FEBRUARY 23, 1978

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RULES AND REGULATIONS

11.3 Average TRS. The average TRS will

be determined as follows:

N

- z TRS1 i = Average TRS= III-B

Average TRS=Average total reduced suflur

in ppm, dry basis.

TRS,=Total reduced sulfur in ppm as determined by Eqiiation 16-2.

N=Number of samples.

B=Fraction of volume of water vapor in

the gas stream as determined by method

4-Determination of Moisture in Stack

Gases (36 FR 24887).

11.4 Average concentration of individual

reduced sulfur compounds.

r S.l

CEquation 16-3

where:

S1=Concentration of any reduced sulfur

compound from the ith sample injection, ppm.

C=Average concentration of any one of the

reduced sulfur compounds for the entire

run, ppm.

N=Number of injections in any run period.

12. Example System. Described below is a system utilized by EPA in gathering NSPS

data. This system does not now reflect all

the latest developments in equipment and

column technology, but it does represent

one system that has been demonstrated to

work.

12.1 Apparatus.

12.1.1 Sampling System.

12.1.1.1 Probe. Figure 16-1 Illustrates the

probe used in lime kilns and other sources where significant amounts of particulate

matter are present. the probe is designed

with the deflector shield placed between the

sample and the gas inlet holes and the glass

wool plugs to reduce clogging of the filter

and possible adsorption of sample gas. The

exposed portion of-the probe between the

sampling port and the sample line is heated

with heating tape.

12.1.1.2 Sample Line Se inch inside diameter Teflon tubing, heated to 120* C. This

temperature is controlled by a thermostatic

heater.

12.1.1.3 Sample Pump. Leakless Teflon

coated diaphragm type or equivalent. The

pump head is heated to 120' C by enclosing

it in the sample dilution box (12.2.4 below).

12.1.2 Dilution System. A schematic diagram of the dynamic dilution system is

given in Figure 16-2. The dilution system is

constructed such that all sample contacts

are made of inert materials. The dilution

system which is heated to 120" C must be capable of a minimum of 9:1 dilution of

sample. Equipment used in the dilution

system is listed below:

12.1.2.1 Dilution Pump. Model A-150

Kohmyhr Teflon positive displacement

type, nonadjustable 150 cc/min. ±2.0 percent, or equivalent, per dilution stage. A 9:1

dilution of sample is accomplishedby cornbining 150 cc of sample with 1.350 cc of

clean dry air as shown in Figure 16-2.

12.1.2.2 Valves. Three-way Teflon solenoid or manual type.

12.1.2.3 Tubing. Tenon tubing and fittings are used throughout from the sample

probe to the GC/FPD to present an Inert

surface for sample gas12.1.2.4 Box. Insulated box, heated and

maintained at 120' C, of sufficient dimensions to house dilution apparatus.

12.1.2.5 Fowmeters. Rotameters or equivalent to measure now from 0 to 1500

ml/min ±1 perdent per dilution stage.

12.1.3 Gas Chromatograph Columns.

Two types of columns are used for separation of low and high molecular weight

sulfur compounds:

12.1.3.1 Low Molecular Weight Sulfur

Compounds Column (GC/FPD-1).

12.1.3.1 Separation Column. 11 ma by 2.16 mm (36 ft by 0.085 in) inside diameter

Teflon tubing packed with 30/60 mesh

Teflon coated with 5 percent polyphenyl

ether and 0.05 percent orthophosphoric

acid, or equivalent (see Figure 16-3).

12.1.3.1.2 Stripper or Precolumn. 0.6 ma

by 2.16 mm (2 ft by 0.085 in) inside diameter

Teflon tubing packed as in 5.3.1.

12.1.3.1.3 Sample Valve. Teflon 10-port

gas sampling valve, equipped with a 10 ml

sample loop, actuated by compressed air

(Figure 16-3).

12.1.3.1.4 Oven. For containing sample

valve, stripper column and separation

column. The oven should be capable of

maintaining an elevated temperature ranging from ambient to 1001 C, constant within

±1" C.

12.1.3.1.5 Temperature Monitor. Thermocouple pyrometer to measure column oven,

detector, and exhaust temperature ±1" C.

12.1.3.1.6 Flow System. Gas metering

system to measure sample flow, hydrogen

flow, and oxygen flow (and nitrogen carrier

gas flow).

12.1.3.1.7 Detector. Flame photometric

detector.

12.1.3.1.8 Electrometer. Capable of full

scale amplification of linear ranges of 10-

to 10-' amperes full scale.

12.1.3.1.9 Power Supply. Capable of deli.

vering up to 750 volts.

12.1.3.1.10 Recorder. Compatible with

the output voltage range of the electrometer.

12.1.3.2 High Molecular Weight Compounds Column (GC/FPD-11).

12.1.3.2.1. Separation Column. 3.05 in by

2.16 mm (10 ft by 0.0885 in) inside diameter

Teflon tubing packed with 30/60 mesh

Teflon coated with 10 percent Triton X-305,

or equivalent.

12.1.3.2.2 Sample Valve. Teflon 6-port gas

sampling valve equipped with a 10 ml

sample loop, actuated by compressed air

(Figure 16-3).

12.1.3.2.3 Other Components. All components same as in 12.1.3.1.4 to 12.1.3.1.10.

12.1.4 Calibration. Permeation tube

system (figure 16-4).

12.1.4.1 Tube Chamber. Glass chamber

of sufficient dimensions to house permeation tubes.

12.1.4.2 Mass Flowmetem. Two mass

flowmeters in the range 0-3 l/min. and 0-10

1/min. to measure air flow over permeation

tubes at ±2 percent. These nfowmeters shall

be cross-calibrated at the beginning, of each

test. Using a convenient flow rate in the

measuring range of both nfowmeters. set

and monitor the flow rate of gas over the

permeation tubes. Injection of calibration

gas generated at this flow rate as measured

by one flowmeter followed by injection of

calibration gas at the same flow rate as measured by the other nfowmeter should agree

within the specified precision limits. If they

do not. then there is a problem with the mass flow measurement. Each mass flowmeter shall be calibrated prior to the first

test with a wet test meter and thereafter, at

least once each year.

12.1.4.3 Constant Temperature Bath. Capable of maintaining permeation tubes at

certification temperature of 30" C. within

±0.1" C.

12.2 Reagents

12.2.1 Puel. Hydrogen (H:) prepurified

grade or better.

12.2.2. Combustion Gas. Oxygen (0) research purity or better.

12.2.3 Carrier Gas. Nitrogen (N,) prepurifled grade or better.

12.2.4 Diluent. Air containing less than

50 ppb total sulfur compqunds and less than

10 ppm each of moisture and total hydrocarbons, and filtered using MSA filters

4G727 and 79030, or equivalenL.Removal of

sulfur compounds can be verified by injecting dilution air only, described In Section

8.3.

12.2.5 Compressed Air. 60 pslg for GC

valve actuation.

12.2.6 Calibrated Gases. Permeation

tubes gravimetrically calibrated and certified at 30.0' C.

12.3 Operating Parameters.

12.3.1 Low-Molecular Weight Sulfur

Compounds. The operating parameters for

the GC/FPD system used for low molecular

weight compounds are as follows nitrogen

carrier gas flow rate of 50 ce/min, exhaust

temperature of 110 C, detector temperature

of 105" C. oven temperature of 40' C. hydrogen flow rate of 80 ce/min. oxygen flow rate

of 20 ce/min, and sample flow rate between

20 and 80 c/min.

12.3.2 Hgh-Molecular Weight Sulfur

Compounds. The operating parameters for

the GC/FPD system for high molecular

weight compounds are the same as in 12.31

except: oven temperature of 70" C, and nitrogen carrier gas flow of 100 cc/min.

12.4 Analysis Procedure.

12.4.1 Analysis. AIIquots of diluted

sample are injected simultaneously into

both GC/FPD analyzers for analysis. GC/

FPD-I Is used to measure the low-molecular

weight reduced sulfur compounds. The low

molecular weight compounds include hydrogen Sulfide, methyl mercaptan, and dlmethyl sulfide. GC/FPD-fl Is used to resolve the high-molecular weight compound.

The high-molecular weight compound Is dimethyl disulflde.

12.4.1.1 Analysis of Low-Molecular

Weight Sulfur Compounds. The sample

valve is actuated for 3 minutes in which

time an aliquot of diluted sample is injected

Into the stripper column and analytical

column. The valve is then deactivated for

approximately 12 minutes in which time,

the analytical column continues to be foreflushed, the stripper column is backflushed.

and the sample loop Is refilled. Monitor the

responses. The elution time for each com- pound will be determined during calibration.

12.4.1.2 Analysis of High-Molecular

Weight Sulfur Compounds. The procedure

Is essentially the same as above except that no stripper column is needed.

13. Bibliogrphly.

13.1 O!Keeffe, A. E. and G. C. Ortman.

"Primary Standards for Trace Gas AnalyFEDERAL REGISTER, VOL 43, NO. 37-THURSDAY, FEBRUARY 23, 1978

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7578

sis." Analytical Chemical Journal, 38,760

(1966).

13.2 Stevens, R. K., A. E. O'Keeffe, and

G. C. Ortman. "Absolute Calibration of a

Flame Photometric Detector to Volatile

Sulfur Compounds at Sub-Part-Per-Mllion

Levels." Environmental Science and Technology, 3:7 (July, 1969).

13.3 Mulick, J. D., R. K. Stevens, and R.

Baumgardner. "An Analytical System Designed to Measure Multiple Malodorous

RULES AND REGULATIONS

Compounds Related to Kraft Mill Activities." Presented at the 12th Conference on

Methods in Air Pollution and Industrial Hygiene Studies, University of Southern California, Los Angeles, CA. April 6-8, 1971.

13.4 Devonald, R. H., R. S. Serenius, and

A. D. McIntyre. "Evaluation of the Flame

Photometric Detector for Analysis of Sulfur

Compounds." Pulp and Paper Magazine of

Canada, 73,3 (March, 1972).

13.5 Grimley, K. W., W. S. Smith, and R.

M. Martin. "The Use of a Dynamic Dilution

System in the Conditioning of Stack Oases

for Automated Analysis by a Mobile Sampling Van." Presented at the 63rd Annual

APCA Meeting in St. Louis, Mo. Juno 14-19,

1970.

13.6 General Reference. Standard Methods of Chemical Analysis Volume III A and

B Instrumental Methods. Sixth Edition.

Van Nostrand Reinhold Co.

FEDERAL REGISTER, VOL 43, NO. 37-THURSDAY, FEBRUARY 23, 1978

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RULES AND REGULATIONS 7579

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RULES AND REGULATIONS

METHOD 17. DETERMINATION OF PARTICULATE

EMISSIONS FROM STATIONARY SOURCES (IN- STACK FILTRATION METHOD)

Introduction

Particulate matter is not an absolute

quantity; rather, it is a function of temperature and pressure. Therefore, to prevent variability in particulate matter emission

regulations and/or associated test methods,

the temperature and pressure at which par- ticulate matter is to be measured must be

carefully defined. Of the two variables (i.e.,

temperature and pressure), temperature has

the greater effect upon the amount of par- ticulate matter in an effluent gas stream; in

most stationary source categories, the effect

of pressure appears to be negligible. In method 5, 250' F is established as a nominal reference temperature. Thus,

where Method 5 is specified in an applicable

subpart of the standards, particulate matter

is defined with respect to temperature. In

order to maintain a collection temperature

of 250' F, Method 5 employs a heated glass

sample probe and a heated filter holder,

This equipment is somewhat cumbersome

and requires care in its operation. Therefore, where particulate matter concentrations (over the normal range of temperature associated with a specified source category) are known to be independent of temperature, it is desirable to eliminate the glass probe and heating systems, and sample at

stack temperature.

This method describes an in-stack sam- pling system and sampling procedures for use in such cases. It is intended to be used

only when specified by an applicable subpart of the standards, and only within the

applicable temperature limits (if specified), or when otherwise approved by the Administrator.

1. Principie and Applicability.

1.1 Principle. Particulate matter is withdrawn isokinetically from the source and

collected on a glass fiber filter maintained

at stack temperature. The particulate mass is determined gravimetrically after removal

of uncombined water.

1.2 Applicability. This method applies to

the determination of particulate emissions

from stationary sources for determining

compliance with new source perf6rmance standards, only when specifically provided for. in an applicable subpart of the standards. This method is not applicable to

stacks that contain liquid droplets or are saturated with water vapor. In addition, this

method shall not be used as written if the

projected cross-sectional area of the probe extension-filter holder assembly covers more than 5 percent of the stack cross-sec- tional area (see Section 4.1.2).

2. Apparatus.

2.1 Sampling Train. A schematic of the

sampling train used In this method Is shown

in Figure 17-1. Construction details for

many, but not all, of the train components are given in APTD-0581 (Citation 2 In Section 7); for changes from the APTD-0581

document and for allowable modifications

to Figure 17-1. consult with the Administrator.

FEDERAL REGISTER, VOL 43, NO. 37-THURSDAY, FEBRUARY 23, 1978

7584-

HeinOnline -- 43 Fed. Reg. 7584 1978
RULES AND REGULATIONS

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RULES AND REGULATIONS

The operating and maintenance procedures for many of the sampling train components are described in APTD-0576 (Citation 3 in Section 7). Since correct usage Is

important in obtaining valid results, all users should read the APTD-0576 document

and adopt the operating and maintenance

procedures outlined in it, unless otherwise

specified herein. The sampling train con- sists of the following components:

2.1:i Probe Nozzle. Stainless steel (316)

or glass, with sharp, tapered leading edge.

The angle of taper shall be 030" and the

taper shall be on the outside to preserve a

constant internal diameter. The probe

nozzle shall be of the button-hook or elbow

design, unless otherwise specified by the Administrator. If made of stainless steel, the

nozzle shall be constructed from seamless

tubing. Other materials of construction may

be used subject to the approval of the Administrator.

A range of sizes suitable for isdkinetic

sampling should be available, e.g., 0.32 to

1.27 cm (Ys to V2 in)-or larger if higher

volume sampling trains are used-inside diameter (ID) nozzles in Increments of 0.16 cm

(Ye in). Each nozzle shall be calibrated ac- cording to the procedures outlined in Section 5.1.

2.1.2 Filter Holder. The in-stack filter

holder shall be constructed of borosilicate or quartz glass, or stainless steel; if a gasket

is used, it shall be made of silicone rubber,

Teflon, or stainless steel. Other holder and

gasket materials may be used subject to the

approval of the Administrator. The filter"

holder shall be designed to provide a positive seal against leakage from the outside or around the filter.

2.1.3 Probe Extension. Any suitable rigid,

probe extension may be used after the filter

holder.

2.1.4 Pitot Tube. Type S, as described in

Section 2.1 of Method 2, or other device approved by the Administrator, thepitot tube

shall be attached to the probe extension to

allow constant monitoring of the stack gas

velocity (see Figure 17-1). The impact (high

pressure) opening plane of the pitot tube

shall be even with or above the nozzle entry

plane during sampling (see Method 2,

Figure 2-6b). It Is recommended: (1) that

the pitot tube have a known baseline coefficient, determined as outlined in Section 4 of

Method 2; and (2) that this known coefficient be preserved by placing the pitot tube

in an interference-free arrangement with respect to the sampling nozzle, filter holder,

and temperature sensor (see Figure 17-1).

Note that the 1.9 cm (0.75 in) free-space between the nozzle and pitot tube shown in

Figure 17-1, is based on a 1.3 cm (0.5 in) ID

nozzle. If the sampling train is designed for

sampling at higher flow rates than that described in APTD-0581, thus necessitating

the use of larger sized nozzles, the freespace shall be 1.9 cm (0.75 in) with the largest sized nozzle in place.

Source-sampling assemblies that do not

meet the minimum spacing requirements of

Figure 17-1 (or the equivalent of these re- quirements, e.g., Figure 2-7 of Method 2)

may be used; however, the pitot tube coefficients of such assemblies shall be determined by calibration, using methods subject

to the approval of the Administrator.

2.1.5 Differential Pressure Gauge, Inclined manometer or equivalent,, device

(two), as described in Section 2.2 of Method

2. One manometer shall be used for velocity

head ap) readings, and the other, for orifice differential pressure readings.

2.1.6 Condenser. It is recommended that

the impinger system described in Method 5

be used-to determine the moisture content

of the stack gas. Alternatively, any system

that allows measurement of both the water

condensed and the moisture leaving the con- denser, each to within 1 ml or 1 g, may be

used. The moisture leaving the condenser

can be measured either by: (1) monitoring

the temperature and pressure at the exit of

the condenser and using Dalton's law of

partial pressures; or (2) passing the sample

gas stream through a silica gel trap with

exit gases kept below 20' C (68' F) and determining the weight gain.

Flexible tubing may be used between the

probe extension and condenser. If means other than silica gel are used to determine

the amount of moisture leaving the condenser, It is recommended that silica gel still

be used between the condenser system and

pump to prevent moisture condensation in

the pump and metering devices and to avoid

the need to make corrections for moisture

in the metered volume.

2.1.7 Metering System. Vacuum gauge,

leak-free pump, thermometers capable of

measuring temperature to within 3* C (5.4'

F), dry gas meter capable of measuring

volume to within 2 percent, and related

equipment, as shown in Figure 17-1. Other

metering systems capable of maintaining

sampling rates within 10 peicent of isokinetic and of determining sample volumes to

within 2 percent may be used, subject to the

approval of the Administrator. When the

metering system is used in conjunction with

a pitot tube, the system shall enable checks

of isokinetic rates.

Sampling trains utilizing metering systems designed for higher flow rates than

that described in APTD-0581 or APTD-0576

may be used provided that the specifications of this method are met.

2.1.8 Barometer. Mercury, aneroid, or other barometer capable of measuring atmospheric pressure to within 2.5- mm Hg

(0.1 in. Hg). In many cases, the barometric

reading may be obtained from a nearby na- tional weather service station, in which case

the station value (which is the absolute

barometric pressure) shall be requested and

an adjustment for elevatioiL differences between the weather station and sampling

point shall be applied at a rate of minus 2.5

mm Hg (0.1 in. Hg) per 30 m (100 ft) elevation increase or vice versa for elevation decrease.

2.1.9 Gas Density Determination Equipment. Temperature sensor and pressure

gauge, as described in Sections 2.3 and 2.4 of

Method 2, and gas analyzer, if necessary, as

described in Method 3.

The temperature sensor shall be attached

to either'the pitot tube or to the probe ex- tension, in a fixed configuration. If the temperature sensor is attached In the field; the sensor shall be placed in an interferencefree arrangement with respect to the Type

S pitot tube openings (as shown in Figure

17-1 or in Figure 2-7 of Method 2). Alternatively, the temperature sensor need not be

attached to either the probe extension or pitot tube during sampling, provided that a

difference of not more than 1 percent in the

average velocity measurement is introduced.

This alternative is subject to the approval

of the Administrator.

2.2- Sample Recovery.

2.2.1 Probe Nozzle Brush. Nylon bristle

brush with stainless, steel wire handle. The

brush shall be properly sized and shaped to

brush out the probe nozzle.

2.2.2 Wash Bottles-Two. Glass wash

bottles are recommended; polyethylene

wash bottles may be used at the option of

the tester. It is recommended that acetone

not be stored in polyethylene bottles for

longer than a month.

2.2.3 Glass Sample Storage Containers.

Chemically resistant. borosillcate glass bottles, for acetone washes, 500 ml or 1000 ml,

Screw cap liners shall either be rubberbacked Teflon or shall be constructed so as

to be leak-free and resistant to chemical

attack by acetone. (Narrow mouth glass bottles have been found to be less prone to

leakage.) Alternatively, polyethylene bottles

may be used.

2.2.4 Petri Dishes. For filter samples:

glass or polyethylene, unless otherwise

specified by the Administrator.

2.2.5 Graduated Cylinder and/or Bal.

ance. To measure condensed water to within

1 ml or 1 g. Graduated cylinders shall have

subdivisions no greater than 2 ml, Most laboratory balances are capable of weighing to

the nearest 0.5 g or less. Any of these bal- ances is suitable for use here and in Section

2.3.4.

2.2.6 Plastic Storage Containers, Air

tight containers to store silica gel. 2.2.7 Funnel and Rubber Policeman. To

aid in transfer of silica gel to container; not

necessary If silica gel Is weighed in the field,

2.2.8 Funnel. Glass or polyethylene, to

aid in sample recovery.

2.3 Analysis.

2.3.1 Glass Weighing Dishes.

2.3.2 Desiccator.

2.3.3 Analytical Balance. To measure to

within 0.1 mg.

2.3.4 Balance. To measure to within 0.5

mg.

2.3.5 Beakers. 250 ml.

2.3.6 Hygrometer. To measure the relative humidity of the laboratory environ.

•ment.

2.3.7 Temperature Gauge. To measure

the temperature of the laboratory environ.

ment.

3. Reagents.

3.1 Sampling.

3.1.1 Filters. The in-stack filters shall be

glass mats or thimble fiber filters, without

organic binders, and shall exhibit at least

99.95 percent efficiency (00.05 percent penetration) on 0.3 micron dioctyl phthalato

smoke particles. The filter efficiency tests

shall be conducted in accordance with

ASTM standard method D 2986-71. Test

data from the supplier's quality coptrol program are sufficient for this purpose.

3.1.2 Silica Gel. Indicating type, 6. to 10-

mesh. If previously used. 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,

subject to the approval of the Administrator.

3.1.3 Crushed Ice.

3.1.4 Stopcock Grease. Acetone-insoluble,

heat-stable silicone grease. This is not nec- essary if screw-on connectors with Teflon

sleeves, or similar, are used. Alternatively.

other types of stopcock grease may be used,

subject to the approval of the Administra.

tor.

3.2 Sample Recovery. Acetone, reagent

grade, 00.001 percent residue, in glass bottles. Acetone from metal containers generally has a high residue blank and should not

be used. Sometimes, suppliers transfer ac- etone to glass bottles from metal containers.

Thus, acetone blanks shall be run prior to

field use and only acetone with low blank

FEDERAL REGISTER, VOL.43, NO. 37-THURSDAY, FEBRUARY 23, 1978

7586

HeinOnline -- 43 Fed. Reg. 7586 1978
RULES AND REGULATIONS

values (00.001 percent) shall be used. In no case shall a. blank value of greater than

0.001 percent of -the weight of acetone used

be subtracted from the sample weight.

3.3 Analysis. -

3.3.1 Acetone. Same as 3.2.

3.3.2 Desiccant. Anhydrous calcium sulfate, indicating type. Alternatively other

types of desiccants may be used, subject to

the approval of the Administrator.

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.

4.11 Pretest Preparation. All components shall be maintained and calibrated ac- cording to the procedure described in

APTD-0576, unless otherwise specified

herein.

Weigh several 200 to 300 g portions of

silica gel in air-tight containers to the near- est 0.5 g. Record the total weight of the

silica gel plus container, on each container.

As an alternative, the silica gel need not be

preweighed, but may be weighed directly in

its impinger -or sampling holder just prior to

train assembly.

Check filters visually against light for irregularities and flaws or pinhole leaks.

Label filters of the proper size on the back

side near the edge using numbering ma- chine Ink. As an alternative, label the shipping containers (glass or plastic petri dishes)

and keep the filters in these containers at

all times except during sampling and weighing.

Desiccate the filters at 20±5.6" C (68±10"

F) and ambient pressure for at least 24

hours and weigh at intervals of at least 6

hours to a constant weight, Le.. 00.5 mg

change from previous weighing;, record re- sults to the nearest 0.1 mng. During each

weighing the filter must not. be exposed to

the laboratory atmosphere for a period

greater than 2 minutes and a relative humidity above 50 percent. Alternatively

(unless otherwise specified by the Administrator), the filters may be oven dried at 105"

C (220" F) for 2 to 3 hours, desiccated for 2

hours, and weighed. Procedures other than

those described, which account for relative

humidity effects, may be used, subject to

the approval of the Administrator.

4.1.2 Preliminary Determinations. Select

the sampling site ind the minimum number

of sampling points according to Method 1 or as specified by the Administrator. Make a

projected-area model of the probe extension-filter holder assembly, with the pitot

tube face openings positioned along the cen- terline of the stack, as shown in Figure 17-2.

Calculate the estimated cross-section blockage, as shown in Figure 17-2. If the blockage

exceeds 5 percent of the duct cross sectional area. the tester has the following options:

(1) a suitable out-of-stack filtration method

may be used instead of in-stack filtration; or,

(2) a special In-stack arrangement, in which

the sampling and velocity measurement

sites are separate, may be used; for details

concerning this approach, consult with the

Administrator (see also Citation 10 in Section 7). Determine the stack pressure, temperature, and the range of velocity heads

using Method 2; It is recommended that a

leak-check of the pitot lines (see Method 2,

Section 3.1) be performed. Determine the

moisture' content using Approximation

Method 4 or its alternatives for the purpose

of making isokinetic sampling rate settings.

Determine the stack gas dry molecular

weight, as described In Method 2, Section

3.6; if integrated Method 3 sampling is used

for molecular weight determination, the integrated bag sample shall be taken simultaneously with, and for the same total length

of time as, the particular sample run.

FEDERAL REGISTER, VOL 43, NO. 37-THURSDAY, FEBRUARY 23, 1978

7587

HeinOnline -- 43 Fed. Reg. 7587 1978
RULES AND REGUlATONS,

ESTIMATED

BLOCKAGE

(%)

[SHADED AREA ), 10

SDUCT AREAJ

Figure 17-2. Projected-area model of cross-section blockage (approximate average for

a sample traverse) caused by an in-stack filter holder-probe extension assembly.

FEDERAL REGISTER, VOL 43, NO. 37-THURSDAY, FEBRUARY 23, 1978

7588

HeinOnline -- 43 Fed. Reg. 7588 1978
RVUES NANP_- E TIQU S 'T

Select a nozzle size based on the range of

velocity heads, such that it is not necessary

to change the nozzle size in order to maintain isokinetic sampling rates. During the

run, do not change the nozzle size. Ensure

that the proper differential pressure gauge

is chosen for the range of velocity heads en- countered (see Section 2.2 of Method 2).

Select a probe extension length such that

all traverse points can be sampled. For large

stacks, consider sampling from opposite

sides of the stack to reduce the length of

probes.

Select a total sampling time greater than or equal to the minimum total sampling

time specified in the test procedures for the

specific industry such that (1) the sampling, time per point is not less than 2 minutes (or some greater time interval if specified by

the Administrator), and (2) the sample

volume taken (corrected to standard conditions) will exceed the required minimum

total gas sample volume. The latter is based on an approximate average sampling rate.

It is recommended that the number of

minutes sampled at each point be an integer or an integer plus one-half minute, in order

to avoid timekeeping errors. In some circumstances, e.g., batch cycles,

it may be necessary to sample for shorter

times at the traverse points and to obtain

smaller gas sample volumes. In these cases,

the Administrator's approval. must first be

obtained.

4.1.3 Preparation of Collection Train.

During preparation and assembly of the

sampling train, keep all openings where con- tamination can occur covered until just

prior to assembly or until sampling is about

to begin

If impingers are used to condense stack

gas moisture, prepare them as follows: place

100 ml of water in each of the first two impfngers, leave the third impinger empty,

and transfer approximately 200 to 300 g of

preweighed silica gel from its container to

the fourth impinger. More silica gel may be

used, but care should be taken to ensure that it is not entrained and carried out from

the impinger during sampling. Place the

container in a clean place for later use in

the sample recovery. Alternatively, the

weight of the silica gel plus mpinger may

be determined to the nearest 0.5 g and recorded.

If some means other than impingers is

used to condense moisture, prepare the con- denser (and, if appropriate, silica gel for

condenser outlet) for use. Using a tweezer or cleah disposable surgi.

cal gloves, place a labeled (identified) and

weighed filter in the filter holder. Be sure that the filter is properly centered and the

gasket properly placed so as not to allow the

sample gas stream to circumvent the filter.

Check filter for tears after assembly Is com- pleted. Mark the probe extension with heat

resistant tape or by some other method to

denote the proper distance into the stack or

duct for each sampling point.

Assemble the train as in Figure 17-1. using a very light coat of silicone grease on all

ground glass Joints and greasing only the

outer portion (see APTD-0576) to avoid posslbility of contamination by the silicone

grease. Place crushed Ice around the hn.

pingers.

4.1.4 Leak Check Procedures.

4.1.4.1 Pretest Leak-Check. A pretest

leak-check is recommended, but not re- quired. If the tester opts to conduct the pretest leak-check, the following procedure

shall be used.

After the sampling train has been assem- bled,- plug the inlet to the probe nozzle with a material that will be able to withstand the

stack temperature. Insert the filter holder

into the stack and wait approximately 5

minutes (or longer, if necessary) to allow

the system to come to equilibrium with the

temperature of the stack gas stream. Turn on the pump and draw a vacuum of at least

380 mm Hg (15 In. Hg); note that a lower vacuum may be used, provided that It is not

exceeded during the test. Determine the

leakage rate. A leakage rate in excess of 4

percent of the average sampling rate or 0.00057 m*/mln. (0.02 efm), whichever Is

less, is unacceptable.

The following leak-check Instructions for

the sampling train described In APTD-0576

and APTD-0581 may be helpful. Start the

pump with by-pass valve fully open and coarse adjust valve completely closed. Partially open the coarse adjust valve and

slowly close'the by-pass valve until the desired vacuum is reached, Do not reverse direction of by-pss valve. If the desired vacuum is exceeded, either leak-check at

this higher vacuum or end the leak-check as

shown below and start over. When the leak-check Is completed, first

slowly remove the plug from the Inlet to the

probe nozzle and immediately turn off the vacuum pump. This prevents water from

being forced backward and keeps silica gel

from being entrained backward.

4.1.4.2 Leak-Checks During Sample Run.

If, during the sampling run, a component

(e.g., filter assembly or impinger) change be- comes necessary, a leak-check shall be con- ducted immediately before the change is

made. The leak-check shall be done according to the procedure outlined in Section

4.1.4.1 above, except that It shall be done at a vacuum equal to or greater than the maxi- mum value recorded up to that point in the

test. If the leakage rate is found to be no greater than 0.00057 ma/min (0.02 cfm) or 4

percent of the average sampling rate

(whichever is less), the results are acceptable, and no correction will need to be applied to the total volume of dry gas metered;

If, however, a higher leakage rate is obtained, the tester shall either record the

leakage rate and plan to correct the sample

volume as shown In Section &3 of this

method, or shall void the sampling run.

Immediately after component changes,

leak-checks ire optional: if such leak-checks are done, the procedure outlined in Section

4.1.4.1 above shall be used.

4.1.4.3 Post-Test LeakCheck. A leakcheck is mandatory at the conclusion of

each sampling run. The leak-check shall be

done in accordance with the procedures outlined in Section 4.1.4.1, except that It shall

be conducted at a vacuum equal to or great- er than the maximum value reached during

the sampling run. If the leakage rate is

found to be no greater than 0.00057 ma/min

(0.02 cfm) or 4 percent of the average sam- pling rate (whichever Is less), the results are acceptable, and no correction need be applied to the total volume of dry gas metered.

If. however, a higher leakage rate is obtained, the tester shall either record the

leakage rate and correct the sample volume as shown in Section 6.3 of this method, or shall void the sampling run.

4.1.5 Particulate Train Operation.

During the sampling run. maintain a sam- pling rate such that sampling is within 10

percent of true Isokinetic, unless otherwise

specified by the Administrator.

For each run. record the data required on the example data sheet shown in Figure 17-

3. Be sure to record the initial dry gas meter

reading. Record the dry gas meter readings

at the beginning and end of each sampling

time Increment when changes in flow rates are made, before and after each leak check,

and when sampling is halted. Take other

readings required by Figure 17-3 at least once at each sample point during each time

Increment and additional readings when significant changes (20 percent variation In ve- locity head readings) necessitate additional

adjustments in flow rate. Level and zero the

manometer. Because the manometer level

and zero may drift due to vibrations and

temperature changes, make periodic checks

during the traverse.

FEDERAL REGISTER, VOL 43, NO. 37-THURSDAY, FEBRUARY 23, 1978

7589

HeinOnline -- 43 Fed. Reg. 7589 1978
RULESAND: REGULATIONS •

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HeinOnline -- 43 Fed. Reg. 7590 1978
Clean the portholes prior to the test run to minimize the chance of sampling the deposited material. To begin sampling, remove the nozzle cap and verify that the pitot tube

and probe extension are properly posi- tioned. Position the nozzle at the first tra- verse point with the tip pointing directly

into the gas stream. Immediately start the

pump and adjust the flow to isokinetic con- ditions. Nomographs are available, which

aid in the rapid adjustment to the isokinetic

sampling rate without excessive computa- tions. These nomographs are designed for use when the Type S pitot tube coefficient

is 0.85±0.02, and the stack gas equivalent

density (dry molecular weight) is equal to

29±4. APTD-0576 details the procedure for

using the nomographs. If C, and 1 are outside the above stated ranges, do not use the

nomographs unless appropriate steps (see

Citation 7 in Section 7) are taken to com- pensate for the deviations.

When the stack is under significant negative pressure (height of impinger stem),

take care to close the coarse adjust-valve

before inserting the probe extension assem- bly into the stack to prevent water from

being forced backward. If necessary, the

pump may be turned on with the coarse - adjust valve closed.

When the probe is in position, block off

the openings around the probe and porthole

to prevent unrepresentative dilution of the

gas stream.

Traverse the stack cross section, as required by Method 1 or as specified by the

Administrator, being careful not to bump the probe nozzle into the stack walls when

sampling near the walls or when removing or inserting the probe extension through the portholes, to minimize chance of extracting deposited material.

During the test run, take appropriate

steps (e.g., adding crushed ice to the impinger ice bath). to maintain a temperature

of less than 20' C (68" F) at the condenser

outlet; this will prevent excessive moisture

losses. Also, periodically check the level and zero of the manometer.

If the pressure drop across the filter be- comes too high, making isokinetic sampling

difficult to maintain, -the filter may be re- placed in the midst of a sample run. It is

recommended that another complete filter

holder- assembly be used rather than attempting to change the filter itself. Before a new filter holder is installed, conduct a leak

check, as outlined in Section 4.1.4.2. The

total particulate weight shall include the

summation of all filter assembly catches.

A single train shall be used for the entire

sample run, except in cases where simnulta- neous sampling is required in two or more separate ducts or at two or more different

locations within the same duct, or, in cases where equipment failure necessitates a change of trains. In all other situations, the use of two or more trains will be subject to

the approval of the Administrator. Note

that when two or more trains are used, a separate -analysis of the collected particulate from each train shall be performed,

unless identical nozzle sizes were used on all

trains, in which case the particulate catches

from the individual trains may be combined

and a single analysis performed.

At the end of the sample run, turn off the

pump, remove the probe extension assembly from the stack, and record the final dry gas

meter reading. Perform a leak-check, as outlined in Section 4.1.4.3. Also, leak-check the

pitot lines as described in Section 3.1 of

Method 2; the lines must pass this leakRULES LAND 'REGULA'TIONS

check, in order to validate the velocity head

data.

. 4.1.6 Calculation of Percent Iokinetic.

Calculate percent Isokinetic (see Section

6.11) to determine whether another test run should be made. If there Is difficulty In

maintaining Isokinetic rates due to source conditions, consult with the Administrator

for possible variance on the Isokinetic rates.

4.2 Sample Recovery. Proper cleanup procedure begins as soon as the probe ex- tension assembly Is removed from the stack

at the end of the sampling period. Allow the

assembly to cool.

When the assembly can be safely handled,

wipe off all external particulate matter near the tip of the probe nozzle and place a cap over it to prevent losing or gaining particulate matter. Do not cap off the probe tip

tightly while the sampling train Is cooling

down as this would create a vacuum In the

filter holder, forcing condenser water backward.

Before moving the sample train to the

cleanup site, disconnect the filter holderprobe nozzle assembly from the probe ex- tension; cap the open inlet of the probe ex- tension. Be careful not to lose any condensate, if present. Remove the umbilical cord

from the condenser outlet and cap the

outlet. If a flexible line Is used between the

first impinger (or condenser) and the probe

extension, disconnect the line at the probe

extension and let any condensed water or liquid drain into the Impingers or condens- er. Disconnect the probe extension from the

condenser, cap the probe extension outlet.

After wiping off the silicone grease, cap off

the condenser inlet. Ground glass stoppers,

plastic caps, or serum caps (whichever are appropriate) may be used to close these

openings.

Transfer. both the filter holder-probe

nozzle assembly and the condenser to the

cleanup area. This area should be clean and

protected from the wind so that the chances

of contaminating or losing the sample will

be minimized.

Save a portion of the acetone used for

cleanup as a blank. Take 200 ml of this ac- etone directly from the wash bottle being

used and place It in a glass sample container

labeled "acetone blank."

Inspect the train prior to and during disassembly and note any abnormal conditions.

Treat the samples as follows:

Container No. J. Carefully remove the

filter from the filter holder and place It in

its identified petri dish container. Use a pair

of tweezers and/or clean disposable surgical

gloves to handle the filter. If It is necessary

to fold the filter, do so such that the partieulate cake is inside the fold. Carefully transfer to the petri dish any particulate matter

and/or filter fibers which adhere to the

filter holder gasket, by using a dry Nylon bristle brush and/or a sharp-edged blade.

Seal the container.

Container No. 2. Taking care to see that

dust on the outside of the probe nozzle or other exterior surfaces does not get hito the

sample, quantitatively recover particulate

matter or any condensate from the probe

nozzle, fitting, and front half of the filter

holder by washing these components with

acetone and placing the wash in a glass con- tainer. Distilled water may be used instead

-of acetone when approved by the Administrator and shall be used when specified by

the Administrator; in these cases, save a water blank and follow Administrator's directions on analysis. Perform the acetone

rinses as follows:

7591

Carefully remove the probe nozzle and

clean the inside surface by rinsing with acetone from a wash bottle and brushing with a Nylon bristle brush. Brush until acetone

rinse shows no visible particles, after which

make a final rinse of the inside surface with

acetone.

Brush and rinse with acetone the inside

parts of the fitting in a similar way until no visible particles remain. A funnel (glass or polyethylene) may be used to aid in transferring liquid washes to the container. Rinse

the brush with acetone and quantitatively

collect these washings in the sample container. Between sampling runs, keep

brushes clean and protected from contamination.

After ensuring that all joints are wiped

clean of silicone grease (if applicable), clean

the inside of the front half of the filter

holder by rubbing the surfaces with a Nylon

bristle brush and rinsing with acetone.

Rinse each surface three times or more if

needed to remove visible particulate. Make

final rinse of the brush and filter holder.

After all acetone washings and particulate

matter are collected in the sample contain- er. tighten the lid on the sample container so that acetone will not leak out when it is

shipped to the laboratory. Mark the height

of the fluid level to determine whether or not leakage occurred during transport.

Label the container to clearly Identify its

contents.

Container No. 3. if silica gel is used in the

condenser system for mositure content determination, note the color of the gel to determine If it has been completely spent;

make a notation of its condition. Transfer

the silica gel back to Its original container

and seaL A funnel may make It easier to

pour the silica gel without spilling, and a rubber policeman may be used as an aid in

removing the silica gel. It is not necessary to

remove the small amount of dust particles

that may adhere to the walls and are difficult to remove. Since the gain In weight is to

be used for moisture calculations, do not use any water or other liquids to transfer the

silica geL If a balance is available In the

field, follow the procedure for Container

No. 3 under "Analysis."

Condenser Water. Treat the condenser or impinger water as follows: make a notation

of any color or film in the liquid catch. Measure the liquid volume to within t1 ml by

using a graduated cylinder or, if a balance is

available, determine the liquid weight to

within t0.5 g. Record the total 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.

4.3 Analysis. Record the data required on the example sheet shown in Figure 17--4.

Handle each sample container as follows:

Container No. . Leave the contents in the

shipping container or transfer the filter and

any loose particulate from the sample con- tainer to a tared glass weighing dish. Desiccate for 24 hours In a desiccator containing

anhydrous calcium sulfate. Weigh to a con- stant weight and report the results to the

nearest 0.1 rag. For purposes of this Section,

4.3, the term "constant weight" means a difference of no more than 0.5 mg or I percent

of total weight less tare weight, whichever is

greater, between two consecutive weighings,

with no less than 6 hours of desiccation

time between weighlngs.

Alternatively, the sample may be oven dried at the average stack temperature or

FEDERAL REGISTER, VOL 43, NO. 37-THURSDAY, FEBRUARY 23, 1978

HeinOnline -- 43 Fed. Reg. 7591 1978
7592 RULES AND REGULATIONS

105 ° C (220 F). whichever is less, for 2 to 3 flied by the Administrator. The tester may whichever is less, for 2 to 3 hours, weigh the

hours, cooled in the desiccator, and weighed also opt to oven dry the sample at the aver- sample, and use this weight as a final

to a constant weight, unless otherwise speci- age stack temperature or 105" C (220 F), weight.

Plant

Date

Run No.

Filter No.

Amount liquid lost during transport

Acetone blank volume, ml

Acetone wash volume, ml

Acetone black concentration, mg/mg (equation 17-4)

Acetone wash blank, mg (equation 17-5)

WEIGHT OF PARTICULATE COLLECTED,

CONTAINER mg

NUMBER

FINAL WEIGHT TARE WEIGHT WEIGHT GAIN

1

2

TOTAL_

Less acetone blank

Weight of particulate matter

VOLUME OF LIQUID

WATER COLLECTED

IMPINGER SILICA GEL

VOLUME, WEIGHT,

ml 9

FINAL

INITIAL

LIQUID COLLECTED

TOTAL VOLUME COLLECTED g I ml

CONVERT WEIGHT OF WATER TO VOLUME BY DIVIDING TOTAL WEIGHT

INCREASE BY DENSITY OF WATER (lg/ml). -

INCREASE, g = VOLUME WATER, ml

1 g/ml

Figure 17-4. Analytical data.

FEDERAL REGISTER, VOL 43, NO. 37-THURSDAY, FEBRUARY 23, 1978

HeinOnline -- 43 Fed. Reg. 7592 1978
RULES AND REGULATIONS

Container No. 2. Note the level of liquid in

the container and. confirm on the analysis sheet whether or not leakage occurred

during transport. If a noticeable amount of

leakage has occurred, either void the sample or use methods,-subject to the approval of

the Administrator, to correct the final re- sults. Measure the liquid in this container

either volumetrically to ±1 ml or gravimetrically to ±0.5 g. Transfer the contents to a tared 250-ml beaker and evaporate to dry- ness at ambient temperature and pressure.

Desiccate for 24 hours and weigh to a con- stant weight. Report the results to the near- est 0.1 mg.

Container No. 3. This step may be con- ducted in the field. Weigh the spent silica

gel (or silica gel plus impinger) to the near- est 0.5 g using a balance.

"Acetone Blank" Container. Measure acetone in this container either volumetrically or gravimetrically. Transfer the acetone to a tared 250-ml beaker and evaporate to dryness at ambient temperature and pressure.

Desiccate for 24 hours and weigh to a constant weight. Report the results to the nearest 0.1 mg.

No E.-At the option of the tester, the

contents of Container No. 2 as well as the

acetone blank container may be evaporated

at temperatures higher than ambient. If

evaporation is done at an elevated temperature, the temperature must be below the

boiling point of the solvent; also, to prevent

"bumping," the evapdration process must be

closely supervised, and the contents of the

beaker must be swirled occasionally to

maintain an even temperature. Use extreme

care, as acetone is highly flammable and

has alow flash point.

5. Calibration. Maintain a laboratory log

of all calibrations.

5.1 Probe Nozzle. Probe nozzles shall be

calibrated before their initial use in the

field. Using a micrometer, measure the

inside diameter of the nozzle to the nearest

0.025 mm (0.001 in.). Make three separate

measurements using different diameters

each time, and obtain the average of the

measurements. The difference between the

high and low numbers shall not exceed 0.1 mm (0.004 in.). When nozzles become

nicked, dented, or corroded, they shall be

reshaped, sharpened, and recalibrated

before use. Each nozzle shall be permanently and uniquely Identified.

5.2 Pltot Tube. If the pitot tube Is placed

In an interference-free arrangement with re- spect to the other probe assembly components, Its baseline (isolated tube) coefficient

shall be determined as outlined in Section 4

of Method 2. If the probe assembly is not Interference-free, the pitot tube assembly co- efficient shall be determined by calibration.

using methods subject to the approval of

the Administrator.

5.3 Metering System. Before Its Initial use in the field, the metering system shall

be calibrated according to the procedure

outlined In APTD-0575. Instead of physically adjusting the dry gas meter dial readings

to correspond to the wet test meter readings, calibration factors may be used to

mathematically correct the gas meter dial

readings to the proper values.

Before calibrating the metering system, it

is suggested that a leak-check be conducted.

For metering systems having diaphragm

pumps, the normal leak-check procedure

will not detect leakages within the pump.

For these cases the following leak-check

procedure is suggested: make a 10-minute

calibiation run at 0.00057 ms/min (0.02

cfm); at the end of the run, take the difference of the measured wet test meter and

dry gas meter volumes; divide the difference

by 10, to get the leak rate. The leak rate

should not exceed 0.00057 ms/mn (0.02

cfm).

After each field use, the calibration of the

metering system shall be checked by performing three calibration runs at a single,

intermediate orifice setting (based on the

previous field test), with the vacuum set at

the maximum value reached during the test

series. To adjust the vacuum, insert a valve

between the wet test meter and the inlet of

the metering system. Calculate the average

value of the calibration factor. If the calibration has changed by more than 5 percent, recalibrate the meter over the full

range of orifice settings, as outlined in

APTD-0576.

Alternative procedures, e.g., using the orifice meter coefficients, may be used, subject

to the approval of the Administrator.

Novr.-If the dry gas meter coefficient

values obtained before and after a test

series differ by more than 5 percent, the

test series shall either be voided, or calculations for the test series shall be performed

using whichever meter coefficient value

(Le., before or after) gives the lower value of

total sample volume.

5.4 Temperature Gauges. Use the procedure in Section 4.3 of Method 2 to calibrate

in-stack temperature gauges. Dial thermometers, such as are used for the dry gas meter

and condenser outlet, shall be calibrated

against mercury-in-glass thermometers.

5.5 Leak Check of Metering System

Shown in Figure 17-1. That portion of the

sampling train from the pump to the orifice

meter should be leak checked prior to initial use and after each shipment. Leakage after

the pump will result in less volume being re- corded than Is actually sampled. The following procedure Is suggested (see Figure 17-5).

Close the main valve on the meter box.

Insert a one-hole rubber stopper with

rubber tubing attached into the orifice ex- haust pipe. Disconnect and vent the low side

of the orifice manometer. Close off the low

side orifice tap. Pressurize the system to 13

to 18 cm (5 to 7 In.) water column by blowing into the rubber tubing. Pinch off the

tubing and observe the manometer for one minute. A loss of pressure on the manometer indicates a leak in the meter box;

leaks, if present, must be corrected.

FEDERAL REGISTER, VOL 43, NO. 37-THURSDAY, FEBRUARY 23, 1978

7593

HeinOnline -- 43 Fed. Reg. 7593 1978
7594 RULES AND REGULATIONS

Lu

CC

Cj34

cn m

0

tz C.z :E -4.

,,

ca P

I-

> ui

Lu C3

u--a

Ca I.-, 

wJ L

Gf.- _0 oLCD 

C, C.

oLfUS

('3 I.

- o 

M uJ

HeinOnline -- 43 Fed. Reg. 7594 1978
5.6 Barometer. Calibrate against a mercury barometer.

6. Calculation. Carry out calculations, re- taining at least one extra decimal figure

beyond that of the acquired data. Round off

figures after the final calculation. Other

forms of the equations may be used as long

as they give equivalent results.

6.1 Nomenclature.

A= Cross-sectionalarea of nozzle, m, (LT).

B,,=Water vapor in the gas stream, propor- .. tionby volume.

Cj=Acetone blank residue concentration,

mg/g.

c,= Concentration of particulate matter In

stack gas, dry basis, corrected to standard conditions, g/dscm (g/dscf).

I--Percent of isokinetic sampling.

",=Maximum acceptable leakage rate' for

either a pretest leak check or for a leak

check following a component change;

equal to 0.00057 ml/min (0.02 cfm) or 4

percent of the average sampling rate.

whichever is less.

I,=Individual leakage rate observed during

the leak check conducted prior to the

"i'' component change (il. 2, 3... n), m3/min (cfm).

,-4=Leakage rate observed during the posttest leak check. m'/min (cfm).

m,=Total amount of particulate matter collected, mg.

M3=Molecular weight of water, 18.0 g/gmole (18.0 lb/lb-mole).

m.=Mass of residue of acetone after evaporation, mag.

Pb=Barometric pressure at the sampling

site, mm Hg (in. Hg).

P,=Absolute stack gas pressure, mm Hg (in.

Hg).

P,=Standard absolute pressure, 760 mm Hg (29.92 in. Hg).

R=Ideal gas constant, 0.06236 mm Hg-m2/

"K-g-mole (21.85 in. Hg-ft/*R-lb-mole).

T;.=Absolute average dry gas meter temperature (see Figure 17-3), "K'(R).

T,=Absolute average stack gas temperature

(see Figure 17-3), °K (°R).

T.,d=Standard absolute temperature, 293YK

(528'R).

V.=Volume of acetone blank, mL

V.,=Volume of acetone used in wash, ml.

V,=Total volume of liquid collected in impingers and silica gel (see Figure 17-4),

mL

V.=Volume of gas sample as measured by

dry gas meter, dcm (dcf).

V.,0=Volume of as sample measured by

the dry gas meter, corrected to standard

conditions, dscm (dscf).

V,,,,=Volume of water vapor in the gas

sample, corrected to standard conditions, scm (scf).

v.=Stack gas velocity, calculated by Method

2, Equation 2-9, using data obtained

from Method 17, m/sec (ft/sec).

W.=Weight of residue in acetone wash, rag.

Y=Dry gas meter calibration coefficient.

AH=Average pressure differential across

the orifice meter (see Figure 17-3), mm

HO (in. HO).

p.=Density of acetone, mg/ml (see label on

bottle).

=.=Density of water, 0.9982 g/ml (0.002201

lb/ml).

8'Total sampling time, min. - O,=Sampling time interval, from the beginning of a run until the first component

change, saiL

01=Sampling time interval, between two

successive component changes, beginning with the interval between the first

and second changes, min.

RULES AND REGULATIONS

0.=Sampling time interval, from the final

(nb) component change until the end of

the sampling run. min.

13.6=Specrlc gravity of mercury.

60=Sec/mIn.

100=Conversion to percent.

6.2 Average dry gas meter temperature

and average orifice pressure drop. See data

sheet (Figure 17-3).

6.3 Dry Gas Volume. Correct the sample

volume measured by the dry gas meter to

standard conditions (20" C. 760 mm Hg or 68 F, 29.92 in. Hg) by using Equation 17-L

Vm(std) V Y (1M ) p +T43]

K V Y Pbar + (AH/13.6)

Equation 17-1

where:

K,=0.3858" K/mm Hg for metric units;

17.64' R/In. Hg for English units.

No r.--Equation 17-1 can be used as written unless the leakage rate observed during

any of the mandatory leak checks (Le.. the

post-test leak check or leak checks conducted prior to component changes) exceeds IU.

If U- or L, exceeds I.. Equation 17-1 must be

modified as follows:

(a) Case L No component changes made

during sampling run. In this case, replace

V. in Equation 17-1 with the expression:

[V.-( -L.)0]

(b) Case IL One or more component

changes made during the sampling run. In

this case. replace V. In Equation 17-1 by the

expression:

n

- (Ll-La) L a1 - i (Li La) 0i

- (L - La) Op]

and substitute only for those leakage rates

(lq or L.) which exceed I.

6.4 Volume of water vapor.

( T\( =RTstd 2

= vw(std vA.4/\stdJ

Equation 17-2

where:

K=0.001333 m2/ml for metric units; 0.04707

ft'/ml for English units.

6.5 Moisture Content.

Vw(std)

Bws = Vmlstd) + Vw(std)

Equation 17-3

7595

6.6 Acetone Blank Concentration.

C a

Ca =Va a

Equation 17-4

6.7 Acetone Wash Blank.

W.=CV..p.

Equation 17-5

6.8 Total Particulate Weight. Determine

the total particulate catch from the sum of

the weights obtained from containers 1 and

2 less the acetone blank (see Figure 17-4).

Nor.--Refer to Section 4.1.5 to assist in

calculation of results involving two or more filter assemblies or two or more sampling

trains.

6.9 Particulate Concentration.

c6==(0.001 g/rag) (m./V.Wi)

Equation 17-6

6.10 Conversion Factors:

Prom To Multiply by

C ......... . . m a - 0.02832

/ft' gr/ft', 15.43

gi/t' lb/ft.-- 2.205- ' gift' glm" 35.31

6.11 Isokinetic Variation.

6.11.1 Calculation from Raw Data.

100 Ts [K3Vjc + (VnY/T) (Pbar + e13.6)1 M 

60e s An

Equation 17-7

where:

K=0.003454 mm Hg-m/ml-K for metric - units; 0.002669 In. Hg-ft/ml-R for English units.

6.11.2 Calculation from Intermediate

Values.

Tnstdst s= d 00

T st d Vs a n Ps 60 (- ws)

K T s V m(std)

= K4 s vs An " "-ws)

Equation 17-8

where:

K.=4.320 for metric units; 0.09450 for English units.

6.12 Acceptable Results. If 90 percent

010110 percent. the results are acceptable. If

the results are low in comparison to the

standard and I is beyond the acceptable

range, or, if I is less than 90 percent. the Administrator may opt to accept the results.

Use Citation 4 in Section 7 to make Judgments. Otherwise, reject the results and

repeat the test.

7. Bibliography.

FEDERAL REGISTER, VOL 43, NO. 37-THURSDAY, FEBRUAIY 23, 1978

HeinOnline -- 43 Fed. Reg. 7595 1978
7596 RULES AND REGULATIONS

1. Addendum to Specifications for Incinerator Testing at Federal Facilities. PHS,

NCAPC. December 6, 1967.

2. Martin, Robert M., Construction Details

of Isokinetic Source-Sampling Equipment.

Environmental Protection Agency. Research Triangle Park. N.C. APTD-0581.

April, 1971.

3. Rom, Jerome J., Maintenance, Calibration, and Operation of Isokinetio SourceSampling Equipment. Environmental Protection Agency. Research Triangle Park,

N.C. APTD-0576. March, 1972.

4. Smith, W. S., R. T. Shigehara, and W.

F. Todd. A Method of Interpreting Stack

Sampling Data. Paper Presented at the 63rd

Annual Meeting of the Air Pollution Control Association, St. Louis, Mo. June 14-19,

1970.

5. Smith, W. S., et al., Stack Gas Sampling

Improved and Simplified with New Equipment. APCA Paper No. 67-119. 1967.

6. Specifications for Incinerator Testing at

Federal Facilities. PHS, NCAPC. 1967.

7. Shigehara, R. T., Adjustments in the

EPA Nomograph for- Different Pitot Tube

Coefficients and Dry Molecular Weights.

Stack Sampling News 2:4-11. October, 1974.

8. Vollaro, R. F., A Survey of Commercially 'Available Instrumentation for the Measurement of Low-Range Gas Velocities. U.S.

Environmental Protection Agency, Emission

Measurement Branch. Research Triangle

Park, N.C. November, 1976 (unpublished

paper).

9. Annual Book of ASTM Standards, Part

26. Gaseous Fuels; Coal and Coke: Atmo.

spheric Analysis. American Society for Testing and Materials. Philadelphia, Pa. 1974,

pp. 617-622.

10. Vollaro, R. F., Recommended Procedure for Sample TraVerses in Ducts Smaller

than 12 Inches in Diameter. U.S. Efviron

mental Protection Agency, Emission Measurement Branch. Research Triangle Park,

N.C. November, 1976.

[FR Doc. 78-4795 Filed 2-22-78; 8:45 am]

FEDERAL REGISTER, VOL. 43, NO. 37-THURSDAY, FEBRUARY 23, 1978

HeinOnline -- 43 Fed. Reg. 7596 1978