Twinning Project BG 06 IB EN 01Twinning Project BG 06 IB EN 01

“Strengthening of Surface Water Monitoring Network Operation”“Strengthening of Surface Water Monitoring Network Operation”

C.3 Act 3.3: Training on chemical analytical methodsC.3 Act 3.3: Training on chemical analytical methods

Methods for determination of priority substances: Methods for determination of priority substances: the experience of ARPA Venetothe experience of ARPA Veneto

Simitli Simitli -- Bulgaria, 17Bulgaria, 17--19 February 200919 February 2009

Roberto LavaARPA Veneto Dipartimento Regionale Laboratori

d 11

Servizio Laboratori di Venezia

Regional Environmental Protection AgencyRegional Environmental Protection AgencyR i n V n t R i n V n t Region Veneto Region Veneto

LABORATORY REGIONAL DEPARTMENTLABORATORY REGIONAL DEPARTMENT

VENICE LABORATORY SERVICEVENICE LABORATORY SERVICE

Organization and ActivitiesOrganization and ActivitiesOrganization and ActivitiesOrganization and Activities

ARPAV

was established with Regional Law nLaw n°°32 of 18th October 199632 of 18th October 1996Law nLaw n 32 of 18th October 199632 of 18th October 1996

and became operative on 3rd October 1997

REGION VENETO THE AGENCY’S FUNCTIONSTHE AGENCY’S FUNCTIONS

The activities carried out by ARPAV are completely synthesised:

REGION VENETO

completely synthesised:

PreventionPrevention

ControlControl

Monitoring Monitoring

Technical supportTechnical support

33

pppp

REGION VENETOREGION VENETO

COMPLEX AREA → DIFFERENT ENVIRONMENTAL SITUATIONS:COMPLEX AREA DIFFERENT ENVIRONMENTAL SITUATIONS

ALPS (DOLOMITI MOUNTAINS)

PIANURA PADANA RURAL & INDUSTRIAL AREAPIANURA PADANA – RURAL & INDUSTRIAL AREA

URBAN AREA (VERONA, PADOVA)

ADRIATIC SEA

INLAND WATER (LAKE GARDA, RIVERS PO-ADIGE-BRENTA)

44VENICE AND VENICE LAGOON

E l h V L h bExample: the Venice Lagoon catchment basin

The Venice Lagoon catchment basin is the area of the Veneto i t it hi h i d i t i t th region territory which conveys rivers and rain waters into the

Venice Lagoon.

The water flow can be obtained naturally or in a mechanical wayThe water flow can be obtained naturally or in a mechanical way.The surface of the basin is approximately 1877.5 km2, to which must be added 503 km2 of the Venice Lagoon for a total surface of about 2380 km2 The basin is limited in the Southern part by of about 2380 km2. The basin is limited in the Southern part by the Gorzone Channel, in the Western part by the line of the Euganei Hills and by the Prealps near Asolo, in the Northern part by the Sile river comprising a small sub-basin physically part by the Sile river, comprising a small sub basin physically separated and connected with undergroud pipe (the Vela basin).

The Venice Lagoon basin conveys its waters into the Venice The Venice Lagoon basin conveys its waters into the Venice Lagoon through 27 points of discharge, rivers and rain waters (900x106 m3 each year, of which 120x106 m3 are civil effluents and 110 x106 m3 industrial effluents)

55

)

Example: the Venice Lagoon catchment basin

66

REGIONAL LABORATORY DEPARTMENTREGIONAL LABORATORY DEPARTMENT

Regional Laboratory Department7 Provincial Departments

under unique coordination (Verona headquarter) andl l l b t i i h

every PD comprises the following structure:

M t t local laboratories in each Province

- Management support

- Environmental Systems

-Territorial Services

77

VENICE LABORATORYVENICE LABORATORYVENICE LABORATORYVENICE LABORATORY

Management BASE CHEMISTRY LAB (water macrodescriptors, food, biota)

Operative

PARTICULAR ENVIRONMENTAL MATRIXES LAB (soil, sediment, solid waste)

supportSPECIAL INSTRUMENTATION LAB (air matrix)

Organic pollutants and dioxin lab (all matrixes)

BASE BIOLOGY LABs

88

Nowday: situation of re-organizationof tasks between provincial labs

The Laboratory Service of Venice is accredited SINAL since 2001

and ISS since 2004 within UNI CEI EN ISO/IEC 17025:2000within UNI CEI EN ISO/IEC 17025:2000

Nowadays 44 procedures are accreditedNowadays 44 procedures are accredited

99

Operative UnitOperative Unit“O i Mi ll t t Di i ”“O i Mi ll t t Di i ”“Organic Micropollutants e Dioxin”“Organic Micropollutants e Dioxin”

MATRIX ANALYZED

SOIL RECLAIMFOOD

WATER

SOIL RECLAIMSEDIMENT

SOLID WASTEBIOTA

drinkable watert t tap water

surface waterground waterwaste water

EnvironmentalEnvironmentalm nit inm nit in

1010

waste watermonitoringmonitoring

Operative UnitOperative Unit“O i Mi ll t t Di i ”“O i Mi ll t t Di i ”

P m t s:P m t s:

“Organic Micropollutants e Dioxin”“Organic Micropollutants e Dioxin”

waterwater Pesticides and metabolites, Policyclic Aromatic Hydrocarbons (PAH) Polychlorobiphenyls (PCB)

Parameters:Parameters:

Hydrocarbons (PAH), Polychlorobiphenyls (PCB), Organotins, Aromatics AminesVOCs BTEX MTBE Hydrocarbons<CVOCs, BTEX, MTBE, Hydrocarbons<C12

Dioxin and Furanssoil andsoil and VOCs BTEX MTBE Hydrocarbons<C12 landland

reclamationreclamation

VOCs, BTEX, MTBE, Hydrocarbons<C12, Pesticides residues, Chlorobenzenes, Organotins, AntifoulingDioxin and Furans

foodfood Multiresidue pesticides analysis, Preservatives, Additives , PCB, Organotins,

1111

gDioxin and Furans

Operative UnitOperative Unit“O i Mi ll t t Di i ”“O i Mi ll t t Di i ”“Organic Micropollutants e Dioxin”“Organic Micropollutants e Dioxin”

Instrumentation of Microrganics Pollutants Lab:Instrumentation of Microrganics Pollutants Lab:

1 GPC (Gel Permeation Chromatography System)1 GPC (Gel Permeation Chromatography System)2 GC/MS (1 Quadrupole 1 Ion Trap)2 GC/MS (1 Quadrupole 1 Ion Trap)2 GC/MS (1 Quadrupole, 1 Ion Trap)2 GC/MS (1 Quadrupole, 1 Ion Trap)3 GC with FID, ECD and NPD detectors3 GC with FID, ECD and NPD detectors1 GC with Head Space system and ECD detector1 GC with Head Space system and ECD detectorp yp y1 GC/MS with Purge & Trap extraction system (2 ??)1 GC/MS with Purge & Trap extraction system (2 ??)1 HPLC with UV PDAD and fluorimetric detector1 HPLC with UV PDAD and fluorimetric detector1 SPE i i ??1 SPE i i ??1 SPE automatic station ??1 SPE automatic station ??

1212

Operative UnitOperative Unit“O i Mi ll t t Di i ”“O i Mi ll t t Di i ”“Organic Micropollutants e Dioxin”“Organic Micropollutants e Dioxin”

Instrumentation of Dioxin Lab:Instrumentation of Dioxin Lab:

Soxhlet Extraction SystemSoxhlet Extraction SystemASE (A l t d S l t E t ti ) S st f ASE (A l t d S l t E t ti ) S st f ASE (Accelerated Solvent Extraction) System for ASE (Accelerated Solvent Extraction) System for solid solid Automated extraction and CleanAutomated extraction and Clean--up System for up System for Automated extraction and CleanAutomated extraction and Clean up System for up System for PCDD/F and PCBPCDD/F and PCBHRGC/HRMSHRGC/HRMSGC/MS Ion Trap DetectorGC/MS Ion Trap Detector

1313

Operative UnitOperative Unit“P ti l E i t l M t i ”“P ti l E i t l M t i ”“Particular Environmental Matrixes”“Particular Environmental Matrixes”

FOOD CONTACT MATERIALS

MATRIX ANALYZEDMATRIX ANALYZEDWASTE WATERMATRIX ANALYZEDMATRIX ANALYZEDW E

classificationdifferent matrixes

drinkable watertap water

surface atersurface waterground waterwaste waterAIR

Monitoring urban air Dry and umid deposition

1414Industrial Emission

p

Operative UnitOperative Unit“P ti l E i t l M t i ”“P ti l E i t l M t i ”

FOOD CONTACT MATERIALS

“Particular Environmental Matrixes”“Particular Environmental Matrixes”

FOOD CONTACT MATERIALS(PET, pot, cans, glass, ceramics, cooking tools)ICP/MS, F-AAS, GF-AAS, CV-AAS, Hg-AASWASTE

Metals with ICP-OESHydrocarbons with IR/GC/FID WATERPAH and PCB’s with GC/MS

pH Cyanide with spectrophotometry

WATERMetals with ICP/MS, F-AAS,GF-AAS, CV-AAS Hg-AAS

PARAMETERSPARAMETERSCV AAS, Hg AAS

SOIL AND SEDIMENTSMetals with ICP-OES BIOTA

Hydrocarbons with IR/GC/FIDPAH and PCB’s with GC/MS ion trap AIR FILTERS

Metals with ICP/MS

BIOTAMetals with ICP/MS, F-AAS,GF-AAS, CV-AAS, Hg-AAS

1515

CV-AAS

Operative UnitOperative Unit“P ti l E i t l M t i ”“P ti l E i t l M t i ”“Particular Environmental Matrixes”“Particular Environmental Matrixes”

Instrumentation used on water analysis:

ICP/OESICP/MS

GF-AAS (Cromium)HG-AAS (Arsenic)CV-AAS (Mercury)

1616

y

Operative UnitOperative Unit“S i l I t t ti “S i l I t t ti Ai ”Ai ”“Special Instrumentation “Special Instrumentation -- Air”Air”

INDUSTRIAL EMISSIONS URBAN QUALITY AIR

AIRAIRAIRAIRMATRIXMATRIXMATRIXMATRIX

RELEVANT INCIDENT EMISSIONS

1717

Operative UnitOperative Unit“S i l I t t ti “S i l I t t ti Ai ”Ai ”

PARAMETERS:PARAMETERS:F l f l P d P

“Special Instrumentation “Special Instrumentation -- Air”Air”

URBAN AIR

- Filters: gravimetric an. of particular matter: PM10 and PM2.5

- Filters: PAHs analysis with HPLC

- Passive sampling: GC analysis of BTEXcolourimetric analysis of NO2colourimetric analysis of O3

-Filters: gravimetric analysis of dust and particulate

INDUSTRIAL EMISSIONS

- Adsorbent solutions: NOx ,SO2 , HCl, HF analysis

- Adsorbent vials: BTEX and VOS analysis via GC

EMERGENCY C i t VOC l i b GC MS

1818

EMERGENCY - Canister: VOC analysis by GC-MS with micro-scale Purge&Trap

Environmental Monitorin Pro ramsEnvironmental Monitorin Pro ramsEnvironmental Monitoring ProgramsEnvironmental Monitoring Programs

SURFACE WATERS Re ional Water Quality SURFACE WATERS → Regional Water Quality Protection Plan

TRANSITIONAL WATERS → Venice Lagoon Catchment basinbasin

GROUND WATERS → Groundwaters monitoringGROUND WATERS → Groundwaters monitoring

BATHING WATERS + Sands’ characterization for coastalW E finterventions + Eutrophic phenomena

1919

MARINE-COASTAL WATERS + Sediments + Biota

Environmental Monitorin Pro ramsEnvironmental Monitorin Pro ramsEnvironmental Monitoring ProgramsEnvironmental Monitoring Programs

URBAN AIR → Particolate Matter URBAN AIR → Particolate Matter (PM10 and PM2.5 monitoring)PAHs analysis in PM + Traffic monitoringAHs analysis in M raffic monitoringIndustrial monitoring programs

SOIL AND SEDIMENTS → Control and characterization of contaminated land and soils

2020

N t l f l b tN t l f l b tNow we present an example of laboratoryNow we present an example of laboratoryactivities in application of the activities in application of the WFDWFDpppp

((WWater ater FFramework ramework DDirective 2000/60EC) irective 2000/60EC) f E P li d C il f E P li d C il of European Parliament and Council of European Parliament and Council establishing a framework for the establishing a framework for the establishing a framework for the establishing a framework for the

community action on field of water policycommunity action on field of water policy

2121

WFD Directive 2000/60/CEWFD Directive 2000/60/CE→ identification of European waters and their characteristic bodies on

individual River Basin Districtindividual River Basin District

→ adoption of management programs and plans specific for eachbody of water → depending from the statusy f w p g f m

AIMS: •Prevent and reduce pollutionp•Promote sustainable water use•Protect aquatic enviroment•Improve the status of aquatic ecosystems•Management of adverse effects (from droughts to floods)

To do this: management and protection measures that preventd i i d h li f f deterioration and enhance or restore quality of surface water

ACHIEVE GOOD ECOLOGICAL STATUS → GOOD CHEMICAL STATUS

2222List of priority substances

WFD requirements for analytical methodsWFD requirements for analytical methods

Annex V, paragraph 1.3.6• the provision of chemical data by Member

States shall be ensured by analytical methods• that conform to relevant international or

i l d d h i l national standards or to other national or international standards

lt ti l b l ti l m th ds th t • or alternatively by analytical methods that are not standardized but provide data of equivalent or better scientific quality and comparability or better scientific quality and comparability than standard analytical methods

2323

Requirements from QA/QC COM decisionRequirements from QA/QC COM decision

Limit of quantification (LOQ) equal or below 30% of the relevant E i l Q li S d d (EQS)

Requirements from QA/QC COM decisionRequirements from QA/QC COM decision

Environmental Quality Standards (EQS)

LOQ versus Lower Limit of Application (LLOA)

LOQ = lab specific performance value LOQ lab specific performance value

LLOA = method specific performance value

Relative Target Uncertainty of 50% measured at the level of the l t EQSrelevant EQS

Validation according to EN ISO/IEC 17025

Results have to be referred to whole water

Analysis of whole water samplesy p

Separate analysis of solid particulate matter (SPM) and the liquid phase

SPM or the filtered water sample may be used as substitute for

2424

SPM or the filtered water sample may be used as substitute for the whole sample

Pesticides Pesticides -- EQS (Proposal EQS (Proposal COM(2006) 397 final)COM(2006) 397 final) and normalized analytical and normalized analytical methodsmethods

Priority Substance

Proposals for EQS for PS and certain other

pollutants of the WFD Standard LOQ µg/Lp[µg/L]

AA-EQS for

inland surface

MAC-EQS for inland surface waterswaters waters

Alachlor 0,3 0,7 EN ISO 10695: 2000 0,04Atrazine 0,6 2 EN ISO 10695: 2000 0,015Chlorfenvinphos 0,1 0,3 EN ISO 10695: 2000 0,01Chlorpyrifos (-ethyl -methyl) 0 03 0 1 EN ISO 10695: 2000 0 01Chlorpyrifos ( ethyl, methyl) 0,03 0,1 EN ISO 10695: 2000 0,01Diuron 0,2 1,8 EN ISO 11369 0,1Endosulfan 0,005 0,01 EN ISO 6468 0,001-0,01Hexachlorobenzene 0,01 0,05 EN ISO 6468 0,001-0,01Hexachlorocyclohexane 0,02 0,04 EN ISO 6468 0,001-0,01Isoproturon 0,3 1 EN ISO 11369 0,1Pentachlorobenzene 0,007 0,08 EN ISO 6468 0,001-0,01Simazine 1 1 EN ISO 10695: 2000 0,012Trifluralin 0,03 0,4 EN ISO 10695: 2000 0,05

DDT not EN ISO 6468 0 001 0 01DDT 0,025not

applicable EN ISO 6468 0,001-0,01

Aldrin

Σ 0.01 not applicable

EN ISO 6468 0,001-0,01Endrin EN ISO 6468 0,001-0,01IsodrinDieldrin EN ISO 6468 0 001 0 01

2525

Dieldrin EN ISO 6468 0,001-0,01

EN ISO 10695:2000Determination of selected organic nitrogen and phosphorus compounds -

Gas chromatography methodsLi id li id t ti ith di hl th lid h t ti Liquid-liquid extraction with dichloromethane or solid phase extraction (SPE) on reversed-phase cartridge C18 or other adsorbent. Elution with e.g. methanol or acetone. After concentration, the sample extracted is analysed by gas chromatography, using a nitrogen-phosphorus (NPD) and analysed by gas chromatography, using a nitrogen phosphorus (NPD) and

eventually confirmation with MS detector

EN ISO 6468:1997Determination of certain organochlorine insecticides, polychlorinated

biphenyls and chlorobenzenesLi id li id i h d f d i i f i Liquid-liquid extraction method for determination of certain

organochlorine insecticides, polychlorinated biphenyls (PCBs) and chlorobenzenes (except the mono and dichlorobenzenes) in drinking

water ground water surface waters and waste waters After water, ground water, surface waters and waste waters. After concentration, the sample extracted is analysed by gas

chromatography, using an electron-capture detector (ECD) and eventually confirmation with MS detector. The method is applicable to

l / f l

2626

samples containing up to 50 mg/L of suspended solids

Multi-residue methods with automated SPE t ti d l i b GC LC MS MSextraction and analysis by GC or LC-MS-MS

cost-selective sensitive accurate cost-efficient

ECD – specific, very sensitive, stable NPD – specific very sensitive less stableNPD specific, very sensitive, less stableMS detector – specific (SIM), less sensitive,

less stable (IS), qualitative info

2727

( ) q

Analytical Method 5060 APAT–IRSA CNR (2003)Analytical Method 5060 APAT–IRSA CNR (2003)

Th th d i li bl t l b f The method is applicable to a large number of HERBICIDES-PESTICIDES including:

Alachlor, Atrazine, Chlorfenvinphos, Chlorpyrifos, Endosulfan, Hexachlorobenzene, Hexachlorocyclohexane, Pentachlorobenzene, Simazine, Trifluralin, DDT (isomers

and metabolites), Aldrin, Endrin, Isodrin, Dieldrin, ), , , , ,Pendimethalin

LLOA/LOQ: 0,01 – 0,05 µg/L depending from the substance and from concentration factor (CF)

→ problems of a ROUTINE LAB different respect a RESEARCH LAB

2828

Analytical Method 5060 APAT–IRSA CNR (2003)

SAMPLEWater (500 2000 ml) added with 5 ml Methyl alcool

Analytical Method 5060 APAT–IRSA CNR (2003)

Water (500-2000 ml) added with 5 ml Methyl alcool

CARTRIDGEC18 (500mg/6ml) or Polymeric (divinylbenzene/ N-vinylpyrrolidone) (60mg/3 ml)C18 (500mg/6ml) or Polymeric (divinylbenzene/ N vinylpyrrolidone) (60mg/3 ml)

CARTRIDGE ACTIVATIONEthyl Acetate 5 ml + Methyl alcool 5 ml + Water 10 ml

EXTRACTIONThe sample is collected on the SPE actived column

The cartridge is eluted with 10 ml of Ethyl Acetate The cartridge is eluted with 10 ml of Ethyl Acetate Residual water is removed drying the cartridge under N2 flux or putting in series a

cartridge containing anhydrous Na2SO4 or diatomaceous earth.The eluate is drying at T≤40°C

Eluate is dissolved with 500 µL of a solution of internal standard Eluate is dissolved with 500 µL of a solution of internal standard (concentration factor 1000)

ANALYTICAL DETERMINATION

2929

GC-MS or GC-ECD/GC-NPDNo further confirmations of the results need using GC-MS

A collaborative study has been conducted in order to verify the performance characteristics and validate the multiresidue method APAT- CNR IRSA 5060 method APAT CNR IRSA 5060. The study has been conducted on the following substances: Alachlor, Atrazine, Chlorpyrifos, Lindane, Linuron, Metalaxyl, Metolachlor Molinate Oxadiazon Oxadixyl Pendimenthalin Metolachlor, Molinate, Oxadiazon, Oxadixyl, Pendimenthalin, Prometryne, Propyzamide, Simazine, Terbumeton, Terbuthylazine, Desethylatrazine and Desethylterbutylazine

Number of laboratories: 10Number of repetitions: 10 on two concentration levels Number of repetitions: 10 on two concentration levels

(0,1 ug/l e 0,5 ug/l)Statistical data analysis was done on the basis of UNI EN ISO 5725

averagesrecovery percentage

bili

y

3030

repeatability reproducibility

The multiresidue SPE method described is applicable with LC-MS-MS analytical determinationy

too (Isoproturon, Diuron, and other HPLC specific pesticides)

Acidic pesticides (phenoxyacids, bentazone, etc.) are extracted from acidified water (pH=2) and analyzed extracted from acidified water (pH=2) and analyzed

by LC-MS-MS

LLOA/LOQ: 0,02 – 0,1 µg/L (depending of the substance) i h i f (CF) 1000 with concentration factor (CF) 1000,

below 0,02 with higher CF

3131

MULTIRESIDUE METHOD SCHEME

N t l ti id

MULTIRESIDUE METHOD SCHEME

idi i idNeutral pesticides Acidic pesticides

Sample Sample

SPE extractionSPE extractionSPE extraction

GC/MS or selective

detectors (ECD LC-MS-MSor HPLC-PDA LC-MS-MS

GC/MS

3232

detectors (ECD or NPD and

confirm by MS)

or GC/MSafter derivatization

SPECIFIC METHOD SCHEMESPECIFIC METHOD SCHEME

i.e.: GLYFOSATE, AMPA herbicidei.e. GLYFOSATE, AMPA herbicide

SAMPLE

DERIVATIZATION (FMOC)( )

SPE EXTRACTIONSPE EXTRACTION

LC-MS-MS or HPLC fluorimetric

3333

detector

STANDARDIZED METHODS

ADVANTAGES → - already validated with interlabs and intralabs tests IF USED - accept by international and EU institutions

- adopted by each institution in the MS - compulsory and total accepted statistical data

DISADVANTAGES ti i ( lid ti t k ti )DISADVANTAGES → - time consuming (validation takes time)IF NOT USED - interlabs validation (collaborative trials)

- lack of RM and CRM (reference materials)

3434

Analytical Method 5080 APAT–IRSA CNR (2003) yPOLYCYCLIC AROMATIC HYDROCARBONS

Sample (1000 ml)Sample (1000 ml)EXTRACTION

LLE SPELLE SPE60 ml dichloromethane in C18 (500mg/6ml) activated with 10 ml

a separatory funnel three times. Methyl alcool and eluted withCombine the three solvent extracts Methylene ChlorideCombine the three solvent extracts Methylene Chloride

CONCENTRATION T 40°C d i l f d i at T≤40°C and using a gentle stream of dry nitrogen

extracts are dissolved with 500 µL of a solution of internal standard(concentration factor 2000)

ANALYTICAL DETERMINATIONGC-MS or HPLC Fluorimetric detector

3535

No further confirmations of the results need using GC-MS

Limits of quantitation

COMPOUNDCOMPOUND LOQ GC/MS (ug/L)LOQ GC/MS (ug/L) LOQ HPLC/FL (ug/L)LOQ HPLC/FL (ug/L)

AnthraceneAnthracene 0.010.01 0.0050.005

FluorantheneFluoranthene 0.010.01 0.0050.005

PyrenePyrene 0.010.01 0.0050.005

Benzo(a)fluoranteneBenzo(a)fluorantene 0.010.01 0.0050.005

ChryseneChrysene 0.010.01 0.0050.005

Benzo(b)fluorantheneBenzo(b)fluoranthene 0.010.01 0.0050.005

Benzo(k)fluorantheneBenzo(k)fluoranthene 0 010 01 0 0050 005Benzo(k)fluorantheneBenzo(k)fluoranthene 0.010.01 0.0050.005

Benzo(a)pyreneBenzo(a)pyrene 0.010.01 0.0050.005

Dibenzo(a,hanthraceneDibenzo(a,hanthracene 0.010.01 0.0050.005

Benzo(g,h,i)peryleneBenzo(g,h,i)perylene 0.010.01 0.0050.005

3636

Indeno(1,2,3Indeno(1,2,3--cd)pyrenecd)pyrene 0.010.01 0.0050.005

Analytical Methods 5140 and 5150 APAT–IRSA CNR y(2003) VOLATILE ORGANIC COMPOUNDS

These methods describe two closed-system processes for the analysis of volatile organic compounds in waterof volatile organic compounds in water

Purge and Trap system IRSA-CNR method

Head-Space system Istisan 2000/14 method

Analytical determinationAnalytical determinationGC-MS or GC-FID GC-ECD

N f th fi ti f th lt d i GC MS

3737

No further confirmations of the results need using GC-MS

P&T GC MSP&T → GC → MS

• Volatile and semivolatile compounds (BTEX, chlorobenzene, CVM)• Notiziario IRSA n.1 (2005) ed on-line 16-21• LOQ (0.1 – 0.7 ug/L)• reproducibility of the system• no pre-treatment of the sample

3838

no pre treatment of the sample

EN ISO 10301:1997VOXs on water

Determination of highly volatile halogenated hydrocarbons in water by a t ti h d th d d h t hi d t ti b ECDstatic headspace method and gaschromatographic detection by ECD

EN ISO 17294-2:2005Metals on water

Determination of 62 elements in water by inductively coupledy y pmass spectrometry (ICP-MS)

3939

LOQPURGE & TRAP and GC-MS

COMPOUNDCOMPOUND LOQ (ug/L) METHODLOQ (ug/L) METHOD LOQ (ug/L) LABLOQ (ug/L) LABCOMPOUNDCOMPOUND LOQ (ug/L) METHODLOQ (ug/L) METHOD LOQ (ug/L) LABLOQ (ug/L) LAB

BENZENEBENZENE 0,030,03 0,30,3

BROMODICHLOROMETANEBROMODICHLOROMETANE 0,030,03 0,10,1

TRIBROMOMETHANETRIBROMOMETHANE 0,020,02 0,30,3RIBROMOME HANERIBROMOME HANE 0,00,0 0,30,3

CARBON TETRACHLORIDECARBON TETRACHLORIDE 0,010,01 0,10,1

CHLORODIBROMOMETHANECHLORODIBROMOMETHANE 0,030,03 0,10,1

TRICHLOROMETHANETRICHLOROMETHANE 0,020,02 0,10,1

1,11,1--DICHLOROETHANEDICHLOROETHANE 0,010,01 0,50,5

1,21,2--DICHLOROETHANEDICHLOROETHANE 0,010,01 0,50,5

1,11,1--DICHLOROETHENEDICHLOROETHENE 0,010,01 0,50,5

1,21,2--DICHLOROETHENE cisDICHLOROETHENE cis 0,010,01 0,50,5

1,21,2--DICHLOROETHENE transDICHLOROETHENE trans 0,010,01 0,50,5

1,21,2--DICHLOROPROPANEDICHLOROPROPANE 0,010,01 0,50,5

ETHYLBENZENEETHYLBENZENE 0,020,02 0,50,5

STYRENESTYRENE 0,020,02 0,50,5

1,1,2,21,1,2,2--TETRACHLOROETHANETETRACHLOROETHANE 0,020,02 0,50,5

4040

TETRACHLOROETHENETETRACHLOROETHENE 0,010,01 0,10,1

… LOQPURGE & TRAP and GC-MS

COMPOUNDCOMPOUND LOQ (ug/L) LOQ (ug/L) METHODMETHOD

LOQ (ug/L) LOQ (ug/L) LABLAB

TOLUENETOLUENE 0 030 03 0 30 3TOLUENETOLUENE 0,030,03 0,30,3

1,2,41,2,4--TRICHLOROBENZENETRICHLOROBENZENE 0,030,03 0,10,1

1,1,11,1,1--TRICHLOROETHANETRICHLOROETHANE 0,020,02 0,10,1

1 2 31 2 3--TRICHLOROPROPANETRICHLOROPROPANE 0 010 01 0 50 51,2,31,2,3 TRICHLOROPROPANETRICHLOROPROPANE 0,010,01 0,50,5

VINYL CHLORIDEVINYL CHLORIDE 0,030,03 0,50,5

oo--XILENEXILENE 0,020,02 0,30,3

m,pm,p--XILENEXILENE 0,010,01 0,30,3m,pm,p X LENEX LENE ,, ,,

NAPHTALENENAPHTALENE 0,010,01 0,50,5

WORK ON PROGRESS TO ARRIVE AT METHOD’S LOQ

→ ADEGUATE INSTRUMENTATION& TECHNOLOGIES

4141

Analytical Method ISO 17294-2:2005yMETALS

This m th d h s b n ppli d t th d t min ti n f: Al As B Cd C C H This method has been applied to the determination of: Al, As, B, Cd, Cr, Cu, Hg, Mn, Ni, Pb, Sb, Se and Zn.

The sample is filtered thruogh a 0.45µm filter and the liquid phase is acidified ith it i idwith nitric acid

All these metals are determined with the ICP-MS technique

ICP-MS methodICP MS methodThe content of the indicated metals in water samples is determined with Mass Spectroscopy with Plasma inductively coupled (ICP-MS). The sample, in case diluted, is sucked up with a peristaltic pump, nebulized and ionized with the plasma (the most of elements is ionized at the 90% level). The formed ionic p ( )stream is filtered with a quadrupole, which selects the mass to be analyzed, and measured by the detector. The use of the internal standard is necessary to compensate drift effects of the tool and effects of suppression of the signal related to the matrix. F i d i l d d h RhFor waters is used as internal standard the Rh.

4242

LOQLOQ

Compoud LOQ

( /l) mp u (µg/l) Al 1.0 As 1.0 B 5 0 B 5.0 Cd 0.2 Cr 1.0 C 1 0 Cu 1.0 Hg 0.2 Mn 0.5 Ni 1 0 Ni 1.0 Pb 0.5 Sb 1.0 S 5 0 Se 5.0 V 1.0 Zn 1.0

4343

CHLOROANILINE AND CHLOROANILINE AND CHLORONITROAROMATIC COMPOUNDS

SAMPLEWater (200 ml) pH=9 10ml Methyl alcool

CARTRIDGECARTRIDGEPolymeric (divinylbenzene/ N-vinylpyrrolidone) (200mg/6 ml) → OASIS HLB

CARTRIDGE ACTIVATIONEthyl Acetate 5 ml, Methyl alcool 5ml and Water pH=9 Methyl alcool 5% 5ml

EXTRACTIONThe sample is collected on the SPE columnThe sample is collected on the SPE column

The cartridge is eluted with 6 ml of Ethyl Acetate Residual water is removed with a cartridge containing anhydrous Na2SO4

The eluate is dryed using a gentle stream of dry nitrogenExt t di l d ith 500 L f l ti n f int n l t nd dExtracts are dissolved with 500 µL of a solution of internal standard

(Concentration Factor = 400)

ANALYTICAL DETERMINATION

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GC-MS

CHLOROANILINE AND CHLORONITROAROMATIC COMPOUNDS

COMPOUND LOQ (ug/L)

- internal method → COMPLETE VALIDATION !!!!!

ANILINE 0.05NITROBENZENE 0.05

2-CHLOROANILINE 0.053-CHLOROANILINE 0.054-CHLOROANILINE 0.05

2-CHLORO-4-AMMINOTOLUENE 0 052 CHLORO 4 AMMINOTOLUENE 0.052-CHLORONITROBENZENE 0.053-CHLORONITROBENZENE 0.054 CHLORONITROBENZENE 0 054-CHLORONITROBENZENE 0.05

3-CHLORO-4-AMMINOTOLUENE 0.054-CHLORO-2-NITROTOLUENE 0.1

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3,4-DICHLOROANILINE 0.051-CHLORO-2,4-DINITROBENZENE 0.5

33 PRIORITY SUBSTANCES (8 priority, 11 priority&hazardous, 14 priority under review):ALACHLORBENZENECHLORFENVINPHOSCHLORFENVINPHOS1,2-DICHLOROETHANEDICHLOROMETHANEFLUORANTHENENICKEL & COMPOUNDSTRICHLOROMETHANEBROMINATED DIPHENYLETHERSCADMIUM & COMPOUNDSC10-13-CHLOROALKANESHEXACHLOROBENZENEHEXACHLOROBENZENEHEXACHLOROBUTADIENEHEXACHLOROCYCLOHEXANE (γ-isomer, lindane)MERCURY & COMPOUNDSNONYLPHENOLSPENTACHLOROBENZENE

not yet developed

PENTACHLOROBENZENEPAHTRIBUTYLTIN COMPOUNDSANTHRACENEATRAZINE

P FCHLORPYRIFOSDEHP Di(2-ethylhexyl)phthalateDIURONENDOSULFAN (alpha & beta)ISOPROTURONLEAD & COMPOUNDSNAPHTALENEOCTYLPHENOLPENTACHLOROPHENOLSIMAZINE

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SIMAZINETRICHLOROBENZENES (1,2,3-trichlorobenzene)TRIFLURALIN

I.S.PER.I.A. Project

Identification od Dangerous Substances in the Hydric Environment

implementation of the Environmental Ministry Decree n.367/2003

combined approachpp

Territorial analysis Monitoring and supported byTerritorial analysisanalytical work

supported by

a) list of dangerous and priority substances in ) f g p yVeneto area

b) list of pressure sources for identified substances

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c) location of the pressure sources

End of presentation …End of presentation …

… thank you!… thank you!

4848Contact/questions: rlava@arpa.veneto.it