HAL Id: hal-00878078 https://hal.archives-ouvertes.fr/hal-00878078 Submitted on 29 Oct 2013 HAL is a multi-disciplinary open access archive for the deposit and dissemination of sci- entific research documents, whether they are pub- lished or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers. L’archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d’enseignement et de recherche français ou étrangers, des laboratoires publics ou privés. Contribution to Surface Water Contamination Understanding by Pesticides and Pharmaceuticals, at a Watershed Scale Stéphanie Piel, Estelle Baurès, Olivier Thomas To cite this version: Stéphanie Piel, Estelle Baurès, Olivier Thomas. Contribution to Surface Water Contamination Un- derstanding by Pesticides and Pharmaceuticals, at a Watershed Scale. International Journal of Envi- ronmental Research and Public Health, MDPI, 2012, 9 (12), pp.4433-4451. 10.3390/ijerph9124433. hal-00878078
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HAL Id: hal-00878078https://hal.archives-ouvertes.fr/hal-00878078
Submitted on 29 Oct 2013
HAL is a multi-disciplinary open accessarchive for the deposit and dissemination of sci-entific research documents, whether they are pub-lished or not. The documents may come fromteaching and research institutions in France orabroad, or from public or private research centers.
L’archive ouverte pluridisciplinaire HAL, estdestinée au dépôt et à la diffusion de documentsscientifiques de niveau recherche, publiés ou non,émanant des établissements d’enseignement et derecherche français ou étrangers, des laboratoirespublics ou privés.
Contribution to Surface Water ContaminationUnderstanding by Pesticides and Pharmaceuticals, at a
Watershed ScaleStéphanie Piel, Estelle Baurès, Olivier Thomas
To cite this version:Stéphanie Piel, Estelle Baurès, Olivier Thomas. Contribution to Surface Water Contamination Un-derstanding by Pesticides and Pharmaceuticals, at a Watershed Scale. International Journal of Envi-ronmental Research and Public Health, MDPI, 2012, 9 (12), pp.4433-4451. �10.3390/ijerph9124433�.�hal-00878078�
Int. J. Environ. Res. Public Health 2012, 9, 4433-4451; doi:10.3390/ijerph9124433
International Journal of
Environmental Research and
Public Health ISSN 1660-4601
www.mdpi.com/journal/ijerph
Article
Contribution to Surface Water Contamination Understanding
by Pesticides and Pharmaceuticals, at a Watershed Scale
Stéphanie Piel 1,2,3
, Estelle Baurès 1,2
and Olivier Thomas 1,2,
*
1 Environment and Health Research laboratory (LERES), EHESP School of Public Health, Avenue
du Professeur Léon Bernard-CS 74312, Rennes Cedex 35043, France;
E-Mails: [email protected] (S.P.); [email protected] (E.B.) 2 Inserm, U 1085 Institute of Research in Environmental and Occupational Health (IRSET), Avenue
du Professeur Léon Bernard-CS 74312, Rennes Cedex 35043, France 3 SAUR Research and Development, 1 rue Antoine Lavoisier Saint Quentin en Yvelines 78064,
France
* Author to whom correspondence should be addressed; E-Mail: [email protected];
Tel.: +33-2-9902-2921; Fax: +33-2-9902-2929.
Received: 10 September 2012; in revised form: 12 November 2012 / Accepted: 19 November 2012 /
Published: 4 December 2012
Abstract: This study aims at understanding the presence of regulated and emerging
micropollutants, particularly pesticides and pharmaceuticals, in surface water, regarding
spatial and temporal influences at a watershed scale. The study of relations between
micropollutants and other water quality and hydroclimatic parameters was carried out from
a statistical analysis on historical and experimental data of different sampling sites from the
main watershed of Brittany, western France. The outcomes point out the influence of urban
and rural areas of the watershed as well as the impact of seasons on contamination
variations. This work contributes to health risk assessment related to surface water
contamination by micropollutants. This approach is particularly interesting in the case of
agricultural watersheds such as the one studied, where more than 80% of surface water is
used to produce drinking water.
Keywords: micropollutants; water quality; watershed; spatial variation; temporal variation
OPEN ACCESS
Int. J. Environ. Res. Public Health 2012, 9 4434
1. Introduction
Among organic micropollutants monitored in water, pesticides are the most important class of
hazardous substances. For example, in Europe, the Water Framework Directive (WFD; Directive
2000/60/EC) provides strategies against chemical pollution of surface waters and notably established
provision for a list of Priority Substances (Annex X of the Directive) [1]. On the other hand the
Drinking Water Directive (DWD) sets quality standards for drinking water quality at the tap
(microbiological, chemical and organoleptic parameters) and the general obligation that drinking water
must be wholesome and clean [2]. World Health Organization (WHO) guidelines are used as a basis
for the standards in the WFD and DWD [3], and precise that “pesticides” means insecticide, herbicide,
fungicide, nematicides, acaricide, algicide, rodenticide and organic slimicide substances and related
products (including growth regulators), their metabolites, their degradation or relevant reaction
products. Two quality limits have been set in water intended for human consumption: 0.10 µg/L for
each substance (except four of them: aldrin, dieldrin, heptachlor and heptachlor epoxide, for which the
applicable limit is 0.03 µg/L, which corresponds to the WHO guideline value) and 0.50 µg/L for total
pesticides quantified.
In the United States, the Clean Water Act (USEPA) is the cornerstone of surface water quality
protection [4]. The statute employs a variety of regulatory and non-regulatory tools to reduce direct
pollutant discharges into waterways, finance municipal wastewater treatment facilities and manage
polluted runoff. These tools are employed to achieve the broader goal of restoring and maintaining the
chemical, physical and biological integrity in the nation’s waters. Secondly, the Safe Drinking Water
Act (USEPA) is the main federal law that ensures the quality of drinking water [5]. Under SDWA,
EPA sets standards and oversees the states, localities and water suppliers who implement them.
National Primary Drinking Water Regulations (NPDWRs or primary standards) are legally enforceable
standards that apply to public water systems. Primary standards protect public health by limiting the
levels of contaminants in drinking water, like some pesticides.
The presence of pharmaceuticals in surface and groundwater resources available for human
consumption is a current worldwide public health issue. No regulation on the monitoring of these
substances and therefore quality standards for the resource or treated water exist today in Europe.
A group of experts was formed in 2009 and commissioned by the WHO to review the available
scientific literature in order to identify key issues related to the health risk of human exposure to
pharmaceutical residues present in trace amounts in water, to judge the potential contributions of
changes of current regulations on drinking water quality and to provide necessary recommendations [6].
Their conclusion is that health risk has not been yet demonstrated. WHO emphasizes in its report the
lack of sufficient knowledge about the health risks associated with chronic exposure to low levels of
pharmaceutical residues present in water as mixtures. Therefore, the WHO urges the scientific
community to further research this topic in order to assess the effects related to multiexposition of
these residues (synergistic and additive effects). Very recently, the European Commission decides to
propose the introduction of four pharmaceuticals (ibuprofen, diclofenac, 17g-ethinyl estradiol,
く-estradiol) in the list of priority substances annexed to the WFD. In the United States also, some
pharmaceuticals are on the Third Contaminant Candidate List (CCL3) in order to evaluate if national
drinking water regulations are needed to protect public health.
Int. J. Environ. Res. Public Health 2012, 9 4435
In this context, the aim of the present study is to contribute to a better understanding of the
contamination of surface waters by some micropollutants (pesticides and pharmaceuticals) at a
watershed scale. More precisely relationships between micropollutants with basic water quality and
hydroclimatic parameters will be studied from historical and recent experimental data. Seasonal and
spatial variations in relation with land use and agricultural practices will also be considered.
2. Material and Method
2.1. Field Characteristics
This study was carried out in Brittany, which is the premier agricultural region of France, especially
in terms of animal farming for milk and meat, corn cultivation, and vegetable crops. Its main activity is
the food industry, which accounts for 80% of the French production [7]. Surface water accounts for
80% of the drinking water resource available in the watershed [8]. The biggest watershed in Brittany is
the Vilaine basin, which covers two thirds of the region (10,500 km²). The main river the Vilaine,
which is about 220 km in length from its source to its mouth and crosses Rennes, a city of
approximately 300,000 inhabitants. Furthermore located at the extreme downstream of the basin is the
largest drinking water treatment plant (DWTP) of the region, with a nominal production capacity of
100,000 m3 per day corresponding to more than 1 million inhabitants connected in summer.
The two sub-watersheds, the Meu and Oust, are predominantly under agricultural pressure. Table 1
gives some characteristics of these two river basins. On the Meu area, agriculture is focused essentially
on mixed farming and stockbreeding and some intensive agricultural production areas exist. On the
other side the upstream part of the Oust basin has an important food industry activity. The median part
of the Oust sub-watershed is mainly oriented towards stockbreeding—65% of farms produce milk
whereas enclosed breeding (poultry, pig, rabbit) represent approximately 22% of holdings. Soilless
cultures are spread uniformly throughout the whole basin. Finally on the downstream part of the Oust
sub-watershed, agriculture is predominantly dairy, but poultry and pig farming are also well
represented.
Table 1. Characteristics of the main sub watersheds of the Vilaine.
Characteristics Meu Oust
Length (km) 87 147
River basin area (km²) 815 3,614
Number of agricultural holdings 1,300 1,789
Utilised agricultural land (ha) 54,000 68,280
2.2. Historical Data Set
Historical data are provided from the Osur Web (Water Agency “Loire-Bretagne”) database for
water quality [9], and from the Banque Hydro (Ministry of Ecology) database for the river flows (Q)
measured at the same sites [10] (Figure 1). Seven sites have been chosen because of the number of data
on pesticides concentrations as well as their strategic location on the main basin, the Vilaine and on the
two main sub-watersheds, the Meu and Oust. They have also been selected for experimental
Int. J. Environ. Res. Public Health 2012, 9 4436
campaigns (see hereafter). Among these seven stations, three are located in the upstream part of the
Vilaine basin (V1, V5 and M12), three in the downstream part (V18, O19 and V25), and one
downstream the main wastewater treatment plant (WWTP), V8, designed for 360,000 inhabitants
equivalent (Rennes). Data acquisition periods are different considering the stations’ histories: from
1997 to 2010 for V5, V18, O19 and V25; from 2002 to 2010 for V1; from 2002 to 2009 for M10 and
from 1997 to 2006 for V8.
Figure 1. Location of stations.
In addition, daily precipitation rates have been collected from the Meteo France database [11].
Among the historical chronicles available, two specific years have been selected, 2002 and 2003,
corresponding to rainy and dry years, respectively. Characteristic temperatures and precipitation rates
are presented in Table 2. The year 2002 presents the highest percentile 90 of daily precipitation rate of
France
Britanny Vilaine’s
watershed
Int. J. Environ. Res. Public Health 2012, 9 4437
all the data acquisition years (from 1997 to 2010) and the year 2003 presents the highest percentile 90
of temperature and the lowest mean and percentile 90 daily precipitation rate.
Table 2. Characteristic temperatures and precipitation rates of historical data sets.
Mean
Temperature
(°C)
Percentile 10
Temperature
(°C)
Percentile 90
Temperature
(°C)
Mean Daily
Precipitation Rate
(mm/day)
Percentile 90 Daily
Precipitation Rate
(mm/day)
2002 (rainy) 13.04 7.54 18.96 2.75 8.42
2003 (dry) 13.20 4.58 21.56 1.68 5.72
Table 3. Pesticides of interest, their usage and quality standards.
Pesticides Nature Usage
European
environmental
quality standards
(µg/L)
European
drinking
water
standards
(µg/L)
US drinking
water quality
standards
(µg/L)
Atrazine *
(AT)
Corn
herbicide Agricultural 0.6
Individual
substance
0.1
Total
pesticides
0.5
3
Desethyl
atrazine
(ATdes) Atrazine
metabolites -
No data
No data 2-hydroxy-
atrazine
(2HAT)
Glyphosate
(GLYP)
Total
herbicide All users 70
AMPA Glyphosate
metabolite - No data
Diuron (DIU) Total
herbicide
Individuals,
local
authorities
0.2 -
Isoproturon
(ISOP)
Cereal
herbicide Agricultural 0.3
No data Mecoprop
(MECOP)
Corn
herbicide Agricultural
No data Trichlopyr
(TRIC)
Total
herbicide All users
* Prohibited in France in 2003.
Concerning water quality, physicochemical parameters have been considered (NH4+: ammonia, KN:
Kjeldhal nitrogen, NO3−: nitrate, “PO4”: orthophosphate, Pt: total phosphorus, TOC: total organic