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PDETERM
CONTAMINAT
1
COLE DES MINES DE DOUAI
EPARTEMENT GENIE CIVIL
ROJECT DISCOVERY RESEARCHINING COST OF EXCAVATION OF LANDD FOR THE CONVERSION OF A BROWN
Encadran
Responsa
DA SILVA, Juliane
DEROCHE, LucLEVACHER, Benoit
Année: 2011/2012
IELD
: T.VALEYRE
le: C.ALARY
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INTRODUCTION
Brownfields are described as former industrial sites - factories and associated land, such aswarehouses or landfills, which are now abandoned or underutilized. Brownfields have the following
characteristics: they are often built or vacant sites contaminated (soil or water) by chemicals or otherpollutants (Ministry of Municipal Affairs and Housing Ontario, 2000). The strong growth urbanpopulation, coupled with the expansion of cities, have refocused these sites once on the outskirts of cities, to densely urbanized spots. Strong pressure on land and urban real estate has pushed to find newareas for urban development. Urban brownfields have a reserve of space but create a problem relatedto the rehabilitation of contaminated land.
Among the issues, assessing the impact of chemical contaminants emitted by past humanactivities is a major scientific question. Thus the realization of their history would be a pre-diagnosisof their toxic potential. Indeed, soils are receptacles, and potential reservoirs of contaminants to whichpeople can be exposed by different routes of contacts. If this toxicity was managed upstream through aconsideration of environmental constraints, clearance and profitable use of brownfield sites would notbe a "burden" for landowners. Indeed, the often high costs of post-decontamination represent a majorobstacle to their redevelopment.
Thus, the geostatistical interpolation of pollutant concentrations in soil, associated withspecific scenarios, cartographic modeling allow a risk of a site and can assist decision-makers toestablish an action plan to put implemented for the success of their projects and optimize costs.
Fig 1: Example of extension and densification of the urban fabric
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MATERIALS AND METHODS
Risk Modeling
Risk and risk assessment:
The health risk is the ratio, depending on environmental parameters, between exposure tosubstances referenced and their toxicity; which beyond a certain threshold characterizes a danger tohumans. Thus if the risk is> 1, there is dangerous toxicity, and vice versa.
Risk = ECD / VTR
The EDI (Acceptable Daily Exposure) refers to the amount of pollutant absorbed by the bodywithin a defined activity. It is calculated from the concentration of pollutants and based on weight of
the individual and the numbers of days of exposure to a carcinogenic substance not, or numbers of days of lifetime, to a carcinogen (Development -durable.gouv, 2011, U.S. EPA, Exposure AssessmentHH).
The VTR, Toxic Reference Value represents the amount of pollutant toxic to humans. It isdescribed as "with threshold" when a maximum level of safe exposure for humans has beenestablished as the principle of the critical dose, and as "with no threshold" when we extrapolate effectsbased concentrations absorbed.
These concepts have been defined by major international organizations responsible forpollution risk (ATSDR, INERIS, Health Canada) creating a consensus around these principlesquantification of absorption of toxic substances by man.
Modeling:
General Principle:
The combination of the intrinsic characteristics of a pollutant to the environmental parametersof the scenario can be modeled for each route of exposure ECD. Indeed, the general idea is to link theproperties of a pollutant from the soil (concentration, volatility...) and its effects on man and on whatterms it will be absorbed by the body. This develops a scenario describing the characteristics of subjects or (weight, quantity absorbed...) and activity (time, effort...).
The choice of scenario is of utmost importance because the substance properties are constantregardless of the choice of the population concerned. Therefore the factors Time / Attendance andabsorbed Quantity / Weight are essential for the accuracy of ECD (Zmirou D. et al. 2003).
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Fig. 1: Modélisation des DJE
Routes of Exposure:
These are the input vectors of substances in the body. They are many due to the fact that thebody is complex and permeable. Only direct exposure pathways, ie having no intermediary betweenman and the pollutant (ie contamination and accumulation of pollutants along the food chain) were
studied (D. et al Zmirou . 2003). It should be distinguished, because despite having the same originsand despite the fact that the effects of pollutants on the body are unchanged, these vectors of contamination have a clean transfer model.
Exposure by Ingestion
In any scenario, the risk of exposure by ingestion is the amount of soil that is absorbed into thebody. These values differ depending on the population concerned (U.S. EPA, Exposure FactorsHandbook).
Ingestion ECD
= ∗ ∗ ∗ ∗
with: , the daily exposure (mg / kg.jour);
C, the concentration at the exhibition in the ground (mg/m3);Qing, the daily amount ingested (mg / day);FE, the exposure frequency (days / year);
DE, duration of exposure (years);P, the body weight of the target (kg);
ECD
AcceptableDaily
Exposure
PollutantCharacteristics
Population
Identification
Activities
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and Tm, the time averaged (days)Tm = DE * 365 for threshold substances,Tm = 70 * 365 for non-threshold substances.
Inhalation Exposure:
Pollutants may dissolve in the water in the soil and end up in the air because of their volatilityand evaporation. Indeed the toxins are transferred from the solid phase to the aqueous phase via theKoc and then to the gas phase via Henry's law (US. EPA).
Inhalation of gases from a contaminated soil
Thus, the concentration of pollutant that can be inhaled from the soil, Ci is:
= × ×
± × × ± ×
with:
H: Henry's law constantKoc: partition coefficient organic carbon / waterCsoil: soil concentration mg/m3Qs: Soil Density: 2.65 kg/m3Ow: Volume of water content in soil: 0.15 DefaultOa: Volume of air in the soil: 0.28 DefaultJib: Proportion of carbon: 0.06 Default
Inhalation ECD
= ∗ ∗ ∗ ∗
with
Ci: concentration of pollutant in the air from soilQi: The amount of air inhaled per hour (for a child: the 0.5 × 30 × 60 = 0.9 m ^ 3, or 1.08 kg) []
ECD Inhalation Interior
Inhalation within the EDI can be calculated from the concentration of pollutants in outdoor airthrough a diffusion factor α. (D. Henryon, 2009).
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ECD or ECD Inh Inh α = int ext (FD Tillman Jr., JW Weaver, 2006)
Diffusion factor α (Johnson and Ettinger, 1991)
Main Target Organs
Each pollutant has own effects on the body. However, the image of their group by chemicalfamily (BTEX, PAHs, COHV, ...) various studies have shown that they could address the same organsas a priority and therefore it was possible to together, either by their composition, but by their behavior(Lemière B. et al., 2008) and therefore according to their main target organs.
Fig.2: Tableaux de Classement des polluants présent par organes cibleFoie Système Nerveux Système
Respiratoire
Reins Système
Immunologique
1,1,2,2-tetrachloroéthane
1,1,2,2-tetrachloroéthane
1,2-dichloroéthane Cadmium Arsenic
1,2-dibromoéthane 1,1dichloroéthylène
Arsenic Chloroforme Benzo[b]fluoranthène
Acénaphtène 1,2-dichloroéthane Cadmium Éthylbenzène Benzo[g,h,i]pérylène
Arsenic 1,2-
dichloroéthylène
Chrome Fluoranthène Benzo[k]fluoranthèn
eChloroforme 1,2-
dichloroéthylène-1Naphtalène Mercure Chrome
Chlorure de vinyle Arsenic Nickel Nickel Chrysène
Chrysène Benzène O-xylène Plomb Plomb
Cuivre Chloroforme Zinc Pyrène Zinc
Éthylbenzène Chrysène Dibromochlorométhane
Bromochlorométhane
Dibromochlorométhane
Fluorène Chlorure deméthylène
Dibromométhane Dibromochlorométhane
Dibromométhane
O-xylène Mercure Benzo(a)anthracène
Dibromométhane Benzo(a)anthracène
1,1,1- O-xylène Antimoine Benzo(a)anthracèn Dibenzo(ah)anthrac
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trichloroéthane e ène
1,1,2-trichloroéthane
Plomb Selenium Selenium
Bromochlorométhane
Toluène
Dibromochlorométhane Trichloroéthylène
Dibromométhane Tétrachloroéthylène
Dibenzo(ah)anthracène
1,1,1-trichloroéthane
Selenium 1,1,2-trichloroéthane
Dibromométhane
Benzo(a)anthracène
Système Gatrique Peau Sang Système Cardio-Vasculaire
Endocrinia
1,2-dichloroéthane Arsenic Arsenic Arsenic Bromodichlorométhane
Arsenic Benzo[a]pyrène Benzène Mercure Dibromométhane
Chlorure deméthylène
Cuivre Fluorène Plomb Selenium
Naphtalène O-xylène Naphtalène Dibromométhane
Zinc Dibromométhane O-xylène Benzo(a)anthracène
Dibromométhane Phénanthrène Zinc Selenium
Benzo(a)anthracène Benzo(a)anthracène Dibromométhane
Antimoine Dibenzo(ah)anthracène
Selenium Selenium
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Summation of the ECD
For a given chemical compound i, its ECDs (after P. Imray, A. Langly, 2001) are cumulative
and are listed by primary target organs j.Therefore there is for each pollutant and by target organ, an ECD as:
= ECDInh + ECDIngand' =/)'
These factors are combining to a single organ, regardless of the component, it helped to modeled riskorgans (E. Nerrière, D. Zmirou, 2001).
' = *)'
APPLICATION:
Study Area:
The application of this methodology was tested on an industrial wasteland: the Union sitelocated in the towns of Roubaix-Tourcoing-Wattrelos in northern France. This site has housed variousindustrial activities on an area of 80 hectares (brewery, textile, petrochemical, metallurgy, gas works,coal yard, yard, etc), as well as the workers' dwellings. This site became an urban industrial wasteland
in the wake of industrial decline that began in the '70s (website of the Union).
Former activities have generated localized contamination of several families of pollutants:trace metals (ETM), aliphatic hydrocarbons (HC), polycyclic aromatic hydrocarbons (PAHs), volatilehalogenated organic compounds (COHV), Polychlorinated biphenyls (PCB) and benzenes,Ethylebenzènes, Toluenes (BTEX).
The urban renewal project provides a very strong imbrication of habitat and economicalactivities. This is part of the sustainable development policy with remediation of land which aims atcreating the first eco-neighborhood of Lille.
Risk mapping will help to better define the areas where excavation of the soil before treatment
is not mandatory and thus validate the adequacy of the project for the built and the unbuiltenvironment in accordance with their health criteria.
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Fig.4:Localisation du site de l'Union
Sampling and Chimical
The diversity of soil composition and their heterogeneity (embankments) led to a samplingcampaign by augers and shovels of 452 samples, following a systematic sampling scheme based on theconstraints facing the field of mesh between 30 and 40 m and at depths between 1 m and 4 m.
Pollutant concentrations have been provided through testing according to standards applicablein France:
− NF ISO 22155 - HS / GC / MS for COHV (assay by gas chromatography;− EN 14039 for Hydrocarbons by GC (assay by gas chromatography in the range C10 to C40);
− XP X 33-012 for PCBs and PAHs (Dose by gas chromatography coupled with tandem mass
spectrometry (GC-MSMS));− NF EN ISO 11885 for Heavy Metals (Dosage of selected elements by optical emission
spectrometry with inductively coupled plasma frequency ICP-OES);
− NF ISO 16772 for Mercury (by atomic absorption spectrometry or cold vapor atomicfluorescence spectrometry cold vapor).
as well as for methods:− NF ISO 11464 (Sample preparation: sieving, storage, etc..);
− NF EN 12457-2 (leaching of waste with a granularity of less than 4 mm);
− NF ISO 11465 (water content of samples, by steaming).
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Creating the Scenario:
Generally, this step leads to determining or estimating for the type of people exposed:
The duration and frequency of exposure. They are estimations based on the habits and activities of the populations concerned. Only chronic exposure (continuous or recurrent exposure corresponding tothe significant fraction of life) are considered.
The physiological characteristics of subjects studied. This information differs depending on the typeof selected populations. They are the specific parameters that differentiate people, as weight, quantitiesintook and inhaled, etc.
Children were preferred in this study because they represent a sensitive population, andbecause of their development and behavior (ingestion of soil during the game, for example (A.Jacquet, 2007)), which makes the action of more harmful toxic substances (U.S. EPA, Human Health
Risk Assessment).A daycare center has been simulated with average attendance as: 8h/day, 5days/week,
47weeks/year. For two years that is:
No threshold: DE x EF = 235 x 2Tm 25550
With threshold: DE x EF = 235 x 2
Tm 730A quantity of soil ingestion of 100 mg / d (A. Jacquet, 2007)And a quantity of air inhaled (taken and adapted from: D. Bérubé et al, 1996)
Computing:
Calculation of risk coefficients for different routes of exposure
According to the compilation of the characteristics of the substances identified, and theparameterization of equations depending on the scenario, Excel spreadsheets © were used to calculatefor each pollutant and for each route of exposure the risk factors.
Ingestion Fig4.Risque
Ingestion Orale / àseuil
(mg/kg.j)
Orale / sansseuil
(mg/kg.j)^-1
Coef Risque
Hydrocarbures par CPG-
C10-C40 0,1 3462,603878
C10-C16 0,1 3462,603878
>C16-C22 2 173,1301939>C22-C30 2 173,1301939
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>30-C40 2 173,1301939
Composés Volatils
Dichlorométhane 0,05 6925,207756
Tétrachlorométhane 0,01 34626,03878
1,2-dichloroéthane 0,2 1731,301939
1,1,1-trichloroéthane 20 17,31301939
1,1,2-trichloroéthane 0,04 8656,509695
Cis-1,2-dichloroéthylène 0,017 20368,25811
Trans-1,2-dichloroéthylène 0,017 20368,25811
Chlorure de vinyle 0,003 115420,1293
1,1-dichloroéthylène 0,05 6925,207756
Bromochlorométhane 0,09 3847,337642
Bromodichloroéthane 0,02 17313,01939
Dibromochlorométhane 0,1 3462,603878Benzène 0,005 69252,07756
Toluène 0,8 432,8254848
Ethylbenzène 0,4 865,6509695
o - xylène 0,4 865,6509695
m+p - xylène 0,4 865,6509695
Hydrocarbures Aromatique Polycycliques(HAPs)
Naphtalène 0,6 577,1006464Acénaphtène 0,6 577,1006464
Fluorène 0,4 865,6509695
Phénanthrène 0,04 8656,509695
Anthracène 10 34,62603878
Fluoranthène 0,4 865,6509695
Pyrène 0,03 11542,01293
Chrysène 2,10E-03 164885,899
Benzo(b)fluoranthène 5,00E-03 6,93E+04
Benzo(k)fluoranthène 5,00E-03 6,93E+04
Benzo(a)pyrène 0,1369 2529,294286
Dibenzo(ah)anthracène 0,0005 692520,7756
Benzo(ghi)Pérylène 500 0,692520776
Indeno(1,2,3-c,d)pyrène 5,00E-03 69252,07756
Métaux par ICP/AES après minéralisation
Arsenic 0,0003 1,5 1154201,293
Cadmium 0,0005 ND 692520,7756
Chrome (VI) 0,003 0,42 115420,1293
Chrome (III) 1,5 ND 230,8402585Cuivre 0,14 ND 2473,288484
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Nickel 0,02 ND 17313,01939
Plomb 0,0035 98931,53937
Zinc 0,3 ND 1154,201293
Mercure par SFA
0,0001 ND 3462603,878
Fig6.Risque Inhalation Extérieur et Intérieur
Inhalation α VTR Inhalation COEF de RISQUES
à seuil(mg/m3)
sans seuil Extériereur
Intérieur
Hydrocarbures par CPG-
C10-C40 0,2 0 0C10-C16 0,2 0 0
Composés Volatils
1,2-dichloroéthane 0,01444
1,34E-06 4846003,533
69976,29101
1,1,1-trichloroéthane 8,21E-04
5,80E-11 6,31E+10 5,19E+07
1,1,2-trichloroéthane 8,21E-04
5,80E-11 6,31E+10 5,19E+07
Cis-1,2-dichloroéthylène 7,62E-04
3,20E-02 230,9726807
0,176093572
Trans-1,2-dichloroéthylène 7,62E-04
6,00E-02 126,5102692
0,096451429
Chlorure de vinyle 5,60E-04
0,1 77,4878649
0,043377707
Benzène 7,98E-04
0,06 121,8894342
0,097206824
Toluène 4,74E-04
3,85 0,41793501
0,000198101
Ethylbenzène 4,17E-04
2 3,324401854
0,001385943
o - xylène 8,90E-
04
0,7 8,8404753
81
0,00787
1559m+p - xylène 7,85E-
040,7 11,071217
10,00868
9245Hydrocarbures AromatiquePolycycliques (HAPs)
Naphtalène 6,62E-04
3,50E-03 142,9229339
0,094586398
Acénaphtène 5,02E-04
0,6 0,072771842
3,65024E-05
Fluorène 4,42E-04
0,4 0,040727555
1,80179E-05
Phénanthrène 1,10E-03 4079,074922 0
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Anthracène 1,10E-03 2,437528688
0
Fluoranthène 1,10E-03 0,259033155
0
Pyrène 3,51E-
04
1,10E-03 0,0002011
63
7,05879
E-08Chrysène (koc: moyenne) 1,64E-04
1,10E-03 0,004103685
6,73004E-07
Benzo(b)fluoranthène (moyennes) 2,91E-04
1,10E-03 5224,522604
1,518768721
Benzo(a)pyrène 1,10E-03 9,81003E-05
0
Benzo(ghi)Pérylène 1,10E-03 4,28765E-09
0
Indeno(1,2,3-c,d)pyrène 1,10E-03 5,72368E-05
0
PCB
PCB 28 a seuil:Sommedes DJE
4,91E-01 0,00E+00
PCB 52 1,51E+00 0,00E+00
PCB 101 1,04E-01 0,00E+00
PCB 118 5,00E-04 0,146831984
0,00E+00
PCB138 2,06E-02 0,00E+00
PCB 153 6,18E-02 0,00E+00
PCB 180 6,89E-02 0,00E+00
Mercure par SFA
3,81E-04
3,10E-05 250330,7433
95,42607933
Modeling and interpolation of concentrations of risk maps
One of the problems of mapping the risk of contaminated land lies in the interpolation of pointdata in order to model spatially throughout a site. That is to say, from the diverse and scattered pointsof which we know the coordinates, and the concentration of pollutants, we need to "estimate" valuesthat can be found anywhere on the site. To do this, geostatistics offers powerful tools for spatialmodeling from mathematical laws.
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where ,ℎ. is the semivariogram, or Act of dispersion, representing the zone of influence of the
pollutant. He characterizes the "Weight" of the component at any point depending on the distance hfrom a known point. (Matheron, 1962-63).
The choice was made the use of Kriging to interpolate the concentrations of differentpollutants and the Rasters to map the site using the software Arcgis 10 ©. This method, besidesproviding a precision much finer than the weighted average of inverse distance, can make a map of "inaccuracies" of uncertainty, represented by the map of standard deviation the error.
"Fig7: Card concentration
Using the calculator Raster Arcgis 10 © and risk coefficients previously calculated, theconcentrations were weighted, creating hazard maps by pollutant for each route of entry.To make their immediate reading possible, their scales of values have been changed in order to showthe areas at risk or not.
"Fig8
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Due to the summation of the ECD of various routes for the same organ, risk maps by bodieshave been established by overlaying the previous models, which, under the precautionary principle,could be superimposed with each other and create a map of general risk for the entire site.
Fig. 9 :
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Fig. 10: Carte Risque Système Nerveux
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DISCUSSION
According to the maps, the site of the Union seem presented areas with very high health risk.
However, given the risk maps Risk Liver and Nervous System, it appears an inconsistency
surévaluante the nervous system. The mere presence of PCBs, certainly very toxic compounds, can
not explain such a discrepancy. Indeed, their concentrations, although scattered throughout the site
are quite low (maximum: 0.5 mg / kg soil).
It seems that the interpolation method (Kriging Ordinary) is not the most relevant especially in the
interpolation of pollutant concentrations throughout the site. Indeed the disparity of data could lead
to errors in spatial modeling and thus estimated. Should be tested with other methods (Kriging
Glissant, the weighted average of inverse distance).
Furthermore, the modeling of risk factors for each pollutant ingestion was overvalued (bad
estimation of the frequency), which, combined with a very unfavorable scenario already have
aggravated this phenomenon.
The main limitations of this study lies in the inaccuracies related to various factors, and the non-
consensus on the calculation of Henry's constant and the diffusion coefficient α (J. Provoost et al.
2010). However, this does not undermine the general principle used and could, for mapping and
charting errors, help refine it.
So it would be interesting to study the predominance of organs or under certain conditions, because
there are few sets of values in the target organ sensitivity to toxic substances. That is to say,
whether, for example, in the case of inhalation of chloroform, the liver is more sensitive than he
nervous system, or conversely that pollutant as they are categorized both as a primary target organ?
If so, they are more serious effects on health in one case or the other? In other words, what is the
"weight" of the body factor in the case of poisoning with chemicals? This would refine this study by
weighting the risk maps of each body and have a finer edge of the area at risk on the entire site
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BIBLIOGRAPHY:
1. A.Jacquet (2007). Thesis: Amount of soil ingested recommended for a child: A choice tooconservative?
2. ATSDR - Glossary. Agency for Toxic Substances and Disease Registry, Atlanta, GA: U.S.Department of Health and Human Services, Public Health Services.(Http://www.atsdr.cdc.gov/glossary.html).
3. B. Lemière et al. - Guide on the behavior of pollutants in soil and ground-Document BRGM-New2008 Edition
4. D. Bérubé et al. (1996). Therapeutic modalities of asthma. Montreal: Publications, Department of Teaching Hospital Sainte-Justine (unpublished paper, presented as part of training for first responders
Line)
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