Development of Improved Detection Systems for CLUSTER...

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CLUSTER CLUSTER MEETING MEETING CRACOVIA CRACOVIA 2 nd nd -4 th th OCTOBER OCTOBER Manuel Valiente Univer sitat Autònoma de Barc elona Unitat Químic a Analític a. Depar tament de Químic a. Edific i-C Campus. Bellaterr a. 08193. Telf. 003493581 2903. Fax. 0034 93581198 5. [email protected] Development of Improved Detection Systems for Development of Improved Detection Systems for Monitoring of Toxic Heavy Metals in Monitoring of Toxic Heavy Metals in Groundwaters and Soils. Groundwaters and Soils. DIMDESMOTOM DIMDESMOTOM EVK1 EVK1-CT CT-1999 1999-00002 00002 01/02/2000 to 31/01/2003 01/02/2000 to 31/01/2003 CLUSTER CLUSTER MEETING MEETING CRACOVIA CRACOVIA 2 nd nd -4 th th OCTOBER OCTOBER PROBLEM Abandoned landfill and Abandoned landfill and/ or uncontrolled dumping areas are the or uncontrolled dumping areas are the most important sources of soil contamination in Europe and most important sources of soil contamination in Europe and others developed countries. others developed countries. Due to human activities soil properties can be modified Due to human activities soil properties can be modified producing a risk for human health and environment. producing a risk for human health and environment. Soil characterization is the first step in the knowledge of the Soil characterization is the first step in the knowledge of the problem problem Cleaning up the site till minimiz e the risk is the final objec ti Cleaning up the site till minimiz e the risk is the final objec tive ve using a cos t effec tiv e tec hnology . using a cos t effec tiv e tec hnology .

Transcript of Development of Improved Detection Systems for CLUSTER...

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Manuel ValienteUniver sitat Autònoma de BarcelonaUnitat Química Analítica. Depar tament de Química.Edific i-C Campus. Bellaterr a. 08193.Telf. 0034935812903. Fax. [email protected]

Development of Improved Detection Systems for Development of Improved Detection Systems for Monitoring of Toxic Heavy Metals in Monitoring of Toxic Heavy Metals in

Groundwaters and Soils. Groundwaters and Soils.

DIMDESMOTOMDIMDESMOTOM

EVK1EVK1--CTCT--19991999--0000200002

01/02/2000 to 31/01/200301/02/2000 to 31/01/2003

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PROBLEM

Abandoned landfill andAbandoned landfill and//or uncontrolled dumping areas are the or uncontrolled dumping areas are the most important sources of soil contamination in Europe and most important sources of soil contamination in Europe and others developed countries.others developed countries.

Due to human activ ities soil properties can be modified Due to human activ ities soil properties can be modified producing a risk for human health and environment.producing a risk for human health and environment.

Soil characterization is the firs t s tep in the knowledge of the Soil characterization is the firs t s tep in the knowledge of the problemproblem

Cleaning up the site till minimize the risk is the final objectiCleaning up the site till minimize the risk is the final objective ve using a cost effective technology.using a cost effective technology.

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Development and validation of sensing devices for real time measurements of Tox ic Heavy Metals

present in contaminated soils and surface waters

! to identify trends of pollution

! to control the efficiency of remediation activities

AIM OF THE PROJECT

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Cranfield University (UK)Dr. Ibtisam Tothill

University College Cork (IRL)Dr. Damien Arrigan

TPA, Técnicas de Protección Ambiental, S.A. (E)Mrs. Maria José Kaifer

IRH Génie de l’Environnement (FR)Dr. Georges Pottecher

Project CoordinatorUniversitat Autònoma de Barcelona (E)Prof. Manuel Valiente

THE CONSORTIUM

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What we want to produce?

A validated set of metal sensorsA portable measuring systemA procedure to determine trends of polutant heavy metalsA software package to assess the management of the problem

Sensorsdevelopment GIS technology

validation

Instrumentationdevelopment

Control of remediation processes

Identification ofpollution trends

RISK ASSESSMENT

Analyicaltechniques for

THM

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MONITORING NEEDS

Needs for contaminated sites monitoring:Needs for contaminated sites monitoring:Typical requirements:Typical requirements:

Not a high accuracy required (screening methods)Not a high accuracy required (screening methods)Concentration range (around ppm)Concentration range (around ppm)Simplicity of the analysis (not expertise technicien)Simplicity of the analysis (not expertise technicien)Short time to get results (around 1 hour)Short time to get results (around 1 hour)HM to include in the project (Cu, Zn, Pb, As, Cr)HM to include in the project (Cu, Zn, Pb, As, Cr)Cost lower or similar to a conventional labCost lower or similar to a conventional lab

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NEEDED INFORMATION

General information

• Historical data of the site

• Industrial information, past and future uses, land uses evolution etc.

• Graphical information: Geographic, Topographic, geological, hydrogeological maps…aerial photographs.

Field data (site specific data)• Soil/gw characteristics • Physical properties: Structure, litology, grain size, permeability, depth etc.• Chemical properties: pH, soil moisture, bulk density, organic mater, etc.• Contamination data: Contaminants of concern, size and contamination level etc.

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PROJECT OBJECTIVES

Development and validation of sensing dev ices for Development and validation of sensing dev ices for real time measurements of tox ic heavy metals present in real time measurements of tox ic heavy metals present in contaminated soils and surface waters. Produce sensors contaminated soils and surface waters. Produce sensors for field trails.for field trails.-- BiosensorsBiosensors (Enzymes, Available antibodies)(Enzymes, Available antibodies)-- Chemical Sensors (StrippingChemical Sensors (Stripping voltammetricvoltammetric analysis)analysis)

Chemically modified surfaces using carbon based Chemically modified surfaces using carbon based electrodes.electrodes.

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BIOSENSOR DEVELOPMENTBIOSENSOR DEVELOPMENT

Optimisation of Urease Biosensors

- Rodinised carbon electrod ( 0.3 V).Rodinised carbon electrod ( 0.3 V).-- NADH concentration (0.3 mM).NADH concentration (0.3 mM).-- Urea concentration and electrode fouling.Urea concentration and electrode fouling.-- UreaseUrease andand GLDH concentration.GLDH concentration.-- Inhibition time (10Inhibition time (10--15 min).15 min).-- Optimum buffer (50mMOptimum buffer (50mM TrisTris--HClHCl, pH 8.0)., pH 8.0).

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Measurements of cadmium (II) in leachate solutions from extracted real soil.

Real Sample AAS (µgl-1) aCCSCP (µgl-1)

No.1 49.72 48.95b

No. 2 28.6 27.2b

No.3 29.7 25.4b

aex periment carried out with 10 mg/l mercury, 40mM Cysteine, 0.025M Tris-HCl/0.1M K Cl in situ plated, 120s, 1 µA.bmean of 4 replicate measurements.

APPLICATION TO REAL SOIL SAMPLES

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BIOSENSOR DEVELOPMENT

Enzyme and amino acids based sensors has been Enzyme and amino acids based sensors has been developeddevelopedInmunosensors, peptide and protein sensors are in Inmunosensors, peptide and protein sensors are in progressprogress

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NMRC Objectives:

Electrodes for heavy metal detection, compatible with the ‘BCR’ sequential extraction media

Bare (un-modified) electrodes and surface modified electrodes.

Electronic instrument for implementation of electroanaly ticalmeasurements (s tripping analysis, pulse voltammetry , etc.)

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MICROFABRICATED ELECTRODE ARRAYS

Test of microelectrodes : Cyclicvoltammetry of ferrocyanide (1mM) in acetic acid (0.11M)

Packaged microelectrode array dev ices

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ANALYSIS OF REAL EXTRACTS

-2.00E-06

-1.00E-06

0.00E+00

1.00E-06

2.00E-06

3.00E-06

4.00E-06

-0.7 -0.5 -0.3 -0.1 0.1 0.3 0.5 0.7 0.9 1.1

Potentia l V (vs Ag/ AgCl)

Curr

ent A

a

b

c

Copper peak

Lead peak

e.g. Cant22 sample extract F1

Dilution to achieve satisfactory voltammogram;a: no dilution; b: 1/10 dilution; C: 1/20 dilution

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ANALYSIS OF REAL SAMPLES

v Name of the

Sample Fraction Conc. Of

Copper S.D. Lead S.D.

Salsigne vil3* F1 410 (ppm) 122 (ppm) no no MadridM3* F1 1019 (ppb) 101 (ppb) no no MadridM4* F1 125 (ppb) 13 (ppb) no no Cant 22* F1 956 (ppb) 410 (ppb) 2118 (ppb) 1436 (ppb) Villa 22* F1 36 (ppb) 10 (ppb) no no Cant 20* F1 1453 (ppb) 147 (ppb) 2613 (ppb) 1286 (ppb) Villa 20* F1 91.6 (ppb) 29.5 (ppb) no no Asturias 29.7* F3 107.4(ppb) 34.33(ppb) no no Villa21* F1 43.15(ppb) Ext. 6A° F1 Ext. 7B° F1 99.77(ppb) no no Ext. 13A° F1

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Prevention of surfactant fouling of sensor surface:

-1.00E-06

0.00E+00

1.00E-06

2.00E-06

3.00E-06

4.00E-06

5.00E-06

6.00E-06

7.00E-06

8.00E-06

0 0.1 0.2 0.3 0.4 0.5 0.6E / V (vs Ag /AgCl)

Cur

rent

/ A

100µΜ80µΜ60µΜ40µΜ20µΜ10µΜ5µΜ3µΜ1µΜ0µΜ

C alibr ation curv e

R2 = 0.9994

0.E+00

1.E-06

2.E-06

3.E-06

4.E-06

5.E-06

6.E-06

7.E-06

8.E-06

0 50 100 150Concentr ation (µM)

Curre

nt /

A

Linear Sweep Anodic Stripping Voltammetry of Copper in sulfuric acid (0.1M) at a MES-modified electrode in presence of 100ppm of Tween 20, n=100mV/s, deposition time=15s, E(dep) = 0V. On the calibration curve, the light blue dots represent the peak current of Copper at a bare electrode in presence of 100ppm of Tween 20.

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Heavy Metal Analyser HEMA 2002.

Parameter window for pulse mode

Measurement screen (1ppm Cu) Data processing screen (1ppm Cu)

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Operationally definedOperationally defined depending the procedures with reagents ordepending the procedures with reagents orextractantsextractants used for the fractionationused for the fractionation

WHY SPECIATION?

Ideal methodIdeal method in vivo, inin vivo, in--situsitu, non invasive,, non invasive,non destructive, let monitoringnon destructive, let monitoring

AVAILABLE CONTENTAVAILABLE CONTENTTOXICITYTOXICITYTOTAL CONTENTTOTAL CONTENT

SpeciesQuantity

Term widely used, but there are many meanings of the word that lead to discrepancies. Used to define

Quantities or classes of species, forms or phases presentsIdentification or quantification process of species, forms or phases presents

IUPAC definitionIUPAC definition process that lead to the identification and determination of process that lead to the identification and determination of the different chemical and physical forms of an element in a samthe different chemical and physical forms of an element in a sampleple

Sequential extraction procedures

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1st Exchangeable + carbonates fraction0.11 M Acetic acid0.11 M Acetic acid

2nd Bound to Fe and Mn oxides fraction0.1 M0.1 M HydroxylammoniumHydroxylammonium chloride (pH=2)chloride (pH=2)

oror0.5 M0.5 M HydroxylammoniumHydroxylammonium chloride (pH<1.5)chloride (pH<1.5)

BCR recommended protocol for sequential extractio

3rd Bound to organic matter fraction

4th Residual fraction Not included in BCR protocolNot included in BCR protocol

8.8 M Hydrogen peroxide8.8 M Hydrogen peroxide++

1.0 M ammonium acetate (pH=2)1.0 M ammonium acetate (pH=2)

AquaAqua regiaregia extractable or Total extractionextractable or Total extraction

Soil heterogeneitySoil heterogeneity SESSES Homogeneous informationHomogeneous information

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SES OVER REAL SAMPLES

0% 2 0% 4 0% 60 % 80 % 100 %

Astu rias Ind ustr ia

Ast urias Min a

Salsigne (CD)

Salsigne ( Villa)

CRM 601 In d

Cd

0% 20% 40% 60% 80% 100%

Astu rias Ind ustr ia

Ast urias Min a

Salsigne (CD)

Salsigne ( Villa)

CRM 601 In d

Cr

0% 20% 40% 60 % 80% 100 %

Astur ia s Indus tria

Astur ias Mina

Sa ls ig ne ( CD)

Salsign e (Villa)

CRM 6 01 Ind

Cu

0% 20% 40% 60% 80% 100%

Astu rias Ind ustr ia

Ast urias Min a

Salsigne (CD)

Salsigne ( Villa)

CRM 601 In d

Pb

0% 20% 40% 60% 80% 100%

As tur ia s Indus tria

Astur ia s Mina

Salsign e (CD)

Salsigne (Villa )

CRM 60 1 Ind

Ni

0% 2 0% 4 0% 60 % 80 % 100 %

Astu rias Ind ustr ia

Ast urias Min a

Salsigne (CD)

Salsigne ( Villa)

CRM 601 In d

Zn

F1

F2 F3 F4

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MODELLING OBJECTIVES

Support to investigations and remediationSupport to investigations and remediation

Understand the origin of water pollution" ranking of source areas contributions

Design the water collection network" minimum sand deposition" minimum flow of polluted water requiring treatment

Identify target areas for actions on soil" removal, coverage, reshaping" re-greening" chemical amendment for reduced availabili ty of pollution

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SALSIGNE SITE

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SALSIGNE SITE

Evaluation of edafological parameterspH, conductivity, organic matter, %CO3

Sequential extraction and speciation patternsCd, Cr, Cu, Ni, Pb, Zn and As

Pseudototal determination and water extracts

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COMBINED MODELLING MEASUREMENT

physical parameters maps

conversion tables

transfer model

Transferparameters

maps

Soil pollution map

Calibration

Measurements Simulations

Geografic informatic system (GIS)Geografic informatic system (GIS)

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MAIN TRANSFER MECHANISMS

Particulate As in ditches•suspended solids•sediments

Adsorption

PrecipitationDissolution

Dust falloutTransport losses

Watererosion

As in wastesore, tailings : AsFeS, CuAs, ..slag, furnace dust : As2O3stabilised waste : Ca-Asalteration minerals : scorodite

Dissolved As Vin runoff water

dissolution

oxidationcarbonatation

oxidationcarbonatation

Diffuse As on soilswaste particlessorbed As V (iron, clay)

Watererosion

precipitationadsorption

oxidation

EquilibriumKinetic control

In model

Salsigne site caseSalsigne site case

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Rainfall event

Runoff Infiltration

Sheet andrillerosion/deposition

Splash erosion Sorption equilibrium

Flow rates in ditches Particulate pollution in ditches

Dissolved pollution

Exfiltration

TRANSFER SIMULATION CAPABILITY

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APPLICATION OF GIS OVER SALSIGNE

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APPLICATION OF GIS OVER SALSIGNE

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APPLICATION OF GIS OVER SALSIGNE