ESTR-80-04 APRIL 1980 t RESULTS OF SOURCE EMISSIONS CHARACTERIZATION AT THE HEMPSTEAD, NY REFUSE ENERGY RECOVERY SYSTEM Submitted to:' ENVIRONMENTAL SCIENCES RESEARCH LABORATORY U& ENVIRONMENTAL PROTECTION AGENCY RESEARCH TRIANGLE RWK, NC 27711 UNDER CONTRACT 68-02-2566 Submitted by NORTHROP SERVICES. INC. ENVIRONMENTAL SCIENCES P.O. BOX 12313 RESEARCH TRIANGLE PARK, NORTH CAROLINA 27709 ------- ES-TR-80-04 APRIL 1980 RESULTS OF SOURCE EMISSIONS CHARACTERIZATION AT THE HEMPSTEAD, NY REFUSE ENERGY RECOVERY SYSTEM Prepared by: Barry Dellinger Chris Fortune Jeff Lorrain Environmental Chemistry and Emissions Sciences Northrop Services, Inc. Environmental Sciences Submitted to: ENVIRONMENTAL SCIENCES RESEARCH LABORATORY U.S. ENVIRONMENTAL PROTECTION AGENCY RESEARCH TRIANGLE PARK, NC 27711 UNDER CONTRACT 68-02-2566 Reviewed and Approved by: w 0 c 4\m A. Stikeleather, Manager Environmental Chemistry and Emissions Sciences Gary F.ฃerio, Manager Environmental Research NORTHROP SERVICES, INC. ENVIRONMENTAL SCIENCES P.O. BOX 12313 RESEARCH TRIANGLE PARK. NC 27709 ------- Environmental Sciences Center ES-TR-80-04 DISCLAIMER This report has been reviewed by Northrop Services, Inc.-Environmental Sciences, and approved for publication. Mention of trade names or commercial products does not constitute endorsement or recommendation for use. ------- 'M Environmental Sciences Center ES-TR-80-04 FOREWORD This report presents the results of work performed by Northrop Services, Inc.-Environmental Sciences, under Contract Number 68-02-2566 for the Stationary Sources Emissions Research Branch, Environmental Sciences Research Laboratory, U.S. Environmental Protection Agency, Research Triangle Park, North Carolina. The source work was conducted in response to Technical Directive 3.3-52, while the laboratory work was conducted under Technical Directive 3.3-1. iii ------- Environmental Sciences Center ES-TR-8Q-Q4 ABSTRACT In response to a request from Region II of the U.S. Environmental Protec- tion Agency, Northrop Services, Inc.-Environmental Sciences was contracted by the Agency's Environmental Sciences Research Laboratory to conduct source sam- pling at the Henpstead Resources Recovery Corporation Facility in Hempstead, New York. Source samples were collected from July 24 to July 26, 1979, and extensive laboratory studies were undertaken to validate the results of sample analysis. Although sampling was hampered by considerable down time at the facility, the measurements for chloride and sulfur oxide emissions indicate low concen- tration levels for these species. Sampling for organic species yielded an average total organic emission rate in excess of 25 lb/h. The majority of organic emissions consisted of commonly-occurring, innocuous compounds, but several materials posing potential hazards were also detected: substituted phthalate isomers, chlorinated phenols, chlorinated biphenyls and related compounds. The results of additional sample analyses currently in progress will be reported at a later date. Analysis by ion chromotography of sample fractions from the sulfur oxide sailing train detected the presence of formate and acetate. Laboratory studies indicated that these species were not the result of artifact forma- tion, but rather could be formed by the oxidation of formaldehyde and acetalde- hyde via the hydrogen peroxide impinger solutions. However, the possibility that the decomposition or oxidation of other species is responsible for the formate and acetate cannot be ruled out entirely. Laboratory studies also showed that the collection efficiency of the sampling train for formaldehyde was less than 100%, which means the reported iv ------- Environmental Sciences Center ES-TR-80-04 emission rates may be considered lower limits. Since the aldehyde results are based on one sampling run, their representativeness cannot be determined with- out additional source testing. ------- ~ Environmental Sciences Center ES-TR-80-04 CONTENTS SECTION PAGE Disclaimer ii Foreword iii Abstract iv Figures viii Tables ix Abbreviations and Symbols x Acknowledgment xi 1 Introduction 1 2 Conclusions 3 3 Recommendations 5 4 Process Description 7 Recycling Processes 7 Energy Recovery Processes 8 5 Results 11 Source Test Results 12 Laboratory Results 21 6 Discussion 31 Inorganic Determinations 31 Organic Determinations 32 Formate and Acetate 33 Collection Efficiency Studies 34 Interference Determinations 36 Relative Impinger Distributions of HCOO and OAc 39 Concluding Remarks 40 References 43 Appendices A. Sailing and Analytical Procedures 45 B. Calculations 56 vii ------- Environmental Science* Center FS-TP-an-na FIGURES NUMBER PAGE 1 Wet process energy recovery system 9 2 Gas chromatogram of the impinger extract from Organic Run #4 . 15 3 Gas chromatogram of XAD-2 cartridge extract from Organic Run #4 16 4 Original IC analysis of CCS-l-Hempstead sample fractions using a strong eluent system 18 5 IC analysis of CCS-l-Hempstead sample fractions using a weak NaHCO^ eluent system 19 6 IC analysis of CCS-l-Hempstead sample fractions using a weak Na^B^O^ eluent system 20 7 Effect of OH concentration on oxidation of CCS-S-^O^ impinger sample 23 8 IC analysis of standards in 0.6% H^O^ using a weak NaHCO^ eluent system 24 9 IC analysis of standards is 16* IPA using a weak NaHCO^ eluent system 25 10 IC analysis of standards treated with H^O^/NaOH using a weak NaHCO^ eluent system 26 11 IC analysis of laboratory sample #6 before and after treatment 27 12 IC analysis of CCS-l-Hempstead sample before and after treatment 30 A-l Schematic drawing of manual acid condensation system. A sampling pump and dry gas meter are contained within the pumping meter box 49 viii ------- jJClJG Environmental Sciences Center ES-TR-80-04 TABLES NUMBER PAGE 1 Hempstead Master Sampling Data 12 2 Chloride Results (ppm) 12 3 Sulfur Oxide Results (ppm) 13 4 Organic Results (mg) 13 5 Acetate and Formate Results (mg) 13 6 Inorganic Species Mass Emission Rates (lb/h) 14 7 Organic Species Mass Emissions Rates (lb/h) 14 8 Major GC Peaks from Organic Run #4 14 9 MS Identification of Gas Chromatogram of XAD-2 Cartridge extract from Organic Run #4 17 10 Laboratory Aldehyde Master Sampling Data 21 11 Formate and Acetate Results CCS Laboratory Samples 22 12 Summary of Carbonyl Interference Studies 28 13 XRF Analyses of CCS-l-Hempstead Sample 28 14 Flue Gas Formaldehyde Content of Various Sources by Formate Analysis of CCS Samples 29 ix ------- Environmental Sciences Center ES-TR-80-04 ABBREVIATIONS AND SYMBOLS ABBREVIATIONS CCS Controlled Condensation System D.I. H2O deionized water DNPH 2,4-dinitrophenylhydrazine EPA -U.S. Environmental Protection Agency ESP electrostatic precipitator GC gas chromatography HC1 hydrochloric acid HCOOH formic acid HPLC high performance liquid chromatography IC ion chromatography Imp impinger IPA isopropyl alcohol MeOH methyl alcohol MS mass spectrometry MW molecular weight NSI-ES Northrop Services, Inc.-Environmental Sciences OAc acetate PCB's polychlorinated biphenyls PCP's polychlorinated phenols PP probe plug PW probe wash RDF refuse-derived fuel RT retention.time XRF x-ray fluorescence QA quality assurance RDF refuse-derived fuel RT retention time VFR volumetric flow rate XRF x-ray fluorescence SYMBOLS Cl~ chloride CH2O formaldehyde C2HJ+0 acetaldehyde c2h6ฐ2 ethylene glycol FeCl^ ferric chloride HCOO formate H2SO4. sulfuric acid Na2C03 sodium carbonate NaHC03 sodium bicarbonate NaOH sodium hydroxide Na2Bi,07 sodium borate SO sulfur oxides x SO2 sulfur dioxide ------- 3 Environmental Sciences Center ES-TR-80-04 ACKNOWLEDGMENT It is with pleasure that we acknowledge the work of Mr. Gary Grotecloss and Mr. Mike Pleasant who conducted the source sampling and participated in the preparation of our initial report. With equal pleasure we acknowledge the assistance of our colleagues, Dr. John Windsor and Mrs. Sandy Parks, for ob- taining and interpreting the gas chromatography/mass spectrometry results presented in this report. We also acknowledge the work of our EPA colleagues, Mr. Jim Homolya and Mr. Jim Cheney, for their many helpful discussions. ------- Environmental Sciences Center ES-TR-80-04 SECTION 1 INTRODUCTION Northrop Services, Inc.-Environmental Sciences (NSI-ES) conducted source sampling on Furnace #2 at the Hempstead Resources Recovery Corporation Facility in Hempstead, New York from July 24 to July 26, 1979. The purpose of this sam- pling was to characterize hydrochloric acid (HC1) and organic emissions pro- duced from the combustion of nonreclaimed refuse. Sampling was also conducted by the U.S. Environmental Protection Agency (EPA) for sulfuric acid (H^SO^) and sulfur dioxide (SO^), while NSI-ES conducted supplementary oxygen monitor- ing. Since the plant was down (out of operation) for considerable periods of time during the week of sampling, only a few runs were completed. EPA Region II has requested follow-up laboratory work in order to validate the results obtained from analyses of the Hempstead field samples. This paper reports this work, conducted by NSI-ES and EPA, and gives the results of addi- tional laboratory experiments conducted by NSI-ES. 1 ------- Environmental Sciences Center Fs_TR_an-n4 SECTION 2 CONCLUSIONS The results of source sampling on Furnace #2 at the Hempstead Refuse Energy Recovery System indicated low concentrations of chloride (CI ) and sulfur oxides (SO ) in the flue gas. Because of the considerable time that x the plant was down during the test, sampling performed on July 26, 1979 is considered to be most representative of the plant operation. At an operating capacity of about 75%, the average mass emission rate for total CI was only 28 lb/h (15 lb/h particulate matter (PM), 13 lb/h gas). The mass emission rate of SO^ averaged 51 lb/h (4.5 lb/h PM, 46 lb/h SO^ gas). Based on past experience with other sources, these levels are not considered environmentally harmful. Source test results for organic emissions were consistent over three days of sampling, producing an average emission rate of 26 lb/h for total organics. This value must be taken as a lower limit, however, because the absolute col- lection efficiency of the sampling train has not been determined. The samples were qualitatively analyzed using gas chromatography (GC) and GC/mass spectro- metry (GC/MS). The samples were found to contain several potentially hazardous materials, including substituted phthalates, chlorinated phenols and chlorinated biphenyls. Since the analysis was not quantitative, whether or not these species were present at levels great enough to pose human/environmental risk could not be determined. Additional analyses have been performed on these samples to identify any other species undetectable by GC/MS surveys. These results will be reported at a later date. 3 ------- Environmental Sciences Center ES-TR-S0-04 SECTION 3 RECOMMENDATIONS For future field collection of flue gas samples at sources similar to the Hempstead plant, methods development and additional source characterization are recommended within the following framework: Development of an organic sampling system designed to collect low molecular weight species quantitatively. This system may be constructed using a cooled resin cartridge and thermal de- sorption recovery. Development and rigorous testing of a source sampling train for aldehyde emissions, possibly using hydrazine impinger solutions with high performance liquid chromatography (HPLC) analysis .techniques. Additional source testing at the Hempstead plant using the developed systems, and simultaneous testing using the techniques within this study. An effort should be made to sample over an extended period since the composition of the refuse-derived fuel (RDF) and consequent stack emissions may vary substantially. Onsite analysis of collected samples, if feasible, when using new or prototype techniques. 5 ------- Environmental Sciences Center ES-TR-80-04 Formate (HCOO ) and acetate (OAc ) were detected in the hydrogen peroxide (HjOj) impinger of the Controlled Condensation System (CCS) by ion chromato- graphy (IC). The identities of these species were verified through numerous laboratory detection methods, confirming that these species are indeed formate and acetate. NSI-ES proposes that the species present in the flue gas of the Hempstead plant were emitted as formaldehyde (CH^O) and acetaldehyde (C^H^O), but were subsequently oxidized to formate and acetate, respectively, in the H2ฐ2 pinger of the CCS sampling train. The efficiency of this oxidation process is less them 100%, however. Literature and laboratory studies have not revealed other species which could be responsible for the observed IC peaks, though time constraints did not permit a complete laboratory interference study. Hence the involvement of another species cannot be ruled out. The lower limits for the mass emissions rates of formaldehyde andซace- taldehyde are calculated at 28 lb/h and 28 lb/h, respectively, although these values may not be truly representative since they are based on only one sample. 4 ------- Environmental Sciences Center ES-TR-80-04 SECTION 4 PROCESS DESCRIPTION The Hempstead recovery plant converts municipal refuse into two usable forms: recyclable and combustible materials (The Black Clawson-Parsons and Whittemore Organization 1974). The plant operations described are the re- cylcing processes and the energy recovery processes. RECYCLING PROCESSES Raw waste entering the plant is first fed into a solid-waste-type hydra- pulper, where it is ground, shredded, and eventually pumped away as a water slurry. Unshredded material heavy enough to sink against a countercurrent of water is removed from the pulper. This material is then treated to remove ferrous metals, nonferrous metals and glass. The ferrous metals are removed by a magnet, and the nonferrous metals are removed by a high-speed, overhead, rotating electromagnetic drum. The nonmagnetizeable fraction drops into the nonferrous hopper, where it is passed over a grizzly screen that removes large nonrecoverable residue. The smaller items are recycled to the hydrapulper for further processing. The original material carried off by the water is treated to recover glass, aluminum, other nonferrous metals, and an assortment of inorganic materials that includes buttons, stones, pieces of broken china, etc. The heavy inorganic fraction is separated in a liquid cyclone and discharged through an opening in the bottom. This heavy fraction is washed to remove any residual light material (which is returned to the hydrapulper), then is rewashed and screened. The over-sized particles are processed again, but the fine particles are dewatered and conveyed to fuel storage. 7 ------- m Environmental Science* Center ES-TR-80-04 The plastics and lighter materials are separated from the heavy fraction by surface skimming in a heavy media separator. This light material is conveyed to fuel storage, where it is dried and sized. A magnet removes residual fer- rous metals and a shaking table removes aluminum foil. Nonconductors are re- moved from conductors by high voltage electrodes that permit the nonconductors to fall into a recovery drum. The remaining nonconducting fraction is mostly glass, china, porcelain and occasional small stones. The glass is separated at a transparency sorter and is actually separated by color with the use of colored filters to identify the clear, amber and green fractions. The energy recovery processes begin with the feeding of the cyclone-treated slurry from the hydrapulper to a large surge tank (see Figure 1). The slurry is pumped into a two-stage dewatering press apparatus where the solid content is raised to about 50%. The water discharge is processed and returned to the cycle; the solid is transferred to the fuel storage area for burning (usually within a week). The fuel is burned in two steam-generating furnaces with a nominal capacity of 200,000 lb/h of steam. The maximum fuel feed rate is 90,000 lb/h. The particulate emissions from the furnaces are controlled by the cyclones and electrostatic precipitators (ESP's) listed below: ENERGY RECOVERY PROCESSES Cyclones Manufacturer FLAKT Type 12 x CKOB 180 Number of units 12 per furnace Electrotatic Precipitators Manufacturer FLAKT Type FAA 323212090-1-SP Number of units 1 per furnace 8 ------- BARREL PRESS (THICKENER) GENERATOR LOW PRESSURE STEAM TO PROCESS u> TO RECOVERY 0T ALUMINUM SMALL FERROUS METALS GLASS(B? COLO") TIPPING FLOOR NONFERROUS MATERIALS RETURN TO PROCESS |<~1^*1 RECOVERED FERROUS METAL Figure 1. Wet process energy recovery system. (ZD O] 5 a 3 ft 3 ? (/> O 5* 3 O * O ft 3 tn i H sO I CO 0 1 o p* ------- Environmental Sciences Canter ES-TR-80-04 In summary, the solid waste that is burned as fuel contains about 25% mois- ture, 20% inorganics, and 35% organic combustibles such as paper, wood, plastics and food waste. Additionally, the water used in the process has been treated with a biocide that is certainly retained in the 25% moisture fraction of the fuel. 10 ------- JSO Environmental Sciences Center ES-TR-80-04 SECTION 5 RESULTS In this section the results from the Hempstead study are given in two parts: source testing and laboratory investigations. The first subsection contains all results thus far obtained from Furnace #2 of the plant pertaining to chloride, sulfur oxides, and other organic emissions of higher molecular weight. Since velocity traverses were not made, a volumetric flow rate previ- ously obtained for Furnace #1 (4.4 x 10ฎ SCF/h) was used for calculating mass emission rates (New York Testing Laboratories 1979). Process load data in Tables 1 and 6 are given so that runs can be compared (Ogg, private communica- tion) . Results of IC analyses on field samples for the formate and acetate ions are also presented in this section. Additional studies were requested by EPA to determine the presence of for- maldehyde and acetaldehyde in the flue gas. Laboratory investigations into the collection and analysis of these species are presented in the latter subsection. 11 ------- 333 Environmental Sciences Center Eo-TR-80-04 SOURCE TEST RESULTS TABLE 1. HEMPSTEAD MASTER SAMPLING DATA Date Time HC1 CCS HC1-ESP Organic % 09 % Operating Run # Run # Run # Run # c Capacity* 7-24-79 14:30-15:30 1 1 11.5 49 16:30-17:30 1 49 7-25-79+ 09:30-10:30 2 56 09:30-10:30 l 56 12:30-12:45 7-26-79 10:30-11:30 3 2 76 15:30-17:00 4 3 7.3 74 16:30-18:00 5 4 9.1 74 * Based on 200,000 lb/h steam generation. ^Sampling was interrupted at 10:30 and resumed at 12:30 due to a plant shutdown from 10:00 to 11:50 and from 12:35 to 13:25 on 7-25-79. TABLE 2. CHLORIDE RESULTS (ppm) HC1 Sampling Train Kun w SCF PP PW x 10"2 Imp x 10"2 Tot x 10~2 l 1.874 8.4 1.2 .87 2.1 2 .910 2.5 o o .00 .025 3 .865 8.2 .37 .31 .77 4 .985 6.5 .29 .30 .66 5 1.331 7.0 .24 .34 .65 HC1-ESP Sampling Train , ESP NaOH , NaOH SCF PU ESP x 10'^ Filter Imp x 10'^ Imp Tot x 10 1 26.241 .63 .55 1.2 2.5 3.2 3.1 12 ------- jjgg _ ... ES-TR-S0-04 Environmental Sciences Center TABLE 3. SULFUR OXIDE RESULTS (ppm) n ^ HC1 Sampling Train SCF PR PW Imp x TO"2 Tot x 10"2 1 1.874 .99 .26 1.8 1.8 2 .910 .44 .16 .00 .0060 3 .865 .95 5.5 .45 .52 4 .985 .76 2.5 .46 .49 5 1.331 .94 2.9 .47 .51 CCS Sampling Train SCF PW Special Filter Plug I PA Imp h2ฐ2 _2 Imp x 10" Tot x 10~2 1 9.121 .09 .37 .18 .00 1.5 1.5 TABLE 4. ORGANIC RESULTS (mg) Run (J Orajnics. SCF Imp XAD-2 Column 1 19.471 * 5.3 2 21.771 3.5 5.3 3 19.798 5.4 4.6 4 23.657 3.1 6.2 f1 Tot x 10"1 5.3 5.7 5.1 6.5 *Saiople discarded. TABLE 5. ACETATE AND FORMATE RESULTS (mg) Formate Acetate IV JII It I PA Imp H2ฐ2 Imp (x TO"1) Tot (x 10"1) I PA Imp H202 Tot x 10'1 Imp (x 10"1) 1 CCS 1.8 3.6 3.8 2.3 3.3 3.5 13 ------- ฃ]ฃ][] _ ES-TR-80-04 Environmental Sciences Center TABLE 6. INORGANIC SPECIES MASS EMISSION RATES (lb/h) Run # % Operating Capacity pm cr (x 10"1) Gaseous CI (x 10"1) Tot cr (x 10"1) PM* S04 Gaseous SOg (x 10-2) Tot S0X (x 10"2) 1 HCl 49 5.2 3.5 8.7 1.4 1.4 1.4 2 HCl 56 .11 .00 .11 . 66 .00 .0066 3 HCl 76 00 1.3 3.1 7.0 .33 .40 4 HCl 74 1.5 1.2 2.7 3.5 .33 .37 5 HCl 74 1.2 1.4 2.6 4.2 .35 .39 * Mass emission rates for oxides of sulfur are based on the analysis of the HC1 sampling train. TABLE 7. ORGANIC SPECIES MASS EMISSION RATES (lb/h) Run # % Operating CHgO x 10"1 CgH^O x 10"1 Organics x 10"1 Capacity 1 CCS 49 2.8 2.8 1 ORG 49 2.6 2 ORG 76 2.5 3 ORG 74 2.5 4 ORG 74 2.7 Figure 2 represents the GC spectrum of the impinger catch of Organic Run #4. Table 8 gives the major peaks in the chromatogram, identified through MS. TABLE 8. MAJOR GC PEAKS FROM ORGANIC RUN #4 Peak # Identification 1.3 2 Polychlorinated phenols (di-, tri-, tetra-, penta-) Phthalates and phthalate isomers 14 ------- LIU l_JL) in 7- t 1 1 1 1 1 1 1 1 1 1 1 r 5 10 MINUTES T 1 . r 15 t 1 1 1 1 1 1 1 r 20 25 Figure 2. Gas chromatogram of the impinger extract from Organic Run #4. CO I I TO l oo 0 1 o ------- G\ 11 ULAJ ~T~ 15 i r Figure 3. Gas chromatogram of XAD-2 cartridge extract from organic run #4. LJ QD r~m 3 3 3 ft 3 sr > o 5* 3 n ft u O ft 3 CO I i yo I CD O I o -F* ------- _JBl] Environments! Sciences Center ES-TR-80-04 TABLE 9. MS IDENTIFICATION OF GAS CHROMATOGRAff OF XAD-2 CARTRIDGE EXTRACT FROM ORGANIC RUN =4 Peak # Identification 1 Butylbenzene isomers 2 c10h12 isomers 3 c11H16 4 C10H12 5 Divinyl benzene isomer (tentative) 6 c11h16 7 Ciqh10 isomer 8 c12h18 isomers 9 Napthalene 10 C10H10O 11 Methyl napthalenes 12 Biphenyl 13 Ethyl napthalene 14 Methyl biphenyl 15 Alkylated tetrahydronapthalenes 16 Methyl biphenyl 17 Ci3H1602 e.g. (tentative) 18 6r?-0 isomer 19 m 0ch,-^Cm. or isomer 20 isomers of 21 isomers of 0~^-c'M5 22 Ci7H10 multialkylated biphenyl isomers H e-9- CHj~0 I Crt 23 Ci7Hio multialkylated biphenyl isomers 24 Anthracene/phenanthrene 25 Methyl anthracene/phenanthrene 26 Dichlorobenzophenone 17 ------- 300 ES-TR-80-04 Environmental Sciences Center CALIBRATION STANDARD A ฆ F" (5 ppm), 2.50 min B - CI" (10 ppm), 3.79 min C - SO3 (30 ppm), 6.43 min D SO4 (50 ppm), 10.38 min CCS-I-H2O2 (Hempstead) A Unknown, 2.73 min B - Unknown, 3.31 min C CI", 3.84 min D -SO4, 10.10 min INSTRUMENTAL CONDITIONS Columns: El Eluent: Flow Rate: Sample Loop: Meter Setting: 3 x 150 mm pre-column 3 x 500 mm Separator column 3 *6!50 mm Supressor column .006 M Na2C03 130 ml/h (25%) 100 m* 10 Mmho/cm full scale CCS - I - IPA (Hempstead) A Unknown, 2.72 min B CI", 3.66 min CALIBRATION STANDARD A - HCOO" (10 ppm), 2.73 min 5 0 15 20 Figure 4. Original IC analysis of CCS-l-Hempstead sample fractions using a strong eluent system. 18 ------- 309 Environmental Sciences Center ES-TR-80-04 B A A B rj A I 1 s J L M 10 15 20 CALIBRATION STANDARD A - F" (5 ppm), 3.45 min B - HCOO" (30 ppm), 5.21 min C Cf (20 ppm), 16.88 min CALIBRATION STANDARD A - OAc' (40 ppm), 4.04 min INSTRUMENTAL CONDITIONS CCS I H202 (Hempstead) A - CO3 =, 2.99 min B - Oac", 3.91 min C- HCOO", 5.16 min D-CI\ 16.84 min Columns: Eluent: Flow Rate: Sample Loop: Meter Setting: 3 x 150 mm pre-column 3 x 500 mm Separator column 6 x 250 mm Supressor column .0015 M NaHC03 103 ml/h (20%) 100 10/imho/cm full scale CCS - I I PA (Hempstead) A - CO3 =, 2.96 min B - HCOO", 4.72 min C-CI", 14.92 min Figure 5. IC analysis of CCS-l-Hempstead sample fractions using a weak NaHCOg eluent system. 19 ------- 309 Environmental Sciences Center ES-TR-80-04 B B I A, CALIBRATION STANDARD A - F" (4 ppm), 2.21 min B HCOO' (20 ppm), 3.48 min C CI' (10 ppm), 13.21 min CALIBRATION STANDARD A OAc* (40 ppm), 2.67 min INSTRUMENTAL CONDITIONS Columns: Eluent: Flow Rate: Sample Loop: Meter Setting: 3 x 150 mm pre-column 3 x 500 mm Separator column 6 x 250 mm Supressor column .005 M Na2B407 156 ml/h (30%) 100 ui 10 /^mho/cm full scale CCS I HqO? (Hempstead) A OAc", 2.64 min B - HCOO', 3.46 min C- CI", 12.54 min A. CCS ฆ I - IPA (Hempstead) A - OAc", 2.46 min B - HCOO', 3.31 min C -CI", 10.13 min D - CO3 =, 17.44 min 10 15 20 Figure 6. IC analysis of CCS-l-Hempstead sample fractions using a weak NagB^Oy eluent system. 20 ------- ~SB Environmental Sciences Center ES-TR-80-04 LABORATORY TEST RESULTS TABLE 10. LABORATORY ALDEHYDE MASTER SAMPLING DATA Run # Sampling Train Description Sample Source standard CCS train: 1st imp 80% IPA 2nd imp 3% ii2ฐ2 same ambient air formalin (3.7% soln) same acetaldehyde (liq) modified CCS train: formalin 2nd imp 3% H^/.IN NaOH (37% soln) modified CCS train: same 3rd imp 3% HjOj/S Fe 4th imp DNPH/HC1 (aqueous soln) modified CCS train: 3rd and 4th inฎ DNPH/MeOH formalin (7.4% soln) 21 ------- ~so Environmental Sciences Center FS-TR-Sn-04 TABLE 11. FORMATE AND ACETATE RESULTS - CCS LABORATORY SAMPLES Run # Sample Description Imp # Imp Contents Analysis for HCOO"/OAc Before Purge Untreated w/added ^ H202/Na0H' After Purge Untreated w/added . H202/Na0HT 1 2 1 2 1 2 3 1 2 1 2 3 80% IPA 3% H_0 2 2 tot 80% IPA 3% H202 tot 80% IPA 3% H202 (1/24/80) 3% H202 (2/29/80) tot 80% IPA 3% H202/.l N NaOH tot 80%.IPA 3* h2o2 3*8,0.,/ 5ppm Fe DNPH/HC1 (aqueous) 14.6 19.3 69.3 52.7 547 201 199 (52.7) 0 0 0 0 0 0 8.2 169 137 18.6 16.1 8.2 17.4 0 0 0 26.6 14.9 41.5 263 566 214 74.9 (17.4) tot 155.9 999.7 60.3 872.3 1 80% IPA - 246 16.3 249 2 3% H202 - 68.6 3.8 75.1 3 DNPH/MeOH - - 1.0 (1.0) 4 DNPH/MeOH - - 0.15 (0.15) tot 314.6 21.3 325.3 * , Total mg/10 ft3 sample. TIPA - sample adjusted to 0.6% H 0 (V/V) and .005 M NaOH; - sample adjusted to .005 M NaOH. 22 ------- u Environmental Sciences Center ES-TR-80-04 [ OH"] moles/liter Figure 7. Effect of OH" concentration on oxidation of CCS-S-H^ impinger sample. 23 ------- 000 Environmental Sciences Center ES-TR-80-04 A^; / I I 1 A i A' 10 15 20 CALIBRATION STANDARD A - OAc' (20 ppm), 3.73 min B - HCOO" (20 ppm), 4.56 min INSTRUMENTAL CONDITIONS REAGENT BLANK (0.6% H2O2 - v/v) A - HO2, 2.47 min Columns: Eluent: Flow Rate: Sample Loop: Meter Setting: QA STANDARD (30 ppm HCOO" in 0.6% H2O2) A - HO2, 2.48 min B - HCOO", 4.59 min QA STANDARD (1.6% I PA in 0.6% H2Q2-v/v) A - HO2, 2.55 min 3 x 500 mm Separator column 6 x 250 mm Supressor column .0015 M NaHC03 130 ml/h (25%) 100 nl 10 /^mho/cm full scale Figure 8. IC analysis of standards in 0.6X ^2 using a weak NaHCC^ eluent system. 24 ------- 3S3 Environmental Sciences Center ES-TR-80-04 INSTRUMENTAL CONDITIONS Columns: 3 x 500 mm Separator column 6 x 250 mm Supressor column Eluent: .0015 M NaHC03 Flow Rate: 130ml/h (25%) Sample Loop: 100^ Meter Setting: 10|imho/cm full scale QA STANDARD (30 ppm HCOO" in 16% I PA ฆ v/v) A - HCOO", 4.55 min QA STANDARD (16% I PA in D.I. H;Q - v/v) (peak not detected) QA STANDARD (16% I PA/0.6% H2Q2 - v/v) A HO"2 ฆ v/v) , 2.53 min Figure 9. IC analysis of standards is 16% IPA using a weak MaHCO^ eluent system. 25 ------- m Environmental Sciences Center ES-TR-80-04 B ar A B \A _J aB! QASTANDARD (0.6% H202/.Q05M NaOH) A H02, 2.53 min B - OH", 3.83 min QA STANDARD (20 ppm HCOO" in 0.6% H2O2/ 0Q5 M NaOH) A - HOj, 2.56 min B - HCOO', 4.34 min INSTRUMENTAL CONDITIONS Columns: Eluent: Flow Rate: Sample Loop: Meter Setting: QA STANDARD (16% I PA/0.6% H202/.005 M NaOH) A - H02- 2.56 min B-OH', 3.45 min 3 x 500 mm Separator column 6 x 250 mm Supressor column .0015 M NaHC03 130 ml/h (25%) 100 (J 10 /xmho/cm full scale QA STANDARD (30 ppm HCOO' in 0.6% H2Q2/16% IPA/.005 M NaOH) A H02, 2.62 min B - OH', 3.48 min C- HCOO", 4.41 min 10 15 20 Figure 10. IC analysis of standards treated with HpOp/NaOH using a weak NaOH eluent system. 26 ------- Environmental Sciences Center ES-TR-80-04 B kj 10x DILUTION A B B 2x DILUTION A I 1 _nL 10 15 20 CCS - 6 - I PA (Before Treatment) A - IPA, 3.40 min B - HCOO', 4.24 min CCS-6- IPA (After Treatment) A - HO2, 2.56 min B HCOO", 4.26 min CCS -6-H202 (Before Treatment) A H02.2.46 min B HCOO'. 4.22 min CCS-6-H202 (After Treatment) A HOjj, 2.55 min B - HCOO", 4.36 min INSTRUMENTAL CONDITIONS Columns: 3 x 500 mm Separator column 3 x 250 mm Supressor column Eluent: .0015 M NaHCO, Flow Rate: 130 ml/h (25%) Sample Loop: 100/4 Meter Setting: 10 jimho/cm full scale Figure 11. IC analysis of laboratory sample #6 before and after treatment. 27 ------- Environmental Sciences Center TABLE 12. SUMMARY OF CARBONYL INTERFERENCE STUDIES Analytical Results Sample Standard Standard After ~24 h After ~96 h Concentration (ug/ml) RT+ (min) RT (min) HCOO" OAc" (ug/ml) (ug/ml) RT (min) HCOO" OAc" (ug/ml) (ug/ml formaldehyde 100 4.41 4.35 7.577 4.40 22.510 acetaldehyde 100 3.61 3.56 1.072 3.57 9.693 propion- aldehyde 100 3.85 4.34 0.541 4.34 4.139 acetone 100 - 3.92 0.244 3.70 4.28 0.219 0.318 butyraldehyde 100 3.99 4.31 1.046 4.35 2.610 benzaldehyde 100 24.01 4.27 0.372 3.53 4.38 0.476 1.380 * 500 mg/ml in 3% H 0^ purged 15 min prior to analysis). with zero air (sample diluted 4:1 at H^O 'standards were prepared solutions of the acid or salt in D.I. H20. TABLE 13. XRF ANALYSIS OF CCS-1-HEMPSTEAD Element IPA Imp* (ug/ml) H70-/Imp (ug/ml) Na 138 107 Mg .11 .09 A1 .17 .01 S .16 47 K .14 .09 V .04 .02 Mn .09 .08 Co .14 .11 Cu .20 .09 Zn .20 .11 Br .71 .18 Cd .015 - Ba .02 .01 Pb .95 .91 * Analysis performed on diluted impinger catches (dilution volume = 100 ml). 28 ------- Environmental Sciences Center TABLE 14. FLUE GAS FORMALDEHYDE CONTENT OF VARIOUS SOURCES BY FORMATE ANALYSIS OF CCS SAMPLES Source Sample HCOO- Found (mg) Converted to ^0 in Stack (ppm) Untreated w/added H202/NaOH HCOO" ch2o HCOO" CH20 refuse-fired IPA imp 1.9 3.9 14.0 29.0 boiler H.O. imp 48.7 101 75.7 157 (Hempstead) tit2 50.6 104.9 89.7 186.0 hogged-fuel- IPA imp 2.0 4.4 18.4 40.8 fired H_0 imp 349 773 474 1050 boiler /. i. tot 351.0 777.4 492.4 1090.8 coal-fired IPA imp 0 0 1.0 1.6 boiler HO imp 13.7 22.6 14.3 23.5 tit2 13.7 22.6 15.3 25.1 * IPA imp - sample adjusted to 0.6* H.O (V/V) and .005 M NaOH, HO imp - sample adjusted to .005 M NaOH. 29 ------- Environmental Sciences Center ES-TR-80-04 -C Ab B B CCS I - I PA (Hempstead) (Before Treatment) A CO3, 3.61 min B - CI', 13.10 min CCS - I - I PA (Hempstead) (After T reatment) A - CO3/OH', 3.65 min B - HCOO', 4.24 min C- CI', 12.91 min INSTRUMENTAL CONDITIONS Columns: 3 x 500 mm Separator column 6 x 250 Supressor column Eluent: .0015 M NaHC03 Flow Rate: 130ml/h (25%) Sample Loop 100 til Meter Setting: 10 At mho/cm full scale CCS I - H2O2 (Hempstead) (Before Treatment) A - CO f/OAc, 3.62 min B - HCOO', 4.47 min C - CI", 13.47 min CCS - I - H2O2 (Hempstead) (After Treatment) A - CO3/OHVOAC, 3.80 min B - HCOO', 4.70 min 0 5 10 15 20 Figure 12. IC analysis of CCS-l-Hempstead sample before and after treatment. 30 ------- f*]~1 Environmental Sciences Center E$-TR-งQ-0'1 SECTION 6 DISCUSSION For clarity, the results of source and laboratory testing have been divided by compound class: (1) inorganics, (2) organics of high molecular weight, and (3) formate and acetate. The inorganic work has been completed; additional analysis of the organic samples is under way and will be reported at a later date. Because of the pertinence to source samples collected at Hempstead, results of a limited laboratory study on the collection and analysis of aldehydes are also reported here. INORGANIC DETERMINATIONS The results presented in Tables 2, 3 and 6 (pp. 12-14) indicate that the emission levels of chloride and sulfur oxides are indeed quite low in com- parison to power plants and other incinerators that have been characterized (Jahnke et al. 1977, Homolya et al. 1976). The average total chloride con- centration emitted as stack effluent at Hempstead was only 120 ppm, while the average gas phase concentration was only 73 ppm. The results from Run #1 of the HC1 train appear inconsistent with the re- sults obtained in Runs #3, 4 and 5 on July 26, 1979. The results of both Run #1 of the HC1-ESP train and Run #2 of the HC1 train appear to be anomalously low. (Since these runs were interrupted by plant down time, they cannot be considered representative of the source emissions.) In addition, the results obtained from all runs made on July 24 appear to be inconsistent with the runs completed on July 26. Although thorough checking of the process data revealed that the plant was operating under a steady load, the percent operating capacity 31 ------- Environmental Sciences Center ES-TR-80-04 was only 49% and the % 0^ was a high 11.5. Run $1 may thus not be representa- tive of the source. If we can exclude the abo^e samples, we obtain average total chloride and gaseous chloride concentrations of 69 ppm and 32 ppm, respectively. The CCS sampling of SO^ was performed only on July 24. Concentrations were very low, with SO^ measured at 150 ppm and H2Sฐ4 at on^Y ppm. Again, the results obtained on July 24 and 25 are not taken as representative of plant operation. Past simultaneous sampling efforts with the HC1 and CCS train have shown that the total sulfur oxides collected agree quite well. If Runs #3, 4 and 5 of the HC1 train for sulfur oxide analysis are assumed valid, an average sulfur oxide concentration of 51 ppm is obtained. Although the existence of irregularities in the samples taken on July 24 (interruption in sampling) and July 25 (apparent disagreement with July 26 samples) has been emphasized, these differences observed during the three days of sampling may be due to the varying composition of the RDF. Since many para- meters may be affecting the source sampling, no one sample should be construed as fully representative of the source emissions. ORGANIC DETERMINATIONS The results of sampling for organic emissions are presented in Tables 4, 7, 8 and 9 (pp. 13-14, 17). The total amounts reported for all four samples are quite consistent, and yield an average mass emission rate of 26 lb/h. The samples were collected in two fractions: species condensable at 0ฐC, and species trapped in the Amberlite XAD-2 cartridge at ambient temperature. Preliminary GC/MS analysis of Organic Run #4 indicated that polychlo- rinated phenols (PCP's) and phthalates were the primary components of the impinger catch. Small quantities of polychlorinated biphenyls (PCB's) were also collected in the cartridge; all other compounds detected were relatively innocuous species. The occurrence of these species in small quantities is not 32 ------- I0B3 Environmental Sciences Center ES-TR-80-04 unexpected, considering the chemical makeup of the RDF and the similar findings at other incinerators that have been reported (Eiceman et al. 1979). The source of the chlorophenols was thought to be the biocide used in treating the refuse (Betz CSD), until an investigation proved this chemical to be a chlorohvdantoin, which could not directly form the chlorophenols. Alternatively, the chloro- phenols may be formed by pyrolysis of phenolic polymers (Bakelite and Formica) and subsequent chlorination by a chlorinating agent, such as chlorohydantoin. The presence of chlorophenols is of prime concern, since these compounds have been reported to undergo condensation to form dioxins under the proper conditions (Buser 1978, Gribble 1974). Additional analyses performed on these samples will be reported at a later date. FORMATE AND ACETATE During the course of routinely analyzing CCS samples for sulfate, a major unidentified peak was observed in both the IPA and H202 impingers at a reten- tion time of 2.73 min (see Figure 4, p. 18). A minor peak of similar retention time had also been observed in an earlier run, and formate was suggested as being the species present. Analysis of a formate standard gave the same reten- tion time as the unknown peak in the Hempstead sample. Since the original eluent system was not suitable for analysis of fast-eluting species, a weaker eluent system was devised for running the samples. Results for both a weak bicarbonate (NaHC03) and a weak borate (Na2B40?) eluent system are presented in Figures 5 and 6 (pp. 19-20). Since the samples were initally prepared in a carbonate eluent (in order to eliminate the water dip which would interfere with analyses of chloride), a reagent blank was run first. This blank did not include peroxide because previous experience has shown that most of the peroxide either reacts or is thermally and photochemically destroyed in field S samples before analysis can be performed. The retention times for CO^ in the NaHC03 and Na2B40? eluent systems were 2.98 and 19.54 min, respectively, and therefore did not interfere in the HC00~/0Ac~ analysis. In addition, dilute IPA solutions have been found to shorten the retention times of all ions. The argument of retention times is actually very good when all the eluent systems 33 ------- JSO Environmental Sciences Center ES-TR-8D-04 are considered, and more firmly identifies these peaks as formate and acetate. Quantitative results are reported in Table 5 (p. 13) and mass emissions rates in Table 7 (p. 14). The formate and acetate were not detected, nor expected, in the NaOH im- pinger of the HC1 train, since these species are acids or salts that would not be collected in a basic solution. Due to the oxidizing nature of anc* ease of oxidation of aldehydes, however, a logical source for the species would be the parent compounds formaldehyde (CH^O) and acetaldehyde (C^H^O). The presence of these species has been reported in low-temperature, inefficient combustion sources (Harrenstien et al. 1979). The fact that the % Ofor the CCS run was relatively high may indicate less efficient combustion during this period of operation and further supports the aldehyde hypothesis. Collection Efficiency Studies Due to recent concern over the possible carcinogenicity of formaldehyde, NSI-ES was requested by EPA to validate the source samples through additional laboratory testing. The first phase of this testing was to determine the possi- bility of artifact formation in the sample train and the collection efficiency of the train for formaldehyde and acetaldehyde. A description of six laboratory runs of the CCS system and the sample source is presented in Table 10 (p. 21) . Table 11 (p. 22) lists the analysis results. No results are listed for analysis of the probe wash, filter and special plug sample fractions, since no HCOO or OAc" was detected in any of these fractions. Run #1 consisted of a blank in which ambient air (laboratory) was sampled to test for artifact formation. In other runs, formaldehyde (g) was generated by bubbling air through an impinger containing formalin. Acetaldehyde (g) was generated and sampled in Run #3. Initially, no formate or acetate was detected in the blank or in the formalde- hyde run, and only small quantities of acetate were detected in the acetaldehyde run. The initial results of these tests indicated either that: (1) a very small amount of CH^O was being generated, even with use of the 37% formalin 34 ------- Environmental Sciences Center FS-TQ-an-ru solution; (2) the IPA and Himpingers have a very poor collection effi- ciency for CH^O; (3) the CH20 is collected by the impinger solutions, but is only very slowly oxidized to HCOO ; or (4) some combination of the above. Of the four possibilities, collection of CH20 with slow oxidation to HCOO appeared to be most likely. Consequently, a test was conducted to deter- mine the effect of acid, base, and transition-metal ions on the oxidation of CH^O in a 3% H2ฐ2 solution. A test solution containing a small amount of 37% formalin in 3% H^O^ was prepared, and three aliquots of this solution were treated individually: one with HC1, another with NaOH, and the third with with ferric chloride (FeCl^), maintaining an untreated aliquot as a con- trol. The samples were analyzed on the following day, with the result that the degree of oxidation of CH^O to HCOO was reduced by a factor of 2 upon treatment with HC1, but was increased by a factor of 15 upon treatment with both NaOH and Fe+3. Since treatment of samples with Fe+3 involves addition of the CI ion (a slowly-eluting ion in weak eluent systems) to the sample, NaOH was used to speed oxidation. A test was conducted to determine the concentration of OH ion required to ensure complete oxidation of CH^O to HCOO in 0.6% H^O^ solution. Using the 3% H^O^ impinger catch from CCS Run #5 (after dilution to 1 liter with D.I. H^O) as a control, aliquots of the sample were treated with additions of .5 N NaOH such that the OH concentration ranged from .0005 to .01 M. The samples were allowed to stand overnight prior to analysis for the HCOO ion. The re- sults of this test, presented in Figure 7 (p. 23), indicate that a OH ion concentration of .005 M is sufficient for complete oxidation of CH^O. Based on these findings, the laboratory samples were routinely treated with NaOH and analyzed for HCOO . Treatment of the IPA impinger with NAOH yielded a slight increase in the amount of HCOO detected, but when these samples were also treated with H202 (0.6%), the increase in HCOO was quite dramatic (Table 11, p.22). Reanalyses of the system blank sanqples (Run #1) after the treatment described above yielded no formate or acetate in either impinger catch. Reanalysis of Run #2 samples after treatment showed the ------- jJB3 Environmental Sciences Center . ES-TR-80-04 presence of HCOO , whereas none was detected in the original analysis. More than 1 month after the original analysis, testing of the ^2^2 imP^n9er catc^ from Run #3 showed that of the total acetate detected in the treated sample, 64% was detected in the untreated sample, and only 3% of the total acetate was detected in the original analysis of January 24, 1980. At this point we may conclude that neither formate nor acetate is the re- sult of artifact formation in the sample train. Both formaldehyde and acetalde- hyde are collected in IPA and peroxide impingers and are converted to their cor- responding acids by the action of 3% hydrogen peroxide, but this reaction is not complete. Thus more aldehyde is collected than is apparent in analysis of the samples as received from the field. The collection efficiency of the train was evaluated by using treated impinger solutions and backup impingers to collect breakthrough. With the exception of the impinger solutions, Runs #4 and 5 were carried through the same conditions as Runs #1, 2 and 3. Addition of NaOH to the impinger in Run #4 produced a large increase in the amount of formate detected relative to the untreated samples. Run #5 indicated that 75% of the formate was collected in the IPA and H202 impingers as configured in the CCS train at Hempstead. In Run #6 an attempt was made to duplicate the level of formate detected in the H202 impinger at Hempstead (80 mg) to more accurately evaluate its collection efficiency. For this run a collection efficiency of nearly 100% was attained by the first two impingers, compared to 75% for Run #5 where considerably more formaldehyde was generated. Apparently the saturation point was attained in Run #5, beyond which the collection efficiency dropped rapidly. Interference Determinations Formaldehyde and acetaldehyde are collected in the sampling train with efficiency near 100%, but cannot be detected by IC with the same efficiency 36 ------- J35 Environmental Sciences Center . ES-TR-80-04 until subjected to the stronger oxidation of the NaOH/H^C^ solution. The final task of our study was then to determine the potentially-interfering compounds (i.e., other species) that may have been converted to formate and acetate by the action of the ^2^2 so^-ut^on- A thorough search of the literature revealed few potentially-interfering species. Only ethylene glycol (C H O ) was clearly documented to be converted 2 6 2 to formate by the action of dilute (Miner and Dalton 1973). A brief mention in the older literature of CO^ reduction by peroxide to produce for- maldehyde or formic acid (HCOOH) was_ not confirmed or even mentioned elsewhere (Fry and Payne 1930). Only the aldehydes appeared to be rapidly oxidized to their acid forms. The breaking of a carbon-carbon bond would be necessary to produce formic acid, for which enough energy does not seem available in the system. Throughout this laboratory study, the following steps were taken to test for possible artifact formation and/or interferences to the analytical tech- nique due to sample preparation and treatment: (1) routine preparation of control standards containing the same amounts of each constituent as in the samples being analyzed, (2) consistency in handling procedures, and (3) analy- sis of each sample under the same conditions on the same day. An example of such a control standard would be a sample prepared to contain 16% IPA (V/V), 0.6% H^O^ (V/V) and .005 mole/liter NaOH in D.I. B^O, and then allowed to stand overnight. This standard would be analyzed along with an IPA impinger sample (200 ml 80% IPA diluted to 1 liter) that had been treated with H^O^ and NaOH. Figures 8-10 (pp. 24-26) are representations of chromatograms of typical laboratory samples and control standards generated in this study. Figure 11 (p. 27) represents chromatograms of a laboratory sample before and after treatment. Analysis of control standards containing IPA/H^O^ and IPA/H202/Na0H of various representative concentrations indicated no oxidation of IPA to HCOO or OAc . The presence of OH ion results in a positive inter- ference to OAc determinations with the NaHCO^ eluent (but not with the NaB,0_ eluent); however, this problem was not too serious since the laboratory 2 4 7 work mostly involved analysis of HCOO ion. 37 ------- Environmental Sciences Center ES-TR-3Q-Q4 Tests were conducted to determine the possibility of interference to HCOO due to either oxidation by H2ฐ2 comPoun<3s other than CH^O, or oxidation by of compounds yielding products having the same retention time as the HCOO ion. Laboratory samples of acetone and various aldehydes of higher molecular weight were prepared at a concentration of 500 ug/ml in 3% ^2^2 ^ aS comParec* to ~400 ug/ml HCOO in 3% H2ฐ2 ^or CCS-l-H^O^, Hempstead), then purged for 15 min using a cylinder of zero air, and allowed to stand overnight. Prior to analysis, aliquots of the samples were diluted 4:1 with D.I. H^O, again duplicating the actual sample recovery procedure. The samples were analyzed a second time approximately 4 days after the initial preparation using the procedure outlined above. The results of these tests and the retention times of the corresponding acids are given in Table 12 (pp. 28). Any confusion with formate or acetate resulting from conversion of these aldehydes to their corresponding acid should be very slight. In most cases, a slow appearance of peaks did seem to occur that could possibly be misinterpreted as formate or acetate, though the degree of interference is probably negligible. Nonetheless, benzaldehyde also yielded a peak at the acetate retention time! Under no circumstances could benzaldehye be oxidized by dilute H2ฐ2 t0 ^onn acetaldehyde, leading us to conclude that the observed peaks are due to formaldehyde and acetaldehyde impurities in the chemicals. The fact that the retention times of the acids of these aldehydes are significantly different from the retention times of formate and acetate, and the fact that the original Hempstead sample identification was confirmed in borate eluent, lead NSI-ES to propose that oxidation of other aldehydes is not responsible for the results obtained at Hempstead. Borate could not be used to analyze these samples due to the interference of ^2^2 in freshly-pre- pared samples. Since the flue gas of a combustion source contains a relatively large amount of carbon dioxide (~10%), tests were conducted to determine the possi- bility of the reduction of CO^ to formic acid in the CCS impinger train. Using 38 ------- Environmental Sciences Center FS-TR-flO-flfl a cylinder of CO^ (5%) in air, a sample was collected in which the I?A impinger was treated with HC1 and the impinger with H2Sฐ4 This step was taken to duplicate the time-averaged concentrations of CI and SO^ that were determined in analyses of the IPA and impinger catches of the CCS-l-Hempstead sample, respectively. A second sample was collected under the same conditions as the first, except that both impingers were spiked with vanadium (0.1 ppm), and the IPA impinger with zinc (1 ppm). Selection of these two metals was based on analysis of the actual field samples by X-ray fluoresence spectrometry (XRF). (The results are presented in Table 13, p. 28.) Analysis of these samples for HCOO yielded negative results in all cases, as well as verified that no reduc- tion of CO^ occurs under these conditions. Relative Impinger Distributions of HCOO" and OAc" The only major discrepancy between the results of anlayses of the labora- tory samples and those of the actual field samples is the relative distribution of HCOO and OAc in the impingers. The two impinger samples from the field test were, of course, reanalyzed using the H^O^/NaOH pretreatment procedure. The values of both HCOO~ and OAc were found to be significantly greater in both samples; however, the amount found in the IPA impinger catch remained quite low with respect to the amount found in the H^O^ impinger catch. Our studies have not shown this condition to be attributable to artifact formation or interferences in the analytical method. Any plausable explanation for changes in the formate and acetate concentra- tions must take into account the highly reactive nature of aldehydes. An IPA impinger catch obtained from am actual source test necessarily contains a com- plex mixture of both organic and inorganic species. It has a relatively long residence time in its concentrated form prior to dilution and subsequent analy- sis. Conversely, an IPA impinger catch obtained from a laboratory-generated sample remains an essentially pure solution, and it has a relatively short residence time in its concentrated form prior to dilution and subsequent analysis. Thus, in the absence of a suitable oxidizing agent such as H^O^ and given sufficient time, reactions involving a large percentage of any 39 ------- !I]SG Environmental Sciences Center FS-TR-an-ru aldehyde species condensed in the IPA solution will probably occur that de- crease their original concentration significantly. As an example of the above, aldehydes are known to be reduced in the presence of a zinc catalyst in acid solution (Morrison and Boyd 1979). XRF analysis detected zinc at 20 ppm; IC analysis detected the presence of the chloride ion, which, as HC1, is sufficient to make the solution acidic. Thus this reaction would not be unexpected. Assuming this explanation of aldehyde chemistry to be valid, the calculated collection efficiency of the various impingers of the CCS train based on the laboratory tests cannot be considered strictly representative of the efficiency of the system in actual field use. Concluding Remarks A complete interference study could not be accomplished within our allotted time period, but the compounds we considered the most likely candidates to cause interference were proven to pose none. We do not discount that another species may be responsible for the formate and acetate peaks, but we do feel that formaldehyde and acetaldehyde are the most likely candidates, if only from the standpoint that they are the most likely combustion products exhibiting the observed properties. Other studies have shown that formaldehyde is a key inter- mediate in low-temperature combustion sources and is the major emitted aldehyde (Harrenstien et al. 1979). In fact, formaldehyde may be formed from thermal decomposition of phenolic polymers, which may be responsible for the observed chlorophenols. If another species is responsible for the observed results, then it must have the following properties: 1) oxidization to formate and/or acetate by 3% H2ฐ2' no aPPreciat>le solubility in IPA/H^C^ or great enough reactivity to be destroyed before analysis, and 3) no appreciable solubility in basic solution (no formate or acetate was observed in the NaOH impingers of the HC1 train) or great enough reactivity to be destroyed before analysis. Clearly, a systematic survey of all compounds exhibiting these properties would be a major undertaking. 40 ------- jl03 Environmental Sciences Center PVTR-ftO-O^1 As a final point of reference, we analyzed other samples available for formate and acetate production. These sources included a hogged-fuel-firec boiler, and a coal-fired power plant. These results along with zhe Hempstead results are summarized in Table 14 (p. 29). The results both before and after treatment are given, and in Figure 12 (p. 30) representations of chromatograms of the Hempstead sample before and after treatment are shown. Since treatment with NaOH may possibly oxidize other species besides aldehydes, the untreated value should be considered a lower limit for the formaldehyde content of the flue gas. Table 14 readily illustrates that the lowest values were obtained for the coal- fired boiler, and by far the highest values for the hogged-fuel-fired boiler. Considering the relative efficiency of the combustion processes, the order of formaldehyde emissions would not appear to be unreasonable. A means of verifying these results would be comparison of our sampling apparatus to another type of aldehyde train. Problems with this approach are that aldehydes are difficult to collect and stabilize, and other aldehyde trains are known to have numerous interfering compounds (Smith et al. 1972). Unique, undocumented problems may also exist with the Hempstead-type of emissions source. 41 ------- j3S3 Environmental Sciences Center ES-TR-80-04 REFERENCES Black Clawson-Parsons and Whittemore Organization, The. 1974. Proposal for Town of Hempstead, New York, for Resource Recovery Plant. Project NY-1369, Vol. I. Prepared for Hempstead Resources Recovery Corporation, Hempstead, New York. October. Buser, H. 1978. Polychlorinated Dibenzo-p-dioxins and Dibenzofurans: Forma- tion, Occurrence and Analysis of Environmentally Hazardous Compounds. Dept. of Org. Chem., Univ. of Umea, Sweden and Swiss Fed. Res. Station, Waedenswil, Switzerland. 449 pp. Cheney, J.L. and J.B. Homolya. 1979. Sampling Parameters for Sulfate Measure- ment and Characterization. Environ. Sci. and Tech., 13:584-588. Eiceman, G.A., R.E. Clement and F.W. Karasek. 1979. Anal. Chem., 51:2343-2350. Fry, H.S. and J.H. Payne. 1930. The Action of Hydrogen Peroxide on Simple Carbon Compounds. I: Methyl Alcohol, Formaldehyde and Formic Acid. J. Am. Chem. Soc., 53:1973-1980. Gribble, G.W. 1974. TCDD - A Deadly Molecule. Chemistry. 747:15-18. Harrenstien, M.S., K.T. Rhee and R.R. Adt, Jr. 1979. Determination of Individual Aldehyde Concentrations in the Exhaust of a Spark Ignited Engine Fueled by Alcohol/Gasoline Blends. Paper No. 790952, SAE Technical Paper Series, Society of Automotive Engineers, Inc., Warrendale, PA. 43 ------- idcJu Environmental Sciences Center Homolya, J.B., H.M. Barnes and C.R. Fortune. 1976. A Characterization of the Gaseous Sulfur Emissions from Coal- and Oil-Fired Boilers. Fourth National Conference on Energy and the Environment, Cincinnati, OH. October 4-7. Jahnke, J.A., J.L. Cheney and C.R. Fortune. 1977. A Research Study of Gaseous Emissions from a Municiple Incinerator. JAPCA, 27:747-753. Lappin, G.R. and L.C. Clark. 1951. Colorimetric Method for Determination of Traces of Carbonyl Compounds. Anal. Chem. 23:541-542. Miner, C.S. and N.N. Dalton. 1953. Glycerol. Reinhold Publishing Corp., New York, NY. Morrison, R.T. and R.N. Boyd. 1973. Organic Chemistry, 3rd ed. Allyn and Bacon, Boston, MA. New York Testing Laboratories, Inc. 1979. Results of Particulate Emission Tests on One Incinerator Stack for Hempstead Resources Recovery Corporation, Lab No. 79-554441. Smith, R.G., R.J. Bryan, M. Feldstein, B. Levadie, F.A. Miller, E.R. Stephens and N.G. White. 1972. Tentative Method of Analysis for Low Molecular Weight Aliphatic Aldehydes in the Atmosphere. Health Lab. Science, 9:75-78. 44 ------- 3D Environmental Sciences Center ES-TR-80-04 APPENDIX A SAMPLING AND ANALYTICAL PROCEDURES This section describes the sampling and analytical procedures implemented in characterizing selected source emissions at the Hempstead Resources Recovery Corporation Plant in Hempstead, New York, from July 24 to July 26, 1979. Also presented are the procedures followed during the course of follow-up laboratory investigations. HYDROCHLORIC ACID DETERMINATIONS The method used for chloride measurement was designed to collect gaseous and particulate chlorides emitted from stationary sources. The method employs a midget impinger sampling train to collect HC1 in the flue gas via passage through a series of impingers containing 0.1 N NaOH; the chloride collected is then analyzed using IC. Apparatus The apparatus consisted of a heated quartz-lined probe, midget impinger sampling train immersed in an ice bath, a pump, and a dry gas meter. Sampling The train was prepared by loading 15 ml of 0.1 N NaOH into the first two midget impingers and 15 ml of 3% hydrogen peroxide *nto t*ie third im- pinger. The fourth impinger remained empty. A piece of Pyrex glass wool was inserted into the inlet of the probe to filter out particulate matter. Im- pinger solutions were allowed to equilibrate in the ice bath and the system 45 ------- jaa Environmental Sciences Center ES-TR-8Q-04 was leak checked. Each sample was pulled for approximately 1 n at a flow rate of about 1 liter/min. The probe was allowed to cool prior to sample recovery. Sample Recovery Recovery of the sampling train entailed collecting three separate frac- tions: (1) the probe plug wash, (2) the probe wash, and (3) the combined 0.1 N NaOH impinger catches. Each fraction was recovered and stored in a separate 125 ml Nalgene polypropylene sample bottle. Sample Analysis All samples were quantitatively transferred to appropriately-sized volu- metric flasks, proportionally diluted, and subsequently analyzed using IC. The IC employed a 3 x 500 mm column in combination with a 3 x 150 mm precolumn. Samples were analyzed on the 10 umho/cm range using 0.006 M sodium carbonate (J^CO^) as the eluent. Results were reported in total milligrams per sample. HYDROCHLORIC ACID - ELECTROSTATIC PRECIPITATOR DETERMINATIONS The current method for characterizing chloride emissions draws the sample first through a glass wool filter plug and then through a solution capable of retaining HC1. Recent studies indicate that significant amounts of HC1 can be retained by the glass wool filter media. In an attempt to alleviate this in- herent source of bias, an electrostatic precipitator (ESP) was utilized (Cheney, personal communication). An integrated sampling system was developed implementing both an ESP to remove particulate chlorides, and impingers containing 0.1 N NaOH to remove HC1. The flow rate required for efficient operation of the ESP necessitated the use of a larger Greenberg-Smith impinger train. 46 ------- 30] Environmental Sciences Center ES-TR-80-04 Apparatus The equipment consisted of a heated quartz-lined probe, an electrostatic precipitator, a sampling module, a sampling pump, and a dry gas meter. The sampling module contained an ice bath for the Greenburg-Smith impingers, along with voltage controls to heat the probe and filters. Samp!ing Sampling preparations involved loading 200 ml of 0.1 N NaOH into the first impinger; 200 ml of 3% H2ฐ2 ^"nto t*ie secon<^ impinger; and filling the last impinger with silica gel. All components were allowed to reach operat- ing temperature and the impinger train was leak checked. The flow controller was adjusted to a flow rate of approximately 15 ft^/h for a sampling time of 2 h. After concluding a run, the probe and ESP were allowed to cool prior to sample recovery. Sample Recovery Recovery of the sampling train required the collection of five different fractions: (1) the probe wash, (2) the ESP wash, (3) the ESP filter, (4) the 0.1 N NaOH impinger catch, and (5) the 3% impinger catch. Fractions were recovered and stored in separate polypropylene sample bottles. Cooled fractions from the ESP were rinsed with three 15-ml portions of distilled deionized water. The washings were saved and stored in a separate polypropylene sample bottle. The ESP filter was stored in a plastic petri dish. Sample Analysis All samples were quantitatively transferred to appropriately-sized volu- metric flasks and diluted to the mark with distilled deionized water. Solutions were analyzed using an IC employing a 3 x 500 mm column combined with a 3 x 150 mm precolumn. Samples were analyzed on the 10 uho/cm range using 0.006 H Na^CO^ as the eluent. Results were reported in total miligrams per sample. 47 ------- Environmental Sciences Center ES-TR-80-04 SULFUR OXIDE DETERMINATIONS The sampling method utilized for the measurement of sulfur oxides was the Controlled Condensation System (CCS) (Cheney and Homolya 1979), designed to separate and collect the various sulfur oxides from stationary sources. Using a Goks^yr-Ross type condensation approach, a heated quartz filter, and a Greenburg-Smith impinger train, the CCS was designed to collect and separate sulfur oxides belonging to four main categories: (1) particulate sulfates and sulfites, (2) sulfuric acid, (3) sulfur trioxide gas, and (4) sulfur dioxide gas. Apparatus The apparatus utilized in the CCS system consisted of a heated quartz- lined probe, a glass filter holder, a glass plug holder, a sampling module, a sampling pump, and a dry gas meter (see Figure A-l). The sampling module con- tained an ice bath for the Greenburg-Smith in^ingers, along with a water bath for the plug holder, and voltage controls for heating the probe and filter. Sampling The system was prepared for sampling by measuring 200 ml of 80% IPA into the first impinger and 200 ml of 3% H2ฐ2 ^nto t*ie second impinger; the last im- pinger was filled with silica gel. All components were allowed to reach operat- ing temperature and the impinger train was leak checked. During sampling all temperatures were monitored and readjusted as necessary. The flow controller was adjusted to maintain a flow rate of 10 liter/min for a sampling time of 0.5 h. Following the conclusion of each run, the im- pingers were purged for 15 min at a 10 liter/min flow rate. The probe and filter were allowed to cool before sample recovery. 48 ------- INSULATION ID \ HEATING MANTLE ป. * \ (BE PLUG HOLDER ""ฆt FILTER HOLDER 1 PUMPING METER BOX SAMPLING MODULE LJ ED L-ZKJ < 3 a 3 sr C/> O S* 3 o C0 O ป 3 U> Figure A-l. Schematic drawing of manual acid condensation system. A sampling pump and dry gas meter are contained within the pumping meter box. ฆ 00 0 1 o ------- Environmental Sciences Center ES-TR-80-04 Sampling Recovery The sampling train was recovered as five fractions in separate bottles: (1) probe wash, (2) filter, (3) plug wash, (4) 80% IPA impinger catch and (5) 3% impinger catch. Each fraction was recovered and stored in a polypropy- lene sample bottle. The filter was stored in a plastic petri dish. Sample Analysis All samples were quantitatively transferred to volumetric flasks and diluted to a known volume. The samples were analyzed by IC, employing a 3 x 500 mm column, combined with a 3 x 150 mm precolumn. Samples were analyzed on the 10 ymho/cm range using 0.006 M Na^CO^ as the eluent. Results were re- ported in total milligrams per sample. ALDEHYDE DETERMINATIONS While analyzing the CCS-1-H202 sample fraction for sulfur oxides by IC, a large peak was detected at a retention time of ~2.70 min in the .006 M Na^CO^ element system. This retention time does not correspond to those of standards used for calibration (F , CI , etc.). Investigations were conducted to determine the identity of this unknown species by using standard solutions of various ions. The peak was thus tentatively identified as the formate ion (HCOO ). Verifications of the peak's identity was achieved by analysis of the sample in two eluent systems using sodium formate reference standards. One system con- sisted of a 0.0015 M NaHCO^ element at a flow rate of 130 ml/h in conjunction with a 3 x 150 mm precolumn, a 3 x 500 mm anion separator column, and a 6 x 250 mm suppresor column. Samples were analyzed on the 10 umho/cm range using an external standard method of analysis. The second system consisted of 0.005 M Na^^O^ element at a flow rate of 156 ml/h in conjunction with a 3 x 150 mm precolumn, a 3 x 500 min anion separator column, and a 6 x 250 mm 50 ------- 303 Environmental Sciences Center Liz TR-80-04 suppressor column. Samples were analyzed on the 10 umho/cm range using an external reference method of analysis. With the much greater resolution of fast-eluting ions attributable to using these weak eluents, the unknown peak originally detected as a solitary peak by the strong eluent (.006 M Na^CO^) was resolved into two peaks. These peaks were positively identified as formate and acetate. All aldehyde determi- nations reported were based on analysis of samples collected using the CCS. LABORATORY ALDEHYDE DETERMINATIONS This section describes the sampling and analytical procedures implemented in the laboratory to examine the reliability of using the CCS for aldehyde emis- sions characterization. Apparatus The apparatus utilized in the laboratory consisted of a sampling train identical to the system utilized in field for the sampling of sulfur oxide. The system consists of a heated quartz-lined probe, a glass filter holder, a glass plug holder (condenser), a sampling module, a sampling pump, and a dry gas meter. The sampling module contains an ice bath for the Greenburg-Smith impingers, a constant temperature water bath for the glass plug holder, voltage controls for heating the probe and filter, and a thermocouple meter for monitor- ing the temperature of the various components of the system. Sampli ng In conducting the laboratory studies, care was taken to duplicate as nearly as possible the operating parameters used in the field when sampling with the CCS. During sampling the probe and filter were maintained at a temperature of 520ฐ F, the plug holder at 140ฐF, and the impinger was immersed in an ice bath. Sampling was conducted for a period of 30 min at a sampling rate of 10 liter/min. 51 ------- . Environmental Sciences Center ES-TR-80-04 The system was prepared for sampling by measuring 200 ml of 80% IPA into the first impinger and 200 ml of 3% into the second impinger. For the blank run, three impingers were used, with the third containing dried silica gel. This arrangement duplicates the impinger train as utilized in the Hemp- stead sampling. In other runs conducted, the solutions contained within the third and fourth impingers depended upon the particular experiment being per- formed. All components were allowed to reach operating temperature and the impinger train was leak checked. During sampling all temperatures were moni- tored and readjusted as necessary. Following each run, the impingers train was purged for 15 min at a 10 liter/min flow rate. The probe and filter were allowed to cool before sample recovery. Formaldehyde gas was generated and sampled by connecting a .5 in Tygon line to the probe liner on one end with a teflon connector, and to the outlet of a Greenburg-Smith impinger with a ground glass joint connector on the other end. The impinger was then changed with 200 ml of a formalin solution in a hood at ambient temperature. Sampling was conducted by pulling ambient air through the impinger solution and into the heated probe of the CCS train. The initial blank run consisted of pulling laboratory air through the Tygon line and into the heated probe. Acetaldehyde gas was generated and sampled in a similar manner, except that the Greenburg-Smith impinger was filled with pure acetaldehyde ("*30 ml) to a level below the glass center tube in the impinger. The incoming air was therefore passed over the liquid surface, rather than bubbled through the liquid. In selected sample runs, 10-ml aliquots of the IPA and ^mP^n^er solutions were extracted for separate analysis after the conclusion of the sample run and prior to the 15 min purge of the impinger train. 52 ------- Environmental Sciences Center ES-TR-Rn-04 In order to determine the effects of high carbon dioxide concentrations (~10% CO^ in stock concentration) in air sampled by the CCS train, a cylinder containing 5% CO^ in air was employed to collect samples using one 80% IPA im- pinger, followed by one 3% H2^2 ^-mP^n(3er- T^e impingers were immersed in an ice bath and the cylinder gas was bubbled through the impinger train at a rate of 10 liter/min for 30 min. Sample Recovery Each sample run was recovered in four separate fractions as follows: (1) the probe wash, (2) the filter, (3) the glass-wool plug wash, and (4) the impinger train (collected separately), each impinger being rinsed with D.I. H20. Except for storage of the filter in a plastic petri dish, all sample fractions were placed in polypropylene sample bottles. Sample Analysis All samples were diluted to a known volume (inyinger catches to 100 ml/ all other fractions.to 100 ml) with D.I. H^O, and then analyzed for formate and/ or acetate ions using a Dionex Model 10 IC. The IC method of analysis consisted of a 0.0015 M NaHCO^ eluent in conjunction with a 3 x 500 mm anion separator column and a 6 x 250 mm anion suppressor column. The samples were analyzed using the 10 umho/cm range of the instrument with the eluent flow rate adjusted to 120 ml/h. An external standard method of analysis was employed using stan- dards prepared from stock standard sodium formate and sodium acetate solutions. During the course of the study, selected samples were pretreated with and/or NaOH prior to analysis. Known amounts of standard stock and/ or NaOH solutions were added to a 50-ml aliquot of the sample and mixed thoroughly, then allowed to stand overnight prior to analysis. The sample, consisting of 10-ml aliquots of the IPA and impinger ex- tracted prior to purging, were diluted to 50 ml with D.I. H^O, thereby monitor- ing the 4:1 dilution ratio used for the individual impinger catches (i.e., 200 ml were diluted to 1000 ml). 53 ------- jJdQ Environmental Sciences Center F5-TR-80-04 Analysis of the DNPH/HC1 impinger catch (CCS Run #9) was performed gravi- metrically; analysis of the DNPH/MeOH impingers (CCS Run #11) was performed by a colorimetric technique (Lappin and Clark 1951). ORGANIC DETERMINATIONS The sampling method utilized for the measurement of total organic emissions from stationary sources was a prototype sampling system. The method was designed to retain the organic emissions in an Amberlite XAD-2 column. Samples were analyzed using GC and GC/MS. Apparatus The apparatus utilized in this sytem consisted of a heated quartz-lined probe, an Amberlite XAD-2 column, a Greenberg-Smith impinger train, a pump, and a dry gas meter. Sampling The sampling train was prepared by inserting the Amberlite XAD-2 column (8 in long x 1/2 in diameter) between the first and second impinger. The first impinger was left empty to condense out water. The second impinger contained 200 ml of 3% H2ฐ2" silica was use<3 in the last impinger. The impinger solutions were allowed to equilibrate in 2m ice bath. The system was leak checked prior to each run. Each run consisted of pulling a gas sample through the heated probe, which contains a glass-wool probe plug, and through the impingers and Amberlite XAD-2 column. The sample was pulled at a rate of approximately 25 ft^/h for 1 h. Sampling Recovery Recovery of the sampling train entailed the collection of two separate fractions (1) the first impinger catch, (2) the Amberlite XAD-2 column catch. 54 ------- ฆm Environmental Sciences Center fs.tr.an-na The contents of the first impinger were transferred to a one-liter glass sam- ple bottle. The impinger was rinsed several times with distilled-deionized water. The washes were stored in the glass sample bottle along with the ori- ginal impinger catch. The ends of the Amberlite XAD-2 column were sealed with glass ball and socket joints. Sample Preparation and Analysis All samples were extracted using methylene chloride. The extracts were quantitatively transferred to 100-ml volumetric flasks and diluted to the mark using methylene chloride. The sample fractions were concentrated down to approximately 1 ml. The samples were transferred to individual, clean, tared 5-ml glass vials with teflon liners. The sample fractions were completely dried under a nitrogen environment. The vials were reweighed and the mass of organic residue in each vial was recorded for the calculation of mass emis- sion rates. Samples were then diluted, using methylene chloride, to a concentration of 15 to 20 ug of organic residue per microliter of methylene chloride. Sample fractions were analyzed by a Hewlett-Packard Model 5985A GC/MS under the follow- ing operating parameters: Maximum Cut-off Temp Desired Actual Temperature, initial ฐC Temperature, final ฐC Injection port temperature, ฐC FID temperature, 0 C TCD temperature, :ฐC AUX temperature, ฐC 350 350 400 400 300 300 50 275 275 300 275 275 51 275 275 300 275 274 Rate, ฐC/min Chart speed Zero Attenuation, 2T FID Signal Slope sensitivity Area reject Flow A, mil/min Flow B, ml/min 6.00 1.00 10.0 4 +B 0.10 1000 8.1 41.2 55 ------- Environmental Sciences Center ES-TR-80-04 Purification of XAD-2/Resin The Amberlite XAD-2 resin was purified prior to sampling using the follow- ing procedure: (1) The resin was washed in a 2-liter roundbottom flask with two 1- liter portions of distilled-deionized water. Care was taken to ensure that the mixture was well shaken. (2) Next, the resin was refluxed with 1 liter of reagent-grade menthanol for 7 h. (3) After removing the methanol, 1 liter of "glass distilled" methy- lene chloride was added to the mixture, which was then allowed to sit for 17 h. The mixture was refluxed for 7 h and the methy- lene chloride decanted. (4) Step 3 was repeated. (5) Finally, the resin was dried in the oven in a glass container at 80ฐ C for 1 h. (6) The resin was stored in a sealed, all-glass container until ready for use. 56 ------- CJSS Environmental Sciences Center ES-TR-80-04 APPENDIX B CALCULATIONS Standard Cubic Feet (SCF) = K x a x V. x /T. (Eq. B-l) dgm bar dgm where K = 17.636 ฐR/irt Hg, a = dry gas meter calibration factor, V, = dry gas meter volume, agin P, = barometric Pressure, in Hg, and oar T, = dry gas meter temperature, ฐR. dgm K, x mg 1 (Eq. B-2) Parts Per Million (PPM) = x scp where K. = 849.52 PPM x 9 x ft 1 mg mg = number of milligrams of pollutant, MW = molecular weight of pollutant, and SCF = standard cubic feet of sample. Mass emissions rate (lb/h) = K2 x mg x VFR/SCF (Eq. B-3) where = 2.205 x 10 6 lb/mg mg = number of milligrams of pollutant, VFR = volumetric flow rate of stack, 4,4 x 106 SCF/h SCF = standard cubic feet. The percent operating capacity was calculated based on a steam generation rate of 200,000 lb/h, equivalent to a 100% operating capacity. 57 ------- Environmental Sciences Center rs-TR-an-n4 A volumetric flow rate (VFR) for the stack had to be assumed in calculating the mass emission rates. The value used, 4.4 x 106 SCF/h, was the average value calculated from three tests (Method 5) performed on Furnace #1 by New York Test- ing Laboratories, Inc. (1979), from April 30 to May 1, 1979 while the unit was operating at 96% capacity. The results in this report are based on samples collected from Furnace #2. The mass emission rates for sulfur oxides are based on the analysis of sulfur oxides collected in the HC1 sampling train. REFERENCES Cheney, J.L. and J.B. Homolya. 1979. Sampling Parameters for Sulfate Measure- ment and Characterization. Environ. Sci. and Tech., 13:584-588. Lappin, G.R. and L.C. Clark. 1951. Colorimetric Method for Determination of Traces of Carbonyl Compounds. Anal. Chem. 23:541-542. New York Testing Laboratories, Inc. 1979. Results of Particulate Emission Tests on One Incinerator Stack for Hempstead Resources Recovery Corpora- tion, Lab No. 79-554441. 58 ------- |