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DIOXIN: PCDDs DAN PCDFs

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DIOXIN: PCDDs & PCDFs

Homologues and Congeners of PCDDs and PCDFs

NUMBER OF CONGENERS HOMOLOLOGUE (ABBREVIATION) Monochloro (M) Dichloro (D) Trichloro (Tr) Tetrachloro (T) Pentachloro (P) Hexachloro (Hx) Heptachloro (Hp) Octachloro (O) Total
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PCDDs 2 10 14 22 14 10 2 1 75

PCDFs 4 16 28 38 28 16 4 1 135
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DIOXIN: PCDDs & PCDFs

International Toxic Equivalent Factors (I-TEFs)

CONGENER 2,3,7,8-TCDD 1,2,3,7,8-PeCDD 1,2,3,4,7,8-HxCDD 1,2,3,7,8,9-HxCDD 1,2,3,6,7,8-HxCDD 1,2,3,4,6,7,8-HpCDD OCDD

I-TEF 1 0.5 0.1 0.1 0.1 0.01 0.001

CONGENER 2,3,7,8-TCDF 2,3,4,7,8-PeCDF 1,2,3,7,8-PeCDF 1,2,3,4,7,8-HxCDF 1,2,3,7,8,9-HxCDF 1,2,3,6,7,8-HxCDF 2,3,4,6,7,8-HxCDF 1,2,3,4,6,7,8-HpCDD 1,2,3,4,7,8,9-HpCDF OCDF

I-TEF 0.1 0.5 0.05 0.1 0.1 0.1 0.1 0.01 0.01 0.001
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SAMPLING AND ANALYTICAL PROTOCOLS

SAMPLING PROTOCOL USEPA METHOD 1 (BAPEDAL,770-0001-96) POINTS USEPA METHOD 2 (BAPEDAL,770-0002-96) USEPA METHOD3 (BAPEDAL,770-0003-96) USEPA METHOD 4 (BAPEDAL,770-0004-96) USEPA METHOD 23

PARAMETER NUMBER OF TRAVERSE

ANALYSIS FIELD DATA

GAS VELOCITY AND FLOW RATE GAS MOLECULAR WEIGHT

FIELD DATA

FIELD DATA

GAS MOISTURE CONTENT

FIELD DATA

DIOXINS

GC/MS

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APPLICABILITY AND PRINCIPLE

APPLICABILITY:
THIS METHOD IS APPLICABLE TO THE DETERMINATION OF POLYCHLORINATED DIBENZO-P-DIOXINS (PCDDs) AND POLYCHLORINATED DIBENZOFURANS (PCDFs) FROM STATIONARY SOURCES.

PRINCIPLE:
A SAMPLE IS WITHDRAWN FROM THE GAS STREAM ISOKINETICALLY AND COLLECTED IN THE SAMPLE PROBE, ON A GLASS FIBER FILTER, AND ON A PACKED COLUMN OF ADSORBENT MATERIAL. THE PCDDs/Fs ARE EXTRACTED FROM THE SAMPLE, SEPARATED BY HIGH RESOLUTION GC, AND MEASURED BY HIGH RESOLUTION MS.
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GLASS CLEANING PROCEDURE (QUALITY ASSURANCE)

1. 2. 3. 4. 5. 6. 7. 8. CLEANED IN ULTRASONIC CLEANER (T > 50C) RINSED 3 X WITH WATER RINSED 3 X WITH HPLC GRADE WATER BAKED AT 230 C FOR 2 HOURS LET AIR COOL RINSED 3 X WITH PESTICIDE GRADE ACETONE RINSED 3 X WITH PESTICIDE GRADE METHYLENE CHLORIDE CAP WITH METHYLENE CHLORIDE RINSED ALUMINUM FOIL.

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FILTER CLEANING PROCEDURE (QUALITY ASSURANCE)

1. 2. 3. 4. USED QUARTZ FILTERS CLEANED IN AN SOXHLET WITH TOLUENE FOR 3 HOURS PLACE FILTERS IN SOXHLET AND REFLUX WITH TOLUENE FOR 16 HOURS SAVE THIS TOLUENE TO ANALYZE FOR DIOXIN/FURANS

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SAMPLING TRAIN PREPARATION (QUALITY ASSURANCE)

1. 2. SAMPLING TRAIN WAS PREPARED IN CLEAN ROOM. PLACED 100 ML OF HPLC GRADE WATER IN IMPINGER 2 AND 3; 200-300 GRAMS OF SILICA GEL IN IMPINGER 4. LEAK-CHECKED FROM THE BACK OF THE SAMPLE TRAIN. USED A TEFLON TAPE TO LEAK CHECK. KEPT ALL TRAIN OPENINGS SEALED WITH EITHER TEFLON OR ALUMINUM FOIL UNTIL READY FOR TESTING.

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ABSORBENT TRAP PREPARATION (QUALITY ASSURANCE)

1. 2. BE LOADED WITH 20-30 GRAMS OF AMBERLITE XAD-2 RESIN PRE-CLEANED IN A SOXHLET EXTRACTOR: A. RINSE WITH WATER FOR 8 HOURS B. RINSE WITH METHANOL FOR 22 HOURS C. RINSE WITH METHYLENE CHLORIDE FOR 22 HOURS D. RINSE WITH FRESH METHYLENE CHLORIDE FOR 22 HRS E. DRY WITH LIQUID NITROGEN 3. TRAPS SHOULD BE PRE-SPIKED WITH KNOWN QUANTITIES OF ORGANIC COMPOUNDS TO CHECK RECOVERY.
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SAMPLING TRAIN ASSEMBLY

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SAMPLING PROCEDURE
1. TURNED ON CIRCULATION PUMP; WATER TEMPERATURE MUST BE
KEPT BELOW 20C 2. ADJUSTED THE FLOW THROUGH ROTAMETER INDICATED BY A MANOMETER BASED ON THE FLOW OF STACK GAS THROUGH STYPE PITOT TUBE INDICATED BY ANOTHER MANOMATER --> TO HAVE ISOKINETIC CORRELATION. 3. THERE WERE 12 TRAVERSE POINTS MEASURED DURING THE TESTS. 4. EVERY MOVING FROM ONE SAMPLING PORT TO ANOTHER LEAK CHECK WAS ALWAYS PERFORMED. 5. PERFORMED POST-TEST LEAK CHECKS. 6. DISASSEMBLED PROBE, FILTER, FILTER HOLDER AND IMPINGERS AND CAPED ALL OPENINGS. 7. BROUGHT THESE 3 SECTIONS TO CLEAN ROOM NEAR THE STACK FOR RECOVERY.
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SAMPLE RECOVERY PROCEDURE

1. ABSORBENT MODULE - CAPED BOTH ENDS, COVERED WITH ALUMINUM FOIL AND STORED ON ICE FOR TRANSPORTATION. CONTAINER 1 - THE FILTER WAS REMOVED FROM THE HOLDER. CONATINER 2 - NOZZLE, PROBE, FILTER HOLDER AND ANY GLASSWARE UP TO ABSORBENT MODULE WAS RINSED WITH ACETONE AND METHYLENE CHLORIDE. PROBE WAS ALSO BRUSHED 3X WITH EACH REAGENT. CONTAINER 3 - REPEATED RINSES DESCRTIBED FOR CONTAINER 2 BUT USED TOLUENE. IMPINGER WATER - MEASURED THE LIQUID AND DISCARDED. SILICA GEL - MEASURED THE WEIGHT OF THE SILICA GEL.

2. 3.

4. 5. 6.

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EXAMPLE OF RESULTS
Run # Test # Total and TEQs of Dioxin in XAD*) Concentration pg

D1

Total PCDD/Fs TEQ (ND=0) TEQ (ND=DL/2) Total PCDD/Fs TEQ (ND=0) TEQ (ND=DL/2) Total PCDD/Fs TEQ (ND=0) TEQ (ND=DL/2)

32.1 0.641 2.57 7.34 0 3.03 265 6.53 7.82

D3

D4

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EXAMPLE OF RESULTS
Run No. 1 Test No. D1 Sample collected* Weight of TEQ of TCDD, pg 2.57 2.89 1.88 7.34 3.03 Corrected value** 2.57 2.89 1.88 7.34 3.03 2.89 1.88 7.80 7.82 2.89 1.88 12.59 Remark

XAD/D-B1 + C1/D-B1 C2/D-B1 C3/D-B1 Total D1

D3

XAD/D-3 + C1/D-3 C2/D-3 C3/D-3 Total D3 XAD/D-4 + C1/D-4 C2/D-4 C3/D-4 Total D4

D4

7.82

Samples from XAD (adsorbent) and C1 (filter) were combined for analysis. * Liquid samples (C2 and C3) analyzed were only from Dioxin test # 1, therefore they were used for correction of the others.

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**Corrected values of dioxin (as 2,3,7,8 TCDD TEQ) are used in calculation.

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EXAMPLE OF RESULTS
Concentration, and emission rate.
DATA RECOREDED Sampling time, min Gas volume, STD m3 Stack tempereature,K Llinier gas vel, m/s Flow rate, @STD m3, dry basis. O2 content, % Isokinetic value, % Conc. (ng/STDm3 of 2,3,7,8 TCDD TEQ, dry basis @ ACT. O2 Emission rate (mg/h of 2,3,7,8 TCDD TEQ, dry basis @ ACT. Fuel consumed in the kiln 7/1/2006 TEST 1 120 2.887 371.5 16.25 730,564 14.9* 110 0.0025 0.0019 9.8 T/h coal+3.1 T/h HWF TEST 3 120 2.944 366.4 17.45 796,195 15.2 101 0.0026 0.0021 11.3 T/h coal+2.4 T/h HWF TEST 4 120 2.902 368 17.7 804,778 15.5 98 0.0043 0.0035 10.9 T/h coal+2.4 T/h HWF 16

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END

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