Spatial and temporal evolution of groundwater metal ...
30
Atelier Scientifique du ROHM : Les OHM et les contaminations métalliques Aix en Provence, 21 – 22 Novembre 2016 Spatial and temporal evolution of groundwater metal contamination in an industrial area: the case study of Estarreja C. Patinha 1 , T. Marques 2 , A. Dias 1 , A. Cachada 3 , N. Durães 1 , E. Ferreira da Silva 1 , M. Matias 1 1 Geobiotec & Geoscience Department, University of Aveiro, Campus de Santiago, 3810-193 Aveiro, Portugal 2 Master's student in Geological Engineering. University of Aveiro, Campus de Santiago, 3810-193 Aveiro, Portugal 3 CESAM & Department of Chemistry, University of Aveiro, Campus de Santiago, 3810-193 Aveiro, Portugal; CIIMAR/CIMAR, University of Porto, Terminal de Cruzeiros do Porto de Leixões, Av. General Norton de Matos s/n, 4450-208 Matosinhos, Portugal
Transcript of Spatial and temporal evolution of groundwater metal ...
3ème Séminaire annuel du Labex DRIIHM 8 et 9 juin 2015, Aix en Provence
Atelier Scientifique du ROHM : Les OHM et les contaminations métalliquesAix en Provence, 21 – 22 Novembre 2016
Spatial and temporal evolution of groundwater metalcontamination in an industrial area: the case study ofEstarreja
C. Patinha1, T. Marques2, A. Dias1, A. Cachada3, N. Durães1, E. Ferreira da Silva1, M. Matias1
1Geobiotec & Geoscience Department, University of Aveiro, Campus de Santiago, 3810-193 Aveiro, Portugal
2Master's student in Geological Engineering. University of Aveiro, Campus de Santiago, 3810-193 Aveiro, Portugal3CESAM & Department of Chemistry, University of Aveiro, Campus de Santiago, 3810-193 Aveiro, Portugal; CIIMAR/CIMAR, University of Porto, Terminal de Cruzeiros do Porto de Leixões, Av. General Norton de Matos s/n, 4450-208 Matosinhos, Portugal
Agriculture
Industry
Nature with brackish and fresh
water systems
Urban
Estarreja – a city of contrasts
Estarreja has always been a region with extensive farming
areas, developing parallel and competing for land with an
important industrial pole - the Estarreja Chemical Complex
(ECC).
The main geological units are:
• Detritic sedimentary deposits (siliceous sediments),
showing high permeability and porosity, and hosting
the superficial aquifer. The characteristics of this unit
allows the contaminant’s dispersion, thus causing
high aquifer vulnerability.
• Bedrock is composed by sandstones and schists. 0 0.5 1 1.5 2km
Legenda
Linhas de água
CQE
Água Superficial
Aluviões, areias de duna e de praia (Holocénico)
Q - Terraços (Plistocénico)
C1A - Grés de Palhaça, Requeixo e Carrascal (Cretácico Inf.)
PCBR - Complexo Xisto-Grauváquico (Pré-Câmbrico)
±
0 0.5 1 1.5 2km
Legenda
Linhas de água
CQE
Água Superficial
Aluviões, areias de duna e de praia (Holocénico)
Q - Terraços (Plistocénico)
C1A - Grés de Palhaça, Requeixo e Carrascal (Cretácico Inf.)
PCBR - Complexo Xisto-Grauváquico (Pré-Câmbrico)
±
Extracted from Branco (2008)
Geological settings
• By the end of 1930s: production of Cl2 and NaOH;
• After the 2nd World War: production of ammonium (for fertilizers);
• 1952: production of ammonium sulphate and sulphuric acid (by pyrite ustulation: As, Cu, Zn, Fe, etc);
• 1956: production of Cl2 and Na;
• 1959: production of Cl2 and Na by electrolytic process using Hg cathodes;
• 1963: started the production of PVC and VCM using Hg catalysers;
• 1970: production of fertilizers and aromatic compounds (mononitrobenzene and aniline);
• 1980 decade: new industrial unit for the production of polyurethanes;
• 1990 decade: new method for aniline production using less amounts and low concentrations of sulphuric acid;
• End of 1990s: production of sulfanilic acid and ciclohexilamine; the Hg cells were replaced by membrane cells.
The evolution of the Estarreja Chemical Industry
• The manufacture technologies have been
experiencing appreciable improvements becoming
more environmentally sustainable;
• Industrial activity continues to be an important
employer in this region. This leads to the growth of
the city and population, approaching from the
industrial pole and occupying the farm lands.
Estarreja Chemical Industry
• Liquids effluents: Cl, Hg, SO4, NO3, NO2, nitrofenols, MNB, aniline, vinyl chloride, methanol.
• In the past, these effluents were discharged directly to the
Aveiro lagoon through sewage channels;
• Nowadays, these effluents are transfer to wastewater
treatment stations, where physical and chemical treatments
are conducted.
Environmental Legacy (more than 85 years of industrial activities)
• Solid wastes: 100 000 tones of muds, mainly composed by Hg, NaCl, CaSO4, CaCO3, Mg(OH)2, Ca(OH)2, Fe, NaOH;
• 150 000 tones of pyrite residues enriched in As, Hg, Zn, Cu, Fe;
Nowadays, these wastes are deposited in confined landfills (concluded in 2005)
• 320 000 tones of Ca(OH)2,muds still exposed to weathering conditions.
Environmental Legacy (more than 85 years of industrial activities)
Aims
To assess the long-term (1989–2016) and spatial distribution of heavy metal concentrations in waters
using geophysical and geochemical data;
To understand the influence of the geological features in the evolution of contamination dispersion;
Linked the contamination evolution with the changes introduced over time in the industrial practices;
• 8 chemical elements (Fe, Cu, Pb, Zn, Mn, Cd, Co, Ni);
• AAS analysis after samples pre-concentration through
lyophilisation;
• 69 chemical elements
• ICP-MS
• 25 chemical elements
• ICP-MS
Sam
plin
g ca
mp
aign
s
1989
60 samples
2006
34 samples
2015
19 samples
2016
32 samples
• 36 chemical elements
• ICP-OES
Sampling and Analysis
Select elements:
Fe, Cu, Zn, Mn, Cd, Co, Ni
Limitations in extrapolating
data
Different elements analyzed
Different analytical methods
Different sampling
points
1989 2006 2015 2016
Sampling and Analysis
Flux direction20161989
Geochemical data: sampling map
20061989
Geochemical data: sampling map
20162015
The spatial distribution of electrical conductivity show the contamination dispersion along the time.
• In 1989 the high values are close to the factories.
• In 2006 and 2016 the contamination is defined in two main areas: close to the factories (with a tendency to
decreasing); and associated with the old sewage channels.
Geophysical results: Electromagnetic survey (1989-2016)
Contamination plume (EM method)
1989 2006 2016
Geochemical results: pH
2
4
6
8
10
12
pH-1989
4
6
8
10
12
pH-2006
2
4
6
8
10
12
pH-2016
2
4
6
8
10
12
pH-2015
• High pH range
• Median near to pH=6
• Anomalous values – occurrence of high acidic waters locally
Geochemical results – Electric conductivity
10
100
1000
10000
100000
µS
/cm
CE-1989
10
100
1000
10000
100000
µS
/cm
CE-2006
10
100
1000
10000
100000
µS
/cm
CE-2016
10
100
1000
10000
100000
µS
/cm
CE-2015
• Considerable high EC values range
• Median values between 500 and 1000 μS/cm
• Anomalous values – occurrence of waters with very high EC values locally
Geochemical results: Cu in water
0.1
1
10
100
1000
10000
Cu-1989
0.1
1
10
100
1000
10000
Cu-2006
0.1
1
10
100
1000
10000
Cu-2016
0.1
1
10
100
1000
10000
Cu-2015
Irrigation waterDrinking water
Limits
• Usually the levels of Cu in waters are low and below the legal limits;
• A general decrease of Cu concentrations in waters;
• Occurrence of anomalous locally Cu concentrations, but showing a general decreasing tendency
0.1
1
10
100
1000
10000
µg/L
Mn-1989
0.1
1
10
100
1000
10000
µg/L
Mn-2006
0.1
1
10
100
1000
10000
µg/L
Mn-2015
0.1
1
10
100
1000
10000
µg
/L
Mn-2016
Limits
Geochemical results: Mn in water
Irrigation water
Drinking water
• The levels of Mn in waters are high (mean values are high or near de drinking water limit);
• A general decrease of mean Mn concentrations in waters, below the limit for irrigation waters;
• Occurrence of anomalous locally Mn concentrations
1
10
100
1000
10000
100000
µg
/L
Zn-1989
1
10
100
1000
10000
100000
µg
/L
Zn-2006
1
10
100
1000
10000
100000
µg
/L
Zn-2015
1
10
100
1000
10000
100000
µg
/L
Zn-2016
Limits
Geochemical results: Zn in water
Irrigation water
Drinking water
• The levels of Zn in waters are high (above the drinking water limits);
• A general decrease of mean Zn concentrations in waters, below the limit for irrigation waters;
• Occurrence of anomalous high locally Zn concentrations
1
10
100
1000
10000
100000
Fe-1989
1
10
100
1000
10000
100000
Fe-2006
1
10
100
1000
10000
100000
Fe-2016
1
10
100
1000
10000
100000
Fe-2015
Limits
Geochemical results: Fe in water
Irrigation water
Drinking water
• A general decrease of mean Fe concentrations in waters, below the limit for irrigation waters and also
the drinking water limits (2015-2016);
• Occurrence of anomalous locally Fe concentrations.
0.01
0.1
1
10
100
1000
µg/L
Cd-1989
0.01
0.1
1
10
100
1000
µg/L
Cd-2006
0.01
0.1
1
10
100
1000
µg/L
Cd-2016
0.01
0.1
1
10
100
1000
µg/L
Cd-2015
Limits
Geochemical results: Cd in water
Irrigation waterDrinking water
• The levels of Cd in waters are in general low (above the drinking and irrigation water limits);
• A general decrease Cd levels in waters over years;
• Occurrence of anomalous high locally Cd concentrations (1989-2006).
1
10
100
1000
10000
100000
1000000
Soma - 1989
10
100
1000
10000
100000
1000000
Soma 2006
1
10
100
1000
10000
100000
1000000
Soma-2016
1
10
100
1000
10000
100000
1000000
Soma 2015
Geochemical results: Metals – (Fe+Mn+Cu+Zn+Co+Ni+Cd)
• In general are occurring a decrease of metals concentrations in waters over years;
• Occurrence of anomalous metal concentrations – locally effects.
1989
Geochemical results: Evolution of metal contamination (Fe+Mn+Cu+Zn+Co+Ni+Cd)
• The main metallic focus are the
factories and the sewage channels
1989-2006
Geochemical results: Evolution of metal contamination (Fe+Mn+Cu+Zn+Co+Ni+Cd)
• Dispersion of the contamination from
the factories
1989-2006-2015
Geochemical results: Evolution of metal contamination (Fe+Mn+Cu+Zn+Co+Ni+Cd)
• Dispersion of the contamination from
the factories and from the sewage
channels
1989-2006-2015-2016
Geochemical results: Evolution of metal contamination (Fe+Mn+Cu+Zn+Co+Ni+Cd)
• Dispersion of the contamination from
the factories and from the sewage
channels following the main
underground flux directions
Zn
Zn
Geochemical results: Main profiles of metal contamination
Concluding remarks
Despite the several limitations in the assessment of metal contamination in a period range of
almost 30 years, it is possible to conclude about the following points:
• In the past exist two main focus of metal contamination: the factories and the industrial sewage
channels;
• Nowadays the main metal contamination focus seems to be the old industrial sewage channels – locally
contamination effects;
• Although the contamination of groundwater is still present nowadays, the improvement of the industrial
production methods, the confinement of the solid wastes, and the treatment of liquid effluents resulted
in a significant reduction of contamination;
• Nevertheless these waters continues to exceed the maximum admissive levels for human consumption,
but its standards improve such they can be used for irrigation.
Concluding remarks
TO THINK ABOUT…
• Metals are not degradable agents as organic compounds, which means that in waters they can only be
attenuated by:
• Dilution (in situ)
• Dilution (ex situ) – dispersion
• Precipitation
• Dispersion seems to be the main process occurring, but this have the disadvantage of affect other sites;
• Precipitation also may occur, but changes in physicochemical conditions may cause the remobilization
and again the entry of these metals into the aqueous system.
3ème Séminaire annuel du Labex DRIIHM 8 et 9 juin 2015, Aix en Provence
Atelier Scientifique du ROHM : Les OHM et les contaminations métalliquesAix en Provence, 21 – 22 Novembre 2016
Thank you for your attention
The authors acknowledge
the Labex DRIIHM and
the Réseau des
Observatoire Hommes-
Millieux - Centre National
de la Recherche
Scientifique (ROHM-
CNRS) for the financial
support.
