conferÊncia: promises of fluorescent tracers techniques in contaminant hydrogeology

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XIX Congresso Brasileiro de Águas Subterrâneas 1 Promises of fluorescent tracers techniques in contaminant hydrogeology Dr Sc. Ph. Meus European Water Tracing Services Sprl XIX Congresso Brasileiro de Águas Subterrâneas Campinas, SP, Brasil, 20-23 Sept 2016

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XIX Congresso Brasileiro de Águas Subterrâneas1

Promises of fluorescent tracers techniques in contaminant hydrogeology

Dr Sc. Ph. MeusEuropean Water Tracing Services Sprl

XIX Congresso Brasileiro de Águas SubterrâneasCampinas, SP, Brasil, 20-23 Sept 2016

XIX Congresso Brasileiro de Águas Subterrâneas2

• A brief history of tracing techniques• Tracer tests as a tool for understanding groundwater• Diversity of applications, performance and limits• Why fluorescent tracers? Principles, tracers, material

and methods• Use of tracer tests for groundwater protection• Promises in contaminant hydrogeology• Questions?

Content

XIX Congresso Brasileiro de Águas Subterrâneas3

History Tracer tests Applications Principles Protection Contaminants Questions

History1845 Discovery of fluorescence by JFW. Herschel, then works of Stokes

1871 First synthesis of fluorescein by Adolf von Baeyer, under the name of resorcinphtalein

1877 1st quantitative tracer test with NaCl and fluorescein in the swallow holes of the Danube, reaching Aach spring (KNOP inKÄSS, 1992)

1904 Birth of a Belgian Committee for Fluorescein by E. Van den Broeck (VAN DEN BROECK, MARTEL, RAHIR, 1910)

1930-59 Works of A. Jablonski and first fluorescence spectrophotometers

1964 First use of active charcoals detectors (GAC) (LALLEMAND & PALOC, 1964)

1980’ First partionning tracer tests

1970-1990 Development of tracers, increasing number of reports dealing with tracer tests in karst areas (mainly linked to speleological research)

1988 Publication of the first guidelines for artificial tracer tests in hydrology (PARRIAUX et al., 1988)

1990’ Progress in fluorescence spectroscopy (LAKOWICZ, 1983), numerous theses on tracing experiments

1992 First monography on tracing techniques (KÄSS, 1992)

1992 First optical fibers spectrophotometers (BARCZEWSKI & MARSCHALL, 1992)

1996 First field fluorometers for continuous in-situ monitoring (BARCZEWSKI et al., 1996, MEUS et al, 1997, SCHNEGG & DOERFLIGER, 1997, GOUZE et al., 2000)

XIX Congresso Brasileiro de Águas Subterrâneas4

JFW Herschel discovers the fluorescence

History Tracer tests Applications Principles Protection Contaminants Questions

XIX Congresso Brasileiro de Águas Subterrâneas5

History Tracer tests Applications Principles Protection Contaminants Questions

History1845 Discovery of fluorescence by JFW. Herschel, then works of Stokes

1871 First synthesis of fluorescein by Adolf von Baeyer, under the name of resorcinphtalein

1877 1st quantitative tracer test with NaCl and fluorescein in the swallow holes of the Danube, reaching Aach spring (KNOP inKÄSS, 1992)

1904 Birth of a Belgian Committee for Fluorescein by E. Van den Broeck (VAN DEN BROECK, MARTEL, RAHIR, 1910)

1930-59 Works of A. Jablonski and first fluorescence spectrophotometers

1964 First use of active charcoals detectors (GAC) (LALLEMAND & PALOC, 1964)

1980’ First partionning tracer tests

1970-1990 Development of tracers, increasing number of reports dealing with tracer tests in karst areas (mainly linked to speleological research)

1988 Publication of the first guidelines for artificial tracer tests in hydrology (PARRIAUX et al., 1988)

1990’ Progress in fluorescence spectroscopy (LAKOWICZ, 1983), numerous theses on tracing experiments

1992 First monography on tracing techniques (KÄSS, 1992)

1992 First optical fibers spectrophotometers (BARCZEWSKI & MARSCHALL, 1992)

1996 First field fluorometers for continuous in-situ monitoring (BARCZEWSKI et al., 1996, MEUS et al, 1997, SCHNEGG & DOERFLIGER, 1997, GOUZE et al., 2000)

XIX Congresso Brasileiro de Águas Subterrâneas6

The speleologist EA Martel spreads the use of fluorescein

History Tracer tests Applications Principles Protection Contaminants Questions

XIX Congresso Brasileiro de Águas Subterrâneas7

Works of Stokes and Jablonski (1930)

History Tracer tests Applications Principles Protection Contaminants Questions

XIX Congresso Brasileiro de Águas Subterrâneas8

History Tracer tests Applications Principles Protection Contaminants Questions

History1845 Discovery of fluorescence by JFW. Herschel, then works of Stokes

1871 First synthesis of fluorescein by Adolf von Baeyer, under the name of resorcinphtalein

1877 1st quantitative tracer test with NaCl and fluorescein in the swallow holes of the Danube, reaching Aach spring (KNOP inKÄSS, 1992)

1904 Birth of a Belgian Committee for Fluorescein by E. Van den Broeck (VAN DEN BROECK, MARTEL, RAHIR, 1910)

1930-59 Works of A. Jablonski and first fluorescence spectrophotometers

1964 First use of active charcoals detectors (GAC) (LALLEMAND & PALOC, 1964)

1980’ First partionning tracer tests

1970-1990 Development of tracers, increasing number of reports dealing with tracer tests in karst areas (mainly linked to speleological research)

1988 Publication of the first guidelines for artificial tracer tests in hydrology (PARRIAUX et al., 1988)

1990’ Progress in fluorescence spectroscopy (LAKOWICZ, 1983), numerous theses on tracing experiments

1992 First monography on tracing techniques (KÄSS, 1992)

1992 First optical fibers spectrophotometers (BARCZEWSKI & MARSCHALL, 1992)

1996 First field fluorometers for continuous in-situ monitoring (BARCZEWSKI et al., 1996, MEUS et al, 1997, SCHNEGG & DOERFLIGER, 1997, GOUZE et al., 2000)

XIX Congresso Brasileiro de Águas Subterrâneas9

History Tracer tests Applications Principles Protection Contaminants Questions

Parallel progress in spectroscopy and tracing techniques in the late 80’s - early 90’s

XIX Congresso Brasileiro de Águas Subterrâneas10

History Tracer tests Applications Principles Protection Contaminants Questions

History1845 Discovery of fluorescence by JFW. Herschel, then works of Stokes

1871 First synthesis of fluorescein by Adolf von Baeyer, under the name of resorcinphtalein

1877 1st quantitative tracer test with NaCl and fluorescein in the swallow holes of the Danube, reaching Aach spring (KNOP inKÄSS, 1992)

1904 Birth of a Belgian Committee for Fluorescein by E. Van den Broeck (VAN DEN BROECK, MARTEL, RAHIR, 1910)

1930-59 Works of A. Jablonski and first fluorescence spectrophotometers

1964 First use of active charcoals detectors (GAC) (LALLEMAND & PALOC, 1964)

1980’ First partionning tracer tests

1970-1990 Development of tracers, increasing number of reports dealing with tracer tests in karst areas (mainly linked to speleological research)

1988 Publication of the first guidelines for artificial tracer tests in hydrology (PARRIAUX et al., 1988)

1990’ Progress in fluorescence spectroscopy (LAKOWICZ, 1983), numerous theses on tracing experiments

1992 First monography on tracing techniques (KÄSS, 1992)

1992 First optical fibers spectrophotometers (BARCZEWSKI & MARSCHALL, 1992)

1996 First field fluorometers for continuous in-situ monitoring (BARCZEWSKI et al., 1996, MEUS et al, 1997, SCHNEGG & DOERFLIGER, 1997, GOUZE et al., 2000)

XIX Congresso Brasileiro de Águas Subterrâneas11

« Tracer: a population (in a statistic meaning) of a detectable or quantifiable substance which is naturally or artificially associated with the population of a process, so that it can provide informations about this process »

After Guizerix et Margrita, 1990

Principle of tracer and tracing

History Tracer tests Applications Principles Protection Contaminants Questions

XIX Congresso Brasileiro de Águas Subterrâneas12

History Tracer tests Applications Principles Protection Contaminants Questions

Parabolic profile of velocities

Heterogeneity of flow

Changes of velocity between pores

Micro dispersion Macro dispersion

After Klinka, 2015

1. Molecular diffusion -> Fick’s law

Scale effect on dispersivity

Transport processes

2. Dispersion

3. Adsorption, decay, degradation…

XIX Congresso Brasileiro de Águas Subterrâneas13

History Tracer tests Applications Principles Protection Contaminants Questions

Porous aquifer/ continuous

Fissured aquifer / discontinuous

Karstic aquifer/ discontinuous and predominantly heterogeneous

Large scale regional

Macro scalelocal

Darcy

Grain scale

Micro/pore scale

Navier-Stokes

Particle/interface scale

After Klinka, 2015

« Tracing-systems » and not the whole aquifer!

The processes and laws differ according to the hydrogeological medium

XIX Congresso Brasileiro de Águas Subterrâneas14

Example of karst

After GombertConsider input-output of tracers!

History Tracer tests Applications Principles Protection Contaminants Questions

XIX Congresso Brasileiro de Águas Subterrâneas15

History Tracer tests Applications Principles Protection Contaminants Questions

After C. C. Smart, 2010

Classification of tracer tests according to the level of information

For each class consider the reliability!

XIX Congresso Brasileiro de Águas Subterrâneas16

Delineation of basins/water divides, water catchments Delineation of protection zones based on transit time Flow and transport parameters, calibration of models Residence/renewal time studies, simulation of spills Vulnerability and risk assessments Discharge, mixing studies of surface water Impacts of contaminated sites or wastes Remediation studies Surface water/groundwater interactions Geothermal applications Wells studies Mine/quarry dewatering Reservoir studies Leakages (pipes, liners, civil engineering works…) Landslides Transboundary studies

Applications of tracer tests

History Tracer tests Applications Principles Protection Contaminants Questions

XIX Congresso Brasileiro de Águas Subterrâneas17

History Tracer tests Applications Principles Protection Contaminants Questions

Type Advantages DisadvantagesFluorescents Very low LOD, direct

analysisInterferences, background

Salts(Cl, I, Li…) Simple analysis Background, toxicity

Spores, bacteria Specificity, possibility of staining

Size, poor sensitivity, complicate analysis

Microspheres Specificity, possibility of staining with fluorescent dyes, size, neutrality

Size, poor sensitivity, complicate analysis

Virus, phages Specificity, multi-tracing

Storage, complicate analysis, expensive

DNA particles Specificity, multi-tracing

Storage, complicate analysis, expensive

Tracers

XIX Congresso Brasileiro de Águas Subterrâneas18Naphthionate Amino-G acid

Fluorescent tracers

History Tracer tests Applications Principles Protection Contaminants Questions

XIX Congresso Brasileiro de Águas Subterrâneas19

Jablonski diagram

History Tracer tests Applications Principles Protection Contaminants Questions

Principle of fluorescence

XIX Congresso Brasileiro de Águas Subterrâneas20

Fixed wavelengths

Emission, excitation or synchronous scan spectra

Total spectra (EEM)

Information >>>

History Tracer tests Applications Principles Protection Contaminants Questions

XIX Congresso Brasileiro de Águas Subterrâneas21

Fluorescent tracer

Limit of detection (ppb)

Uranine 0.002

Sulforhodamine B 0.006

Eosine 0.01

Tinopal 0.01

Amino G acid 0.02

Pyranine 0.02

Naphthionate 0.05

Photine 1

Instrumental limits

History Tracer tests Applications Principles Protection Contaminants Questions

Performance of uranine

1 g of uranine instead of 50 kg of salt!

XIX Congresso Brasileiro de Águas Subterrâneas22

XANTHENIC TRACERS (UR, SUB, RH, EOS)

TRACEURS UV (NAP-AGA)

HYDROCARBURES

Excitation/Emission wavelength

Fluo

resc

ence

sig

nal

Incr

easi

ng li

mit

of

disc

rimin

atio

n

Solvent (water)

Water + NOM

Water + NOM + particles

Water + NOM + particles+ organic pollutants

« Someone else’s tracer »

« Searched tracer »

Excitation/Emission wavelength

Fluo

resc

ence

sig

nal

Incr

easi

ng li

mit

of

disc

rimin

atio

n

Solvent (water)

Water + NOM

Water + NOM + particles

Water + NOM + particles+ organic pollutants

« Someone else’s tracer »

« Searched tracer »

History Tracer tests Applications Principles Protection Contaminants Questions

Experimentally the background is a strong limitation

XIX Congresso Brasileiro de Águas Subterrâneas23

After C.C. Smart, 2005

History Tracer tests Applications Principles Protection Contaminants Questions

Up to 3 sampling techniques can be used complementarily

XIX Congresso Brasileiro de Águas Subterrâneas24

History Tracer tests Applications Principles Protection Contaminants Questions

Each method (sampling + analysis) is more or less sensible to errors

Blanks are critical!

XIX Congresso Brasileiro de Águas Subterrâneas25

History Tracer tests Applications Principles Protection Contaminants Questions

Positive results

Negative results

After Jozja et al., 2012

Scale of reliability

XIX Congresso Brasileiro de Águas Subterrâneas26

History Tracer tests Applications Principles Protection Contaminants Questions

XIX Congresso Brasileiro de Águas Subterrâneas27

History Tracer tests Applications Principles Protection Contaminants Questions

27

XIX Congresso Brasileiro de Águas Subterrâneas28

0.1

1

10

100

0 5 10 15 20 25 30 35 40 45

Minutes

Con

cent

ratio

n (m

g/l)

UranineRhodamineTinopal

LED 365 nm

LED 316 nm

History Tracer tests Applications Principles Protection Contaminants Questions

Separation of tracers for multi-tracing

Uranine + éosineNaphthionate + amino G acid

XIX Congresso Brasileiro de Águas Subterrâneas29

Model for borehole (50 mm, 100 m length, 70 m depth).

Field fluorometers

History Tracer tests Applications Principles Protection Contaminants Questions

Pros ConsCompacity Lower limit of detectionTime resolution Lower selectivityFreeze proof Clogging of optical windowOn line results and alarms Interferences not totally

solvedNo contamination nor storage problem

Electronic device

Turbidity correctionCorrection of interferences between tracersAdditional parameters : conductivityNo head limitAutonomy (several months, thousands of data)3 fluorescence channels + turbidity

LEDs (nm)

280 -> HC

316 -> NAP

365 -> AGA, TIN

470 -> UR, EOS

525 -> RWT, SUB, SUG

XIX Congresso Brasileiro de Águas Subterrâneas30

History Tracer tests Applications Principles Protection Contaminants Questions

Surface model

Warnings SMS

Borehole model

Application of telemetry

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History Tracer tests Applications Principles Protection Contaminants Questions

Our data are available quasi

instantaneously (a simple clic!)

XIX Congresso Brasileiro de Águas Subterrâneas32

History Tracer tests Applications Principles Protection Contaminants Questions

Peak of uranine 500 nm

Robust and practical method even if poorly selective and hampered by the background

Spectral identification needed!

Active charcoal method (GAC)

XIX Congresso Brasileiro de Águas Subterrâneas33

History Tracer tests Applications Principles Protection Contaminants Questions

Groundwater protection

Method applied almost everywhere

in the EU for drinking water

protection

Wallonia Luxembourg

France

XIX Congresso Brasileiro de Águas Subterrâneas34

Example: Luxembourg sandstone (lower Lias) aquifer

History Tracer tests Applications Principles Protection Contaminants Questions

Karstification

XIX Congresso Brasileiro de Águas Subterrâneas35

History Tracer tests Applications Principles Protection Contaminants Questions

93 waterworks studied 87 injections (mainly

fluorescent tracers) 176 relations checked 70 % for injections through

boreholes/wells Mean mass of fluorescent

tracers = 1246 g (total 106 kg)

Mean distance = 453 m (max. 1900 m)

XIX Congresso Brasileiro de Águas Subterrâneas36

History Tracer tests Applications Principles Protection Contaminants Questions

Transport processes along fissures

XIX Congresso Brasileiro de Águas Subterrâneas37

History Tracer tests Applications Principles Protection Contaminants Questions

After P. Pessoa & al., 2014

Rain controlled injector

XIX Congresso Brasileiro de Águas Subterrâneas38

History Tracer tests Applications Principles Protection Contaminants Questions

How tracer tests can help in contaminant hydrogeologyTypically, contaminated sites characterization and remediation are facing this :

High heterogeneity (aquifer usually not « porous equivalent ») Uncertainties on the source itself and its infiltration Insufficient knowledge of the real flow pattern Complex behaviour of contaminants Models insufficiently calibrated Poor evaluation of the risk and its evolution based on concentrations (need

for fluxes and discharges)

Properly designed tracer tests may help in solving these questions!

But such tracer tests may be longer, more sophisticated and more expensive than classical ones…

XIX Congresso Brasileiro de Águas Subterrâneas39

After N. Kresic, Amec Foster Wheeler

History Tracer tests Applications Principles Protection Contaminants Questions

Heterogeneity of subsurface

XIX Congresso Brasileiro de Águas Subterrâneas40

Heterogeneity of source penetration at local scale

After N. Kresic, Amec Foster Wheeler

History Tracer tests Applications Principles Protection Contaminants Questions

XIX Congresso Brasileiro de Águas Subterrâneas41

History Tracer tests Applications Principles Protection Contaminants Questions

Complex processes

Involving more than 3 phases

Retardation

Immobile water effects

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History Tracer tests Applications Principles Protection Contaminants Questions

The model must reflect the reality

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History Tracer tests Applications Principles Protection Contaminants Questions

Control panels based on mass flux-discharge assessment rather than concentrations

After Annable, 2016

After Brouyère, 2015

Needs a more precise assessment of filtration velocities (Darcy velocities) and their variations

Allows for a better site management

XIX Congresso Brasileiro de Águas Subterrâneas44

History Tracer tests Applications Principles Protection Contaminants Questions

Mass discharge must also take layering into account

After E. Lanna, 2015

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History Tracer tests Applications Principles Protection Contaminants Questions

Breakthrough curves contain a lot of information about the aquifer and the potential behaviour of contaminants

Natural or forced gradient tests Radial convergent Single well Specifically designed well network

-> Tracer results can be used for fitting analytical solutions or numerical models

XIX Congresso Brasileiro de Águas Subterrâneas46

History Tracer tests Applications Principles Protection Contaminants Questions

TRAC software (BRGM)

After Klinka, 2015

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History Tracer tests Applications Principles Protection Contaminants Questions

Hydrodynamical parameters: dispersivities and effective porosity

After Frippiat et al. 2015

Decomposition of individual layer contributions thanks to the high

resolution of the fluorometer during a forced gradient tracer test:

XIX Congresso Brasileiro de Águas Subterrâneas48

History Tracer tests Applications Principles Protection Contaminants Questions

Partitionning tracers

After Annable, 2016

XIX Congresso Brasileiro de Águas Subterrâneas49

History Tracer tests Applications Principles Protection Contaminants Questions

Intelligent tracers

Resazurine + e- ResorufineReduction due to microbiological activity

XIX Congresso Brasileiro de Águas Subterrâneas50

History Tracer tests Applications Principles Protection Contaminants Questions

The Finite Volume Point Dilution Method (FVPDM): a smart single well method for measuring filtration velocities

After Brouyère, 2015

• The method works well if Qinj < Qcritical• It allows for variations of water fluxes

XIX Congresso Brasileiro de Águas Subterrâneas51

History Tracer tests Applications Principles Protection Contaminants Questions

FVPDM can be combined with integrating methods such as passive sampling

After Lanna and Brouyère, 2015

XIX Congresso Brasileiro de Águas Subterrâneas52

History Tracer tests Applications Principles Protection Contaminants Questions

Passive sampling of contaminants are improving and they can be combined with tracer techniques: passive flux meters (PFM)

After Annable, 2016

Improved meter for fractured media

XIX Congresso Brasileiro de Águas Subterrâneas53

History Tracer tests Applications Principles Protection Contaminants Questions

PFM used in different aquifer settings depending on fluxes characteristics

After Annable, 2016

XIX Congresso Brasileiro de Águas Subterrâneas54

History Tracer tests Applications Principles Protection Contaminants Questions

Another example of passive sampling of contaminants: the CHLOROKARST project

Chlorinated hydrocarbons in Switzerland

TCE and PCE

XIX Congresso Brasileiro de Águas Subterrâneas55

History Tracer tests Applications Principles Protection Contaminants Questions

Detection of gasoil in water by fluorescence

PAH

XIX Congresso Brasileiro de Águas Subterrâneas56

History Tracer tests Applications Principles Protection Contaminants Questions

Field test – detection of gasoil in water

System calibrated with amino G acid with varying discharge

Times series of fluorescences

Substraction

HC signature

XIX Congresso Brasileiro de Águas Subterrâneas57

History Tracer tests Applications Principles Protection Contaminants Questions

Downhole fluorometer for layered aquifers

D’après Flynn et al. 2005

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History Tracer tests Applications Principles Protection Contaminants Questions

Tracer tests in LNAPL

Spectra showing the breakthrough of the UV tracer at 370 nm

Laboratory tests• Background of the product• Response of the tracer

XIX Congresso Brasileiro de Águas Subterrâneas59

History Tracer tests Applications Principles Protection Contaminants Questions

Tests of interference between gasoline and uranine

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History Tracer tests Applications Principles Protection Contaminants Questions

Fluorescence can also be used to characterize leachates from wastes or effluents

Tryptophan

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Muito obrigado pela sua atenção!

Algumas perguntas?