Development of Improved Detection Systems for CLUSTER...
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
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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