AD-752 523'

AIR POLLUTION POTENTIAL FROM ELECTRO-PLATING OPERATIONS

Philip Diamond i

Environ'mental Health La.boratoryMcClellan Air Force Babe, Californ'ia

April 1969

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DISTRIBUTED BY:

National Technical Information Service I

U. S. DEPARTMENT OF COMMERCE -5285 Port Royal Road, Springfield Va. 22151

1.

Report No. 69M-15(Project No. E68-63)

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"AIR POLLUTION POTENTIALFROM ELECTROPLATING OPERATIONS

SF~~hilip DiatmondII ----. ) ;

SNATOINAL TECHNICALINFORMATiON SERV.-CE .

U S A F ENVIRONMENTAL HEALTH LABORATORY

SMcCLELLAN AFB, CA. 95652 s

USAF ENVIRONMENTAL HEALTH LABORATORY

McClellan Air Force Base, California

AIR POLLUTION POTENTIALFROM ELECTROPLATING OPERATIONS

Report No. 69M-15

(Project No. E68-63)

April 1V69 i

Prepared by:t

PHI1iP DIAMONDIndustrial Hygienist

Reviewed by: Approved by-

"HARRYfJc SUG0.1i FRANCIS S. SMITHMajor, ,UIAF, BSC Colonel, USAF, BSCChief. B2io-Envi-op-mental CommanderEng'neering DivisionIN

UnclassifiedSecuntv Classificatinn

DOCUMENT CONTROL DATA - R & D,Scrulity ctassitbataon of title, body of 4bstfact and inderyn. •ntnotation must Le entered when the overa&4 report Is cla.,slted)

,. ORIGINATING ACTIVty V (Corporte author) -'a. REPUnT SECURITY CLASSIICATION

uSAr'Envir0nmetCaI Hf't• f UnclassifiedW-1-1,0 1 1re, CA 2b. GROUP

3. REPORT TITLE

AIR POLLUXI ION POTENTIAL FROM ELECTROPLATING OPERATIONS

O DESCRIPTIVE NOTES (Type of report and inclusive dates)

- ETNAT,5. AUTHORIS) (Fitat name. middle initial, last name)

PHILIP DIAMOND

6• REPORT DATE 7a. TOTAL NO. OF PAGES 0b. NO. OF RPFS

Anril 1969 13 82*. CONTRACT OR GRANT NO. 9d. ORIGINATOR'S REPORT ,UMBAERiS)

b. PROJECTNo. 69O_15

c. 9b. OTHER REPORT NOIS) (Any other numbers that nmy be assignedthis report)

10. DISTRIBUTION STATCMENT

Distribution of this document is unlimitedIt. SUPPLEUC"NTARY NOTES 12. SPONSORING MILITARY ACTIVITY

USA.,- r t 2 Lab

13. AOSTRACT

Measurements were made of emission rates from electroplating operationsconsidered to have maximum air pollution potential. Sampling was performed atMcClellan and additional data from a previous survey at Hill Air Force Base was ZIAused. Values obtained were extremely low. Based on existing Federal standards,no collectors are specifically required for electroplating emissions. Experienceof State and industry air pollution personnel, however, indicates that chromegand stron1 caustic emissions do require collectors.

Z -IkiDD"W::,,1473 Unclassified -•g

Sect-rity Classification

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111ELECTROPLATINGAIR POLLUTIONEMISSIONS

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Unclassified- -- Stcurity Classification

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TABLE OF CONTENTS

SECTION P.,GE

I Introduction 1

fl Procedures z

III Results

IV Discussion 5

V Conclusions & Recommendations 6

VI References 7

LIST OF TABLES

TABLES

I Tank Surface Samples 3

- Duct Effluent Samples 4

APPENDIX

I Chapter IV Air Pollution Control 8

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SECTION I

INTRODUCTION

As suggested in Hq AFLOk (AMCDPE) letter, 7 November 1968, asampling study was undertaken to define the air pollution potentialfrom electroplating operations. A Los Angeles County EngineeringManual published by the USD-HEW (Ref. 1) defines the air pollution

•- • problem from electroplating as follows: "Most of the electrolyticplating and cleaning processes are of little interest from a standpointof air pollution because the emissions are inoffensive and of negligible

volume, owing to low gassing rates. Generally, air pollution controlof air ~ ~ ~ A. polyo becaese phsin reioffensives andep ofnglgbe ho

equipment is not required for any of these processes except the chro-miu. latngprocess. " Chrornic acid mist emissions have caused

problems by spotting car finishes in the vicinity of discharge ducts.Even though the concentrations are relatively low, they may still behigh enough to cause property damage.

Mr. Schuman of the State of Michigan, Department of Health (Ref. 2)

indicated that a collector is mandatory, based on his experience forchromic acid and alkali mists. In a personal discussion he indicatedthat he feels the alkali control requirement applies only to concentratedalkali emissions. He mentioned, for example, a 10 percent or moreconcentrated sodium hydroxide bath.

The direction provided by USAr (AFOCE) !tr, 9 Dec 66, Tables 11

and 12, are based on a now obsolete New York State Guide. This hasbeen modified to the statute shown in Appendix IL "EnvironmentalRatings" of "B and C" as defined in Table II of Appendix I are usuallyassigned to areas surrounding plating shops according to I. Kingsley(N. Y. State Plans Review Engineer), and collectors are not normallyrequired for plating discharges.

IBM Corporation's experience (Ref. 5) indicates that in the severalIBM plating shops checked, the only fallout ever detected was chromicacid.

Emission figures for plating operationz were not found in theliterature surveyed (Ref. 3, 4, and 5) and contact with HEW, the DetroitBureau of Industrial Hygiene, and New York State engineers disclosed Ithat thei were not aware of quantitative information available on platingdischarge levels. No emnission information was available from controlequipment manufacturers. They generally z eport collector efficiencyfigures but do not indicate contaminant levels before and after scrub-bing.

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SECTION HI

PROCEDURES

The plating and pr~ocess tanks were selected for sampling on the

basis of the following criteria:

1. A suitable and accessible sampling location was necessary.A straight run of duct away from elbows or constrictions and not re-quiring scaffolding was a minimum requirement.

2. Highest potential emission rates were anticipated (Ref. 6),based on emission tables published originally by New York State.

3. Plating, stripping, or cleaning operations were in progressin the tank during sampling.

4. Either a noticeable odor, irritation, or visible contaminantwas perceived.

5. After selecting tanks which met most of the criteria outlinedabove, a pitot traverse was made at appropriate and accessible locationsin the duct as far from a bend or obstruction as possible. The samplingprocedure used was described by R. W. Sexton (Ref. 7). The point ofaverage velocity was used to locate the sampling probe tip and isokineticsampling was performed by adjusting the correct precalibrated pumpsarnpling rate. A 1/4" I. D. pyrex probe with a 900 bend (openingfacing into air stream) in series with an impinger containing 125 ml ofappropriate sampling solution was used to collect samples.

Distilled water was used for sampling acids and bases and 0. 1 NNaOH for cyanide sampling. M.S. A. tubes were used for NO2 testingand surface sampling for HCN. The probe contenLt were carefullywashed and added to impinger contents after sampling. A minimumsampling time of 10 minutes was used. If ventilation was inadequate, orproper sampling locations were not available, samples were taken abovethe tank liquid surface at a height of 10 - 15 inches above the point ofmaximum plating or stripping activity (as shown by bubble evolution orparts placement).

SECTION III

RESULTS

Results are summarized in Tables I and II below and bracketed

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values were samples taken above the same tank. j

TABLE I

TANNK SURFACE SAMPLES

Operation Base* Contaminant Concentration

Silver Strike M -HCN 12 ppm

Silver Plating M HCN 12 ppm A

Cadmium Plating M HCN 2 ppm

Cadmium Barrel Plating M HCN 0 ppm

Cadmium Stripping M N02 0 ppm

Sulphuric Anodizing M H2 SO4 0 ppm.

Hard Chrome Plating H CrO3 0. 52 mg/ma0.28 mg/mi

Hard Chrome Plating H CrO3s fo. 14 mg/m'-N0. 16 rmg/ma

Hard Chrome Plating H CrO3 - 0. 13 m- /,r,a0r 8 C eg /-H

SHard Chrome Plating H GCrO,= 0.314 .. gl a":II~~~4 2 .,-,:

Hard Chrom-,e PIat~ng H CrO,3= P,0 ••

-M - McClellan AF'B,

S~~H - Hill AFB _

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4)30 0 4)N

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SECTION IV

DISCUSSION

Tark surface samples for chromic acid were taken at Hill AirForce Base in an industrial hygiene survey performed in February1967. Our essential piuspose in taking these particular samples was

to provide an indication of the quantity of chromic acid mist escapinginto the atmosphere and provide data for comparison with existinginformation. Ventilation rates varied from 85 - 400 cfm/ft2 .

The ventilation oi the chrome plating tanks at McClellan AFBaveraged only 85 cfm/fe, and the results of duct sampling are shownin Table .. Ventilation was poorly distributed on these tanks, andthe results of surface samples taken for CrO3 concentration rangedfrom 0.13 to 10.0 mgm/m3.

Silver plating and cadmium plating tanks are cited in the literature(Ref. 6) as releasing no contaminants to the atmosphere. Samplingdirectly above these c-:axide baths, we were unable to obtain concen-trations of HCN above 12 ppm.

Cadmium stripping was performed with amrnonium nitrate, andwe were unable to find any NO2 cr NH3 at the surface of the tank duringthe operation.

Results of samples taken directly above the sulphuric acidanodizing tank witi anodizing in progress were negative for sulphuric iacid.

The chromic acid anodizing tank sampled had two exhaust ducts,and the total Cr0 3 emitted amounted to 0. 10 pounds per hour. This

value was significantly higher than the CrO3 emission from the chrome |plating tanks.

The only HCl tank in the plating shop that appeared to give off Inoxious fumes was the one in the cadmium area containing 50 - 55percent by volume HC1 where an emission rate of 0.57 pounds per hour jwas found.

The greatest emission of any contaminant obtained in the ductssampled was 0.76 pounds of NaOH per hour from the silver strippingoperation. Even this value is considerably below the New York Statepermissible limit of 10 pounds per hour.

Nickel plating involves no major health problems, and most baths

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can be operated without ventilation (Ref. 8). No air pollution problemsshould result from nickel plating. I

We recognize that there are a number of variables which baveaffected the results obtained, and they must be taken into considerationif the results are to be applied to a new installation, i. e., theventilation of the tank, freeboard, current density, cross-drafts, make-up air, etc. However, the results do indicate the order of magnitudeof the concentrations to be expected and their relative insignificanceV ifrom an air pollution standpoint.

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CONCLUSIONS AND RECOMMENDATIONS

1. Plating discharges (except for chromic acid, concentrated sodiumhydroxide, or dilute sodium hydroxide with high current densities) aregenerally considered below levels which can constitute an air pollutionproblem from either a legal, aesthetic, or health standpoint. I2. Results indicate that the air pollution potential is negligible foralmost all the plating and cleaning processes investigated.

3. A scrubber is recommended for silver stripping because of therelatively high concentration of strong caustic discharged.

4. Because of the car-spotting resulting from chromic acid discharges, Ia collector is recommended on chromic acid plating and chromic acidanodizing.

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SECTION VII

REFERENCES |

1. Air Pollution Engineering Manual, Air Pollution Control District,County of Los Angeles, complied and edited by John A. Danielson,1967.

2. M. Schuman, "Designing Ventilation for Electroplating. Plants,"Air Engineering (7 July 1968), Vol 10, No. 7.

3. "Hazards in the Plating Industry," Michigan's Occupational Health(Winter 1965 - 1966), Vol 1I, No. 2.

4. D. Moore and I. W. Dyer, "New Way to Collect Plating Fumes,"Air Engineering (April 1959).

5. "New Ventilation Design Cools Plating, Heat Treating Plant,"Heating, Piping and Air Conditioning (September 1960).

6. Industrial Ventilation, American Conference of Governmental

Industrial Hygienists, 9th Ed. Tables 5-5-5, 6.

t. R. W. Saxtt., "Stack Sampling of Chemical mists and Vapors,"Reprint No. Z70-PB, American Air Filter Company.

8. L. E. Vager, "Hazards in the Plating Industry," Michigan'sOccupational Health (Winter 1965-66), Vol. IU, No. 2.

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"* Appendix 1

Chapter IV Air Pollution Control

New York State Public Health Law

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QUHATZR TV AIR POLXAMTON CON(TROU 78.

PART 187 :CON'rA31MANT EMSSONS

FROM

'(Statutosy authority: Public Health law, 10 1211 MG7) I

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NowTor tocontaminant atsasfonpoee n xoa n etlto 3

a %ecie. ircontamnai~mon sucta a hl aeIrApm= hnbappmein bPlaoof tbh aruL

a ~Soc. adde Mil J16 an. 12. IM6 to be off.

1 S72 De OON&(a) EwvkroxwesWa ratbig. A ratgindiaegb hletrA;aCo cD ser -the environmental eKccte a! &a air otdrin

sour A rtingtakes Into acauiit, properties and quanLlties of contamnannts qemited;effctson unan, plant. cr animal life, or property; in teoreolgical para-ý

mees ekh t mcnara..aristics of thle commiunity; and amoblent alt qualityclasifictionofat e La In whic the omirce to located or which% It affects.M

(b) Xpotenti Taf The rate In Pounds per hour at which ai contain-*nns M bemitted to the outer air in the aeneOf air 001101ti12 control

faditls o otercontrol measure& The emission rate potential for cyclic opera-OVshlbedetermined by considering both the lnstazataneom emission potential

an h **Xaiso potential ovrthe time period athen cycie.

(C Bsis o e.su Any point at Which air contamianwts enter the outer airr p n exbauxt and ventilation systewAL

(d)SS.j M veMttstk#syte mf Any syxtemowhc removeasandan aewo a borne products from their point of generation to the outer air.R!

(a) ernin"emnisaion roafi The maximnum rate In pounds per hour at whichair ontnduntsareallowed to be emitted to the outer air.

M Proven eght. The total weight of. all naterials Intzode~ed, into any spe-cifc poces wichmay cause any discharge Into the atmosphere Sold fuels usedIn heprces wllbe. conuldered as purtof the proemweight, butlSIM~and

gaew tI uncomiiinii water and combustion air will noL

Wg Provens welght per hoor. The total process weight dMded by the Munaberat hours In one completsi operation froin thle beginning of a cycle to the Cognpleonthereoa. DFr cetinuoua proeses process wekght ado"i be deter"Misou an daftybad&.

ame adasi, SIa"j it, 1%3W A be em J

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* * TiTLE 10 HEOALrH5187.3

S Of air rontsmlnanta ~rom~ an emission source -e~mli~ng from an operation begun ve

accordance with table U*.(b) On January 1. 1971. or such later date as established by an order ot the.

Coinmimloner, the permissible emission rates specified In abdivision (a) shallbecome applicable to emission sources In exlbtence on or prior to the effectiv6 dateat this Part.

* person to emit air contaminants In quantities which alone or In combinattom withother acurres woulZ u-7atravene any established ahi qizality standards.

H istorical Note 1

Sec added. flied Jan. 12. IM1 to be eN.ZFeb. 6. UL.

1 S7A Abatement. (a) The commissioner may rejulre the person operating ormaintaining emission sources to provide pcrtinent data etoncerning, emissions so antAo show compliance with ýhe requirements of se-tlon 187.3.

(b) When required by the conml.sLwoner, the person operating cr maint~ining

emnissfons eoures In operation before theefciedtofhsPathllubta

detaledreprticluingemisio added, pertleant enirnena 1actor tnd a pro.

] ~ ~ ore*v mt eomiresand tchat ul for larfe nptiatutm I the s r~rtepr Isbmattedpriore theub

3 ~ cmmissionerowithin . 0Fdayow of such o otice, the preimnary rerter shal eale pranta eanorri

Part larlo wle requirted tno submitte to the commissioner or his representativeete ro

to*4 or 14148enll wihsbiso fpasadoSaeitotos napasl

th tm etoe ntbeI ntefr farpr nldn h rpuratig tobe sed " deignpurpsas

(d) Th.omsinrmysa n rcmeupetc rhbtayoea

~ii aAPPENDIX 4

TABLEIEnvirownentnal lHattog

A Includes processes. an~d oxhaust and ventilation systems whrro the discharge ofacontaminant or contaminants results, or would reiu:onnbily bo expe.cted to re-sl.In aerious adverse effeeta or. receptors or !ne environment. These elrecte

may be of A hcalth, economic or Aesthetic natture or any combinat'on of these

B Includes processes. and exhaust and ventilation systems where the discharge

result, in only mode-ate and essentially localized effects; or where the multi%-plicity of sour%!e of the contaminant o)r contaminants In any given area Is suchan to require an overall reduction'ef1 the atmospheric burden of that contaminantor contaminants.

C Includes processes, and exhsaust and ventilation systcms where the discharge ')Ia contaminant or contaminants would reasonably be expected to result In local-ized adverse effects of an aesthetic or nuisance nature.

1) Includes jprocesser. and emhaust and ventilation systems whcre, in view of prop-erties and concentrations of the emiessons. Isolated tonditions. stack height, andother factors. it can be clearly demonstrated that discharge of the contaminantor contaminants will not result In measu~rable or observable effects on receptors.nor add to an existing or predlUbie atmospheric burden of that contaminant

~1 or contaminants which would ressozably be expected to cause adverse effects.

The following Items will be considered in making a determination of the environmentalrating to be applied to a particular source:

a) properties, quantities and rottex of the emission1b) physical surroundings of emission sourcec) population denslty of rurrounding area. Including anticipated future growthd) dispersion characteristics at or neer sourceel, locAtion of emisscon source relative to ground level and surrounding buildings.

mcunitaIns, hills. etc.17) current or anticipated ambient air quality In vicinity of sourceZ) latest findings relating to effects of ground-level concentrations of the emission

on receptorsh) possible luxxrrdous side effects of contamina~nt in question mixing with contami.

nants already In ambient air1) engineering guiden, which are acceptabie ta the commissioner

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