SAMPLING AND ANALYSIS OF DIOXINS AND FURANS (PCDD/PCDFs)

ANDREA SBRILLI UNIDO CONSULTANT

ESEA FORUM NATIONAL AWARENESS WORKSHOP FOR DEMONSTRATION OF BAT/BEP IN FOSSIL FUEL-FIRED UTILITIES AND INDUSTRIAL BOILERS ON PERSISTENT ORGANIC POLLUTANTS (POPS) BANGKOK, THAILAND 13 JUNE 2011

MAIN OUTPUTS OF DIOXINS AND FURANS FROM INDUSTRIAL SOURCES

THE FOLLOWING POINTS SHOULD BE MONITORED

BOTTOM ASHES, SLAGS AND FILTER ASHES

WASTEWATERS FROM SCRUBBERS SYSTEMS

EMISSIONS AT THE STACK

AS RESEARCH ACTIVITY ONLY: RAW GASES BEFORE AND AFTER SCRUBBERS AND BEFORE AND AFTER FILTER DEVICES

INTRODUCTION
AS FOR ANY OTHER CHEMICAL ANALYSIS, DIOXINS AND FURANS ANALYSIS INCLUDES THE FOLLOWING THREE MAIN STEPS:

SAMPLING

TRANSPORT AND STORAGE OF THE SAMPLES

ANALYSIS EXTRACTION PURIFICATION SEPARATION IDENTIFICATION QUANTIFICATION REPORTING

MAIN PARAMETERS TO MONITOR AT THE STACK ALONG WITH DIOXINS AND FURANS
OXYGEN AND TEMPERATURE PROCESS MONITORING (ALSO IN THE BURNING CHAMBER) NORMALIZATION OF DATA CARBON MONOXIDE (ALSO IN THE BURNING CHAMBER) FOR PROCESS MONITORING) PARTICULATE MATTER (CORRELATION WITH PCDD/PCDFs AND PAHs ACIDS (HCl, HF AND HBr) CORRELATION WITH PCDD/PCDF

SULPHUR AND NITROGEN OXIDES

CONTINUOUS EMISSIONS MONITORING SYSTEMS (CEMS)

ANALYSERS
CO, CO2 , SO2 e NOx NON DISPERSIVE INFRARED OXYGEN PARAMAGNETIC METOD PARTICULATE MATTER OPTICAL METHOD

ELECTROCHEMICAL CELLS OR INFRARED PORTABLE 5-10 KG

BUBBLING WASHERS FOR ACIDS AND SO2

PCDD/PCDF SAMPLING METHODS FOR FLUE GAS EMISSIONS

EPA 23/0023

EN 19481

ENVIRONMENT CANADA METHOD EPS 1/RM/2

JAPANESE METHOD JIS-Z-8808

KOREAN METHOD APTM 3C29

GENERAL CONSIDERATIONS

THE SAMPLING PROCEDURE IS THE MOST IMPORTANT STEP

IT IS INDISPENSABLE TO ENSURE THE REPRESENTATIVENESS AND INTEGRITY OF THE SAMPLE DURING THE WHOLE SAMPLING PROCESS

QUALITY ASSURANCE/QUALITY CONTROL (QA/QC) PROCEDURES FOR SAMPLING SHOULD BE PUT IN PLACE

METHOD EPA 23

EN 1948-1 THREE ALTERNATIVE METHODS AVAILABLE

SAMPLING TOOLS
S-TYPE PITOT TUBE AND THERMOCOUPLE DIFFERENTIAL PRESSURE DETERMINATION STACK GAS RATES MASS FLOW RATE CHOICE OF SAMPLING POINTS

NOZZLES WITH DIFFERENT DIAMETER FOR DIFFERENT FLUE GASES RATE NEEDED FOR ISOKINETIC SAMPLING

PROBES CAN BE IN TITANIUM, STEEL AND GLASS (MORE FRAGILE) INSERTED IN HEATED VESSEL TO AVOID CONDENSATION

PROBES FOR PCDD/PCDF SAMPLING

AVOID INTERFERENCES BETWEEN NOZZLES AND PITOT THIS COULD HARDLY AFFECT SAMPLING!

THE PROBE SHOULD BE FIXED IN THE DESIDERED SAMPLING POSITION WITH APPROPRIATE RING NUT AND FLANGE TO AVOID SWINGING ANY LEAKAGE MUST BE AVOIDED

APPROPRIATE FLANGE TO FIX THE PROBE TO THE STACK

ISOKINETIC SAMPLING
A PROPER ISOKINETIC SAMPLING RATE MUST BE MAINTAINED IN ORDER TO AVOID TO COLLECT MORE OR LESS PARTICULATE MATTER, WHERE PCDD\F ARE ADSORBED MOVE THE PROBE IN MANY (CALCULATED) POINTS OF THE STACK DIAMETER WITH DIFFERENT GAS VELOCITY OR POSITION THE PROBE IN A POINT WITH A MEAN GAS VELOCITY

FILTERS
A FILTER HOLDER OF BOROSILICATE GLASS WITH A TEFLON FRIT FILTER SUPPORT SHOULD BE USED. LEAKAGE MUST BE AVOIDED

IN CASE OF FILTER OUTSIDE THE STACK, THE FILTER HOLDER MUST BE HEATED, IN ORDER TO AVOID THE CONDENSATION OF WATER VAPOUR OR VOLATILE COMPOUNDS

COMPARISON OF DIFFERENT PROCEDURES

LABELLED STANDARDS ARE SPIKED IN THE FILTERING SYSTEM

LABELLED DIOXINS ARE NOT ADDED IN THE EN 1948

EPA 23

EN 1948

SAMPLING (SURROGATE) STANDARDS

37CL -2,3,7,8-TCDD 4 13C -1,2,3,4,7,8-HxCDD 12 13C -2,3,4,7,8-PeCDF 12 13C -1,2,3,4,7,8-HxCDF 12 13C -1,2,3,4,7,8,9-HpCDF 12

13C -1,2,3,7,8-PeCDF 12 13C -1,2,3,7,8,9-HxCDF 12 13C -1,2,3,4,7,8,9-HpCDF 12

CONDENDER AND TRAP METHOD EPA 23

A GLASS CONDENSER IS USED TO COOL THE SAMPLE GAS PRIOR TO ENTRY INTO THE SORBENT MODULE.

20 g UP TO 40 g SOLID SORBENT (XAD-2) ARE NEEDED

THE SORBENT TRAP CONFIGURATION IS VERTICAL TO ALLOW CONDENSATE DRAIN TO THE SORBENT

FREQUENT CHANGE OF SORBENT TRAP CAN OCCUR.

CONDENDER AND TRAP METHOD EN 1948-1

NOT CORRECT!
THE THIMBLE FILTER WAS KEPT ATOPEN AIR CONDITIONS
AND NOT AT CONSTANT HEATED CONDITION.

MAIN SAMPLING EQUIPMENT QA/QC

THE PRE-SAMPLING PROCEDURES ARE VERY CRITICAL FOR A CORRECT SAMPLING OF PCDD/F.

CALIBRATION OF: NOZZLE INTERNAL DIAMETER PITOT TUBE THERMOCOUPLES PUMP MANOMETER FOR PRESSURE

LEACK CHECK BEFORE EACH TEST OF: WHOLE SAMPLING TRAIN DRY GAS METER PITOT TUBE

SAMPLING PROCEDURE

A SAMPLING VOLUME OF ABOUT 10 Nm3 IS REQUIRED FOR COLLECTING A REPRESENTATIVE SAMPLE

SAMPLING TIME DEPENDING ON EXPECTED CONCENTRATION AND FLUE GAS CHARACTERISTICS (USUALLY 8 HOURS FOR LOW CONCENTRATIONS)

SHORT SAMPLING TIME (AND LOW VOLUMES) COULD LEAD TO FALSE NEGATIVES

AND IN THE FUTURE ?

CONTINUOUS PCDD/PCDF SAMPLING
CUMULATIVE SAMPLERS (1 DAY TO 2-3 WEEKS) MONITORING OF START AND STOP OPERATION PCDD/PCDF RESULTS EVERY 2 WEEKS DECS TECORA (ITALY) TRAP ADSORBING METHOD AMESA (GERMANY) COOLED PROBE METHOD DIOXIN MONITORING SYSTEMS (AUSTRIA) DILUTION METHOD WITH FILTER AND PUF

ALL COMMERCIALLY APPLIED

MAIN SAMPLING DEVICES FOR AMBIENT AIR

TO CONTROL POPs, VOCs AND SO2 AND NOX IN THE AMBIENT AIR, THE FOLLOWING METHODS CAN BE APPLIED:

HIGH VOLUME SAMPLERS MOSTLY USED

MEDIUM VOLUME SAMPLERS

PASSIVE SAMPLERS NOT COMMON FOR PCDD/PCDF

AIR SAMPLING
VOCs AND POPs in PTS and PM10

HIGH-VOLUME SAMPLER

LOW-VOLUME SAMPLER

SAMPLING METHODS FOR AMBIENT AIR

USEPA METHODS N.
T09
DETERMINATION OF POLYCHLORINATED, POLYBROMINATED DIBENZO-P-DIOXINS AND DIBENZOFURANS IN AMBIENT AIR

T13
DETERMINATION OF POLYCYCLIC AROMATIC HYDROCARBONS (PAHS) IN AMBIENT AIR USING GAS CHROMATOGRAPHY/MASS SPECTROMETRY (GC/MS)

SAMPLING METHODS FOR AMBIENT AIR

EPA T04
DETERMINATION OF PESTICIDES AND PCBs IN AMBIENTAIR USING HIGH VOLUME POLYURETHANE FOAM (PUF) SAMPLING FOLLOWED BY GAS CHROMATOGRAPHIC/MULTI-DETECTOR DETECTION (GC/MD)

EPA T10
DETERMINATION OF PESTICIDES AND PCBs IN AMBIENT AIR USING LOW VOLUME POLYURETHANE FOAM (PUF) SAMPLING FOLLOWED BY GAS CHROMATOGRAPHIC/MULTI-DETECTOR DETECTION (GC/MD)

HIGH VOLUME SAMPLERS FOR POPs

HIGH VOLUME SAMPLERS SHOULD HAVE A SIZE-SELECTIVE INLET FOR COLLECTING ONLY THOSE PARTICLES SMALLER THAN 10 MICROMETERS DIAMETER

PARTICLES ARE SEPARATED FROM GASES USING THE COMBINATION OF GLASS FIBRE FILTERS WITH GAS ABSORBANTS. PUF FOAM XAD RESINS ACTIVE CARBON FIBRE DISKS

SAMPLING TIME IS USUALLY 1 - 2 DAYS EVERY WEEK OR TWO WEEKS.

FUMES SAMPLING BY HIGH VOLUME SAMPLER IN SIMULATED FIRE IN MEXICO

PASSIVE SAMPLERS FOR MICROPOLLUTANTS

POLLUTANTS ARE ADSORBED IN A POROUS MATERIAL BY DIFFUSION

PUF FILTER EQUIPPED WITH THE METAL INSERT

READY TO BE HUNG TO SAMPLE SAMPLING TIME CAN BE WEEKS UP TO SEVERAL MONTHS

EXTRACTION AND PURIFICATION OF THE SAMPLES FOR PCDD/PCDF ANALYSIS

THERE ARE VARIOUS METHODS FOR SAMPLE EXTRACTION, WHICH INCLUDE:

SOXHLET ASE (ACCELERATED SOLVENT EXTRACTION SPE (SOLID PHASE EXTRACTION) MICROWAVE SONICATION SFE (SUPERCRITICAL FLUID EXTRACTION) PLE (PRESSURISED LIQUID EXTRACTION) LIQUID-LIQUID EXTRACTION

AFTER EXTRACTION, THE EXTRACT IS CONCENTRATED BY EVAPORATION UNDER VACUUM OR WITH NITROGEN

INTERNAL RECOVERY STANDARDS

BEFORE EXTRACTION, INTERNAL STANDARDS CAN BE ADDED TO CONTROL THE EXTRACTION EFFICIENCY

THE RECOVERIES OF THE EXTRACTION STANDARDS DIFFER WITH POP TO BE ANALYZED AND MATRIX.

RECOVERIES: FOR PCB AND PESTICIDES: 80 %-120 % (FOR TETRA- AND PENTA-CHLORINATED PCB, RECOVERIES DOWN TO 60 % CAN BE ACCEPTED)

FOR PCDD/PCDF: 50 %-130 % (FOR HEPTA- AND OCTA-CHLORINATED PCDD/PCDF 40 %-150 % CAN BE ACCEPTED)

SOXHLET EXTRACTION

1: Stirrer bar/anti-bumping granules 2: Still pot (extraction pot) 3: Distillation path 4: Soxhlet Thimble 5: Extraction solid (residue solid) 6: Syphon arm inlet 7: Syphon arm outlet 8: Expansion adapter 9: Condenser 10: Cooling water in 11: Cooling water out

THE ADVANTAGE OF THIS SYSTEM IS THAT JUST ONE BATCH OF SOLVENT IS USED AND RECYCLED

SOXHLET ADVANTAGES

THE CYCLE MAY BE REPEATED MANY TIMES, OVER HOURS UNTIL THE EXTRACT IS CONCENTRATED IN THE DISTILLATION FLASK.

AFTER EXTRACTION THE SOLVENT IS REMOVED, BY A RORATY EVAPORATOR YIELDING THE EXTRACTED COMPOUND.

THE NON-SOLUBLE PORTION OF THE EXTRACTED SOLID REMAINS IN THE THIMBLE, AND IS USUALLY DISCARDED.

THE ADVANTAGE OF THIS SYSTEM IS THAT JUST ONE BATCH OF SOLVENT IS USED AND RECYCLED

ACCELLERATED SOLVENT EXTRACTION (ASE)

ASE IS A PATENTED TECHNIQUE FOR THE EXTRACTION OF SOLID AND SEMISOLID SAMPLE MATRICES USING COMMON SOLVENT OR SOLVENT MIXTURES AT ELEVATED TEMPERATURES (40200 C AND PRESSURES THAT INCREASE EXTRACTION EFFICIENCIES.

ASE ADVANTAGES

EXTRACTIONS MUCH SHORTER TIME THAN SOXHLET OR OTHER TECHNIQUES

INCREASED SOLUBILITY INCREASE THE EFFICIENCY

STRONG SOLVENT REDUCTION

WIDE RANGE OF APPLICATIONS HANDLES ACIDIC AND ALKALINE MATRICES

COMPARISON

Solvent Savings Soxhlet Automated Soxhlet Microwave PSE PLE

Labor Savings

EPA Metho dology

Increased Acid or Productivity Alkaline with In-Cell Matrices Clean-up

Flexible Sample Size

ASE 100,200 and 300

ASE 150 and 350

PURIFICATION COLUMNS
PURIFICATION IS CARRIED OUT BY MEANS OF MULTILAYER CHROMATOGRAPHIC COLUMS TO REMOVE INTERFERING SUBSTANCES/ FROM THE SAMPLE DIOXIN PREP SYSTEM PROVIDES: REDUCED SOLVENT USAGE DECREASE IN SAMPLE PREPARATION TIME (BY 2 DAYS RELATIVE TO CONVENTIONAL METHODS)

EXTRACTION RECOVERIES
GREATER THAN 85%

PURIFICATION PROCEDURES EUROPEAN 1948-2 METHOD

Sample Aqueous/Solid/Emission Surrogate Spike (labeled analogs)
13 EXTRACTION LABELLED STANDARDS

Solvent Extraction Liq-Liq/Soxhlet/Microwave Solvent Exchange Extract Cleanup (acid/base/silver nitrate/silica column) Fractionation alumina column HCB Concentration Add Recovery (Internal) Standard GC-MS PCDD/PCDF Carbon Column Dryness Add Recovery (Internal) Standard GC-HRMS

USEPA METHOD 1613

15 LABELLED STANDARDS SOXHLET EXTRACTION

37CL -LABELED

2,3,7,8-TCDD CLEAN-UP STANDARD

MULTI LAYER SILICA COLUMN CLEAN UP

ACTIVE CARBON CLEAN UP

INJECTION STANDARD

HRGC-HRGC

DATA PROCESSING

POWER PREP SYSTEM

AUTOMATED SAMPLE-CLEANUP EACH OF THE FIVE, CHROMATOGRAPHY PANELS CONSISTS OF A VALVE MODULE AND A PUMP MODULE. THE STANDARD DIOXIN CONFIGURATION USES DISPOSABLE SILICA (ACID, BASE, AND NEUTRAL MIX), BASIC ALUMINA, AND AX-21 CARBON COLUMNS THESE COLUMNS ARE MADE OF TEFLON AND INDIVIDUALLY SEALED IN MYLAR PACKAGING. COLUMNS AND ALUMINA HAVE A SHELF-LIFE OF AT LEAST ONE YEAR.

ANALYSIS TECHNIQUES
CHEMICAL ANALYSES ARE GENERALLY SENSITIVE AND SPECIFIC. FOR DIOXINS AND FURANS CHEMICAL ANALYTICAL TECHNIQUES ARE THE ONLY METHODS THAT PROVIDE QUANTITAVELY EXACT AND COMPARABLE DATA.

ANALYSIS INVOLVE THE USE OF HIGH RESOLUTION MASS SPECTROMETRY, AND ISOTOPE LABELED ANALYTICAL STANDARDS,

THE ANALYSIS IS MUCH MORE EXPENSIVE THAN FOR OTHER POLLUTANTS

IN DEVELOPING COUNTRIES EQUIPPED LABORATORIES SHOULD BE AT LEAST AVAILABLE ON A REGIONAL SCALE.

ALTERNATIVES
SOME EMERGING NEW ANALYTICAL TECHNIQUES MAY BE USED IN DEVELOPING COUNTRIES IN THE NEAR FUTURE

LOW RESOLUTION MASS SPECTROMETRY (LRMS) METHODOLOGY COULD BE USED FOR SCREENING PCDD/F AND PCBs,

HOWEVER, THERE IS THE NEED TO DEVELOP RESULTS CONSISTENT WITH EXISTING NATIONAL AND GLOBAL PROGRAMS ON PCDD/FS, BASED ON HIGH RESOLUTION

DIFFERENT ANALYTICAL OPTIONS

COMMON GAS-CHROMATOGRAPHIC COLUMNS

AN APPROPRIATE GC PHASE HAS TO BE SELECTED AND ENOUGH GC PEAK SEPARATION MUST BE ACHIEVED TO ALLOW ACCURATE QUANTIFICATION

Length (m) VF-Xms (Varian) 60

I.D. (mm) 0.25

Film (m) 0.25

DB-DIOXIN
SP-2331

(J&W)
(Supelco)

60
60

0.25
0.25

0.25
0.25

RTX-5ms
ZB-5

(Restek)
(Phenomenex)

30
60

0.25
0.25

0.25
0.25

CP SIL-88
VF-5ms

(Varian)
(Varian)

50
60

0.25
0.25

0.20
0.25

MASS SPECTROMETRY ION TRAP

COMPARISON AMONG TECHNIQUES

Performances 100 80
%
ION-TRAP HRMS

60 40 20 0
%
QUADRUPOLE

Management

100 80
45000 70000 300000

HRMS

60 40 20 0 45000
QUADRUPOLE

IONTRAP

70000

300000

2,3,7,8-TCDD

1,2,3,4-TCDD* 2,3,7,8-TCDD*

HRMS
2,3,7,8-TCDF*

vs MS/MS (ION TRAP)

IMMUNOABSORBENT ASSAYS

ENZYME LINKED IMMUNOABSORBENT ASSAYS (ELISAS) HAVE BEEN USED TO QUANTIFY MOST POPS IN ENVIRONMENTAL SAMPLES INCLUDING: DDT/DDE, TOXAPHENE CYCLODIENE PESTICIDES PCBS AND PCDD/FS. ELISAS OFFER THE POTENTIAL FOR RAPID SCREENING OF CLASSES OF POPS IN THE CASE OF PCBs AND ORGANOCHLORINE PESTICIDES, DETECTION LIMITS FOR ELISAS ARE 1000 FOLDS OR MORE HIGHER THAN FOR GC-ECD FOR TCDD-ACTIVITY, HOWEVER, THERE IS AN ELISA WITH DETECTION LIMITS WITHIN A FACTOR OF 10-100 OF MASS SPECTROMETRY

INNOVATIVE TECHNIQUES
HYBRIZYME CORPORATION AhRC PCR Kit REPORTS THE CONCENTRATION OF ARYL HYDROCARBON (AH) RECEPTOR BINDING COMPOUNDS IN A SAMPLE, AND THE UNITS ARE REPORTED AS AH RECEPTOR BINDING UNITS (AhRBU).

TESTS CARRIED OUT BY USEPA WERE USED AS A SCREENING TOOL

IT IS A PORTABLE SCREENING TECHNOLOGY THAT CAN HELP TODETERMINE AREAS OF GREATEST CONCERN FOR CLEANUP AT A SITE

CAN HELP TO GIVE A BETTER REPRESENTATION OF THE TRUE TOXICITY FROM A RISK ASSESSMENT STANDPOINT AND REDUCE COST OF ANALYSIS

THANK YOU FOR YOUR ATTENTION !

Andrea Sbrilli, UNIDO consultant andrea.sbrilli@alice.it

ESEA FORUM NATIONAL AWARENESS WORKSHOP FOR DEMONSTRATION OF BAT/BEP IN FOSSIL FUEL-FIRED UTILITIES AND INDUSTRIAL BOILERS ON PERSISTENT ORGANIC POLLUTANTS (POPS) BANGKOK, THAILAND 13 JUNE 2011