A CONTRIBUTION TO THE METHODOLOGY FOR DETERMINING IMPACTS

ON THE CHEMICAL STATUS OF GROUNDWATER WITHIN THE WATER

FRAMEWORK DIRECTIVE. APPLICATION TO A BASIN IN SOUTHERN

Damián Sánchez García, Francisco Carrasco Cantos Canales

Centre of Hydrogeology, Department of Geology, Faculty of Science, University of Málaga. Campus de

Teatinos s.n., 29071 Málaga, Spain

Abstract In this paper a practical interpretation of the criteria established in the water framework directive (WFD) to evaluate the impacts on the groundwater chemical status is carried out by means of physicochemical parameters and related threshold values. The result has been the identification of 67 parameters to evaluate the chemical status of groundwater as well as the proposal of threshold values for each of them. Thus, when the concentration of a pollutant exceeds any of these values, it would be indicative of the failure to comply with the environmental objectives of the WFD and, therefore, it would reflect the existence of an impact on the chemical status of the groundwater body. Besides, groundwater bodies designated as protected areas in the WFD for having a special use have also been taken into account. This is the case of groundwater bodies used for the abstraction of drinking water and groundwater bodies designated as nitrate vulnerable zones. Finally, this proposed procedure has been applied in a pilot Mediterranean river basin located in southern Spain. Results show that groundwater bodies identified in aquifers with intergranular porosity in general have important impacts on their chemical status, whereas those identified in carbonate aquifers have a good chemical status. The main pollutants responsible of impacts are nitrogen and phosphorus compounds (related to agricultural practices), hydrocarbons and metals.

Keywords: water framework directive; impacts; groundwater chemical status; Mediterranean river basin; nitrogen compounds; phosphorus compounds

status of surface water and groundwater, which

1. INTRODUCCIÓN forms part of the initial characterisation of water bodies. This study consists of two parts: firstly, it According to Article 5 of the water framework focuses on an analysis of the pressures affecting directive (European Commission, 2000) all water bodies, and secondly, an assessment of the Member States are required to conduct a study impact produced by these pressures on the status determining the impact of human activity on the

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of water bodies. The combined results of these monitoring networks established under Article 8 analyses (both pressures and impacts) permits the of the directive. Furthermore, an example is given identification of water bodies at risk of not that shows the application of this methodology by reaching the environmental objectives set out in using groundwater bodies within the Article 4 of the water framework directive River basin (southern Spain). (WFD) by the year 2015 (Barth and Fawell, 2001; Due to the complexity of impact assessments in all Mostert, 2003). types of water bodies established in the WFD In accordance with the deadlines defined (inland surface waters, groundwaters, transitional in the WFD, the first analysis of pressures and waters and coastal waters), many of the works impacts was to be completed in December 2004. carrying out this evaluation focus on only one This first assessment of pressures and impacts type of water body. affecting groundwater bodies was in many cases The more frequent works that assess impacts are carried out with insufficient time or without the carried out by considering only a few parameters necessary data, this was due to several reasons: or a single one: Fernández-Ruiz et al. (2005) use the mentioned obligatory timeframes for delivery, four variables to determine the impact on the publication of methodological guidelines only groundwater (nitrates, chlorides, sulphates and shortly before the studies were to be completed, electrical conductivity), Kay et al. (2009) determine and the difficulty involved in carrying out the the impact derived from agricultural activities by study for the first time which, in many respects, is using three parameters (total organic carbon, innovative. nutrients and pesticides), and Giupponi and The analysis of pressures and impacts Vladimirova (2006), Glavan (2007) and Krause et should be reviewed and updated in each al. (2008) assess the impact by only using European river basin district by December 2013, concentrations of nutrients. Kunkel et al. (2007), and thereafter every six years. Data collected from however, significantly extend the range of groundwater quality monitoring networks should hydrochemical parameters considered (40) to be taken into account when assessing impacts. evaluate the chemical status of groundwater These monitoring networks were established bodies, whilst Carrasco et al. (2008) do so from within Article 8 of the directive and according to the water chemistry, nitrogen and phosphorus the deadline given by the directive had to be compounds, total organic carbon and various implemented by December 2006. physicochemical parameters such as electrical The aim of this work is to propose a conductivity and dissolved oxygen content. procedure to evaluate the impact on the chemical Andreadakis et al. (2007) use mathematical status of groundwater bodies, which may be a models to identify the impacts on the chemical procedure to be used in the review to be status of water bodies instead of data originating completed in 2013 in all European river basins. from monitoring networks. Comber et al. (2008) This is done by taking into account, in particular, proposed a method based on data collected from the definition of a good chemical status of water quality monitoring networks that assesses groundwaters, the environmental objectives that the presence of an impact on the chemical state of the directive provides for them, as well as water caused by metals, which can originate from physicochemical data collected through both natural and contaminant sources. More

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recently, Quevauviller (2009) describes legally- groundwater monitoring (European Commission, binding aspects of the evaluation of the chemical 2007a) provides guidance on establishing status of groudwaters as well as efforts groundwater monitoring programmes to meet undertaken at the European level to harmonise the requirements of the WFD and of the new analytical methods. Groundwater Directive. The guidance document During the 2005-2006 two-year period the number 16 (European Commission, 2007b) deals European project BRIDGE (Background criteria for with groundwater in drinking water protected the identification of groundwater thresholds) was areas and explains the obligations set out for them developed, in which several European countries under Article 7 of the WFD. Finally, the guidance participated, and whose aim was to develop a number 18 (European Commission, 2009) gives methodology for estimating contaminant Member States support to the establishment of threshold values in groundwater bodies. A threshold values and background levels, as well as summary of the methodology proposed in the to the assessment of groundwater status and framework of this European project can be trends in pollutant concentrations. consulted in Grima et al. (2006).

Especially since the publication in 2006 of the 2. ENVIRONMENTAL OBJECTIVES Daughter Directive 2006/118/EC on the 2.1.Preliminary considerations protection of groundwater, new attention has As previously stated, Article 5 of the WFD been paid to terms related to groundwater requires that an initial characterisation of water chemical status, such as background levels bodies is completed, which includes the analysis (Wendland, 2005), threshold values (Kmiecik et al., of pressures and impacts. The ultimate goal of this 2006; Hinsby et al., 2008; Marandi and Karro, analysis is to identify water bodies at risk of not 2008; Preziosi et al., 2008; Wendland et al., 2008; meeting their environmental objectives by the Blum et al., 2009), quality standards (Müller, 2008) year 2015. It is necessary to keep this frame of and pollution trends (Batlle Aguilar et al., 2007). reference in mind when assessing impacts, Apart from these works, it is worth mentioning especially because an impact occurs when a given the reports that were elaborated in 2005 by the body of water fails to meet the environmental various competent river basin authorities in objectives that the directive sets out in Article 4. compliance with the requirements of Article 5 of This leads to the conclusion that as a preliminary the directive, which include, among other things, step towards the identification of impacts on the identified impacts on the chemical status in their chemical status of groundwater bodies, it is respective groundwater bodies. These Article 5 necessary to review the environmental objectives reports, elaborated in all European river basin of groundwater bodies, which are defined in districts, can be consulted in the CIRCA web site Article 4 of the WFD and are further addressed in (http://circa.europa.eu/Public/irc/env/wfd/library) the Annex V. . 2.2. Groundwater bodies The European Commission, in the frame of the Common Implementation Strategy, has published The objective that the WFD establishes for several guidance documents especifically on groundwater bodies is to achieve a good status by groundwater. The guidance number 15 on 2015. A good groundwater status is achieved

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when both its chemical and quantitative status can be recognised as being good. Therefore By revising the above criteria, is clear that groundwater bodies will be at risk of not achieving good status for groundwater bodies is achieving their environmental objectives when largely conditioned by the fact that no damage is one of these status fails to be good. caused to surface water bodies or ecosystems that The parameters that should be used to directly depend on the groundwater body. evaluate the chemical status of groundwater bodies are electrical conductivity and the 2.3. Protected areas concentration of pollutants (Annex V of the WFD). Some groundwater bodies constitute In order to achieve good chemical status, the protected areas in accordance with Article 6 of electrical conductivity must not indicate the the WFD due to a certain use or special protection existence of salinisation or other types of of their waters. This is the case of groundwater intrusions, and concentrations of pollutants must used for the abstraction of drinking water, or be below the quality standards (maximum areas that have been declared as nitrate permissible concentrations) established in vulnerable zones due to agricultural activities. Directive 2006/118/EC (Groundwater Directive, The environmental objectives that the European Commission, 2006). Furthermore, the directive establishes for these areas are, in chemical and ecological status of surface water addition to those described in the previous section bodies and ecosystems that directly depend on (good chemical and quantitative status), those the groundwater body should not be deteriorated specified in European Community legislation (Table 1). through which they were designated as protected Table 1. Definition of good groundwater chemical areas. status according to the WFD.

Objetive Parameters Criteria Reference Good Conductivity Not indicative of Annex V, 3. PROPOSED PROCEDURE TO EVALUATE Chemic saline or other section IMPACTS ON GROUNDWATER CHEMICAL al status intrusion 2.3. STATUS Concentrati Do not exhibit the on of effects of saline or 3.1. Background pollutants other intrusions No common or single methodology exists Do not exceed the quality standards that can be applied to a European river basin applicable under district to assess impacts. This is because it would Diective mainly depend on the characteristics of each river 2006/118/EC basin, especially as far as the type, quantity and Do not result in failure to achieve the availability of data related to the groundwater’s environmental chemical status is concerned. On the other hand, objectives nor any the guidance document dealing with the analysis significant of pressures and impacts prepared by the diminution of quality of associated surface European Commission (European Commission, waters 2003) did not clarify well in this regard. In regards to published scientific works, as a conclusion it can

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be affirmed that the employment of four options: a) important impact, b) slight impact, methodologies is clearly heterogeneous: c) no impacts reported and d) no data found. parameters used to deduce the existence of an Thus, an important impact will be present impact are highly different from one another, as when one of the parameters used to assess the well as the procedure used to identify impacts chemical status does not meet the quality (through threshold values, models, temporal standard. The slight impact is reserved for those trends, and so on). Given this situation, it was cases which do not exceed the quality standard, necessary to establish an appropriate however the concentration or value of the methodology to assess impacts on the chemical parameter considered indicates that the natural status of groundwater bodies. status of a water body has been altered due to The objective of an impact assessment on human activity. If neither of these cases applies, the chemical status is to identify all the chemical the water body will be defined as no impacts substances or physicochemical parameters that reported, and where no data is available for can cause a groundwater body to not meet its evaluation, the classification no data found will be environmental objectives. Therefore, the list of assigned. pollutants and indicator parameters considered to assess impacts should be as extended as possible. 3.3. Impact assessment on the chemical status of groundwater bodies

3.2. Impact classes proposed The proposed procedure for assessing Presumably, the result of an impact impacts on groundwater bodies uses the assessment on a water body should be one of the environmental objectives to be achieved as a following: a) impacts are found, b) no impacts reference point. In this way the impact assessment reported or c) no data found. However, there may is based on criteria established in the directive to be situations where these three categories do not achieve good groundwater chemical status. sufficiently describe the kind of impact affecting a The requirements for a groundwater water body, this occurs for example when the body to have a good chemical status can be concentration of a pollutant is higher than normal summarised into the following: values in the water body although lies within the 1. No evidence exists of salinisation or seawater permissible limits set out by environmental intrusion. authorities. In this case the water body meets the 2. The concentrations of contaminants do not environmental quality standard for that exceed the quality standards set in the parameter, although at the same time it remains Groundwater Directive (Directive 2006/118/EC). clear that there is an impact given that the 3. The chemical or ecological status of surface average concentration has increased significantly. water bodies and terrestrial ecosystems that In order to be able to assess situations depend on these groundwater bodies do not such as the example given, the definition of two deteriorate. types of impacts is proposed: an important impact Table 2 shows the list of the 67 and a slight impact. Consequently, the result of an physicochemical parameters proposed in this impact assessment may be one of the following work to identify the impacts on the chemical

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status of groundwater bodies, as well as the important impacts. threshold values proposed to define the slight and Table 2. Parameters and criteria for assessing the impacts on the chemical status of groundwater bodies. (All concentrations are expressed in μg/l unless otherwise indicated.)

Impact Impact Parameter SlightImportant Parameter Slight Important 1. Electrical conductivity (d) Benzo(g,h,i)-perylene Presence MA: Σ>0.002 2. Chloride (e) Indeno(1,2,3-cd)-pyrene Upward temporary evolutions 3. Sodium 35. Simazine Presence MA>1 >4 4. Sulphate 36. Tributyltin compounds Presence MA>0.0002 >0.0015 5. Nitrates 20-50 mg/l>50 mg/l 37. Trichloro-benzene Presence MA>0.4 6. Pesticides Presence >0.1 (indiv.) >0.5 (total) 38. Trichloro-methane Presence MA>2.5 7. Alachlor Presence MA>0.3 >0.7 39. Trifluralin Presence MA>0.03 8. Anthracene Presence MA>0.1 >0.4 40. (a) Total DDT Presence MA>0.025 9. Atrazine Presence MA>0.6 >2.0 (b) P,p-DDT Presence MA>0.01 10. Benzene Presence MA>10 >50 41. Aldrin 11. Brominated diphenylether PresenceMA>0.0005 42. Dieldrin Presence MA: Σ>0.01 12. Cadmium: <40 mg/l CaCO3 - MA>0.08 >0.45 43. Endrin 40-50 mg/l CaCO3 Presence MA>0.08 >0.45 44. Isodrin 50-100 mg/l CaCO3 >0.45 MA>0.09 >0.60 45. Carbon tetrachloride Presence MA>12 100-200 mg/l CaCO3 >0.60 MA>0.15 >0.90 46. Tetrachloro-ethylene Presence MA>10 ≥200 mg/l CaCO3 >0.90 MA>0.25 >1.50 47. Trichloro-ethylene Presence MA>10 13. C10-13 Chloroalkanes Presence MA>0.4 >1.4 48. Chloro-benzene Presence MA>20 14. Chlorfenvinphos Presence MA>0.1 >0.3 49. Dichloro-benzene Presence MA>20 15. Chlorpyrifos Presence MA>0.03 >0.10 50. Ethyl-benzene Presence MA>30 16. 1,2-Dichloroethane PresenceMA>10 51. Metolachlor Presence MA>1 17. Dichloromethane PresenceMA>20 52. Terbuthylazine Presence MA>1 18. Di(2-ethylhexyl)-phthalate PresenceMA>1.3 53. Toluene Presence MA>50 19. Diuron Presence MA>0.2 >1.8 54. 1,1,1-Trichloro-ethane Presence MA>100 20. Endosulfan Presence MA>0.005 >0.010 55. Xilene Presence MA>30 21. Fluoranthene Presence MA>0.1 >1.0 56. Cyanides Presence MA>40 22. Hexachloro-benzene Presence MA>0.01 >0.05 57. Fluoride >1.0 mg/l MA>1.7 mg/l 23. Hexachloro-butadiene Presence MA>0.1 >0.6 58. Arsenic 10-50 MA>50 24. Hexachloro-cyclohexane Presence MA>0.02 >0.0459. Cupper: ≤10 mg/l CaCO3 >2.5 MA>5 25. Isoproturon Presence MA>0.3 >1.010-50 mg/l CaCO3 >11 MA>22 26. Lead and its compounds >10MA>7.2 50-100 mg/l CaCO3 >20 MA>40 27. Mercury Presence MA>0.05 >0.07>100 mg/l CaCO3 >60 MA>120 28. Naphthalene PresenceMA>2.4 60. Total chromium >10 MA>50 29. Nickel and its compounds >10MA>20 61. Chromium VI >1 MA>5 30. Nonylphenol Presence MA>0.3 >2.0 62. Selenium >1 MA>1 31. Octylphenol PresenceMA>0.1 63. Total zinc: ≤10 mg/l CaCO3 >6 MA>30 32. Pentachloro-benzene PresenceMA>0.007 10-50 mg/l CaCO3 >40 MA>200 33. Pentachloro-phenol Presence MA>0.4 >1.050-100 mg/l CaCO3 >60 MA>300 34. Polyaromatic hydrocarbons:>100 mg/l CaCO3 >100 MA>500 (a) Benzo(a)pyrene Presence MA>0.05 >0.10 64. Total phosphorus >12 >50 (b) Benzo(b)fluor-anthene 65. Biological oxygen demand >2.5 mg/l >4.0 mg/l Presence MA: Σ>0.03 (c) Benzo(k)fluor-anthene 66. Ammonium Presence >0.5 mg/l 67. Phosphate Presence >0.5 mg/l “MA”: mean annual concentration; the other values are expressed as maximum allowable concentrations

Salinisation or seawater intrusion ­ Chloride concentration

Four physicochemical parameters are ­ Sodium concentration proposed to identify the existence of an impact ­ Sulphate concentration made by salinisation or seawater intrusion The criteria proposed to identify an (parameters 1 to 4 in Table 2): impact by salinisation or seawater intrusion are ­ Electrical conductivity based on the existence of increasing trends over

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time with respect of any of these parameters. mere existence in water as evidence of a slight Given the difficulty of establishing a single impact. quantitative threshold to differentiate between the important and slight impacts, a distinction Surface water bodies and associated ecosystems based on the following characteristics of One of the requirements of the WFD for a increasing trends is proposed: groundwater body to have a good chemical ­ number of control points showing an status is that the status of associated surface water upward trend bodies and dependent ecosystems does not ­ number of physicochemical parameters deteriorate by its action. showing an upward trend Many groundwater bodies have been ­ clarity or evidence of trends defined in aquifers that discharge through one or more springs that in many cases feed rivers and

Quality standards established in Directive lakes, which, in turn, can constitute surface water 2006/118/EC bodies. There are stretches of streams, especially at the headwaters, where groundwater from The content of the Directive 2006/118/EC springs greatly contributes to the volume of water. is addressed to groundwater bodies that Consequently, a deterioration in the status of this following the initial characterisation have been groundwater would result in a deterioration of identified as being at risk of failure to reach the the quality of surface water bodies and associated environmental objectives. Two quality standards ecosystems (Castro and Hornberger, 1991; Winter are established in Annex I of this directive related et al., 1998; Winter, 1999; Woessner, 2000; to the concentration of nitrate (50 mg/l) and Hancock et al., 2005). For this reason, it was pesticides (0.1 μg/l for a single pesticide and 0.5 considered necessary to include in the list of μg/l for the sum of pesticides). parameters used to assess the chemical status of These two parameters (5 and 6 in Table groundwater bodies, those parameters which are 2) apply to all groundwater bodies given that they necessary to evaluate the chemical status of should be used to evaluate their chemical status in surface waters. These substances are numbered accordance with Annex V of the WFD. These from 7 to 65 in Table 2. quality standards are proposed to identify the The parameters 7 to 47 in Table 2 were existence of an important impact given that going obtained from the Directive 2008/105/EC over this limit would imply that a groundwater (European Commission, 2008), which defines body fails to reach the good chemical status. quality standards that set maximum permissible Furthermore, it is necessary to define another concentrations allowed in surface water for 33 threshold value to identify the existence of a slight priority substances (those substances posing a impact. In the case of nitrate, a compound that significant risk to, or via, the aquatic environment) can be found naturally in water, it is proposed to in addition to 8 other pollutants. These maximum define a slight impact when the concentration is concentrations or quality standards are expressed between 20 and 50 mg/l. With respect to in two different manners: as average annual pesticides, which are substances that do not come values and as maximum allowable concentrations. from natural sources, it was decided to consider its

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In this proposal, surpassing these concentrations is - In the case of arsenic (number 58 in considered as evidence of an important impact Table 2), which unlike the above substances can since they will prevent an associated surface water have a natural origin, the threshold considered body to reach a good chemical status. was 10 μg/l which is the maximum concentration

In regards to slight impacts, the 41 recommended by the World Health Organization substances have been grouped into two types: (after Baird, 1999). those that are not naturally found in water (all of - Concentrations assigned to the them except for cadmium, lead and nickel), and parameters fluoride, copper, total chromium, those that can originate from both natural sources chromium VI, selenium and zinc to detect a slight as well as polluting activities. In regards to those impact have been established within the not naturally found in water, it was decided that framework of this work. their mere presence in water is indicative of a Finally, the substances 64 and 65 (total slight impact, and with respect to cadmium, lead phosphorus and biological oxygen demand and nickel (numbers 12, 26 and 29 respectively in respectively) were obtained from Annex VIII of the Table 2), a slight impact is present when WFD and thresholds considered were taken from concentrations surpass 10 μg/l for lead and nickel, the guidance document on the analysis of and 0 to 0.9 μg/l (depending on water hardness) pressures and impacts elaborated by the for cadmium. In the case of lead, the value European Commission (European Commission, corresponds to the maximum concentration 2003). recommended by the World Health Organization

(after Baird, 1999), whilst values of nickel and Other Pollutants cadmium have been established within the Ammonium and phosphate (parameters framework of this work as no previous 66 and 67 in Table 2) are not included in the information was found. definition of good chemical status for Substances from 48 to 63 in Table 2 were groundwaters, however they can be found in obtained from the Royal Decree 995/2000, which other parts of the WFD: ammonium is one of the defined the quality objectives for certain core parameters that must be monitored in all pollutants (Official [Spanish] State Gazette, BOE groundwater monitoring networks of chemical No. 147, 20.6.2000). The maximum status (Annex V, section 2.4.2), and phosphate is concentrations established in the Royal Decree included in the list of the main pollutants have been interpreted as indicating the existence established in Annex VIII of the WFD. Therefore, of an important impact. In regards the thresholds both ammonium and phosphate have been that identify the existence of a slight impact, its considered in the list of parameters used to assess estimate is calculated using the following three the chemical status of groundwater bodies. criteria: Their mere presence in groundwater has - For chemical substances that do not been interpreted as indicative of a slight impact have a natural origin, their mere presence in the since they rarely have a natural origin, whereas water reflects the existence of a slight impact (cells concentrations greater than 0.5 mg/l are with the term "Presence" in Table 2).

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indicative of an important impact (value on Groundwater in Drinking Water Protected established within the framework of this work). Areas; European Commission, 2007b).

Water intended for human consumption

3.4. Impact assessment in protected areas is regulated by the Directive 98/83/EC (European Commission, 1998). Annex I of this directive In Annex IV of the WFD, the types of establishes the minimum requirements, expressed protected areas to be considered are specified: as maximum allowable concentrations of a variety 1. Areas designated for the abstraction of water of microbiological (Part A) and chemical (Part B) intended for human consumption which provide parameters that water must meet in order to be more than 10 m3 per day or serve more than 50 considered as suitable for human consumption. people. Part C of the annex presents other parameters, 2. Areas designated for the protection of named indicators, which unlike the former economically significant aquatic species. parameters, do not indicate that water is unfit for 3. Bodies of water designated as recreational human consumption if its limit is breached, but waters, including areas designated as bathing will require a study to clarify whether this waters. represents a risk to human health. The 4. Nutrient-sensitive areas, including areas interpretation made in this work is that the failure designated as vulnerable zones and areas of complying with parameters specified in Parts A designated as sensitive areas. and B as well as in Part C, denote the existence of

5. Areas designated for the protection of habitats an impact on the status of water bodies which or species where the maintenance or provide water for human consumption. For this improvement of the status of water is an reason, the 48 parameters found in parts A, B and important factor in their protection. C of Annex I of this directive (not including those required by water commercially bottled) are taken Out of these five categories of protected into account in assessing the impacts in these areas, the only ones that can be defined in protected areas (Table 3). groundwater are areas designated for drinking water catchments and areas vulnerable to nitrate In accordance with the procedure pollution from agriculture; these will be addressed followed in the preceding paragraph, the in this work. maximum permissible concentrations set out in the directive are considered as indicative of an

important impact, except for colour, odour, taste Water intended for human consumption and turbidity (parameters 33, 38, 42 and 46 Groundwaters used for the abstraction of respectively in Table 3). Directive 98/83/EC drinking water are considered in a special way in provides a qualitative threshold for these four the WFD because of the importance of their use parameters; it indicates that its value must be (human consumption). Article 7 of the Directive is "acceptable for the consumers and without specifically devoted to these waters and there is a anomalous changes" which makes assessment guidance document on groundwater intended for difficult. For this reason, in this work the use of human consumption (Guidance Document nº16 numerical thresholds for these four parameters was preferred. These numerical thresholds were

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established by the Royal Decree 140/2003 of 7 3. Finally, for substances that may originate from February (Official [Spanish] State Gazette, BOE No. both natural sources and polluting activities, a less 45, 21.2.2003) which incorporated the Directive demanding threshold was selected usually 98/83/EC into the Spanish legal system. corresponding to 50% of the threshold associated

Thresholds that indicate a slight impact have been with important impacts. established within the framework of this work and Nitrate vulnerable zones were established using the following criteria: The Directive 91/676/EEC (European 1. It was considered that a slight impact does not Commission, 1991) concerning the protection of apply to parameters where their mere presence in waters against nitrate pollution originating from water indicates an important impact (parameters agricultural activities aims at reducing pollution 1, 2, 32 and 44 in Table 3) or those that are caused by nitrates and preventing further evaluated in terms of the existence of "anomalous contamination. This requires Member States to changes” (parameters 43 and 45 in Table 3). designate nitrate vulnerable zones, which are

2. In the case that substances are not derived from areas where runoff flows into surface waters that a natural source, once again their presence in water indicates the existence of a slight impact (cells with the term "Presence" in Table 3).

Table 3. Parameters and criteria for assessing impacts in water bodies designated as protected areas for supplying water for human consumption. (All concentrations are expressed in μg/l unless otherwise indicated.)

Impact Impact Parameter SlightImportant Parameter Slight Important Microbiological parameters 25. Selenium >5 >10 1. Escherichia coli ->0 CFU/100 ml 26. Tetrachloroethene Presence >10 2. Enterococci - >0 CFU/100 ml 27. Trihalomethanes — Presence >100 Chemical parameters Total 3. Acrylamide Presence>0.1 28. Vinyl chloride Presence >0.5 4. Antimony Presence >5.0 Indicator parameters 5. Arsenic >5>10 29. Aluminium >100 >200 6. Benzene Presence>1.0 30. Ammonium >0.25 mg/l >0.5 mg/l 7. Benzo(a)pyrene Presence>0.01 31. Chloride >125 mg/l >250 mg/l 8. Boron >0.5 mg/l>1 mg/l 32. Clostridium perfringen - >0 CFU/100 ml 9. Bromate Presence>10 33. Colour >7.5 mg/l Pt >15 mg/l Pt 10. Cadmium >2.5>5.0 34. Conductivity >1250 µS/cm >2500 µS/cm 11. Chromium >25>50 35. pH <7 or >9 ≤6.5 or ≥9.5 12. Copper >1 mg/l>2 mg/l 36. Iron >100 >200 13. Cyanide Presence>50 37. Manganese >25 >50 Dilution index >2 Dilution index >3 at 14. 1,2-dichloroethane Presence>3 38. Odour at 25ºC 25ºC 15. Epichlorohydrin Presence>0.1 39. Oxidisability >2.5 mg/l O2 >5.0 mg/l O2 16. Fluoride >1 mg/l>1.5 mg/l 40. Sulphate >125 mg/l >250 mg/l 17. Lead >5>10 41. Sodium >100 mg/l >200 mg/l Dilution index >2 Dilution index >3 at 18. Mercury Presence>1 42. Taste at 25ºC 25ºC 19. Nickel >10>20 43. Colony count 22° - No abnormal change 20. Nitrate 20-50 mg/l>50 mg/l 44. Coliform bacteria - >0 CFU/100 ml 21. Nitrite >0.25 mg/l>0.5 mg/l 45. Total organic carbon - No abnormal change 22. Pesticides Presence>0.1 46. Turbidity >2.5 NTU >5.0 NTU 23. Pesticides — Total Presence>0.5 47. Tritium >50 Bq/l >100 Bq/l 24. Polycyclic aromatic hydrocarbons Presence>0.1 48. Total indicative dose >0.05 mSv/year >0.10 mSv/year Values are expressed as maximum allowable concentrations; "CFU": colony-forming units; "NTU": nefelometric turbidity unit; "Bq": becquerel; "Sv": sievert

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have, or may have, a nitrate concentration above Alpujarride and Malaguide are largely made up of the 50 mg/l concentration limit specified in metamorphic rocks (metapelites and marbles), Directive 75/440/EEC (European Commission, whereas in the Dorsal complex limestones and 1975), or into groundwaters that contain or could dolomites are the most representative rocks. contain more than 50 mg/l of nitrate. The Flysch unit lies between the Internal Consequently, the only parameter to be and External Zones of the Cordillera. It is made up considered in assessing impacts in this type of of detrital rocks (sandstones, clays and marls) of protected areas is the nitrate ion, and exceeding Cretaceous and Tertiary ages. Within the External this concentration limit (50 mg/l) will determine Zone, the Subbetic domain is mainly made up of the existence of an important impact. In regards to Mesozoic materials such as Triassic clays and the slight impact, the same threshold has been evaporites, and Jurassic limestones and dolomites. considered for groundwater bodies and water intended for human consumption, and is Figure 1. Location and geologic map of the established at a concentration between 20 and 50 Guadalhorce River basin mg/l of nitrate.

4. RESULTS OF THE APPLICATION OF THE METHODOLOGY IN A CASE STUDY AREA

4.1. Description of the case study area

The pilot area where the proposed methodology to identify impacts has been applied corresponds to the Guadalhorce River basin. It is located in the Málaga province (southern Spain), in the western Mediterranean (Fig. 1). Covering an area of almost 3200 km2, it is one of the main Mediterranean basins in southern Spain.

The climate of the region is characterised by rainy winters and dry and hot summers, with Groundwater in the study area can be mean annual temperatures ranging between found in carbonate, porous, evaporitic and even 13ºC and 18ºC. The mean annual values of in low permeability rocks. Carbonate rocks are precipitation range from less than 400 mm to made up of Mesozoic limestones, dolomites and 1100 mm in mountainous areas and there is a marbles in which fracturation and karstification seasonal rainfall pattern coherent with the permit water storage. In general, these aquifers Mediterranean climatic context. have large water storage capacities and they are

Rocks that outcrop in the Guadalhorce frequently used for the abstraction of water River basin (Fig. 1) belong to the Betic Cordillera. intended for human consumption due to their The southern sector is constituted by rocks of the good chemical quality. Internal Zone of the Cordillera, divided into the Aquifers with intergranular porosity are Alpujarride, Malaguide and Dorsal complexes. The formed by modern deposits (Neogene and

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Quaternary) such as calcareous sandstones or networks: a self-monitored network established as alluvial sediments. Evaporitic rocks (gypsum and part of this work, and the monitoring networks of halite) are found exclusively inside large outcrops the Spanish Geological Survey (IGME) and the of Triassic rocks (Fig. 1), which are mainly Andalusian Water Agency (AAA). A total of 301 constituted by low permeability deposits (clays points were controlled from which 1541 samples and marls). The evaporites can be easily dissolved, were taken from the period 1974 to 2007 (Table creating local high permeability zones by 4). karstification processes. Table 4. Groundwater chemical status monitoring

The groundwater bodies that have been networks used in this work. Nº of considered in this work were defined in a previous Groundwater monitor Nº of study carried out by the same authors (Sánchez et monitoring Period ing samples network al., 2009), in which groundwater bodies were points delineated in the Guadalhorce River basin Established in 78 247 2004-2007 according to their own methodology. The result this work Spanish was the delineation of 24 groundwater bodies Geological 202 1215 1974-2003 covering areas between 2 and more than 900 Survey (IGME) km2 (Fig. 2). The nature of the materials where Andalusian these water bodies are located is variable: 14 Water Agency 21 79 2002-2004 (AAA) carbonate, 9 detrital and 1 evaporitic materials. Total 301 1541 1974-2007

Figure 2. Bodies of groundwater in the Guadalhorce A total of 105 physicochemical River basin (Sánchez et al., 2009). parameters were analysed in the three control networks including electrical conductivity, temperature, pH, dissolved oxygen, redox potential, total organic carbon, major ions, nitrogen and phosphorus compounds, metals, hydrocarbons, organophosphate and organochlorine pesticides, volatile organic compounds, trihalomethanes and triazines.

4.3. Impacts on groundwater chemical status

To assess the impact on the chemical status of groundwater bodies in the Guadalhorce River basin, data from the monitoring networks 4.2. Data used previously described and the list of Identifying impacts on the chemical status physicochemical parameters and threshold values of groundwater bodies in the Guadalhorce River given in Table 2 have been used. basin was carried out from the analysis of Before commencing the assessment is it physicochemical data from three control necessary to identify groundwater bodies that

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feed a surface water body or ecosystem. In this Sierra de Guaro and Bajo Guadalhorce case, it would be necessary to also analyse the groundwater bodies (16 and 23 respectively in physicochemical parameters which assess the Figure 2), of which the first lacks significant chemical status of surface water bodies springs and the second discharges directly to the (parameters 7 to 65 in Table 2). On the other sea. hand, groundwater bodies that are not associated The 67 physicochemical parameters with any surface water body or ecosystem do not necessary to assess the impacts on the chemical need to be analysed for these parameters. status of groundwater bodies have been grouped All groundwater bodies within the into six categories according to their nature and Guadalhorce River basin, except for two, are application. These categories are: 1. Parameters associated with surface waters. In some cases, that indicate salinisation or seawater intrusion, 2. springs feed the surface water bodies, and in Nitrogen and phosphorus compounds, 3. other cases groundwater resources contribute to Pesticides; 4. Metals, 5. Hydrocarbons and 6. wetlands in the basin. The two exceptions are the Others (Table 5).

Table 5. Distribution of the physicochemical parameters necessary to assess the impacts on the groundwater chemical status into the 6 categories proposed

Category Parameters Salinisation Electrical conductivity, Chloride, Sodium, Sulphate Nitrogen and phosphorus compounds Nitrate, Total Phosphorus, Ammonium, Phosphate Total Pesticides, Alachlor, Atrazine, Chlorfenvinphos, Chlorpyrifos, Diuron, Endosulfan, Hexachlorocyclohexane, Pesticides Isoproturon, Pentachlorobenzene, Simazine, Tributyltin Compounds, Trifluralin, DDT, Aldrin, Dieldrin, Endrin, Isodrin, Metolachlor, Terbuthylazine Cadmium, Lead, Mercury, Nickel, Arsenic, Copper, Total Metals Chromium, Chromium VI, Zinc Anthracene, Benzene, Brominated Diphenyl Ether, C10-13 Chloroalkanes, 1,2-Dichloroethane, Dichloromethane, Di(2- ethylhexyl) Phthalate, Fluoranthene, Hexachlorobenzene, Hexachlorobutadiene, Naphthalene, Nonylphenol, Hydrocarbons Octylphenol, Pentachlorophenol, Polyaromatic Hydrocarbons, Trichlorobenzene, Trichloromethane, Carbon Tetrachloride, Tri- and Tetrachloroethylene, Chloro- and Dichlorobenzene, Ethylbenzene, Toluene, 1,1,1-Trichloroethane, Xylene Cyanide, Fluoride, Selenium, Biological Oxygen Demand Others (BOD)

The only groundwater bodies where an identified (Figure 3 a, b and c). In view of these impact has been identified due to salinisation are results, this groundwater body has been classified the Aluvial del Bajo Guadalhorce and Vega de as bearing an important impact (Table 6). groundwater bodies. In the case of the In the Vega de Antequera water body, 13 control Aluvial del Bajo Guadalhorce groundwater body, network points have been analysed with data the temporal trends of 16 control points have series reaching up to 24 years, out of these only been analysed from records that reach up to a one point shows an increasing temporal trend of period of 27 years. In six control points, an chloride and sodium concentrations (Figure 3 d). increasing trend over time regarding the electrical Given the localised nature of the salinisation, this conductivity, chloride and sodium have been water body was assigned a slight impact (Table 6).

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Figure 3. Temporal evolution of electrical conductivity and concentration of sodium and chloride in three control points of the Aluvial del Bajo Guadalhorce water body (a, b and c) and one control point in the Vega de Antequera water body (d).

(a) (b)

(c) (d)

Data analysis on the chemical state related Bajo Guadalhorce water bodies (1, 3, 7 and 22 in to nitrogen and phosphorus compounds has lead Figure 2). In the Aluvial del Bajo Guadalhorce and to the conclusion that an important impact exists the Vega de Antequera water bodies, an in the Aluvial del Bajo Guadalhorce and Vega de important impact has been identified due to water Antequera water bodies due to concentrations of concentrations exceeding the environmental nitrate, ammonium and phosphate, and in the quality standard with respect to total pesticides, Llanos de and Llanos de atrazine and endosulfan. In the Sierra de water bodies due to concentrations of nitrate and Archidona water body, a slight impact is assigned ammonium (Table 6). Moreover, in four other resulting from concentrations of total pesticides groundwater bodies a slight impact has been and endosulfan (Table 6). identified due to nitrate concentrations (Table 6). Only four groundwater bodies dispose of pesticide data, these are the Sierra de Archidona, Vega de Antequera, Sierra de and Aluvial del

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Table 6. Results of the impact assessment on the chemical status of groundwater bodies in the Guadalhorce River basin. (II: important impact; SI: slight impact; NI: no impacts reported; empty cell: no data found; "-": not applicable).

Chemical status Drinking water

Body of groundwater Other Other Metals Metals Bacteria Pesticides Salinisation Salinisation Hydrocarbons Hydrocarbons N-P compunds Vulnerable zones N and pesticides

1. Sierra de Archidona SI SI NI II NI NI SI NI II NI - 2. Sierra de Gibalto-Arroyo Marín NI SI NI NI NI SI NI - 3. Vega de Antequera SI II II II II II ------II 4. Acuífero de la Magdalena NI NI ------5. Llanos de Campillos II NI ------6. Llanos de Almargen II NI ------7. Sierra de Teba NI SI NI NI II NI SI SI NI II NI - 8. Sierra de Cañete NI SI NI NI NI SI NI - 9. Sierra del Valle de Abdalajís NI NI II NI NI SI NI SI NI - 10. Torcal de Antequera NI NI NI NI NI NI NI NI - 11. Sierras Cabras-Camarolos-San Jorge NI NI NI NI NI NI NI NI NI - 12. Sierras Blanquilla-Merinos NI NI NI NI NI NI NI NI - 13. Sierra Hidalga NI NI NI ------14. Sª Nieves-Prieta-Alcaparaín NI NI NI NI NI NI NI NI NI - 15. Serrezuela de NI NI NI ------16. Sierra de Guaro NI - - - NI NI NI - 17. Sierra Blanca NI NI NI NI NI NI NI NI - 18. Sierra de NI NI NI NI NI NI NI - 19. Hacho de Álora NI NI ------20. Hacho de NI NI NI NI NI - 21. Sierra Llana-Mioceno de El Romeral NI NI NI NI NI - 22. Aluvial del Bajo Guadalhorce II II II II II II II II II II II II 23. Bajo Guadalhorce NI - - - NI NI NI NI NI 24. Trías de Antequera NI NI NI NI ------

Three groundwater bodies have been anthracene, of which data is available for seven identified with impacts associated to metal other water bodies. In the four named water concentrations: the Vega de Antequera water bodies, an important impact was defined due to body, with an important impact due to lead, the presence of hydrocarbons in the water at a copper and zinc concentrations; Aluvial del Bajo concentration above the threshold value (Table Guadalhorce, with an important impact because 6). In the Aluvial del Bajo Guadalhorce of lead concentrations, and Sierra del Valle de groundwater body, monitoring points that Abdalajís, also with an important impact, in this detected hydrocarbons are located near industrial case associated with zinc concentrations (Table 6). areas and Malaga airport. Only the Sierra de Archidona, Vega de In regards to the ‘Other components’ Antequera, Sierra de Teba and Aluvial del Bajo category (Table 5), the Aluvial del Bajo Guadalhorce groundwater bodies, dispose of Guadalhorce and Vega de Antequera hydrocarbon data with the exception of groundwater bodies were defined as bearing an

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important impact due to their concentration of Table 8. Distribution of the 48 physicochemical selenium (Table 6). parameters necessary to assess the impacts on drinking water protected areas into the 6 categories proposed. Category Parameters 4.4. Impacts in protected areas Electrical conductivity, Chloride, Sodium, Salinisation This section assesses the impacts on Sulphate groundwater bodies defined as protected areas in Escherichia coli, Enterococci, Clostridium accordance with Article 6 and Annex IV of the Bacteria perfringens, Colony count 22°, Coliform WFD. The types of groundwater protected areas bacteria Nitrogen present in the Guadalhorce River basin are: Nitrate, Nitrite, Ammonium, Pesticides, compounds and Total Pesticides 1 Groundwater intended for human consumption pesticides 2 Nitrate vulnerable zones Antimony, Arsenic, Boron, Cadmium, Metals Chromium, Copper, Lead, Mercury, Nickel, Aluminium, Iron, Manganese Groundwater used for the abstraction of drinking Acrylamide, Benzene, Benzo(a)pyrene, water 1,2-Dichloroethane, Epichlorohydrin, Table 7 shows the 16 groundwater bodies Hydrocarbons Polycyclic aromatic hydrocarbons, whose resources are used for human supply. Tetrachloroethylene, Total Trihalomethanes, Vinyl Chloride

Bromate, Cyanide, Fluoride, Selenium, Table 7. Groundwater bodies designated as protected Colour, pH, Odour, Oxidisability, Taste, Others areas for providing water destined to human Total Organic Carbon, Turbidity, Tritium, consumption Total indicative dose Sierra de Archidona Nieves-Prieta-Alcaparaín Sierra de Gibalto-Arroyo Marín Sierra de Guaro An important impact associated to Sierra de Teba Sierra Blanca salinisation has been identified in the Aluvial del Sierra de Cañete Sierra de Mijas Bajo Guadalhorce groundwater body (Drinking Sierra del Valle de Abdalajís Hacho de Pizarra water columns in Table 6). Here, the Sierra Llana-Mioceno de concentrations of various parameters assessed Torcal de Antequera El Romeral exceed the established threshold. Sierras de las Cabras-Camarolos- Aluvial del Bajo In the Sierra de Teba and Sierra del Valle San Jorge Guadalhorce Sierras Blanquilla-Merinos Bajo Guadalhorce de Abdalajís water bodies, a slight impact has been identified respectively (Table 6). The first is The impacts on the status of these due to all four parameters indicating a salinity groundwater bodies will be evaluated based on greater than that expected for a carbonate the parameters and criteria set out in Table 3, aquifer. This may be due to the infiltration of which have been grouped into six different water from Venta River into the aquifer in the area categories: 1. Parameters that indicate salinisation, known as Tajo del Molino, where the river runs 2. Bacteria, 3. Nitrogen compounds and directly above permeable rocks (Carrasco et al., pesticides, 4. Metals, 5. Hydrocarbons and 6. 2007) (Fig. 4). Water from Venta River in this Others (Table 8). stretch has an electrical conductivity greater than 2000 μS/cm and chloride, sulphate and sodium contents between 250 and 500 mg/l. With

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respect to the Sierra del Valle de Abdalají¬s protagonism, where an important impact groundwater body, a monitoring point was associated with all parameters (nitrate, nitrite, detected with chloride and sulphate ammonium and pesticides; Table 6) is observed. In concentrations and electrical conductivity values another four groundwater bodies a slight impact above the threshold established. This salinisation has been defined, mainly due to nitrate seems to be related to water infiltrating from concentrations (Table 6). Guadalhorce reservoir or the Villaverde water In the Aluvial del Bajo Guadalhorce and deposit, which store water with a high degree of Sierra del Valle de Abdalajís groundwater bodies, mineralisation (Fig. 5). important and slight impacts have been identified Figure 4. The area known as Tajo del Molino where respectively due to metal (manganese) Venta River runs through limestones in the Sierra de concentrations (Table 6). Teba groundwater body. In regards to hydrocarbon concentrations, an important impact has been detected in three groundwater bodies (Sierra de Archidona, Sierra de Teba and the Aluvial del Bajo Guadalhorce) due to concentrations of benzene, 1,2- dichloroethane and trihalomethanes. Finally, the analysis of the parameters Figure 5. Sierra del Valle de Abdalajís groundwater included in the category ‘Other components” body, Guadalhorce reservoir, Villaverde water deposit shows an important impact in the Aluvial del Bajo and monitoring point showing salinisation, with Guadalhorce groundwater body (Table 6) due to indication of topographic heights. selenium.

Vulnerable zones Three groundwater bodies are located in nitrate vulnerable zones within the Guadalhorce River basin; these are the Vega de Antequera, Aluvial del Bajo Guadalhorce and Bajo Guadalhorce groundwater bodies. In nitrate vulnerable zones, nitrate is the only chemical substance that must be analysed in these water bodies to verify whether or not an impact exists. Since threshold values used in

nitrate vulnerable zones are the same as those In the absence of data it was not possible used to assess impacts on the chemical status of to assess the impacts arising from the presence of groundwater bodies, the results are the same, bacteria in groundwater bodies (Table 6). which is an important impact on Vega de With regard to nitrogen compounds and Antequera and Aluvial del Bajo Guadalhorce pesticides category (Table 8), the Aluvial del Bajo water bodies, and no impact present in the Bajo Guadalhorce groundwater body takes Guadalhorce water body (Table 6).

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5. DISCUSSION OF RESULTS available data does not indicate the presence of

According to the results obtained in the any kind of impact. However, in 4 of these 15 previous section (Table 6), in the river basin 7 groundwater bodies, the serious lack of data lead groundwater bodies (29%) have at least one to them being classified as no data found instead important impact, in 2 groundwater bodies (8%) of no impacts reported (Table 9). at least one slight impact has been identified, and in the remaining 15 water bodies (63%) the

Table 9. Distribution of groundwater bodies in the Guadalhorce River basin depending on the type of impact identified in its chemical status. It also indicates the nature of each water body (C: carbonate; D: detrital; E: evaporitic).

Important impact Slight impact No impact No data Sierra de Gibalto- Acuífero de la Sierra de Archidona (C) Torcal de Antequera (C) Arroyo Marín (C) Magdalena (D) Vega de Antequera (D) Sierra de Cañete (C) Sª Cabras-Camarolos-San Jorge (C) Hacho de Álora (D) Llanos de Campillos (D) Sierras Blanquilla-Merinos (C) Hacho de Pizarra (D) Sª Llana-Mioceno de Llanos de Almargen (D) Sierra Hidalga (C) El Romeral (D) Sierra de Teba (C) Sª Nieves-Prieta-Alcaparaín (C) Sª del Valle de Abdalajís (C) Serrezuela de Carratraca (C) Aluvial Bajo Guadalhorce (D) Sierra de Guaro (C) Sierra Blanca (C) Sierra de Mijas (C) Bajo Guadalhorce (D) Trías de Antequera (E) Out of the 7 water bodies where an to this reason); these compounds, especially important impact was observed, the Aluvial del nitrate concentrations, are the main responsible of Bajo Guadalhorce groundwater body is to be impacts on the chemical status of other pointed out as being the one covering the groundwater bodies at European level (Mohaupt greatest range of parameters rated with an et al., 2005; Andreadakis et al., 2007; Pintar et al., important impact: 12 of 13 that were evaluated 2007; Carrasco et al., 2008). Following this are (Table 9). This is due to its proximity to the town of parameters which indicate salinisation and Malaga, which has caused many industrial, hydrocarbons (responsible for 4 impacts on water commercial and transport infrastructures bodies respectively), and pesticides and metals (highways, airports) to be built in the area. (responsible for 3 impacts on water bodies

In the Llanos de Campillos and Llanos de respectively). Almargen groundwater bodies, an important Groundwater bodies defined as no impact exists (due to nitrogen and phosphorus impacts reported correspond to areas barely compounds) that seems to be related to local affected by human activities. With the exception intensive livestock production. of two groundwater bodies (Bajo Guadalhorce

In regards the factors that generate the previous and Trías de Antequera), they are all found in impacts, concentrations of nitrogen and carbonate aquifers. In these areas, the abrupt phosphorus compounds in water are mainly relief, difficult access, the great depth to the water responsible (8 water bodies have an impact due table and the lack of soil are factors that reduce

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human activities when compared to detrital groundwater bodies used for the abstraction of aquifers. The characteristics of detrital aquifers, drinking water), two with a slight impact, eleven which are rather opposite to carbonate aquifers, with no impact reported and four with no data favour the development of human activities (Vías found. In regards to the factors that cause these 2005; Perles Roselló et al., 2009). This explains impacts, the nitrogen and phosphorus why out of the five groundwater bodies in detrital compounds (mainly nitrate) are the most aquifers and with sufficient data to assess impacts, remarkable, especially in bodies of groundwater four have been defined with an important impact. used for the abstraction of drinking water. Their

In regards to the 16 groundwater bodies origin is most likely related to the agriculture and used for the abstraction of drinking water, in 6 of livestock activities carried out above these water them a slight or important impact has been bodies. Groundwater bodies of a detrital nature identified, with nitrate concentrations being the stand out for having the greatest amount of main responsible of that impacts. impacts present. On the contrary, all groundwater bodies except for one with no impact reported are

of a carbonate nature, this is due to the scare 6. CONCLUSIONS development of human activities in these areas. This work presents a methodology for The results of this study show that some assessing the impacts on the chemical status of bodies of groundwater used for the abstraction of groundwater bodies. The proposed procedure drinking water have important impacts that could has been developed on the basis of the make them not to comply with the environmental environmental objectives of the WFD for objectives established under Article 4 of the WFD. groundwater bodies, including the objectives Due to the special use of this groundwater bodies required for groundwater in protected areas: (human consumption), the measures that each those intended for human consumption as well as Member State must establish to ensure the nitrate vulnerable zones. Following this, criteria compliance with Article 4 objectives, should be based on a series of physicochemical parameters prioritized taking into account first these and threshold values were established, arising groundwater bodies. from their respective environmental objectives, from which the existence of an impact has been determined. In the case of groundwater bodies, REFERENCES 67 parameters have been proposed, 48 for water Andreadakis, A., Gavalakis, E., Kaliakatsos, L., intended for human consumption and 1 (nitrate) Noutsopoulos, C. and Tzimas, A. (2007). The for vulnerable zones. Finally, two possible implementation of the Water Framework Directive classifications to define the impact on (WFD) at the river basin of Anthemountas with groundwater have been established in function of emphasis on the pressures and impacts analysis. their magnitude, slight and important. Desalination, 210: 1–15. The result of the application of this methodology in the Guadalhorce River basin has Baird, C. (1999). Environmental Chemistry. W.H. been the identification of seven water bodies with Freeman and Company, 2nd edition, 557 pp. an important impact (four of them being

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Barth, F. and Fawell, J. (2001). The Water European Commission (1975). Council Directive Framework Directive and European Water Policy. concerning the quality required of surface water Ecotoxicology and Environmental Safety, 50: 103– intended for the abstraction of drinking water in 105. the Member States (75/440/EEC). Official Journal, L 194, 25.7.1975, pp. 26–31. Batlle Aguilar, J., Orban, P., Dassargues, A. and Brouyère, S. (2007). Identification of groundwater European Commission (1991). Council Directive quality trends in a chalk aquifer threatened by 91/676/EEC concerning the protection of waters intensive agriculture in Belgium. Hydrogeology against pollution caused by nitrates from Journal, 15(8): 1615–1627. agricultural sources. Official Journal, L 375, 31.12.1991, pp. 1-8. Blum, A., Legrand, H., Grath, J., Scheidleder, A., Broers, H.-p., Tomlin, C. and Ward, R. (2009). European Commission (1998). Council Directive Threshold Values and the Role of Monitoring in 98/83/EC on the quality of water intended for Assessing Chemical Status Compliance. In: human consumption. Official Journal of the Groundwater Monitoring (P. Quevauviller, A.-M. European Communities, L 330, 5.12.1998, pp. 32- Fouillac, J. Grath and R. Ward, eds.). John Wiley & 54. Sons, Ltd, Chichester, UK. European Commission (2000). Directive Carrasco, F., Sánchez, D. and Vadillo, I. (2007). 2000/60/EC of the European Parliament and of Atlas hidrogeológico de la provincia de Málaga, the Council Establishing a Framework for volume 2, chapter Sierra de Teba-Almargen- Community Action in the Field of Water Policy. Campillos, 95–100. Instituto Geológico y Minero Official Journal of the European Communities, L de España y Diputación Provincial de Málaga. 327, 22.12.2000, pp. 1-72.

Carrasco, F., Sánchez, D., Vadillo, I., Andreo, B., European Commission (2003). Analysis of Martínez, C. and Fernández, L. (2008). Application Pressures and Impacts. Guidance document nº3. of the European water framework directive in a Office for Official Publications of the European Western Mediterranean basin (Málaga, Spain). Communities. Produced by Working Group 2.1 - Environmental Geology, 54: 575–585. IMPRESS. Common Implementation Strategy for the Water Framework Directive (2000/60/EC). Castro, N.M. and Hornberger, G.M., (1991). 150 pp. Surface-subsurface water interactions in an alluvial mountain stream channel. Water Resources European Commission (2006). Directive Research, 27: 1613–1621. 2006/118/EC of the European Parliament and of the Council on the protection of groundwater Comber, S.D.W., Merrington, G., Sturdy, L., against pollution and deterioration. Official Delbeke, K. and van Assche, F. (2008). Copper and Journal of the European Union, L 372, zinc water quality standards under the EU Water 27.12.2006, pp. 19-31. Framework Directive: The use of a tiered approach to estimate the levels of failure. Science European Commission (2007a). Guidance on of the Total Environment, 403: 12–22. Groundwater Monitoring. Guidance document

Ambientalia SPI (2011) 20

D. Sánchez and F. Carrasco (2011)

nº15. Office for Official Publications of the agricultural pressures and impacts on water European Communities. Technical Report 002 – quality on a European scale. Science of the Total 2007. Common Implementation Strategy for the Environment, 359: 57–75. Water Framework Directive (2000/60/EC). 54 pp. Glavan, M. (2007). Investigation of the impact of European Commission (2007b). Guidance on land use management scenarios on diffuse source Groundwater in Drinking Water Protected Areas. nutrients in the River Axe catchment. PhD thesis, Guidance document nº16. Office for Official Cranfield University, 206 pp. Publications of the European Communities. Grima, J., Martínez, C. and de la Orden, J.A. Technical Report 2007 – 010. Common (2006). Método para el establecimiento de valores Implementation Strategy for the Water umbral de contaminantes en agua subterránea. Framework Directive (2000/60/EC). 35 pp. Proyecto BRIDGE. In: Congreso Internacional European Commission (2008). Directive sobre el Agua Subterránea en los Países 2008/105/EC of the European Parliament and of Mediterráneos, Málaga, Spain, volume 17 (J.A. the Council on environmental quality standards in López-Geta, R. Fernández-Rubio and G. Ramos- the field of water policy, amending and González, eds.), 187–192. subsequently repealing Council Directives Hancock, P.J., Boulton, A.J. and Humphreys, W.F. 82/176/EEC, 83/513/EEC, 84/156/EEC, (2005). Aquifers and hyporheic zones: towards an 84/491/EEC, 86/280/EEC and amending Directive ecological understanding of groundwater. 2000/60/EC of the European Parliament and of Hydrogeology Journal, 13: 98–111. the Council. Official Journal of the European Union, L 348, 24.12.2008, pp. 84-97. Hinsby, K. , Condesso de Melo, M.T. and Dahl, M. (2008). European case studies supporting the European Commission (2009). Guidance on derivation of natural background levels and Groundwater Status and Trend Assessment. groundwater threshold values for the protection Guidance document nº18. Office for Official of dependent ecosystems and human health. Publications of the European Communities. Science of the Total Environment, 401(1-3): 1–20. Technical Report 2009 – 026. Common Implementation Strategy for the Water Kay, P., Edwards, A.C. and Foulger, M. (2009). A Framework Directive (2000/60/EC). 82 pp. review of the efficacy of contemporary agricultural stewardship measures for ameliorating water Fernández-Ruiz, L., Danés-Castro, C. and Ocaña- pollution problems of key concern to the UK Robles, L. (2005). Metodología de evaluación water industry. Agricultural Systems, 99(2-3): 67– preliminar de presiones e impactos en las masas 75. de agua subterránea. In: VI Simposio del Agua en Andalucía, Sevilla, Spain, volume 14 (J.A. López- Kmiecik, E., Stach-Kalarus, M., Szczepańska, J., Geta, J.C. Rubio-Campos and M. Martín-Machuca, Twardowska, I., Stefaniak, S. and Janta-Koszuta, K. eds.), 1197–1208. (2006). Assessment of groundwater chemical

Giupponi, C. and Vladimirova, I. (2006). Ag-PIE: A status based on aggregated data from a GIS-based screening model for assessing monitoring network exemplified in a river

Ambientalia SPI (2011) 21

D. Sánchez and F. Carrasco (2011)

drainage basin. In: Progress in Biomedical Optics Thompson and T. Simonart, eds.). John Wiley & and Imaging - Proceedings of SPIE Volume 6377, Sons, Ltd, Chichester, UK. Article number 63770M. Perles Roselló, M.J., Vías Martinez, J.M. and Krause, S., Jacobs, J., Voss, A., Bronstert, A. and Andreo Navarro, B. (2009). Vulnerability of Zehe, E. (2008). Assessing the impact of changes human environment to risk: Case of groundwater in landuse and management practices on the contamination risk. Environment International, 35: diffuse pollution and retention of nitrate in a 325–335. riparian floodplain. Science of the Total Pintar, M., Globevnik, L. and Bremec, U. (2007). Environment, 389: 149–164. Harmonisation of water management and Kunkel, R., Wendland, F., Hannappel, S., Voigt, H.J. agricultural policies in Slovenia. Journal of Water and Wolter, R. (2007). The influence of diffuse and Land Development, 11: 31–44. pollution on groundwater content patterns for Preziosi, E., Giuliano, G. and Vivona, R. (2010). the groundwater bodies of Germany. Water Natural background levels and threshold values Science & Technology, 55(3): 97–105. derivation for naturally As, V and F rich Marandi, A. and Karro, E. (2008). Natural groundwater bodies: a methodological case study background levels and threshold values of in Central Italy. Environmental Earth Sciences, monitored parameters in the Cambrian-Vendian 61(5): 885–897. groundwater body, Estonia. Environmental Quevauviller, P. (2009). Evaluation de l'état Geology,54(6): 1217–1225. chimique des eaux de surface et souterraines au Mohaupt, V., Richter, S. and Rohrmoser, W. (2005). titre de la directive cadre sur l'eau - normes de Ergebnisse der Bestandsaufnahme zur qualité et surveillance [Evaluation of the chemical Wasserrahmenrichtlinie - Der Zustand der status of surface and ground waters under the Gewässer in der Bundesrepublik Deutschland Water Framework Directive - Quality standards [Results of the impact analysis according to the and monitoring]. Houille Blanche, 4: 72–76. water framework directive - The status of the Sánchez, D., Carrasco, F. and Andreo, B. (2009). water bodies in Germany]. GWF, Wasser – Proposed methodology to delineate bodies of Abwasser, 146(10): 718–722. groundwater according to the European water Mostert, E. (2003). The European Water framework directive. Application in a pilot Framework Directive and water management Mediterranean river basin (Málaga, Spain). Journal research. Physics and Chemistry of the Earth, 28: of Environmental Management, 90(3): 1523– 523–527. 1533.

Müller, D. (2008). Establishing Environmental Vías, J.M. (2005). Desarrollo metodológico para la Groundwater Quality Standards. In: The Water estimación y cartografía del riesgo de Framework Directive: Ecological and Chemical contaminación de las aguas subterráneas Status Monitoring (P. Quevauviller, U. Borchers, C. mediante SIG. Aplicación en acuíferos del Sur de

Ambientalia SPI (2011) 22

D. Sánchez and F. Carrasco (2011)

España. PhD thesis, Universidad de Málaga, 424 pp.

Wendland, F., Hannappel, S., Kunkel, R., Schenk, R., Voigt, H.J. and Wolter, R. (2005). A procedure to define natural groundwater conditions of groundwater bodies in Germany. Water Science and Technology, 51(3-4): 249–257.

Wendland, F., Berthold, G., Blum, A., Elsass, P., Fritsche, J.-G., Kunkel, R. and Wolter, R. (2008). Derivation of natural background levels and threshold values for groundwater bodies in the Upper Rhine Valley (France, Switzerland and Germany). Desalination, 226(1-3). 160–168.

Winter, T.C., Harvey, J.W., Franke, O.L. and Alley, W.M. (1998). Groundwater and surface water. A single resource. US Geological Survey Circular, 1139.

Winter, T.C. (1999). Relation of streams, lakes and wetlands to groundwater flow systems. Hydrogeology Journal, 7: 28–45.

Woessner, W.W. (2000). Stream and fluvial plain ground-water interactions: rescaling hydrogeologic thought. Groundwater, 38(3): 423–429.

Acknowledgements

This work forms part of the projects REN2003- 01580 and CGL2008-04938 of DGICYT, the Research Group RNM-308 of the Andalusian Government and the associated unit IGME- GHUMA ‘‘Unidad de Estudios Hidrogeológicos Avanzados’’.

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