- r 

# ENVIRONMENTAL PROTECTION AGENCY

KRAFT PULP MILLS

Standards ofPerformance 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]

Title40-Protection ofthe Environment CHAPTER I-ENVIRONMENTAL PROTECTION



### AGENCY
SUBCHAPTER C-AIR PROGRAMS



### EFRL833-1]

PART 60-STANDARDS OFPERFORMANCE FOR NEW STATIONARY SOURCES

Kraft Pulp

### Mills

AGENCY: Environmental Protection Agency. ACTION:Final rule.
SUMMARY: Thestandards limitemissions of total reduced sulfur (TRS) and particulate matter from new, modified, and reconstructed kraftpulp 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 ofthese standards is to require new, modified, and recon- structed kraft pulp mills to use the best demonstrated system of continu-

ousemission 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 forinspection and copying during normal business hours atEPA's Public Information Reference Unit, Room 2922 (EPA Library), 401 MStreet 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 AirAct, 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-offinalrulemaking. THE STANDARDs
Thestandards limit emissions ofparticulate 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.

Thestandards also limit emissions of TRS.from eight affected facilities at kraftpulp mills. Thelimits are: 5parts .per million (ppm) by volume at 10percent oxygen from the digester systems, multiple-effect evaporator systems, brown stock, washer' systems, black liquor oxidation systems, and condensate strippersystems; 5 ppmby volume at 8 percent oxygen from straight kraft recovery furnaces, 8 ppm by volume at 10 percent oxygen fromlime kilns; and 25 ppm byvolume 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 sulfidityof atleast 28 percent. In addition, TRS emissions from smelt dissolving tanks arelimitedto 0.0034 g/kg BIS.

The proposed TRS standard for the lime kilnhasbeen changed, a separate TRS standard for cross recovery fur-

naceshas beendeveloped, 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 forthe otherfacilities, however, are essentially the

same asthoseproposed.

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 ofachieving such emissionre- 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 ofnational ambient air quality standards (NAAQS) designed to protect public health and welfare. For that purpose SIP's must in some cases require greater emissionreductions than those required by standards of performance for new sources. Section 173(2) of the Clean AirAct, as amendedin 1977, re- quires, amongother things,that a new or modified source constructed In an
area which exceeds the NAAQS must reduce emissions to thelevel 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 ofperformance.

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 ofair quality provisions ofthe 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 toregulation 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 suchpollutant. In noevent 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 ofthis 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 ofperformance applicable to all areas ofthe country (clean as well as dirty). Costs must be accorded far less weight in determining the "lowest achievable emission rate" fornew 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 emissiolirate."

In addition, States are free under section 116 ofthe Actto 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,

newsources mayin some cases be subjectto 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 suchfacilities.

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 ofthe 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 publicnotice in the FEDERAL REGISTER ofa meeting ofthe-National AirPollution 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 ofproposal. The public com- ment periodextended from September 24, 1976, toMarch 14, 1977, andresulted in 42 comment letters with 28 of these letters coming from the industry, 12 from various regulatory agencies, and two fromU.S. citizens. Several comments resulted in changes to the proposed standards.A detailed discussion of the comments and changes which resulted ispresented inVolume 2 ofthe SSEIS.A summary ispresentedhere.



### SIGNIFIcATr COMM=S AND 

### CHANGES MADE INTHEPROPOSED REGULATIONS

Most of the comment letters re- ceived contained multiple comments. The most significant comments and changes made to the proposed regulations arediscussed below.

IMPACTS OF THEPROPOSED STANDARDS


### Several commenters expressed con-
cern about the increased energy con- sumption which would result from compliance with proposed standards. These commenters felt thatthis would conflict with the Department ofEnergy's goal to reduce total energy con- sumption in the pulp andpaper industryby 14 percent.This factor was con- sidered in the analysis of the energy impact associated with the standards and is discussed in the SSEIS. Althoughthe standards will increase the difficulty of attaining this energy re- duction goal, the 4.3 percent increase in energy usage that will be required bynew, 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 CONTROLTECHNOLOGY

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 ofthe 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 8percent oxygen forthe 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 kilnor recoveryfurnace with

a highoxygen 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 8percent oxygen, as appropriate,in allcases.



### 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 ofthemud washingfacilities 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 limekilnE,with TRS emissions during normal operation at lime kiln E when caustic is being added tothe 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 limekilns which employed only efficient mud washing and-good limekiln 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 ofmud 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 lowTRS emissions observed at this kiln. With the data available, however, It is not possible to separate therelative contribution ofthese mud washing facilities to the low TRS emissions observed from the relative contributions of goodprocess operationofthe limekiln and caustic scrubbing.

Comments questioning theadequacy of the data base used in developing the standards for lime kilns were mainly directed toward the following points: theTRS standardwasbasedon 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 andthe 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 otherlime kilnin the United States is currently achieving the TRS emission levels observed atlime kilnE,there is

no otherlimekilnintheUnitedStates which is using the same-emission con- trolsystem thatis employed atthis facility. As discussed In the SSEIS, an analysis of the various parameters Influencing TRS emissions from lime kilns indicates that this system of emissionreduction 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 ofperfor-

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 emissionreduction, and any nonairquality health and environmental impact and energy requirements) the Administrator determines has been adequately demonstrated for that category of sources." Litigation of standards ofperformance has resulted in clarification ofthe 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 ofthe emissioncontrol 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 notreflect 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 withthe 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 ofthese 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 ofparticulate matter permitted in the gases discharged to the atmosphere, however, the potential contribution of sodium fume from caustic scrubbing is quite small.Consequently, withproper operation and maintenance, sodium fume due to caustic scrubbing will not

cause particulate emissions from a lime kiln to exceed the numerical emission limitincluded in the promulgated standard.

RecoveryFurnace. Anumber ofcom- 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 thatthe operation ofcrossrecov- 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 of25 ppm for crossrecovery 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 ofemissions perunit 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 solidsproduced perton of air-dried pulp, however, can vary substantiallyfrom mill to mill.A standard in terms of emissions per unit of airdried pulp, therefore, requires greater control ofemissions atkraft pulpmills 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 isroutinelymonitored atkraft 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 isboth 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 notbe 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 forthese monitors.

At the time ofproposal 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 ajoint EPA/industry effort,the compatibility of various TRS emission monitoring

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### RULES AND REGULATIONS

methods with Reference Method 16, which is the performance testmethod 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 includeTRS continuous emission-monitoring requirements. These requirements,however,willnot become effective until performance specifications forTRS continuous emission monitoring systems have been developed. To accommodate this situation, not only for the promulgated standards for kraft pulpmills, but also for standards ofperformance thatmaybe developed in the future that may also face this situation, section 60.13 ofthe General Provisions for subpart 60 is amended tobrovide 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 allfacilities which are covered-by standards ofperformance will eventually install continuous emission monitoring systems whererequired.

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 briefxeview of tjiis con- cept is appropriate.

Standards of performance have two major objectives. The first is installation ofthe best system ofemission 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 theperformance 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 oftentime consuming and complex. As a-result,-whiletheperformance 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 meetingthese objectives.

Excess emissions-are defined-as emissions exceeding the miumerical emission limit included in a standard of performance. Continuous emission monitoring, therefore, identifies periods ofexcess emissions andwhen combined with the requirement that these periods bereported toEPA. It provides the Agency with a useful mechanism for achieving the previously men- tionedobjectives.

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 dueto start-ups, shutdowns, andmalfunctions, for example, areun- avoidable or beyond the control of an
owner or operator and cannot be attributed to Improper operation and maintenance. Similarly, excess emissionsas aresult ofsome 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 effecton emissions.

To quantify the potential for excess emissions due to Inherent variability in a process, continuous monitoring data are usedwhenever possible tocalculate an excess emission allowance. For TRS emissions atkraft pulp mills, this allowance Is defined asfollows. 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 asthe result ofunavoidable 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 thedata generated bythe

excess emission reporting requirements.

Althoughthe excess emissionreporting requirements provide a mechanism for achieving the objective of proper operation and maintenance ofthe best system of emission reduction, this mechanism Is not necessarily a direct indicator of improper operation and maintenance. Consequently, excess emissionreports mustbereviewed 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 forrecovery furnaces.

With regard to the adequacy of the TRS excess emissions allowance for lime kilns, a reevaluation of the TRS emission data from limekiln Eled the Agency to the conclusion that, for a TRS emission limit of 5 ppm, an excem emission allowance of6 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 stillrequire installation ofthe best systemofemissionreduction, con- sidering costs (Le., efficientmudwashing, good lime kiln process operation, and caustic scrubbing; or an alternative system equivalent to the perfor-

mance ofthissystem).

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 operatedrecovery furnacewhichcould 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 ofrecovery furnaceD concerning this point.

A review ofthe data indicates that, while some of the excursions of TRS emissions above5 ppmreflected either Improper operation and maintenance,

or start-ups, shutdowns, or malfunctions,most ofthese 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 toiniproper operation and maintenance, or start-ups, shutdowns, or malfunctions indicates that

anexcess 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 forlimekilns, is a reversal ofthe 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 forre- covery furnaces is. based consists of black liquor oxidation and good pro-
cess operation ofthe recovery furnace for direct recovery furnaces, and good process operation aloneforindirectre- coveryfurnaces.Neitherofthese 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 asfluctuations in TRS

### emissions.

The emission control system upon whichtheTRS standardforlimekilns

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### 7572

is based consists of efficient mud* washing,goodprocess operation ofthe lime kiln, andcaustic scrubbing ofthe 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 notparticularly well suitedto controllingfluctuations in thekraftpulpingprocess. Thethird emissioncontrol technique, however, caustic scrubbing, is an "add-on" emission control technique that can be designed to accommodate fluctuations inTRS 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 tothe validityoftheresults obtained by Reference Method 16, as mentioned earlier, during the emission testing program, it was not widely known thatsample 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 notconsidered 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, sincethe amount of sample loss that occurs within the TRS emission measurement systemduring 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 testare accurate.

Ithas alsobeen confirmedthathigh concentrations of SO2 

### will interfere 

### with the determination ofTRS emissions to some extent. At this point, however, it is not known what SO2 

### concentration levels willresult inasig- nificant loss of accuracy in determining TRS emissions. The ability ofa citrate scrubber to selectively remove
S02 

### prior to measurement of TRS 

### emissions isnowbeing tested. In addition, various chromatographic columns might exist which would effectively resolve thisproblem. As soon as
anappropriate technique is developed to overcome this problem, Reference Method 16willbe amended.

This problem of S02 

### interference 

### will not present major difficulties to the use ofReference Method 16. RelaRULES AND REGULATIONS

tively high S02 

### concentration levels

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

### concentration levels are probably not

a frequent occurrence within kraft pulp mills. More importantly, however,high S02 

### concentrations only interferewith the determination ofmethyl 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 ofwhich 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 CircularA-107.

Dated:February 10, 1978.

BARBARA BLUm, 

### ActingAdministrator.

Part 60 of Chapter I, Title 40 ofthe Code of Federal Regulations is amended asfollows: Subpart A-General Provisions


### 1. Section 60.13 is amended to clarify the provisions in paragraph (a) by revisingparagraph (a) toreadasfollows:
§60.13 Monitoringrequirements.

(a) Forthe purposes of this section, all continuous monitoring systems re- quired under applicable subparts shall be subject tothe provisions of thissec- tion upon promulgation of perfor-

mance specifications for continuous monitoring system under Appendix B to thispart,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 orby the Administrator.

* * * * S 

### 2. Part 60 is amended by adding subpartBB asfollows:
Subpart BB-Standardsof Performanc, for Kraft Pulp

- Mills
Sec. " 

### 60.280 Applicability and designation 

### bf affectedfacility. 60.281 Definitions. 60.282 Standard forparticulate matter, 60.283 Standard for total reduced sulfur (TRS). 60.284 Monitoring of emissions and operations. 60.285 Testmethods andprocedures.

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 ofaffected facility. (a) The provisions of this subpart

are applicable to the following affected facilities in kraft pulp mills: digest-

er system, brown stockwasher 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 ofthlssubpart.
§60.281 Definitions.

Asused in this subpart, allterms not defined herein shall have the same meaning given them in the Act and in Subpart A.

(a) "Kraft pulpmill" 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 kraftpulp 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 ofwood in white liquor, and associated flash tank(s), below tank(s), chipsteamer(s), and condenser(s),

(e) "Brown stock washer system"

meansbrown stockwashers 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 followingthe 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 vesselsused tooxidize, with air or oxygen,theblack liquor, and as- sociated-storagetank(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 kraftrecovery furnace"

means- a furnace used to recover chemicals consisting primarily of sodium and sulfur compounds by burningblack liquorwhich 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 of28 percent orless.

C) "Cross recovery furnace" means a furnace used torecover chemicals con- sistingprimarily 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 liquorsulfidity of-morethan 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 thesulfidity ofthe liquorwhich leaves thesmelt dissolvingtank.

(m)"Smelt dissolvingtank"means a vessel used for dissolving the smelt collectedfrom therecovery furnace.

(n)'ULme kiln"means a unitused to calcie lime mud, which consists pri- marily of calcium carbonate, into Quicklime,whichis 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 kraftpulp mill.
§60.282 Standard forparticulate matter.

Ca) On and after the date on which the performance test required to be conducted 'by§60.8 is completed, no
owner oroperator subjectto the provi-- sions of this subpart shall cause to be discharged intotheatmosphere:-

(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 8percent-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 liquorsolids (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 fossilfuel isburned.

(ii) 0.30 g/dscm (0.13 gr/dscf) cor- rected to 10 percent oxygen, when liquidfossil fuel isburned.
§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 theprovi-' sions of this subpart shall cause to be discharged into theatmosphere:

(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 5ppm byvolume on a dry basis, corrected to 10 percent oxygen, unless the following conditions are met:

(1)The gases-arecombusted in a lime kiln subject to the provisions ofparagraph (a)(5) ofthis 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 kilnorrecovery furnacenot subject to the provisions ofthis subpart, and are subjected to a minimum temperature of 1200' F. foratleast 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, orreconstructed 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 canbe incinerated.

(2) From any straightkraft recovery furnace any gases which contain TRS in excess of 5 ppm by volume on a dry basis,corrected to 8percent oxygen.

(3) From any cross recovery furnace any gaseswhich contain TRS in excess of 25 ppm by volume on a dry-basis, corrected to8 percent oxygen.

(4) From any smelt dissolving tank any gases whichcontainTRS in excess of 0.0084 g/kg blackliquor solids (dry weight) [0.0168 lblton liquor solids (dryweight)].

(5) From any lime kiln any gases which contain TRS in excess of 8ppm by volume on a dry basis, corrected to 10percent oxygen. 

### §60.284 Monitoring ofemissions and operationL 

### (a) Any owner oroperator subject to theprovisions ofthis subpart shallinstall, 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 anyrecoveryfurnace. The span ofthis 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) andthe span(s) ofthese 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 at50 ppm.

(I1) At 20 percent oxygen for the continuous oxygen monitoring system.

(b)Any owner or operatorsubject to the provisions ofthis subpart shallinstall, 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 certifiedbythemanufacturer tobe ac- curate within ±1percent of the temperature beingmeasured.

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

(i) A monitoring devicefor 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 gagepressure). *

(WI) Amonitoring device forthe conitinuous measurement ofthe 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

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### RULES 'AND -REGULATIONS

be located close to the scrubber liquid discharge point. The Administrator maybe consulted for approval ofalternative 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) ofthis 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 tobe corrected to (8 percent forrecovery furnaces and 10 percentfor lime kilns, incinerators, or other devices). Y=the measured 12-hour average volumetricoxygenconcentration. (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 35percent.

(2) For emissions fromany lime kiln, periods of excess emissions are all 12- hour average TRS concentration above 8ppm 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 underparagraph (d) ofthis 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 fromrecovery furnaces.

(i) Six percent for average opacities fromrecovery furnaces.

(2) The Administrator determines thatthe 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 Testmethods andprocedures.

(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 ofparticulate matter and the associatedmoisture content,

(2) Method 1for sample and velocity traverses,

(3) When determining compliance with §60.282(a)(2), Method 2 forvelocity and volumetric flow rate,

.

(4) Method 3forgas analysis, and (5) Method 9for visible emissions. (b) ForMethod 5, the sampling time for each run shall be at least 60 minutes and the sampling rate shallbe at least 0.85 dscm/hr (0.53 dscf/min) except that shorter sampling times, whennecessitated 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 inMethod 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 Isno 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 ofTRS,

(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 ofTRS emitted per unity ofblack 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 thetestperiod, PPM. Fm =0.001417 g/ms PPMformetric units

= 0.08844 lb/ft' PPMforEnglish units Finsu= 0.00200g/m' PPMfor metric units

= 0.1248 lb/ftsPPMforEnglish units

Ems = 

### 0.002583 g/m,PPM formetric units

= 0.1612lb/ft,PPM forEnglish units FDs = 

### 0.003917 g/m' PPM for metric units

= 0.2445lb/ftsPPM forEnglish units Qd

### = dry volumetric stack gasflowrate 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 (Na2

### O) and substituted into the following equation to determine the green liquor sulfidity: GLS = 100 CV.P/CH' + CN.,, + CN.Wo Where: GLS =percent greenliquorsulfidity CNv = average concentration of NaIL9 ex- pressed asNaO 

### (mg/i) CN.OH =average concentration of NaOH expressed asNaO (mg/1) Cx..CO. = average concentration of 

### NaCO, expressed asAVa.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

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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 ofSection 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. Thisinterference must be eliminatedbyuse ofa probefilter. (3) Method 16 and Method 17 are 3.4 Sulfur Dioxide. SO, is not a specific added'to Appendix A as follows: interferent butmaybe presentin suchlarge 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 thesample. 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 ofgas chromatographic separation source to be tested. Acceptable systems and flame photometric detection. Since shall showbaseline separation with the am- there are many systems or sets ofoperating plifier attenuation set so that the reduced conditions thatrepresent usable methods of sulfur compound of concern Is at least 50 determining sulfur emissions, all systems percent offull 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. thatthecriteria setbelow aremet. 4.1 GC/FPD and Dilution System Call.

1. PrincipleandApplicability. brationPrecision. A series ofthree 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 notvary by more than ±3percent from sample is then analyzed for hydrogen sul- themean ofthe 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 hourperiod shall notexceed ± percent. collectively astotal reduced sulfur(TRS). 4.3 System Calibration Accuracy. The

1.2 Applicability. Thismethod is applica- complete system must quantitatively transble for determination of TRS compounds port andanalyze with an accuracyof20per. from recovery furnaces, lime kilns, and cent.A correction factor is developed to smeltdissolving tanks atkraftpulp mills, adjust calibration accuracyto 100 percent.

2.RangeandSensitivity. 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 ofthe 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 limitisexpanded by dilution of theprobe at ornear thesample entrypoint. the sample gas before analysis. Kraft mill Anyportion oftheprobenot 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 turecondensation. ppmforeach compound. 5.1.2 Sample Line. The Sample line must

-Forsources with emission levels between be made ofTeflon., no greater than 1.3 cm 10 and 100 ppm, themeasuring range canbe (M) inside diameter. All parts from the best extended by reducing the sample size probe to the dilution system must be ,therto 1 milliliter. mostaticallyheated 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. ofthe dilution system, the pump headmust 3.1 Moisture Condensation. Moisture be heatedto 120- C. condensation in thesample delivery system, 5.2 Dilution System. The dilutionsystem the analytical column, or the FPD burner must be constructed such that all sample block can cause losses orinterferences. This contacts are made of inert materials (e.g.. potential is eliminated by heating the stainless steel orTeflon). It must be heated sample line, and by conditioning the sample to 120' C. and becapable ofapproximately a with dry dilution air to lower-its dew point 9:1 dilution ofthe sample. below the operating temperature of the 5.3 Gas Chromatograph. The gas chroGC/FPD analytical systemprior toanalysis. 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 bysubmitting chroma- and carrier gasflows. tograms ofcalibration gases with and without CO. in the diluent gas. The CO. level 'Mention of trade names orspecific prod. should be approximately 10 percent for the ucts doesnot constitute endorsementby the

case with CO present. The two chromato- Environmental Protection Agency. 

### 7575

5.3.4 FlamePhotometric Detector. 5.3.4.1 Electrometer.Capable offull scale amplification oflinearranges of 10- to 10-4 amperesfull scale.

5.3.4.2 Power Supply. Capable of deliverlngup to 7150volts.

5.3.4.3 Recorder. Compatible with the outputvoltagerange ofthe electrometer.

5.4 Gas Chromatograph Columns. The column system mustbe demonstrated to be capble of resolving the four major reduced sulfur compounds: H.S. MeSH. DMS. and DMDS. It must also demonstrate freedom fromknown interferences.

To demonstrate that adequate resolution hasbeen achieved, thetester must submit a chromatograph ofacalibration gascontaining all four of the TRS compounds in the concentration range of the applicable standard. Adequate resolution will be definedas base line separation ofadjacent peaks when the amplifier attenuation is set so that the smaller peak is at least 50 percent of full scale.Base line separation isdefined in Section 3.4. Systems not meeting this criteria may be considered alternate methods subjectto theapproval oftheAdminstrator.

5.5. Calibration System. The calibration system must contain the following components.

5.5.1 TubeChamber. Chamber ofglass 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 testserieswith awettestmeter.If the flow measuring device differs from the wet testmeter by 5 percent, the completed test shall be discarded. Alternatively, the tester may elect to use the flow data that would 

### yield thelowestflow measurement. Calibration with a wet test meter before a test Is optional. '5.5.3 ConstantTemperature Bath. Device capable of maintaining the permeation tubes atthe 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 gradeorbetter.

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

6.3 Carrier Gas. Prepurifled grade or better.

6.4 Diluent. Air containing less than 50 ppb total sulfur compounds and lessthan 10 ppm each of moisture and total hydrocarbons. This gas must be heated prior to mixing withthe sample to avoid watercon- densationatthepoint ofcontact.

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. Theenclosed gas permeates throughthe tubing wall at a con- stant rate. When the temperature is con- stant, calibration gases coverning a wide range ofknown concentrations canbe generatedby varyingand accurately measuring theflow rate ofdiluent gaspassing overthe tubes. These calibration gases are used to calibrate the GC/FPD system and the dilutionsystem.

7. Pretest Procedure& Thefollowing procedures are optional but would be helpful in preventing any problem which might occur later andinvalidatethe entiretest.

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### RULES -ANDr'REGULATIONS'

7.1 After the complete measurement

- system has been set up at the site and

deemed tobe operational, thefollowing procedures should be completed before sam- plingis initiated.

7.1.1 Leak Test. Appropriate leak test procedures should beemployed 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 offthe pump outlet,and then stop the pump and ascertain thatthere isnoleak 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 thepresence of aleak.

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 canbeperformed by observing the response of flowmeters or oftheGC output to changes inflowrates or calibration gas concentrations and ascertaining the response to be within predicted limits.In any component, or ifthe complete system fails to respond ina normal and predictable manner, the source of the discrepancy should be Identified and corrected beforeproceeding.

8. Calibration. Prior to any sampling run, calibrate the system using the following procedures. (If more than one run is performed duringany 24-hourperiod, acalibration 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-hourperiod.)

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 instructionsbecause the operation ofthesesystems 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 themeasurement system.In addition, the operator should be familiar with the operating principles ofthe components; particularly the GC/FPD. The citations in the Bibliography atthe end ofthismethod are recommended forreview forthispurpose.

8.2 Calibration Procedure. Insert the permeation tubes into the tube chamber. Check the bath temperature to assure agreement with the calibration temperature ofthe 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 precisionlimits of Section 4.1.

Vary the amount of air flowing over the tubes to produce the desiredconcentrations 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 asfollows: p

Equation 16-1 where:
C=Concentration of permeant produced in ppm. P,=Permeation rate ofthe tube in pg/min. M=Molecular weight of the permeant (g/gmole). L=Flow rate, 1/min, of air overpermeant @ 20' C,760mmHg. K=Gas constant at 20' C and 760 mm Hg=24.04 1/gmole.
8.3 Calibration of analysis system. Generate a series of three or more known con- centrations spanning the linearrange ofthe 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- rectedbefore 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 foreach sulfur compound. Alternatively, a least squares equation may be generated from the calibration data.

8.5 Calibration ofDilution System. Generate a known concentration of hydrogen sulfide using the permeation tube system. Adjust the flow rate of diluent air for the firstdilution stage sothat the desired level ofdilution is approximated. Inject thediluted 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 inthis step is anindication 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 ofdilution required. Alternatively, the GC/FPD system may be calibrated by generating a series ofthree or
more concentrations of each sulfur compound and dilutingthese 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. Samplingand Analy/sisProcedure 9.1 Sampling. Insert the sampling probe into the testport making certain that no dilution air enters the stack.throughthe port. Begin sampling and dilute the sample approximtely 9:1 using the dilution system. Note that the precise dilution factor isthat 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 hoursormore than 6hours. 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 probeis cloggedwith particulate matter. If the probe isfound to be clogged, the test mustbe stopped and the results up to thatpoint discarded. Testing may resume after cleaning the probe orreplacing It with

a clean one. After each run, the sample probe must be inspected and, if necessary, dismantled andcleaned.

10.Post-TestProcedures.
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 ofthe 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 systemloss ofmore than 20percent Is unacceptable. Sampling losses of 0-20 percent must be corrected for by dividing the resulting sample concentration by the fractionofrecovery. Theknown gas samplemay 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 aseries ofruns made within a 24-hour period, perform apartial 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 underparagraph 10.1. The calibration drift should not exceed the limits set forth in paragraph 4.2. Ifthe 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 wouldgive the highest samplevalues.

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.

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### RULES AND REGULATIONS

11.3 Average TRS.The average TRS will be determined asfollows:

N

- 

### z TRS1 i = Average TRS= III-B

Average TRS=Average total reduced suflur inppm, drybasis. TRS,=Total reduced sulfurin ppm as determinedby Eqiiation 16-2. N=Number of samples. B=Fraction of volume of water vapor in the gas streamas determined bymethod 4-Determination of Moisture in Stack Gases (36 FR24887).
11.4 Average concentration of individual reduced sulfur compounds.

r S.lCEquation 16-3 where:

S1=Concentration of any reduced sulfur compound from the ith sample injection,ppm. C=Average concentration of any one ofthe reduced sulfurcompounds forthe entire
run,ppm. N=Number ofinjections in any run period.

12. ExampleSystem. 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 shieldplacedbetween the sample and thegas inletholes andthe 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 isheated with heating tape.

12.1.1.2 Sample Line Se inchinside diameter Teflon tubing, heated to 120* C. This temperature iscontrolled by a thermostatic heater.

12.1.1.3 Sample Pump. Leakless Teflon coated diaphragm type or equivalent. The pump head isheated to 120' Cby 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 whichisheated to 120" Cmustbe capable of a minimum of 9:1 dilution of sample. Equipment used in the dilution system islistedbelow:

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 dryair asshown inFigure 16-2.

12.1.2.2 Valves. Three-way Teflon solenoid ormanualtype.

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 forsample gas12.1.2.4 Box. Insulated box, heated and maintained at 120' C, of sufficient dimensions to housedilution apparatus.

12.1.2.5 Fowmeters. Rotameters or 

### equivalent to measure now from 0 to 1500 ml/min ±1perdentper dilutionstage.

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 (seeFigure 16-3).

12.1.3.1.2 Stripper or Precolumn. 0.6 ma by 2.16mm (2 ftby0.085 in)inside diameter Teflon tubing packed as in5.3.1.

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 exhausttemperature ±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-' amperesfullscale.

12.1.3.1.9 Power Supply. Capable of deli. vering up to750 volts.

12.1.3.1.10 Recorder. Compatible with the output voltage range of the electrometer.

12.1.3.2 High Molecular Weight CompoundsColumn (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 10percent Triton X-305,

orequivalent.

12.1.3.2.2 SampleValve. Teflon 6-portgas sampling valve equipped with a 10 ml sample loop, actuated by compressed air (Figure 16-3).

12.1.3.2.3 Other Components. All componentssame 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 permeationtubes.

12.1.4.2 Mass Flowmetem. Two mass flowmeters in therange 0-3 l/min. and0-10 1/min. to measure air flow overpermeation tubes at ±2percent. These nfowmeters shall be cross-calibrated at the beginning,ofeach 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 atthis flowrate as measured by one flowmeter followed by injection of calibration gas atthesameflowrate asmeasuredby the other nfowmeter should agree withinthe 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
testwith a wettestmeter and thereafter, at least onceeach 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 orbetter.

12.2.2. Combustion Gas. Oxygen (0) research purityorbetter.

12.2.3 Carrier Gas. Nitrogen (N,) prepurifledgrade orbetter.



### 12.2.4 Diluent. Air containing less than 50ppb total sulfur compqunds andless than 10 ppm each of moisture and total hydrocarbons, and filtered using MSA filters 4G727 and 79030, or equivalenL.Removal of sulfur compounds canbe 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 at30.0' C.

12.3 Operating Parameters. 12.3.1 Low-Molecular Weight Sulfur Compounds. The operating parameters for the GC/FPD system used for lowmolecular weight compounds are as follows nitrogen carrier gas flow rate of 50 ce/min, exhaust temperature of110 C, detectortemperature of105"C.oven temperature of40' C.hydrogenflow rateof80 ce/min. oxygenflow rate of20 ce/min, and sample flow ratebetween 20and 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 asin 12.31 except: oven temperature of 70" C, and nitrogen carrier gasflow of100 cc/min.

12.4 AnalysisProcedure. 12.4.1 Analysis. AIIquots of diluted sample are injected simultaneously into both GC/FPD analyzers for analysis. GC/ FPD-I Isusedtomeasure thelow-molecular weight reduced sulfur compounds. The low molecular weight compoundsinclude hydrogen Sulfide, methyl mercaptan, and dlmethyl sulfide. GC/FPD-fl Is used to resolve the high-molecular weight compound. The high-molecular weight compound Isdimethyl 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 ofdiluted sample isinjected Into the stripper column and analytical column. The valve is then deactivated for approximately 12 minutes in which time, the analytical column continues to beforeflushed, thestripper column isbackflushed. and the sample loop Isrefilled. 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 Isessentially the same as above except that

no strippercolumn isneeded.

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 AirPollution and Industrial Hygiene Studies, University of Southern California, LosAngeles, 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 ofChemical Analysis Volume IIIA and B Instrumental Methods. Sixth Edition. VanNostrand 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 oftemperature 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. Ofthe two variables (i.e., temperature andpressure), temperature has the greater effect upon the amount of par- ticulate matter inan effluent gas stream; in most stationary source categories, the effect ofpressure appears to benegligible.

In method 5, 250' F is established as a nominal reference temperature. Thus, where Method 5 is specifiedin an applicable subpart ofthe 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 normalrange oftemperature 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 stacktemperature.

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 andApplicability. 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 ofuncombined 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 ofthe stack cross-sec- tional area (see Section4.1.2).

2.Apparatus.
2.1 Sampling Train. A schematic of the sampling train used Inthis 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-

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### RULES AND REGULATIONS

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### RULES AND REGULATIONS

The operating and maintenance procedures for many ofthe 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 ofthefollowing 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 thebutton-hook or elbow design, unless otherwise specifiedby theAdministrator. If made of stainless steel, the nozzle shall be constructed from seamless tubing. Othermaterials ofconstruction may be used subject to the approval of theAdministrator.

A range of sizes suitable for isdkinetic sampling should be available, e.g., 0.32 to 1.27 cm (Ysto V2in)-or larger if higher volume sampling trains are used-inside diameter (ID) nozzles inIncrements of0.16 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; ifa gasket is used, it shall be made of silicone rubber, Teflon, or stainless steel. Other holder and gasket materials maybe used subject tothe approval of the Administrator. The filter" holder shall be designed to provide a positive sealagainst leakage from the outside or around thefilter.

2.1.3 Probe Extension. Any suitable rigid, probe extension may be used after thefilter holder.

2.1.4 Pitot Tube. Type S, as described in Section 2.1 ofMethod 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). Theimpact (high pressure) opening plane of the pitot tube shall be even with orabove thenozzle entry plane during sampling (see Method 2, Figure 2-6b). It Is recommended: (1) that the pitottube have a known baseline coefficient,determined as outlined in Section 4of Method 2; and (2) that this known coefficient be preserved by placing the pitottube inan 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, isbased on a 1.3 cm (0.5 in) ID nozzle. Ifthe sampling train is designed for sampling at higher flow rates than thatdescribed in APTD-0581, thus necessitating the use of larger sized nozzles, the freespace shall be 1.9 cm (0.75 in) withthe largest sizednozzle inplace.

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) maybe used; however, the pitot tube coefficients of such assemblies shall be determined by calibration, using methods subject to the approval oftheAdministrator.

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 inMethod 5 be used-to determine the moisture content of the stack gas. Alternatively, any system that allows measurement ofboth the water condensed and themoisture leaving thecon- 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 determiningthe 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 isrecommended 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 meteredvolume.

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 ofisokinetic and of determining sample volumes to within 2percent maybe used, subject to the approval of the Administrator. When the metering system isused in conjunction with

a pitot tube, the system shall enable checks ofisokinetic rates.

Sampling trains utilizing metering systems designed for higher flow rates than that describedin APTD-0581 orAPTD-0576 may be used provided that the specifications ofthismethod aremet.

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 ofminus 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 describedin Sections 2.3 and 2.4of Method 2, and gas analyzer, ifnecessary, as describedin Method 3.

The temperature sensor shall be attached to either'the pitot tube or to the probe ex- tension,in afixed configuration. If thetemperature sensor isattached 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 inFigure 2-7 ofMethod 2).Alternatively, the temperature sensor need not be attached to either the probe extension or pitot tube during sampling, provided that a difference ofnotmorethan 1 percent in the average velocity measurement isintroduced. This alternative is subject to the approval oftheAdministrator.

2.2- SampleRecovery. 2.2.1 Probe Nozzle Brush. Nylon bristle brush with stainless,steel wire handle. The brush shall be properly sized and shaped to brush outthe probenozzle. 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 amonth.

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 attackby acetone. (Narrow mouth glass bottles have been found to be less prone to leakage.) Alternatively, polyethylene bottles may beused.

2.2.4 Petri Dishes. For filter samples: glass or polyethylene, unless otherwise specified bythe Administrator.

2.2.5 Graduated Cylinder and/or Bal.

ance. Tomeasure condensed water towithin 1 ml or 1 g. Graduated cylinders shall have subdivisionsno greater than 2 ml, Most laboratory balances are capable ofweighing to the nearest 0.5 g or less. Any of these bal-

ances is suitable foruse here and in Section 2.3.4.

2.2.6 Plastic Storage Containers, Air tightcontainers to storesilica gel.

2.2.7 Funnel and Rubber Policeman. To aid in transfer of silica gel to container; not necessary Ifsilica gel Isweighed in thefield,

2.2.8 Funnel. Glass or polyethylene, to aidin samplerecovery.

2.3 Analysis. 2.3.1 GlassWeighing 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. 250ml. 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 99.95percent 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 datafrom the supplier'squality coptrolprogram are sufficient forthis purpose.

3.1.2 Silica Gel. Indicating type, 6. to 10- mesh. If previously used. dry at 175' C (350' F) for 2hours.New silica gel may be used as received. Alternatively, othertypes ofdesiccants (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. othertypes 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- etoneto glass bottles frommetal 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 

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### RULES AND REGULATIONS

values (00.001 percent) shall be used.In no
case shall a. blank value of greater than 0.001 percent of-theweight of acetone used be subtracted fromthesample 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 maybe used, subject to the approval oftheAdministrator.

4. Procedure. 4.1 Sampling. The complexity of this methodis such that,in order to obtain reliable results, testers should be trained and experienced with thetestprocedures.

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 itsimpinger-orsampling holderjustprior 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 shippingcontainers (glass orplasticpetri dishes) and keep the filters in these containers at all times except during sampling andweighing.

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 3hours, desiccated for 2 hours, and weighed. Procedures other than those described, which account for relative humidity effects, may be used, subject to theapproval oftheAdministrator.

4.1.2 Preliminary Determinations. Select the samplingsite ind the minimumnumber of samplingpoints according toMethod 1 or
as specified by the Administrator. Make a projected-area model of the probe extension-filter holder assembly, with the pitot tubeface openings positioned alongthe cen- terline ofthestack,as shown inFigure17-2. Calculate the estimated cross-section blockage, as showninFigure 17-2. Iftheblockage exceeds 5percentofthe ductcross sectional

area. the tester has the following options: (1) a suitable out-of-stack filtration method maybe usedinstead ofin-stack filtration; or, (2) a special In-stack arrangement, in which the sampling and velocity measurement sites are separate, maybe 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 pitotlines (seeMethod 2, Section 3.1) be performed. Determine the moisture' content using Approximation Method 4 oritsalternatives for thepurpose ofmaking isokinetic sampling rate settings. Determine the stack gas dry molecular weight, as described In Method 2, Section 3.6; ifintegrated Method 3 sampling is used for molecular weight determination, the integrated bag sample shall be taken simultaneouslywith, and for the same totallength oftimeas,theparticular samplerun.

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

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### RULES AND REGUlATONS,

ESTIMATED 

### BLOCKAGE (%) [SHADED 

### AREA ), 

## 10 

# SDUCT AREAJ

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

asampletraverse) 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 notnecessary 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 ischosen fortherange ofvelocity heads en- countered (see Section2.2 ofMethod 2).

Select aprobe extension length suchthat all traversepoints 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 testprocedures for the specific industry such that (1) the sampling, time perpoint isnotless than 2minutes (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 isbased

onan approximate average sampling rate.

It is recommended that the number of minutessampled ateach point be aninteger

oran integer plus one-half minute, in order
to avoidtimekeeping 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 oruntil sampling is about to begin

If impingers are used to condense stack gas moisture, prepare themas follows: place 100ml ofwater in each ofthe 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 maybe used, but care should be taken to ensure thatit 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 usedto condense moisture, prepare thecon- denser (and, if appropriate, silica gel for condenseroutlet) foruse.

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 gasketproperly placed so asnotto allow the sample gas stream to circumvent the filter. Check filter fortears afterassembly Iscom- pleted.Mark the probe extension withheat resistant tape or by some other method to denote the proper distance into the stack or ductforeach samplingpoint.

Assemble the train as inFigure 17-1. using

a very light coat of silicone grease on all ground glass Joints and greasing only the outer portion(seeAPTD-0576) to avoid posslbility of contamination by the silicone grease. Place crushed Ice around the hn. pingers.

4.1.4 Leak CheckProcedures. 4.1.4.1 Pretest Leak-Check. A pretest leak-check is recommended, but not re- quired. If the tester opts to conductthe pretest leak-check, the following procedure shall be used.

After the sampling train has been assem- bled,-plug theinlet to the probenozzle with

amaterial thatwill beable towithstand 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 ofat least 380 mm Hg (15 In. Hg); note that a lower

vacuum maybe used, provided thatItisnot 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,isunacceptable.

The following leak-check Instructions for the sampling train described InAPTD-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 desiredvacuum is reached, Donot reverse direction of by-pss valve. If the desired

vacuum is exceeded, either leak-check at thishigher vacuum orend theleak-check as shown belowandstart over.

When the leak-check Is completed, first slowlyremove theplug fromthe Inletto the probe nozzle and immediately turn off the

vacuum pump. This prevents water from being forced backward and keeps silica gel from beingentrained backward.

4.1.4.2 Leak-Checks During Sample Run. If, during the sampling run, a component (e.g., filter assembly orimpinger) change be-

comes necessary, a leak-check shall be con- ducted immediately before the change is made. The leak-check shallbe done according to the procedure outlined in Section 4.1.4.1 above, exceptthatIt shallbedone at
avacuum equalto orgreater than themaxi-

mum value recorded up tothatpoint in the test. If the leakage rate is found to be no greater than 0.00057 ma/min (0.02 cfm) or4 percent of the average sampling rate (whichever is less), the results are acceptable, and no correction will need to be applied to thetotalvolumeofdry gas metered; If, however, a higher leakage rate is obtained, the tester shall either record the leakage rate and plan to correctthe sample volume as shown In Section &3 of this method, orshall voidthe samplingrun.

Immediately after component changes, leak-checks ire optional: if suchleak-checks

are done, the procedure outlined in Section 4.1.4.1 above shallbeused.

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 withthe procedures outlined in Section 4.1.4.1, except that It shall beconducted ata vacuum equaltoor great-

erthan themaximum valuereached during the sampling run. If the leakage rate is foundto be no greater than 0.00057 ma/min (0.02 cfm) or 4percent ofthe average sam- plingrate(whichever Isless), theresultsare acceptable, and no correction need be appliedto thetotal volume ofdrygasmetered. 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 shallvoidthe samplingrun.

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 bythe Administrator.

Foreach run. record the datarequired on the example data sheetshown in Figure 17- 3. Besureto record theinitial dry gasmeter 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 ateach sample point during eachtime Increment and additional readings when significant changes (20 percentvariation Inve- locity head readings) necessitate additional adjustments in flow rate. Level and zerothe manometer. Because the manometer level and zero may drift due to vibrations and temperature changes, make periodic checks duringthe traverse.

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

### 7589

HeinOnline -- 43 Fed. Reg. 7589 1978

### RULESAND: REGULATIONS •

LUJ

Lu

N Q

LU

C)

< ui

ccL 

### =

E

E CC

LU

C.3

Lu .J C4-



# II ~~ I

LUI LUJ

LU LU 2

LU U)
0

LC
0

ICL

ILLU C)

C.

LU C., LU Ci

<
- SCD > cn0 LUU- U

LU

LU _j LU

U 0

. 00- UJLU

-J

(n 

## ~ C.)i 0

U., -j

cn -Jcm

cne

CD

LUuCun c.L

LU L

-n CC. I. =

CDLu

U.

LU)

LU

ILE



### cn

0W c

LUz< Sc 0. 

## cli

cL r.

LL.

HeinOnline -- 43 Fed. Reg. 7590 1978Clean the portholes prior to the test run tominimize the chance ofsampling the depositedmaterial. To begin sampling,remove thenozzle cap andverify thatthe pitottube 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 aidin therapid adjustment tothe 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, and1 are outside the above stated ranges, do not usethe nomographs unless appropriate steps (see Citation 7 in Section 7) are taken to com- pensate forthedeviations.

When the stack isunder 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 theprobe and porthole to prevent unrepresentative dilution ofthe 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 extractingdeposited material.

During the test run, take appropriate steps (e.g., adding crushed ice to the impinger ice bath).to maintain a temperature ofless than 20' C (68" F) at the condenser outlet; this will prevent excessive moisture losses.Also, periodically check thelevel and

zero ofthemanometer.

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
newfilter holder isinstalled, conduct aleak check, as outlined in Section 4.1.4.2. The total particulate weight shall include the summation of allfilter 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 oftrains. In allother situations,the

use oftwo ormore 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 casethe particulate catches from theindividual trains maybe combined and asingle analysis performed.

Atthe end ofthe sample run,turn offthe pump,remove the probe extension assembly from thestack, and record the final dry gas meter reading.Perform aleak-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 leak

### RULES LAND 'REGULA'TIONS

check, in order to validate thevelocity head data.

.4.1.6 Calculation of Percent Iokinetic. Calculate percent Isokinetic (see Section 6.11) to determine whether anothertestrun 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 endofthe sampling period.Allow the assembly tocool.

When theassembly canbe safely handled, wipe offallexternal particulate matter near the tip of the probe nozzle and place a cap
over it to prevent losing or gainingparticulate 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 ofthe probe ex- tension. Be careful not to lose any condensate, if present. Remove the umbilical cord from the condenser outlet and cap the outlet. Ifa flexible line Is used between the first impinger (or condenser) andthe 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 extensionfrom 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 protectedfrom thewind sothatthe chances of contaminating or losing the sample will beminimized.

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 Itin aglass sample container labeled "acetone blank."

Inspect the train prior to and during disassembly andnote any abnormal conditions. Treat thesamples as follows:

ContainerNo. J. Carefully remove the filter from the filter holder and place It in itsidentified petri dish container.Use apair oftweezers and/or clean disposable surgical gloves to handle the filter. IfIt is necessary to foldthe filter,do so suchthatthe partieulate cake is insidethe 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.

ContainerNo. 2. Taking care to see that dust on the outside of the probe nozzle or other exterior surfaces doesnotget 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 thewash 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 rinsingwith acetone from awash bottle and brushing with

a Nylon bristle brush. Brush until acetone rinse shows no visible particles, afterwhich make afinal rinse oftheinside surface with acetone.

Brush and rinse with acetone the inside parts ofthe fitting in asimilar way until no visible particles remain. A funnel (glass or polyethylene) may be used to aid in transferringliquid washes tothe 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 ofsilicone grease (if applicable), clean the inside of the front half of the filter holderbyrubbingthesurfaces withaNylon 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 gelisused in the condenser system for mositure content determination, note the color ofthe gelto 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 beused as an aid in removingthe silicagel. It isnotnecessary to

remove the small amount of dust particles thatmay adhere to the walls and are difficultto remove. Sincethe gainInweightisto beusedformoisture calculations, donotuse 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."

CondenserWater.Treat the condenser or impinger water as follows: make a notation ofany color orfilmin the liquidcatch.Measure the liquid volume to within t1 mlby using a graduated cylinder or,ifabalance is available, determine the liquid weight to within t0.5 g. Record the total volume or weight ofliquid present.Thisinformation is required to calculate the moisture content ofthe effluent gas.Discard the liquid after measuring and recording the volume or weight.

4.3 Analysis.Record the datarequired on the example sheet shown in Figure 17--4. Handle each sample container as follows:

Container No.

. Leavethe contents inthe shipping container ortransferthe filterand any loose particulate from the sample con- tainerto 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 0.1rag.Forpurposes ofthisSection, 4.3, the term "constantweight" means a difference ofnomore than 0.5mg or I percent oftotal weightlesstareweight, whichever is greater,between two consecutive weighings, with no less than 6 hours of desiccation timebetween 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 2to 3 flied by the Administrator. The tester may whichever isless, for2 to3hours,weigh the hours,cooled in the desiccator, and weighed also opt to ovendry thesample atthe aver- sample, and use this weight as a final to aconstant weight,unless otherwise speci- age stack temperature or 105" C (220 F), 

### weight.

Plant

Date



### Run No.

Filter No.

Amount liquid lost duringtransport

Acetone blank volume, ml

Acetonewash volume, ml

Acetone blackconcentration, mg/mg (equation 17-4)

Acetonewash 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 ofparticulate matter

VOLUME OF LIQUID WATER COLLECTED

IMPINGER SILICAGEL 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
1g/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 thelevel ofliquidin the container and. confirm on the analysis sheet whether or not leakage occurred during transport. Ifa noticeable amount of leakagehas occurred, eithervoidthe 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 thecontents 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- stantweight.Reportthe results tothe near- est0.1 mg.

Container No. 3. This step may be con- ducted in the field. Weigh the spent silica gel (orsilica gel plus impinger) to the near- est0.5 g usingabalance.

"AcetoneBlank" Container.Measure acetone inthis container eithervolumetrically

orgravimetrically. Transferthe acetoneto a tared 250-ml beaker and evaporate to dryness at ambient temperature and pressure. Desiccate for 24 hours and weigh to a constantweight.Reportthe results to thenearest 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 boilingpoint ofthe solvent; also, to prevent "bumping," theevapdration process mustbe closely supervised, and the contents of the beaker must be swirled occasionally to maintain aneven temperature. Use extreme care, as acetone is highly flammable and has alowflash point.

5. Calibration. Maintain a laboratory log ofallcalibrations.

5.1 Probe Nozzle. Probe nozzles shall be calibrated before their initial use in the field. Using a micrometer, measure the inside diameter ofthe 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 lownumbers 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 shallbepermanently and uniquely Identified.

5.2 PltotTube. Ifthe pitottube Isplaced Inan interference-free arrangement withre- spect to the other probe assembly components, Itsbaseline (isolatedtube) coefficient shallbe determined as outlined in Section 4 ofMethod 2. If theprobe assembly isnotInterference-free, the pitot tube assembly co- efficient shall bedetermined by calibration. using methods subject to the approval of theAdministrator.

5.3 Metering System. Before Its Initial

use in the field, the metering system shall be calibrated according to the procedure outlined InAPTD-0575. Instead ofphysically adjusting the dry gas meterdial readings to correspond to the wet test meter readings, calibration factors may be used to mathematically correct the gas meter dial readings tothe propervalues.

Before calibrating the metering system, it issuggested thata 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); atthe end ofthe 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 fielduse, thecalibration ofthe 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 valuereached duringthe test series. To adjust the vacuum, insert a valve between the wet testmeter 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., usingthe orifice metercoefficients, maybe used, subject
to theapproval oftheAdministrator.

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 bevoided, orcalculations for the test series shall be performed using whichever meter coefficient value (Le., before orafter)givesthelowervalue of total samplevolume.

5.4 Temperature Gauges. Use the procedure in Section 4.3 ofMethod 2 to calibrate in-stack temperature gauges.Dial thermometers, suchas are used forthe drygasmeter and condenser outlet, shall be calibrated againstmercury-in-glass thermometers.

5.5 Leak Check of Metering System Shown in Figure 17-1. That portion of the sampling train fromthe pump to the orifice metershouldbeleak checkedpriorto initial

use and after each shipment. Leakage after thepump will result in less volumebeingre- cordedthan Isactually sampled. Thefollowingprocedure Issuggested (seeFigure 17-5). Close the main valve on the meter box. Insert a one-hole rubber stopper with rubber tubing attached into the orifice ex- haustpipe.Disconnect andventthelow side ofthe orifice manometer. Close off the low side orifice tap. Pressurize the system to 13 to 18 cm (5 to7 In.) water column byblowing 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, mustbecorrected.

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 CD 

### oL C, C.

oLfUS ('3 I.

o

- 

### M uJ

HeinOnline -- 43 Fed. Reg. 7594 19785.6 Barometer. Calibrate against a mercurybarometer.

6. Calculation. Carry outcalculations, re- taining at least one extra decimal figure beyondthatofthe acquireddata.Roundoff figures after the final calculation. Other forms ofthe equations maybeused aslong

asthey giveequivalent results.

6.1 Nomenclature.

A=Cross-sectionalarea ofnozzle,m, (LT). B,,=Water vaporin the gas stream, propor-

..tionbyvolume. Cj=Acetone blank residue concentration, mg/g.
c,=Concentration of particulate matter In stack gas, dry basis, corrected to standardconditions, g/dscm (g/dscf). I--Percent ofisokinetic sampling. ",=Maximum acceptable leakage rate' for either a pretest leak check orfor a leak check following a component change; equalto 0.00057 ml/min (0.02 cfm) or4 percent of the average sampling rate. whicheverisless. 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 posttestleak check. m'/min (cfm). m,=Total amount ofparticulate matter collected,mg. M3=Molecular weight of water, 18.0 g/gmole (18.0 lb/lb-mole). m.=Mass ofresidue of acetone after evaporation, mag. Pb=Barometric pressure at the sampling site,mmHg (in.Hg). P,=Absolute stack gas pressure, mmHg (in. Hg). P,=Standard absolute pressure, 760 mm Hg (29.92in. 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 (seeFigure 17-3), "K'(R). T,=Absolute average stack gas temperature (seeFigure 17-3), °K (°R). T.,d=Standard absolute temperature, 293YK (528'R). V.=Volume ofacetone blank,mL V.,=Volume of acetone used inwash,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 fromMethod 17,m/sec (ft/sec). W.=Weight ofresidue inacetone wash, rag. Y=Dry gasmeter 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 ofwater, 0.9982 g/ml (0.002201 lb/ml). 8'Total samplingtime, min.

- O,=Sampling time interval, from the beginning ofa 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 samplingrun.min. 13.6=Specrlcgravityofmercury. 60=Sec/mIn. 100=Conversion topercent.

6.2 Average dry gas meter temperature and average orifice pressure drop. See data sheet (Figure 17-3).

6.3 Dry Gas Volume. Correct thesample 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. HgforEnglish units.

No r.--Equation 17-1 canbe used as written unless the leakage rate observed during any of the mandatory leak checks (Le..the post-test leak check orleak checks conducted prior to component changes) exceedsIU. If U-orL,exceeds I..Equation 17-1 mustbe modified asfollows:

(a) Case L No component changes made during sampling run. In this case, replace V. inEquation 17-1withthe expression: [V.-( -L.)0] (b) Case IL One or more component changes made during the sampling run. In this case.replaceV.InEquation 17-1 bythe expression:

n L

- 

### (Ll-La)a1
- 

### i (Li La) 0i

- (L

- La) Op]

and substitute only for those leakage rates (lq orL.)which exceedI.

6.4 Volume ofwatervapor.

( T\( =RTstd 2


### vw(std = vA.4/\stdJ

Equation 17-2
where:

K=0.001333 m2/ml formetricunits; 0.04707 ft'/mlforEnglishunits.

6.5 Moisture Content.

Vw(std)
Bws = Vmlstd) + Vw(std)

Equation17-3 

### 7595

6.6 Acetone BlankConcentration.



### C



### a Ca =Va a

Equation 17-4 6.7 Acetone WashBlank. W.=CV..p. Equation 17-5
6.8 Total Particulate Weight. Determine the total particulate catch from the sum of the weights obtained fromcontainers 1and 2less theacetoneblank(seeFigure 17-4).

Nor.--Refer to Section 4.1.5 to assist in calculation ofresults involving two ormore filter assemblies or two or more sampling trains.

6.9 ParticulateConcentration. c6==(0.001 g/rag)(m./V.Wi)
Equation 17-6 6.10 ConversionFactors:

Prom To Multiplyby

C

......... . . ma

- 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 fromRaw Data.

100 T s [K 3Vjc + (VnY/T) (Pbar + M e13.6)1 

### 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 forEnglishunits.
6.11.2 Calculation from Intermediate Values.

s= Tnstdst d 00 T st d V s a n Ps 60 (- ws)

K T s V m(std)

= 

### K 4 s vs An " "-ws)

Equation 17-8 

### where:

K.=4.320 formetric units; 0.09450 forEnglishunits.
6.12 Acceptable Results. If 90 percent 010110 percent. theresults are acceptable. If the results are low in comparison to the standard and I is beyond the acceptable range, or,ifIislessthan 90percent. theAdministrator may opt to accept the results. Use Citation 4 in Section 7 to make Judgments. Otherwise, reject the results and repeatthe 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 PaperNo. 67-119. 1967.

6. Specifications forIncinerator 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.,ASurvey ofCommercially'Available Instrumentation for the Measurement ofLow-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 forSample TraVerses inDucts 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