Monitoring and environmental risk assessment of pesticide residues and some of their degradation products in natural waters of the Spanish vineyard region included in the Denomination of Origin Jumilla☆
Graphical abstract
Introduction
Sustainability is the main focus of the European agricultural model, in which agricultural production is one of the main pillars (Scherer et al., 2018). It is supported by, among other production media, the application of agrochemicals. The use of these compounds arises from the need to ensure the production of crops in sufficient quantity and quality to satisfy the population’s nutritional needs. Agriculture today is based on obtaining maximum yields and profit, and to achieve these objectives conventional agriculture undertakes a series of agronomic practices which frequently do not consider the long-term effects of their use.
In 2017, Spain was the European country with the highest consumption of pesticides, followed by France and Italy (MAPA, 2019). These compounds are used on most crops (vegetables, olive and fruit trees, wheat, vineyards, etc.) in different forms and at different times. This application could have an impact on water and soil pollution, with a knock-on effect on human and animal health or the loss of biodiversity. Water is a key feature of agriculture, being a crucial factor in plant growth, but the use of groundwater for human consumption could be critical if pesticides and nitrates reach the water by leaching processes (Pérez-Lucas et al., 2018). The agricultural sector consumes a third of Europe’s water reserves, with this percentage being higher in Spain’s case. Agriculture influences both the quantity and the quality of water available for other uses. In some areas of Europe, pollution caused by the pesticides and fertilizers used in agriculture is in itself one of the main causes of poor water quality (EEA, 2018).
Surface and ground waters can become polluted by pesticides, with this process being governed by the physicochemical characteristics of these compounds and the environment in which they are applied, as well as by other external factors such as local rainfall, wind and topography, which determine their dissipation or degradation (Pérez-Lucas et al., 2018). Modern pesticides are more effective and selective, using lower doses. However, the environmental fate of these compounds is currently a major concern because of the increasing number of pesticides detected in the waters of different European countries, such as France (Cotton et al., 2016), the UK (Casado et al., 2018), Italy (Triassi et al., 2019), Greece (Papadakis et al., 2018; Kapsi et al., 2019), and Portugal (Palma et al., 2009). As well as in more or less developed countries all over the world, such as Costa Rica (Carazo-Rojas et al., 2018), India (Mondal et al., 2018), Chile (Climent et al., 2019), and Rwanda (Houbraken et al., 2017). These pesticide residues could have an adverse impact on waters used for human consumption or if they reach non-target aquatic organisms which are susceptible to their toxic effects. The bioaccumulation of pesticide residues in waters through aquatic life on different trophic levels could pose a risk for humans depending on food sources (Mondal et al., 2018).
Accordingly, the European Community (EC) has established different directives to protect water quality (Directive, 2000/60/EC and Directive, 2008/60/EC) (European Commission, 2000; 2008). Both have been amended by Directive 2013/39/EU in which more contaminants and other issues have been added to the list of controlled substances (European Commission, 2013). Furthermore, other directives on water for human consumption and on the protection of groundwater against pollution and deterioration (Directive 98/83/EEC (European Commission, 1998) and revised Directive 2006/118/EC (European Commission, 2006)) establish the individual threshold for a pesticide (0.1 μg L−1) and the total concentration of pesticides (0.5 μg L−1) permitted in waters. Other European guidelines also include assessing the risk pesticide residues pose for aquatic organisms (European Commission, 2003; 2011). The indicators Toxic Units (TUs) and Risk Quotients (RQs) for evaluating the ecological or exposure effects involving pesticides at different trophic levels in the ecosystem have been reported of interest for assessing the biological risks of different compounds (Ccanccapa et al., 2016a).
In Spain, agriculture plays a very important role in the economy, and the environmental fate of the pesticides used is currently a major concern. In recent years, several studies have reported the presence of pesticides and other substances in river basins: Ebro (Ccanccapa et al., 2016a), Júcar and Turia (Ccanccapa et al., 2016b), Júcar (Pascual Aguilar et al., 2017), Turia (Carmona et al., 2017), Llobregat (Masiá et al., 2015; Quintana et al., 2019), Guadalquivir (Hermosín et al., 2013; Masiá et al., 2013), Guadiana (Palma et al., 2009) and Miño (Dagnac et al., 2012), and in the Mediterranean’s coastal waters (Köck-Schulmeyer et al., 2019). In some cases, irrigation has also contaminated aquifers above the peak levels allowed in European legislation for drinking water. However, the number of studies that include a large amount of groundwater samples is scarce (Hildebrandt et al., 2007, 2008; Herrero-Hernández et al., 2013, 2016, 2017).
Specifically, a large number of herbicides, insecticides and fungicides are used annually in vineyard agricultural areas (AEPLA, 2015). Recent studies have estimated that fungicides and bactericides are the main type of pesticides applied, accounting for 53% of the total amount used (MAPA, 2019). This is because wine is an important economic sector in Spanish agriculture, with over a million ha of cultivated land and more than 90 protected DO wine regions (MAPA, 2019). Some studies have been conducted to evaluate the presence of these compounds in areas where vineyards are the main activity, such as in the qualified DO Rioja (Herrero-Hernández et al., 2013, 2016, 2017), or in some areas of Galicia (Hildebrandt et al., 2008). However, these studies have not been extended to other areas where viticulture is also an important agricultural activity, such as DO Jumilla in the Murcia region (SE Spain). Additionally, this area is located in a Spanish region with the fifth highest investment per hectare in crop protection products, with a pesticide consumption of 27.8 kg ha−1 in 2015 (MAPA, 2019).
Accordingly, the aims here were as follows: (i) to conduct a thorough monitoring of natural waters in the DO Jumilla area, where vineyard cultivation is the main activity, and evaluate possible pollution due to pesticides and their degradation products, (ii) to estimate the local ecotoxicological risk towards the aquatic organisms in three taxonomic groups (algae, Daphnia magna, and fish) using the TUs for each sampling site and RQs for each pesticide. To the best of our knowledge, this is the first study on the occurrence of pesticides and degradation products considering their ecotoxicological risk in DO Jumilla, an area of intense anthropogenic activity.
Section snippets
The study area
The wine-producing area in DO Jumilla covers around 25,000 ha of vineyards, of which 40% are located within Jumilla’s municipal boundaries, with the rest being in the province of Albacete, involving almost 2000 winegrowers (Fig. 1). The geographical area is located in the southeast of Spain, in a transition zone between the Murcia coast and the Castilla-La Mancha plateau. Its terrain consists of a series of mountain ranges, separated by valleys, ravines, woodlands and plains, located at heights
Occurrence of pesticide residues in natural waters
The pollution of natural waters by 69 pesticides and some of their degradation products was evaluated in the DO Jumilla wine region by an optimized SPE-LC-MS method. A total of twenty-six different pesticides (11 insecticides, 9 herbicides and 6 fungicides) were detected in one or more of the samples, and 15 were detected in concentrations over 0.1 μg L−1. The distribution of the concentrations detected for each pesticide is included in Fig. S1 and Table 1 compile the median and maximum
Conclusions
The analysis of 21 natural waters, corresponding mostly to groundwater, located in the DO Jumilla wine region revealed the presence of ten or more compounds in four of the samples analyzed. Some of the compounds studied were detected at all the sampling points, despite the depth of some of the wells, reaching down to 400 m. The herbicides diflufenican and pendimethalin, the insecticides pirimicarb, indoxacarb, and λ-cyhalothrin, and the fungicide kresoxim-methyl were detected in more than half
CRediT authorship contribution statement
Eliseo Herrero-Hernández: Conceptualization, Methodology, Investigation, Validation, Supervision, Formal analysis, Writing - original draft, Writing - review & editing. Ana B. Simón-Egea: Investigation. María J. Sánchez-Martín: Resources, Project administration, Validation, Supervision, Formal analysis, Writing - original draft, Writing - review & editing. M. Sonia Rodríguez-Cruz: Resources, Funding acquisition, Writing - original draft, Writing - review & editing. M. Soledad Andrades:
Declaration of competing interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgements
A. B. Simón-Egea thanks the University of La Rioja the financial support to perform this research. The authors thank S. Sánchez-González from the European University Miguel de Cervantes for compiling a GIS map of the sampling area.
References (48)
- et al.
Pesticide monitoring and ecotoxicological risk assessment in surfacewater bodies and sediments of a tropical agro-ecosystem
Environ. Pollut.
(2018) - et al.
Multi-residue determination of 47 organic compounds in water, soil,sediment and fish. Turia River as case study
J. Pharmaceut. Biomed. Anal.
(2017) - et al.
Occurrence and seasonal distribution of polycyclic aromatic hydrocarbons and legacy and current-use pesticides in air from a Mediterranean coastal lagoon (Mar Menor, SE Spain)
Chemosphere
(2017) - et al.
Multi-residue analysis of pesticides in surface water by liquid chromatography quadrupole-Orbitrap high resolution tandem mass spectrometry
Anal. Chim. Acta
(2018) - et al.
Pesticides in the Ebro River basin: occurrence and risk assessment
Environ. Pollut.
(2016) - et al.
Spatio-temporal patterns of pesticide residues in the Turia and Júcar Rivers (Spain)
Sci. Total Environ.
(2016) - et al.
Residues of pesticides and some metabolites in dissolved and particulate phase in surface stream water of cachapoal river basin, Central Chile
Environ. Pollut.
(2019) - et al.
Development and validation of a multiresidue method for the analysis of more than 500 pesticides and drugs in water based on on-line and liquid chromatography coupled to high resolution mass spectrometry
Water Res.
(2016) - et al.
Impact of herbicides used in olive groves on waters of the Guadalquivir river basin (southern Spain)
Agric. Ecosyst. Environ.
(2013) - et al.
Occurrence of pesticides and some of their degradation products in waters in a Spanish wine region
J. Hydrol.
(2013)
Seasonal distribution of herbicide and insecticide residues in the water resources of the vineyard region of La Rioja (Spain)
Sci. Total Environ.
Impact of pesticides used in agriculture and vineyards to surface and groundwater quality (North Spain)
Water Res.
Multi-residue determination and ecological risk assessment of pesticides in the lakes of Rwanda
Sci. Total Environ.
Environmental monitoring and risk assessment of pesticide residues in surface waters of the Louros River (N.W. Greece)
Sci. Total Environ.
Medium to highly polar pesticides in seawater: analysis and fate in coastal areas of Catalonia (NE Spain)
Chemosphere
Biocides in the Yangtze River of China: spatiotemporal distribution, mass load and risk assessment
Environ. Pollut.
Screening of currently used pesticides in water, sediments and biota of the Guadalquivir River Basin (Spain)
J. Hazard Mater.
Pesticide monitoring in the basin of Llobregat River (Catalonia, Spain) and comparison with historical data
Sci. Total Environ.
GC-MS/MS determination and ecological risk assessment of pesticides in aquatic system: a case study in Hooghly River basin in West Bengal, India
Chemosphere
Risk assessment of representative and priority pesticides, in surface water of the Alqueva reservoir (South of Portugal) using on-line solid phase extraction-liquid chromatography-tandem mass spectrometry
Environ. Int.
Pesticide occurrence in the waters of Júcar River, Spain from different farming landscapes
Sci. Total Environ.
Monitoring the complex occurrence of pesticides in the Llobregat basin, natural and drinking waters in Barcelona metropolitan area (Catalonia, NE Spain) by a validated multi-residue online analytical method
Sci. Total Environ.
Opportunities for sustainable intensification in European agriculture
Global Environ. Change
Ecological risk and estimates of organophosphate pesticides loads into the central mediterranean sea from volturno river, the River of the “land of fires” area
southern Italy. Sci. Total Environ.
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