Document gbgr1wOa7R97xx214KqQVjZQG

2 -. APPENDIX B ^ ,, -- "> . ' "*1, -',>V?-^-' NEIC AIR AND WATER SAMPLING AND ANALYTICAL PROCEDURES "- a- t Jf ATTACHMENT 1 ATTACHMENT 2 [Air] Volatile Organic Pollutant Analysis Sample Trap Preparation, January 1980r~~Sz.:/ ... t.'.'- Si f;` ;i"S^'r5:x [Air] Volatile Organic Pollutant-Analysis,-- ' Permeation Tube Preparation and Calibration, January 1980 - t ^ :j>-.r.: *> ATTACHMENT 3 - [Air] Volatile Organic Pollutant Analysis,.. Sample Collection, January 1980 -/ N ATTACHMENT 4 - [Air] Volatile Organic Pollutant Analysis; ` GC/MS Analysis, January 1980 ATTACHMENT 5 ATTACHMENT 6 -r] *'**'* ATTACHMENT 7 [Water] Organic Characterization and Priority Pollutant Procedures - :-v>; . ... ^ * ,, -V P 'v' r ` -2 ' -y ' -rt*- [Water] Inorganic Analytical Methodology^*h ; . : [Air] Vinyl Chloride - Charcoal Tubes'!:V:;:^:'i^^5'^'''';'f'' NEIC - January 1979 v-^K^: ............ ' T' .v .-X^r - r rh.il [KlFDtBdlMnrD^ PTH 000023407 Q * q q q q. q q q q q c q n Vii r p -janit 4ji siK^J /r\ lb, Sjf.ptfe'nr a1?' ^TSpabrtT January 1980 B-l 1.0 Introduction 1.1 Sampling for organics in air is performed by drawing air through a glass tube-packed with the porous polymer resin Tenax GC. The traps and resin must be thoroughly cleaned before use to minimize the trap background. Clean traps ready for field use must also be carefully packed in clean glass tubes to avoid contamination during handling. 2.0 Materials 2.1 Glass sampling traps. Pyrex glass traps constructed as shown in Figure 1. 2.2 Resin. Tenax GC, 35/6C: mesh. 2.3 Glass wool. 2.4 Culture tubes. Pyrex glass screw cap tubes 25 mm x 110 mm. Pyrex 9825 or equivalent. ' 2.5- Teflon backed silicone septa. Pierce 12722 or equivalent. 2.6 Bakelite screw caps to fit culture tubes. Pierce 13219 or equivalent. 2.7 Dessicator. Glass dessicator with activated charcoal adsorbant. 2.8 Quart paint cans with pressure fit lids. 3.0 Resin Preparation 3.1 Extract new and used Tenax GC with methanol followed by pentane in a soxhlet extractor. Extract with each solvent at least 6.hours. 3.2 Dry the resin under vacuum for at least 4 hours. 3.3 Sieve the dried resin to the 35/60 mesh particle size range. 3.4 Seal the cleaned and sieved resin in a glass jar capped with a teflon liner. Store in a dessicator containing activated carbon. 4.0 Trap and Container Cleanup 4.1 Hash new and used glass sampling traps and culture tubes with lab soap and hot tap water. Rinse at least three times with organics free water (Millipore or equivalent). Rinse with methanol and let air dry. PTH 0000234OH 4.2 Bake the Remove f carbon. it 1 hour, ri g^ctivated 4.3 Wash glass wool with inetharn', air dr> and sake in an oven at 220C for.at least 1 hour. Kamovs from the oven and store in a dessicator containing activiated cnarcaal. 4.4 Bake teflon backed seota in an oven at 80DC for-JO minutes. Remove ' from the oven and store in a dessicator containing activated charcoal. f | 4.5 Bake paint cans in oven at 100C for 1 hour. 1 5.0 Trap Preparation 5.1 Pack about a 1 cm plug of glass wool into the trap followed by 6 cm of cleaned Tenax GC. Lightly tap the trap on the bench to pack the resin. Add another 1 cm glass wool plug to hold the resin in place. 5.2 Condition each trap at 270C with 20-30 ml/min helium flowrate for 30 minutes. 5.3 Remove the hot trap and place into a culture tube with a glass wool plug to cushion the trap. Immediately cap the tube with a teflon lined septum cap. Store the tubes in batches oTT traps in quart paint cans. 6.0 Quality Control 6.1 Prior to sending traps to the field, remove one trap from each paint can and analyze it for contaminants. If the traps are clean, the batch is acceptable for use. Nark the trap "Field blank - label and return" and replace it in the can. 6.2 Prior to sending traps to the field, remove one trap from each paint can and spike with known amounts of chemicals from the permeation tube system. Mark the trap "Field spike - label and return" and replace it in the can. 7.0 Options 7.1 Traps with longer resin beds may be packed in order to increase the retention volumes of pollutants. 8.0 References 8.1 "Selection and Evaluation of Sorbant Resins for the Collection of Organic Compounds", EPA-600/7-77-044, April 1977. 8.2 "Development of Method for Carcinogenic Vapor Analysis in Ambient Atmospheres", EPA-650/2-74-121, July 1974. DTH 000023409 Attachment to: 1 "ti'rL'v' bcck&st Silicon^ Scptllun 1 a a a B-3 gloS; tb'OC'i > t-n <rr> _f_ IS, figure 1. Sampling trap and culture tube holder design. DTH 000023410 A frlACHpVr lkcrgprric. A rj Po yn^Tubp F r5 NEIC - January 1!)30 1.0 Introduction 1.1 Quantitative analysis cf orgaiic air pollutants requires sampling traps, identical to those used in tne field, be loaded-with known amounts of chemicals. Thse standards are most easily prepared by sampling the effluent gas stream from a cnamber containing calibrated permeation tubes. 1.2 Permeation-tubes are generally Teflon tubes containing a pure chemical .and plugged to form gas tight seals at each end. The organic chemical then permeates through the Teflon tubing-at a rate dependent upon the temperature and length of the tube. The rates are also dependent upon the chemical and vary over several orders of magnitude. 2.0 Tube Materials 2.1 FEP Teflon Tubing. Fluorinated ethylene and propylene tubing 1/4" o.d. and 0.03" wall. e' 2.2 TFE Teflon Tubing. Tetrafluoroethylene tubingTTV' o.d. and 0.03" wall. ' 2.3 Teflon Rod. Kel-F roc 3/16" o.d. 2.4 Crimp band. 5/16" o.d. and 0.028" wall 316 stainless steel band 3/16" long. 2.5 Crimp tool. Nicopress 31-CJ tool to crimp to 1/4" o.d. 3.0 Permeation Chamber 3.1 Temperature bath. Recirculating heating/cooling water bath capable of maintaining a temperature of 30 +- 0.1 deg. C. 3.2 Water Jacket. Glass water jacketed tube with Teflon screw in plugs at ends. Typical dimensions 3 cm i.d. x 20 cm long. 3.3 Flow limiter. Stainless steel capillary tube capable of delivering 40 cc/min of Ng from a 20 psig supply. 3.4 Switching valve. Teflon 2-way solenoid valve. . 3.5 Charcoal Trap. Low back pressure trap filled with about 100 grams of charcoal. 4.0 Tube Preparation 4.1 Cased on the data in Table I or experimental data, select tubing and cut to the desired active permeation length plus 2 cm. DTH 000023411 4.2 Plug one "iis1 Label the^' (! over it. !_=J B-5 4.3 Fill the tube to about ce.pacity of the active length. CAUTION: Scire chemical; may be carcinogen-c, toxic or hazardous.. Research its tox-c effects arc: take the necessary precautions. 4.4 Insert another 1 cm FEP plug in the open end and crimp a band in place. 4.5 Visually inspect the tube for signs of leaking. 4.6 Place the tube in the permeation chamber and maintain at a constant temperature (typically 30C). Condition for 2 weeks before beginning the calibration procedure. 5.0 Tube Calibration 5.1 Maintaining the tubes at constant temperature with about 40 ml/min N~ flowing over them, measure changes by weighing the tubes weekly. L Use a balance with +- 0.1 mg accuracy. 5.2 Before every weighing, weigh a standard weight and record its value. Changes greater than +- 0.2 mg requires-correction of the-balance calibration. 5.3 Record weight changes for each tube on the form in Figure 1. Calculate the permeation initial rate from the week to week weight changes (see section 6.1). After the rates stabilizes, the tube is ready for routine use. 5.4 Monitor the weight changes of calibrated tubes every 2 to 4 weeks for,the life of the tube. 6.0 Calculations 6.1 Average Rate *w 6.1.1 Weekly rate: Rate * weight change minutes between weighings 6.1.2 Typically weight change is less than 10 mg arid time between weighings is about 10000 minutes (about 1 week). 6.1.3 Average the weekly rates. 6.2 Regression Rate 6.2.1 Tabulate the weight of the tube vs. time from the point the weekly rate stabilized. (WO! ITH 000023412 Also calculate :he ocrrelat.ion coef-'icient as an indication of the statil'iy of ti e calibratior data.. 7.0 References 7.1 Anal. Chem., 49, 1278 (1977). 7.2 "Measurement of Carcinogenic Vapors in Ambient Atmospheres", EPA600/7-77-055, June 1977. t>. j. IT. DTH 000023413 Attachment I. Permeation tube chamber schematic. DTH OOOO January 1930 1.0 Introduction 1.1 Sampling for organics in air is performed by drawing air through a glass tube packed with the porous polymer resin Tenax GC. Air is drawn through each trap at 0.1 to 1 liter per minute using a cali brated personnel sampler. The sampler 'is calibrated before sampling using a mass flow meter. 2.0 Equipment 2.1 Sampler. MSA model S or equivalent personnel sampler. Capable of adjusting and monitoring the flow over the range of 0.1 to 1 liter per minute (1pm) with a trap in place. 2.2 Mass flow meter. Portable unit equipped with a teflon fitting to measure the flow through a sampling trap. It should have a range of 0 - 2 1pm and 0 - 10 1pm. 2.3 Sample traps. Glass sampling traps packed witit_Tenax GC. 2.4 Sampling line. 2-5 feet of 1/4" o.d. tygon tubing with a teflon fitting at one end to attach to the sampl ing traps. 2.5 Dummy Sampling- Trap. One trap taken from the batch to be sampled. 3.0 Calibration Procedure 3.1 Attach the dummy sampling trap to the sample pump. Attach the mass flow meter over the inlet of the sample trap. Se't'the mass flow ' meter to the appropriate range and zero with no flow. 3.2 Start the sampling pump and adjust for a stable flow at the desired rate. Note the flow meter reading on the personnel sampler at the desired flow rate. 3.3 Record the mass flow meter reading and the sampler flow meter reading. 3.4 Detach the mass flow meter and the dummy trap. 3.5 Recalibrate the sample pump at the beginning of each"sampling day, whenever the sample flow meter reading deviates from that at cali bration or whenever necessary. 3.6 Flow rate variation between these traps is less than 5. 4.0 Sample Collection 4.1 Using a clean tissue or wearing a nylon cloth glove, remove a sample trap from its culture tube being careful to reseal the culture tube. 1 LZD DTH 000023415 a 1 E J i 1 1 1 I f I 4.2 Inspect 1 loose or 11\i| l{^ Nile n Sy n -r.u i f '-t re culture tube and retjrr to the laboratory unused. woa1 plugs uTsze in B-9 4.3 Attach the trap tc the calibrated sampler. See Figure 1. 4.4 Begin sampling noting the start time and sample pump flow meter reading. Collect sample volumes depending uponjthe suspected levels of contaminants. Generally: Dumpsites: 1 1pm for 5-30 min. Offsite: 1 1pm for 15-120 min. Ambient: 1 1pm for 60-120 min. or .1 1pm for 1-24 hr. 4.5 Stop sampling noting the end time and sample pump flow meter reading. Replace the trap into the culture tube being sure the glass wool cushions the trap. Reseal with the teflon lined septum cap and tag. 4.6 Replace sample traps in culture tubes into the tin can and reseal the can. Be sure to tag the "field blank" and "field spike" samples in each tin can. 5.0 Quality Control ~~--- 5.1 Sample pumps are calibrated daily and any flow rate changes noted by monitoring the flow meter on the sampler. 5.2 Contamination in each sample transport container is monitored by a "field blank". 5.3 Deterioration of the samples is monitored by a "field spike". 6.0 Options 6.1 In the event of unknown atmospheres suspect of containing. Jvigh levels of contaminants, two samples should be collected at flow rates of 1 and 1/10 or 1/100 rate (1 1pm and 10 ccpm for example). 7.0 Limitations 7.1 The sample traps are essentially short chromatographic columns. Retention of chemicals is dependant upon absorbtion characteristics of the chemical/resin system. Factors influencing retention include: temperature, flow rate, air volume and vapor pressure'of the chemical. Volatile species like vinyl chloride are only moderately retained while other chemicals like chlorobenzene are retained very well. All chemicals will experience breakthrough under the correct conditons however. Table I lists breakthrough volumes for some relevant chemicals. The volumes represent the amount of air sampled where 502 of the collected chemical is lost through the trap. Data for chemicals where the sample volume exceeded the breakthrough volume represent at least that amount in the air. DTH 000023416 0 References ,,n , a j, T 3* j= ju ,L=a 8.1 Development oiMnalj/ncal Tacnmqjes -cr i*!easurmg Ambient Atmos pheric Carcinogenic Vapors", ;iPA-630/2--75-375, November '975. 8.2 Env, Sci. Tech., 9, 555 (1975). 8.3 Pellizzari, E. D., Quarterly Report Nc. 1, EPA Contract Mo. 68-022262, February 1976. 8.4 Anal Lett., 9_, 45 (1975). DTH 000023417 Ic I 9 9 3 9 t \ % lT 3i 4D SO CN O O <n o N CD -pH Px CN n- cn so m m o cn eo prm^o- PH cn cn 1-4 CO H- 2 H ZP J o c- CJ PX 0 LJ cto o " H < pJ td > UP to co o Ik co kJ x. *3 o > G o r*\ tk -s o w \S c V n, u Cm ^ z A r- c u <? CJ >* cc x CJ % 8-- o Os o co o px 60 O in y-x c- o O JZ H < u: s o o x 2 30 U3 c H3 o c. e CN o 1u < a f--4 *3 * H pH *9 U V) *p V) eR c MX u o cn PH CO <T cn cn CO O' SO CO CS O cs rx px o in X? Px . MX MX PX C CN x m cs m px c sT o PX CN *o xc p4 o m CO sO cn CN <T CO cn cn H Cs CS sO o pH X CN H < cn pH pH co cn rx CN n o in pH PX pH cn sO m CN m rx <T pH MX in sO O SO Hx vn <r xy CN CN px Px cn px -x CN CN CN cn PX cs m PX pH px co O pX X CN rx px o PX pH pH X x2 CM pH px SO CM m . X px H CO rx. px O CN cn cn X? m SO so cn m 5C cn CN <r px sO O CN CN so m X? MX px cn m in in pH CN x CN pH PM o P-4 Px P^ ^x CO cn CN p* <N xC .cn xc m m CN i--4 1 cn H pH Px NT' NO rx c CJ o fH u l4 f4 oo s u --4 5 XM u H o JO u iN 1^ X >s pH MX >s 13 xJ CJ S CeJ H > o CJ H "Z w *H o kl O ^2 --4 w c uk s <i-J CJ k> CJ c o xJ CJ S-X x* o > k O ,,2 o mJ H k cj R E u CJ *2 -- CJ o kl 3 c c to* fl cj u CO 1o-4 ou m >s 22 ~z cn m H O sO Cs Cs CO o X Px sO m CN so as CN CN CN o ^H CN sR xO cn cn cn CN PX cn m h rx co r- CN CO H 4J c PC CJ CJ ^2 c e xJ CJ CJ R CJ x 2 ^2 o 5h C Xrf u j2 px CJ o XJ >4 o V mZ k ^2 O o <j U J H o o ^2 kl M- u u mJ z o X 1 W P"O px n mZ 1 Xu u CN pN XJ *H M X CJ w H xX 4J xJ CO CN SO px a cj cc CJ CJ z s oo W kl C. Ca px px >N >% ^2 ---- xJ xJ j a EE ii CN CN || oo uu oo PH 1--4 o .z oo 1f h cn m pH Cs CN pH sO pX pH * t o k- o- PH -H CJ O CJ 1 PS c z P- CJ R Rw C C- C- O c o c Ck w u P o c. =- u w o o -z -a. ki u >> >N o co X px MM o o j2 JO u c. u M u -X POX CJ 1 a "z .s cn i iu cn cn X CN M M Ck pH ^ Cl >y in in -C sO sZ Px 00 CJ CJ CJ z 2c CJ CJ CJ xJ c mJ iml 3 "C z O *o X .3 1k XO I pH I CN l C .o O O U u w ki o cc p* pp mZ > JO z ux w w 1 p^ 1 1 cn (3 ssr H 1 x- <n cn Cs cc in n * X'H CN CN cn cn px pH X MM /X "C CJ 23 C XX u c o u s-x CJ o cz CJ k N* ,N ftj c Z C CJ CJ c3 o N0o Cww 0J o o pO -- "" o JO o kl k u o -- ^4 n? nr JZ i j w Ol S', nthm DTH 000023418 B-l 2 i ( >c i1 I K -G * f f i rji i S . CM r-- G o SO i-H o CN CM G >C r v so CS O 4 o CM tn un m CM G P'J o --4 mt m<m n- --4 4 ^4 f4 -- G GG /s >4 44 CM n P-> cc i--1 44 m CM o i-4 CM Go G r- vO r-* 1 n* GG m cn ,C --4 NO r*. cn un G in in in 1-4 -- MT *--. 44 44 -- o G U* p--4 #"4 44 c w m 'C cc _ CN G *4 NO . ^--4 P4. un CJ rsi cni vO 3 NO o 44 ^4 CN CM NO 44 CM ^4 4 Li CM n CM 44 ON 44 in G n- CM m 5 ` - XJ 44 --- CM P>4 -44 44 #9 L Cl C. S CJ o H r- CN CM G un CM P-4 -- -> 44 r4 44 vO in CM o o ON CM -- OG 44 SO -4 r- 1--4 p4* cn O CM G NO m r*- r-- p*. NO ^4 G ---- ---- CN 44 m un CM r-> o -- CM CM in CM ^4 NO un 44 NO VO r*^ *0 --NO , CM *c . NO in CM r>* G 44 CM CM G CM G o CM m cn NO CM G o-- -- CM 44 -4 CM NO 4C un -- -- -- * *-4 44 cn CM G -- CM <N r- G CO un. in OS C7N in NO CN f --4 un vT NO CN G CM H NO cn CM cn r-4 r CM 4? *C . o r- wn w4 a. ? CN cn in -- cn --4 r- * -- > -- G -- m CM CM PM ^4 CM wn CM un c- u o o C 3 o s o u 44 <9 Uw H aj En o u CN ^4 m p-* m 44 ^4 ^4 *4 09 Oi 44 n* m r-- ' 44 cn mi cn l CM MT CM r4 cn G un 44 ^4 CM 44 NT oG 4H 44 G G CM c ou CJ oE no o *4 u U CJ Oc 44 "O CJ sN u u CJ c O 4J CJ (4 c >v o o N > s o CJ Li 4-J *d -- o-- n -o CJ o 4J c /--s c <9 G c L) GO ou 4- p; 4J c o u Li CJ --u xCJl Cl 44 CJ aO >v CJ JZ CJ > 5 0 4-> L CJ O O 1-4 L CW a-- Vm** < 1 U V) 1 *4 CM G Cl c E-- <9 S 44 (5 >, ^ 44 CJ *J ea 41 `4 no -a oo (0 V) oo WL 44 c= 1 1 GG CJ o >S CJ no c --* 4J f9 CJ "O ^4 .o u Li >> U 4(9 G CJ o w X CJ o "3 -- CJ x -* O -o CJ CJ cc CJ CJ 4 *4 >s "Z Cm fZ O XJ 3 CJ XJ C CJ u> G Ud OO ?9 -4 G uj V) CJ 4 4* E <e in O L LJ G V) c "3 C CJ XJ k- flj P3 cu cj e G *4 >s -r x >> O-- CJ 3 4 ej Xc o CJ CJ c no CJ `H cX CJ o X c 4-> cu c .9 o 44 CJ o CJ c<8 4-1 CJ CJ CJ CJ c c. cl Eo ococo O mH 44 u L. c 4J >S CJ CJ 4um+m S u 4^ xJ 4 >s J o 1 ' p4 c u Vi c- e Cc 09 Vi c 3o O CL CJ n Gu Oo L Id XJ ^4 G c Lm 44 3 CJ 4-J c CJ Lh c r-i ct 3 JO v> -* a <--< E >N 44 >N CJ "** -J G CJ VI 3 C U --* o C' I $ I S I l I r ) i f [ D 3 f E J E DTH 000023419 l cl 5 'V < r. i: i t, ijl,1: ? f (Q)jL5J B-l 3 .b CS p ir> o o rv n o -C n < p p^ pp in O o cn n o o <N -- o o U* o o u 3. u CJ E oo S- CN S<-OH <N SCOO L/~ SO SO co ^ cn <r r-- m cn rp vo e o ^m CM * CN nnn CN O co pp co r-4 in NT i/P <n r-* co m CO o UP o CN co p- co o CN CM O o <n \n eo r- p* *- en CN P ^ r> c <N pj so co cn CD up vo n in p* sC uP o esi up o o co <r -* co ^K iKn CmO LinO co cn (SI <N UP. m CN CN ON H o co eo m CM C O mnco cn r*. cn p- o p- cn <n *-h ccn cm eo cs c CO cn pp c o u m cn --< rH .-* r** cn xn m <N <l o ^* co up r- i-h so vn * <n p- c o KCCC Own <<N -co N cn CP r>j p* pp GO so CP a H QJ c Cl cc C) e O o moJ *3 c 3 O c o u E CJ C <; C 3 CJ /-p c *- F* > = C3 >% 5k.*- -3 JZ -J 5k i jJ 3 ^ Cl QJ -3 3 K-/ S *- O w J3 1 `M1 T3 4-11*3 Co --c -o f4 ^4 U >M 5k 3 f0 QJ u "3 CJ X 3 O ^ o c 3 5k MuB 5k C. CHJ o u 3 a. c j >Us tJ c u -- o <3 U>p cua U (S c *--< >v 5k bJ +J -> 3 &J t> E c Cl JC Jcj fN rnmt Cl 5k 5k' c 4m> CF o 2 Cl > a Cl C o >% 5K o -C o u c 5j o u ae c --Cl "C3l 5k 5k JZ JZ CJ CJ * <0 c ^N Cl 3 U Cl (3 JO O 3 O o Cr 3 * Oca 3 3 C O u >s F-- CJ 4 31 * a U (/) co SO QJ F-- -= u u M CJ c w u c U2 (MM cuo v CO CO CJ c o J o CO CJ CO 5k o JSZ JZ CJ o u << DTH 000023420 i.-l 4 S-` i ( ; K-i --0 c - c o U W cn < O ph re H i 1 o CN o m *H co CO CN <n M3 O' CN 'O vT *C pH C cn CN o c c oo c CO. co o /s ct to w C w - 2o H> CO (9 U c c. E CJ H o n% 50 60 p"n &u O XI w -- C 3 O Ce o u * pH <0 u 10 P* e to c s H u u ph CN "s? o CN CN o UO ph cn r*. on o ro ao NT to CN c\ *>? o CO ro p-. PH co ph co to pp o pH <r in cn uO to NT cn <N CN M3 inp pH CN in ph m r-. m ph r- pH cn pH ct CN >o * co O mm ^h cn pH cn to CZ3 o Ct SO CN r-* CO r* r-- CO CO o t_O CN cn S? CN O M3 CN C-s pH c* CN m O o CN NO cn co <--> O c O o p- pH "C cn o ph cn CN cn cn eo M3 CN CO CN in n cn o >0 Os *? sO CN < o e M3 CN CO ^4 CO in pH pH ph p** NT co CO M3 cn in SO cn cn \D e\ IN m GO et c cn eo in . ph c ec CJ e CJ N C CJ c CJ ** O CJ CJ sj N c ~ pH >N CJ e oCJ hi X) Hi CJ W * so u h H> fj O u < CJ CJ c cre X p CJ o _s 11 c --1 M C o JU3 Q CJ OU -2 5k sz m o CJ c 22 u CJ n X CJ CJ 11 fH CJ CJ CJ cnc Q u CJ H c HJ 3 J c JO C- CJ 5k & 1 *J 3 1 CJ CJ " 3n h c -3 j 1 CJ CN <T e i CN CN mt . CJ (D X o .20 o pH o >* u o c o CN o. o oo o o o CN <n O c oo o o o cn sC o o oo ooo mm o c Q^O o o c so vO Oc oo to fij CO *H u o H re u ec c pH G E re to e * *H "3 CJ co N r *< SO <2 ^ HO o- N NS r t* N -. > ?t *N n G o 1 1H CJ H CJ X oo H X o p* H X oH CJ CJ s CHJ CO ou u 3 u u Hi b Hi pcH H --i CJ H> H *H .22 H *n ccu 3 *uH c re oc in CJ o Vi c PH stzo CJ w **" H X re t: ^ ^ c CJ ^i H Hw ^ to *i n CN U- ^ ^ v) CN . m^ -v VVJ 1Z. -- 'n. ^ u H - c C) -b c CJ V .w> ^ ,o ~T, 00 *r to H pr\ r*,^ t V J* r CJ -E n/ nx poH o sO ' ^ IjO -C; ^ > \ 2. ^ , * jt:o - -W ^ 0. ^ ^ o ui u ^ 'H re P" cr u reG vt DTH 000023421 Sample Collection 0.4 c? "Plouu iv\2 ozr id r 5*/ H i 0.1 V CALI &iiA7UY| TCP con p)(T/n4 B-l 5 I I I I I I'TH 000023422 r-.| .fiuary 1930 1.0 Introduction 1.1 Resin traps from field sampling are thermally desorbed using the technique described by Pellizzari into an analytical system con sisting of a gas chromatograph (GC), mass spectrometer (MS) and computerized 'data system (DS). 1.2 Pollutants trapped on resin traps are thermally transferred to a nickel trap, held at liquid nitrogen (LN?) temperature. After transfer to the cold trap, the pollutants are rapidly transferred to' the analytical GC column for analysis.. Eluting GC peaks are analyzed by mass spectrometry. The spectra of the unknown GC peaks are compared to computer libraries of known spectra. Eval uation of spectra then leads to identification of unknowns. Iden tified chemicals are quantified by intergrating specific ions and referencing the response of standards of known concentrations. 2.0 Limitations 2.1 Often, standard reference materials are not reacTTTy available and only tentative identifications of unknowns can be determined. 2.2 Because of the long time required to prepare accurate quantifi cation standards, a limited number of chemicals can be measured. The number of chemicals available shall increase as more standards are prepared and verified. 3.0 Equipment and Reaoents 3.1 Thermal Desorber. Nutech 320 or equivalent desorber capable of describing sample traps at 200 to 300C onto a nickel cold trap at LNp temperature (-196C). Then capable of desorbing the cold trap at 150-250C onto a GC column. See figure 1. 3.2 Gas Chromatograph. Vartan 37C0 or equivalent equipped with a linear temperature programmer and capability for packed and/or capillary columns. 3.3 Packed Column. 6' x 2 mm I.D. column packed with 60/80 mesh Carbopack C coated with 1 SP1000. Condition overnight --at 220C with 20 ml/min flowrate. Other packed columns yielding the de- * sired separations may be used. 3.4 Capillary Column. 25 to 100 meter glass or metal SCOT (support coated open tubular) column coated with 0V-101, SP-1000, CW-2QM or SE30. Other phases yielding the desired chromatographic sep- PTH 000023423 J Li LnJ Lrs ent .quadripole mass spectrometers may tie u:;c as well) moss spectrometer capable of scanning ^rorr 35 t(i 3 50 emu n 3 seconcs or less. 3.6 Data System. Fcnn'gan ItCOS or equivalent capable of accuirinn and storing continuous -epetitive mass spectra from the mass spec trometer above. The system must be able to match unknown spectra to the EPA/tilH/MSDC mass spectral library and integrate ions for quantification. 3.7 Culture tubes. Pyrex glass screw cap tubes 25 mm x 150 mm. Pyrex 9825 .or equivalent washed, dried, and baked as described in reference (10.5). 3.8 Calcium sulfate or sodium sulfate. Anhydrous, non-indicating. Baked at 220C for at least 1 hour prior to use. 4.0 Instrument Conditions 4.1 Desorber. 4.1.1 4.1.2 4.1.3 4.1.4 Block Temperature 220C - 270C __ Desorb flowrate' 15 ml/min Cold Trap temperature -190C (-150 on meter) Trap desorb temperature 150C 4.2 Gas Chromatograph (Packed Column) 4.2.1 4.2.2 4.2.3 4.2.4 4.2.5 4.2.6 4.2.7 Carrier (helium) flowrate 30 ml/min Initial temperature 60C Initial hold time 4 minutes Program rate 8C/minute Final temperature 220C Final hold time 15 minutes GC/MS separator oven 230C 4.3 Mass Spectrometer 4.3.1 4.3.2 4.3.3 4.3.4 4.3.5 4.3.6 Source temperature 220C^ Source pressure =4 x 10" torr Mass range 35-350 amu Scan time 3 seconds Electron energy 70 ev Emission current 1.5 ma. 4.4 Overall Inlet Timing t = 0, Insert trap, trap at -150C B -17 DTH 000023424 t 8 mi ojro. $^r.m an, MU /rlhU? t 8 mi tb'H. t 10 min. 5t.)p doscrb .and switch valva to desorb t 11 min. off diverter t 11 min. Sw tch or ionizei t -38 min. Analysis complete 4.5 All GC/HS and acquisitan timing is shown in figure 2. Timing and parameters shown a~e for the exact equipment configuration des cribed here and are set up for the computer to keep track of the timing. 0 Procedure 5.1 At-least 16 hours before analysis of sample traps, carefully trans fer each trap to clean culture tubes containing about 10 grams of anhydrous calcium or sodium sulfate. Cap the culture tube with a teflon backed silicone septum and place the tube in a dessicator with charcoal adsorbant. This operation removes water absorbed onto the Tenex during sampling. 5.2 Set up instrument conditions as described in section 4. 5.3 Spike the trap with 25 u1 of the internal standard- as prepared in section 6. 5.4 Begin the analysis by inserting the trap into the desorber. Pro ceed as specified in 4.4 5.5 After the analysis is complete, proceed with data output and eval uation. 0. Internal Standards* 6.1 Static Standard 6.1.1 6.1.2 6.1.3 6.1.4 6.1.5 ^ To a clean 300 ml glass gas sampling bulb filled to atmos pheric pressure with N--, add 5.0 ul of perfluorobenzene. Mix the contents of the bulb by shaking with glass beads inside. Maintain the bulb in a waterbath at 30C. Withdraw 25 ul aliquotes using a gas tight syringe for injec tion onto sampling traps. Perfluorobenzene has a density of 1.607 g/ml at 25C. 5 ul = 8.035. 8.035 mg in 300 ml = 26.78 ng/ul. 25 ul times 26.78 ng/ul = 670 ng. 6.2 Dynamic Standards 6.2.1 Prepare permeation tubes for the standards of interest. After stabilization, load traps with known amounts of the DTH 000023425 7.0 Standards 7-1 Static Method 7.1.1 Using the same procedure as in 5.1, prepare standards as needed. Calculate the concentrations based upon the den sity and amount of chemical added and the volume of the I container. 7.1.2 Inject aliquots of these standards onto traps for analysis. ! 7-2 Dynamic Method i ,7.2.1 7.2.2 Prepare permeation tubes and calibrate as described in reference (10.6). Load traps with various known amounts of these standards for analysis. 8.0 Quantifications 8.1 Chemicals identified from their mass spectra may be quantified by comparison of the responses of the unknowns to the responses of known amounts of pure standards. The prefemeed method is the use of relative responses and internal standards. I 8.2 Calibration is performed*by analyzing a mixture of chemicals at known concentrations containing an internal standard (perfluorobenzene for example) added at a fixed concentration. The instru ment repsonses for selected ions are measured and compared for each component. A response factor is calculated for each compon ent by: Resp. fact. = Area * Ref. Amt/(Ref. area * amt.) (Eq. 1) Where: (Resp. fact. = response factor) Area Ref. Area Ref. Amt. Amt. area of ion in component area -of ion in internal standard amount of internal standard added amount of component. 8.3 Quantification of identified chemicals is done by determining the areas of the appropriate ions and calculating the amount from equation 1 re-arranged ( Amt = Area * P.ef, amt/(Ref. area * amt.) (eq. 2) # 9.0 Quality Control 9.1 Calibration of response factors is done daily at a midrange con- mmm M m DTK 000023426 B-20 \ \JU.L centratios. Linearity'o*' -espcnse is cfet^'-mined at lea>l once during a project. 9.2 Laboratory b'anks .ire run wi ;h eaci day's .analysis. 9.3 The response of the internal standard is monitored from run to run. Any deviations outside oast ranges are investigated and the sample re-run if possible. 9.4 Table I lists typical response, precision, and recovery data. 10.0 References 10.1 ES&T, 9 (6), 552 (1975). 10.2 ESSJ, 9 (6), 556 (1975). 10.3 Development of Method for Carcinogenic Bapor Analysis in Ambient Atmospheres", EPA-650/2-74-121, July 1974. 10.4 "The Measurement of Carcinogenic Vapors in Ambient Atmospheres", EPA-600/7-77-055, June 1977. 10.5 "Volatile Organic Air Pollutant Analysis", NEIC, January 1930. * 10.6 "Volatile Organic Air Pollutant Analysis - Permeation Tube Preparation and Calibration", NEIC, January 1980 t 0 '.U .5(J !'-< ; DTH 00002342? cc I Name Organic Air FolUtants - GC/ -IS Analys is Response : Factors3 Mean Z Std. Oev. Precisionc % difference I Methylenechloride Acetone Trans-1 ,2-dichloroethylene i Chioroform 1 ,2-dichloroethane Trichloroethylene Benzene Y Hexane Toluene Chlorobenzene Ethylbenzene \ Perfluorobenzeneb 0.82 0.59 1 .37 1.62 1 .04 0. S3 2.33 1 .81 2.57 1 .84 4.13 1.0 11 20 IS 3.8 3.8 4.3 3.2 8.4' 3. > 9.6 6.4 NAe r;4 2.7 1 .6 4.1 4.1 3.3 2.7 19.7 5.2 3.2 12.2 HA Recovery^ % Recovery 85 95 88 90 88 98 94 114 92 98 87 NA i a Ranges as low as 5 ng to over 3200 ng ______ i b Internal reference standard c Measured from two injections of standards at mid range concentrations. & d Measured from sample trap Spiked with standards, transported to field, returned and analyzed 3 weeks after spiking. i e Not applicable i r Ta'ole I. Summary of Typical response, precision and recovery data. i i i i DTH 000023428 ATTACHMENT 5 Organic Characterization and Priority Pollutant Procedures Sample Preparation Water Samples - Extractables: Samples were extracted with CH^CK at a basic pH to extract neutrals and bases and then at an acidic pH to extract acids (phenols). The extracts were dried and filtered by passing over anhydrous Na-SO. and concentrated to 5-10 ml in a Kuderna-Danish (K-D) apparatus, then concentrated to 1 ml under a gentle stream of purified air. The concentrated extracts were sealed in 1 ml serum vials and stored in a refrigerator until analysis. This procedure is in the method "Adjusted pH Extraction Technique for Organics Analysis, NEIC.January 1979". To monitor the general performance of the method, each sample was spiked with 300 ug/1 of o, a, a-Trifluoro-m-cresol and 100 ug/1 of D,QBiphenyl. These "surrogate" spike recoveries were monitored to show the u overall efficiency of the preparation procedures. Analytical Procedures Volatile Organics Analysis: An aliquot of sample was purged with an inert gas and the volatile organics were then trapped on a porous polymer resin trap. The trapped organics were then thermally desorbed onto an analytical GC column. The components were separated and mass spectra were obtained as they eluted from the column. Com ponents were identifed by comparison of their mass spectra to the spectra of standards. The specific procedure is detailed in "Volatile Organics by GC/MS, NEK - March 1980". Extractable Organics: * An aliquot of sample extracts, in acetone, was injected into a gas chromato graphic column. The eluting components were detected by a mass spectrometer. Identifications were made by comparison of the sample mass spectra to the mass spectra of pure compounds within specific GC retention-time windows. Quantification was by measurement of the area of specific ion fragments of each component. Retention time and response references were made to the internal standard. The detailed procedure is in "Base/Neutrals, Acids, and Pesticides Method 625", Federal Register, Monday, December 3, 1979. Starting at section 11. Quality Control Volatile Organics Analysis: The precision of technique was measured using the PPG-01-01 duplicate sample. Results are in "Volatile Priority Pollutants Quality Control Report". An aliquot of the same sample was spiked with known amounts of chemicals and their recoveries measured. The same table shows the results. All the samples were screened for an additional compound (acetonitrile). The lower limit of detection was 200 ug/1. DTH 000023429 I I^ ( I^ V J! Lx tractable OrganicsSl>' Z1 J\ Lid The precision of techniciue was mens ired usirg the DuPont-01-01 duplicate sample. These samples were also spike J with kro.vn amouits of chenncils ant their recov- eries measured. Table "Organic Priority Pol 1 utaats Quality Control Report" shows the results. I I i t I DTH 000023430 B-24 ATTACHMENT - INORGANIC ANALYTICAL METHODOLOGY Parameter Methocloloqy Reference CN Manual Distillation #1, Method 335.2 Colorimetric As, Sb, Se, T1 HN03/H202 Digestion Furnace Atomic Absorption #1, Methods 206.2, 204.2, 270.7, and 279.2 Hg KMn04/K2S208 Digestion #1, Method 245.1 Cold Vapor Atomic Absorption Spectroscopy Other Elements HNOg/HCl Digestion Inductively Coupled Argon Plasma Atomic Emission Spectroscopy #2 * #1: Methods for Chemical Analysis of Water and Wastes, EPA-600/4-79-020. #2: Federal Register Vol. 44, No. 233, p. 69559, Appendix IV. DTH 000023431 I I IC I if I I I I I l I L i B-25 ATTACHMENT 7 Vinyl Oh or ice: in Air - Charcoal Tubes fJEIC - January '.979 1.0 Introduction 1.1 This method is applicable to the measurement of vinyl chloride monomer (VCM) in ambient and contaminated atmospheres. Other volatile organic pollutants may be measured by adjusting the sampling and analytical conditions. 2.0 Summary of Method 2.1 VCM that has been trapped on charcoal is extracted witn carbon disulfide. The extract is analyzed by flame ionization detector (FID) gas-chromatography (GC) and VCM identified by the GC retention time. The amount is determined by comparision of the GC peak response to the response of standard solutions of VCM. 2.2 Samples containing concentrations of VCM above about 0.005 mg/sainple should be verified by GC-mass spec trometry (MS). 2.3 This method is based on the "Vinyl Chloride In Air" analytical method described by NIOSH in reference 1. 3.0 Interferences 3.1 Because routine identification of VCM is done by GC retention time, unidentified chemicals having the same GC retention time will interfere. Samples of the at mosphere being tested should be checked, prior to routine analysis for interfering peaks. Chromatogrcohic parameters may then bo optimized for the particular sample type. GC/MS verification will reduce the possibil ity of errors. Analysis of samdes collecteu from an atmosphere of VCM in air yielded average controtions of 86.5 and 73.5 ppm at 0 and 100" relative humidity respectively. 4.0 Range and Sensitivity 4.T Standard solutions of VCM were analyzed using the conditions described in this method. The measured areas were linear (correlation coefficient R greater than 0.999) over a range of 0 - 0.050 mg/sample. DTH 000033432 4.2 Typically, no background above 25 counts is detectable near the GC retention time of VCM. Amounts as low as 0.45 ng/ul (0.00045 mg/sample) have been detected. The detection limit is thus at leas-t 0.09 ppm in air, if 2 i of air are sampled. - 5.0 Apparatus 5.1 Charcoal traps: Glass tubes packed with 2 sections of activated coconut shell charcoal'. Available from SKC Inc., Eighty Four, PA 15330. See reference 1 for exact specifications. 5.2 Gas chromatograph: Hewlett-Packard 5700 or equivalent equipped with a flame ionization detector, automatic sampler and electronic peak integrator. 5.3 GC column: 10 ft. x 1/8 in. stainless steel packed with 60/80 mesh Gas-Chrom Q coated with 10C 0V1O1 followed by 20 ft. x 1/8 in. stainless steel packed with 80/100 mesh acid washed DHCS Chromosorb W coated with 10C FrAF. Other columns may be performing the desired separations. 5.4 Vials: 1 ml with septum seal aluminum crimp caps. 5.5 Pipet: 1.0 ml glass delivery pipet. 5.6 Syringes: 10 ul, 50 ul and 100 ul for preparation of standards. 5.7 10 cc/min ai- stainless steel capillary tube for delivery of pure VCM. 6.0 Reagents 6.1 Analytical Reagent grade carbon disulfide (CS^). Each bottle must be checked for background prior to use. 6.2 Vinyl chloride monomer, lecture bottles 99.9% purity. 6.3 Analytical Reagent grade toluene. 7.0 Standards Preparation 7.1 Concentrate - Add 5.0 ml of toluene to a 10 ml volumetric flask and weigh to the nearest 0.1 mg. Attach the stainless steel capillary tube to the VCM . lecture bottle and place the open end into the toluene. Open the cylinder and bubble VCM into the toluene for . about 5 minutes. mmm a DTH 00002343': Rewehjh the flask and detern ne the amount or VCM added f-om the ino'ease in >,/eight. Dilute the solution to 10 ml with caroon disulfide. The concentration of this solution snould be about 10 mg/ml. 7.2 Diluted solutions are prepared by adding ul alicuots of the concentrate to 1.0 ml of carbon disulfide in vials. 7.3 Mark the liquid level, label and store all standards in a freezer at -20C. The concentrated solutions should be stable at least 2 weeks. 7.4 Caution - VCM has been identified as a human carcinogen and appropriate precautions must be taken in handling the gas. See the Federal Register, Vol. 39, No. JS4, Friday, October 4, 1974, pp 35390-35S9S. 8.0 SamDle Analysis 8.1 Prepare each sample by carefully breaking open the charcoal trap above the glass v/ool. Remove the glass wool and carefully dump each section of the charcoal into two vials. . Using a pipet, add 1 ml of CSo to each vial and seal. Label each vial with the sample number and F or B fnr front and back resoectively. Shake and let stand 30 minutes before analysis. SamDles should be prepared on the same day as analysis if possible. But may be stored in a-freezer at -20C overnight if necessary. 8.2 Analyze the samples by injecting 1-2 ul into the GC. Typical conditions are as follows: 1. 150C injector temperature 2. 65C initial column temperature 3. 4 minutes hold time 4. lGC/min program to 13CC 5. 12 minute hold 6. 20 ml/..iin carrier flow rate 2.3 An automated oedk identification and r.uantiflection method for the Hewlett-Packard 3353 data system is shewn in Table 1. 5.4 At least 3 standards covering the range of the analysis must be analyzed to estaolisn the standard curve. After linearity is determined, a single point calibration may be used. DTH 00002343 B^28 > i * i i i CC Table 1 - Automatic integrali'ion Darameters for HP 3353: M: VCM 8 JAN, 79 15:29 1, ESTD, HE, H, NO, NO, JG , PROJ. 615 CHAR. TUBES 50, 25.33, YES 25, .015, 0.00, 0.00 .30, 2, 25, 0.0000E+ 0 2 7.32, 4.5000E+ 1, 1.1633E- 3, VINYL CHLO 11.21, 0.0020E- 0, 0.0000E+ 0, irSOLVENT 9.0 Quality control 9.1 Collection e^ficency: l samples of VCM at 94 ppm were collected in dry air at 100 ml/min sampling rate. The resultant recoveries were 104 and BIS. 9.2 Because the entire sample is used for analysis, no duplicates can be prepared. Duplicate injections can, however, be.made to verify the instrument response and 102 of the injections should be repeated. 9.3 SamDles containing more than about 0.005 mg/sample should be analyzed by GC/MS to verify that VCM is indeed the GC peak being measured. 10.0 Calculations 10.1 A response is calculated using two variable regression analysis or plotted.on graph paper. If the responses are linear, a one point calibration in the middle of the working range may be used to determine the slope. 10.2 The total concentration (mg/sample) is the sum of the front and back trap amounts. 10.3 The air concentration may be calculated as follows: mn/samole x 1000 l/'ii^ mg/iir * air volume sampled l f Or, the concentration in ppm at standard conditions may be calculated: - 24.45 x 760 ..(T+273) ppm ~ ing/iTr x MW P 298 Where: P = pressure in mm Hg during sampling T = temperature in C during sampling 24.45 = molar volume at 25C and 760 mm Hg KW = molecular weight of chemical 760 = standard pressure in mm Hg 293 = standard temperature in C DTH 00002343E 11.0 References C (1) "Vinyl Chloride n Ar", MICSH Manta' of Analytical Methods, (Volume 1), Depu. of Heaitr, taucation ancTlTeTrere, *pn i i977. DTH 000023436