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

BOTTOM ASHES, SLAGS AND FILTER ASHES

WASTEWATERS FROM SCRUBBERS SYSTEMS

EMISSIONS AT THE STACK

THE FOLLOWING POINTS SHOULD BE MONITORED

AS RESEARCH ACTIVITY ONLY:

RAW GASES BEFORE AND AFTER SCRUBBERS

AND BEFORE AND AFTER FILTER DEVICES

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

INTRODUCTION

MAIN PARAMETERS TO MONITOR AT

THE STACK ALONG WITH DIOXINS AND FURANS

SULPHUR AND NITROGEN OXIDES

OXYGEN AND TEMPERATURE

PROCESS MONITORING (ALSO IN THE BURNING CHAMBER)

NORMALIZATION OF DATA

PARTICULATE MATTER

(CORRELATION WITH PCDD/PCDFs AND PAHs

ACIDS (HCl, HF AND HBr)

CORRELATION WITH PCDD/PCDF

CARBON MONOXIDE

(ALSO IN THE BURNING CHAMBER) FOR PROCESS MONITORING)

CO, CO2 , SO2 e NOx

NON DISPERSIVE INFRARED

OXYGEN

PARAMAGNETIC

METOD

ANALYSERS

CONTINUOUS EMISSIONS

MONITORING SYSTEMS (CEMS)

PARTICULATE MATTER

OPTICAL METHOD

ELECTRO-

CHEMICAL

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

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

GENERAL CONSIDERATIONS

METHOD

EPA 23

EN 1948-1

THREE ALTERNATIVE METHODS AVAILABLE

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

S-TYPE PITOT TUBE AND THERMOCOUPLE

DIFFERENTIAL PRESSURE DETERMINATION

STACK GAS RATES

MASS FLOW RATE

CHOICE OF SAMPLING POINTS

SAMPLING TOOLS

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

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

A PROPER ISOKINETIC SAMPLING RATE MUST BE MAINTAINED

IN ORDER TO AVOID TO COLLECT MORE OR LESS PARTICULATE

MATTER, WHERE PCDD\F ARE ADSORBED

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

EPA 23 EN 1948

SAMPLING (SURROGATE) STANDARDS

37CL4-2,3,7,8-TCDD -

13C12-1,2,3,4,7,8-HxCDD -

13C12-2,3,4,7,8-PeCDF 13C12-1,2,3,7,8-PeCDF

13C12-1,2,3,4,7,8-HxCDF 13C12-1,2,3,7,8,9-HxCDF

13C12-1,2,3,4,7,8,9-HpCDF 13C12-1,2,3,4,7,8,9-HpCDF

LABELLED STANDARDS ARE SPIKED IN

THE FILTERING SYSTEM

LABELLED DIOXINS ARE NOT ADDED IN THE EN 1948

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 EPA 23

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

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

THE PRE-SAMPLING PROCEDURES ARE VERY CRITICAL

FOR A CORRECT SAMPLING OF PCDD/F.

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

A SAMPLING VOLUME OF ABOUT 10 Nm3

IS REQUIRED FOR COLLECTING

A REPRESENTATIVE SAMPLE

SAMPLING PROCEDURE

AND IN THE FUTURE ?

CONTINUOUS PCDD/PCDF SAMPLING

DECS TECORA (ITALY)

TRAP ADSORBING METHOD

AMESA (GERMANY)

COOLED PROBE METHOD

DIOXIN MONITORING SYSTEMS (AUSTRIA)

DILUTION METHOD WITH FILTER AND PUF

ALL COMMERCIALLY APPLIED

CUMULATIVE SAMPLERS

(1 DAY TO 2-3 WEEKS)

MONITORING OF START

AND STOP OPERATION

PCDD/PCDF RESULTS EVERY 2 WEEKS

MAIN SAMPLING DEVICES

FOR AMBIENT AIR

“HIGH VOLUME” SAMPLERS

MOSTLY USED

“MEDIUM VOLUME” SAMPLERS

PASSIVE SAMPLERS

NOT COMMON FOR PCDD/PCDF

TO CONTROL POPs, VOCs AND SO2 AND NOX IN THE AMBIENT AIR,

THE FOLLOWING METHODS CAN BE APPLIED:

HIGH-VOLUME

SAMPLER

LOW-VOLUME

SAMPLER

AIR SAMPLING

VOCs AND POPs in PTS and PM10

SAMPLING METHODS FOR AMBIENT AIR

USEPA METHODS N.

T09DETERMINATION OF POLYCHLORINATED,

POLYBROMINATED DIBENZO-P-DIOXINS

AND DIBENZOFURANS IN AMBIENT AIR

T13DETERMINATION OF POLYCYCLIC AROMATIC

HYDROCARBONS (PAHS) IN AMBIENT AIR USING GAS

CHROMATOGRAPHY/MASS SPECTROMETRY (GC/MS)

EPA T04DETERMINATION OF PESTICIDES AND PCBs

IN AMBIENTAIR USING HIGH VOLUME POLYURETHANE

FOAM (PUF) SAMPLING FOLLOWED BY

GAS CHROMATOGRAPHIC/MULTI-DETECTOR

DETECTION (GC/MD)

EPA T10DETERMINATION OF PESTICIDES AND

PCBs IN AMBIENT AIR USING LOW VOLUME POLYURETHANE

FOAM (PUF) SAMPLING FOLLOWED BY

GAS CHROMATOGRAPHIC/MULTI-DETECTOR

DETECTION (GC/MD)

SAMPLING METHODS FOR AMBIENT AIR

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

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

EXTRACTION AND PURIFICATION

OF THE SAMPLES FOR PCDD/PCDF ANALYSIS

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)

INTERNAL RECOVERY STANDARDS

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 (40–200 °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

Solvent

Savings

Labor

Savings

EPA

Metho

dology

Increased

Productivity

with In-Cell

Clean-up

Acid or

Alkaline

Matrices

Flexible

Sample

Size

Soxhlet √ √

Automated

Soxhlet √ √ √

Microwave √ √ √

PSE √ √

PLE √ √

ASE

100,200 and

300

√ √ √ √

ASE 150

and 350 √ √ √ √ √ √

COMPARISON

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%

Aqueous/Solid/Emission

Sample

Solvent Exchange

Extract Cleanup

Surrogate Spike

(labeled analogs)

PCDD/PCDF

Carbon Column

Dryness

(acid/base/silver nitrate/silica column)

Fractionation

alumina column

HCB

Liq-Liq/Soxhlet/Microwave

Solvent Extraction

Add Recovery (Internal) Standard

GC-HRMS

Concentration

Add Recovery (Internal) Standard

GC-MS

PURIFICATION PROCEDURES

EUROPEAN 1948-2 METHOD

13 EXTRACTION LABELLED STANDARDS

SOXHLET EXTRACTION

MULTI LAYER SILICA COLUMN CLEAN UP

DATA PROCESSING

ACTIVE CARBON CLEAN UP

HRGC-HRGC

INJECTION STANDARD

USEPA METHOD 1613

37CL -LABELED 2,3,7,8-TCDD

CLEAN-UP STANDARD

15 LABELLED STANDARDS

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.

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.

ANALYSIS TECHNIQUES

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

ALTERNATIVES

DIFFERENT ANALYTICAL OPTIONS

Length (m) I.D. (mm) Film (μm)

VF-Xms (Varian) 60 0.25 0.25

DB-DIOXIN (J&W) 60 0.25 0.25

SP-2331 (Supelco) 60 0.25 0.25

RTX-5ms (Restek) 30 0.25 0.25

ZB-5 (Phenomenex) 60 0.25 0.25

CP SIL-88 (Varian) 50 0.25 0.20

VF-5ms (Varian) 60 0.25 0.25

COMMON GAS-CHROMATOGRAPHIC COLUMNS

AN APPROPRIATE GC PHASE HAS TO BE SELECTED AND

ENOUGH GC PEAK SEPARATION MUST BE ACHIEVED TO ALLOW

ACCURATE QUANTIFICATION

MASS SPECTROMETRY ION TRAP

Performances

0

20

40

60

80

100

45000 70000 300000 €

% QUADRUPOLE

ION-TRAP

HRMS

Management

0

20

40

60

80

100

45000 70000 300000€

%ION-TRAP

HRMS

QUADRUPOLE

COMPARISON AMONG TECHNIQUES

2,3,7,8-TCDD

1,2,3,4-TCDD*

2,3,7,8-TCDD*

2,3,7,8-TCDF*

HRMS

MS/MS (ION TRAP)

vs

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

IMMUNOABSORBENT ASSAYS

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