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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
XIX Congresso Brasileiro de Águas Subterrâneas31
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
XIX Congresso Brasileiro de Águas Subterrâneas42
History Tracer tests Applications Principles Protection Contaminants Questions
The model must reflect the reality
XIX Congresso Brasileiro de Águas Subterrâneas43
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
XIX Congresso Brasileiro de Águas Subterrâneas45
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
XIX Congresso Brasileiro de Águas Subterrâneas47
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
XIX Congresso Brasileiro de Águas Subterrâneas58
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
XIX Congresso Brasileiro de Águas Subterrâneas60
History Tracer tests Applications Principles Protection Contaminants Questions
Fluorescence can also be used to characterize leachates from wastes or effluents
Tryptophan