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Is the EU Drinking Water Directive Standard for Pesticides in Drinking Water Consistent with the Precautionary Principle?
Abstract
Regulations based on the precautionary principle should undertake a comprehensive assessment of all available scientific and technical data to identify sources of epistemic uncertainty. In the European Union (EU), environmental regulation is required to fulfil the principles established in Article 174 of the EU Treaty, such that it offers a high level of protection, and is consistent with the precautionary principle. Pesticides in drinking water are currently regulated by the Drinking Water Directive using a maximum allowable concentration of 0.1µg/l. This standard (a surrogate zero) was consistent with the precautionary principle when it was originally set in 1980 and remained consistent when retained in 1998. However, given developments in EU pesticide and water policy, international experience in regulating pesticides, and an increasing knowledge of pesticide toxicity, it can be argued that the level of epistemic uncertainty faced by regulators has substantially decreased. In this paper, we examine the extent to which such developments now challenge the basis of European drinking water standards for pesticides and whether, for substances for which there is good toxicological understanding, a regulatory approach based upon the World Health Organisation (WHO) Guideline Value (GV) methodology would be more consistent with the principles underpinning European environmental policy.
... The need for a more holistic approach to water resources management triggered a reform in water policies and the EU Council Directive 2000/60/EC Water Framework Directive (WFD), the embodiment of the integrated catchment management approach (ICM), was introduced in 2000 (Giakoumis and Voulvoulis, 2018). Article 7 of the WFD obligates Member States to depart from end-of-pipe treatment and adopt a prevention-led approach to achieve DWD compliance (Dolan, 2013;Dolan et al., 2013). As a preliminary mitigation measure, surface and ground waters that are intended for potable consumption were established as Drinking Water Protected Areas (DrWPAs) as required by Article 6 of the WFD. ...
... The need for a more holistic approach to water resources management triggered a reform in water policies and the EU Council Directive 2000/60/EC Water Framework Directive (WFD), the embodiment of the integrated catchment management approach (ICM), was introduced in 2000 (Giakoumis and Voulvoulis, 2018). Article 7 of the WFD obligates Member States to depart from end-of-pipe treatment and adopt a prevention-led approach to achieve DWD compliance (Dolan, 2013;Dolan et al., 2013). As a preliminary mitigation measure, surface and ground waters that are intended for potable consumption were established as Drinking Water Protected Areas (DrWPAs) as required by Article 6 of the WFD. ...
... Metaldehyde removal at conventional WTW that utilises granular activated carbon filtration is relatively poor, especially at higher concentrations due to its low tendency to attach to organic carbon (Castle et al., 2017;Davey et al., 2013;Dillon et al., 2011;Tao and Fletcher, 2016;University of Hertfordshire, 2018). As a result, its removal from potable water at peak concentrations has been challenging for water companies (Dillon et al., 2011;Dolan, 2013). Furthermore, water companies in England and Wales were issued with 'Undertakings' (Section 19, Water Industry Act 1991) by the Drinking Water Inspectorate to take an ICM approach to meet the DWD standards and report the findings to this regulatory body by 31 March 2020. ...
In the agriculture intensive eastern region of England, plant protection products are widely applied to protect crops such as wheat and oilseed rape from pests and diseases, thus creating a risk of reaching nearby water courses through surface runoff. The EU Drinking Water Directive sets a stringent limit of 0.1 μg/l and 0.5 μg/l for individual and total pesticides respectively in treated potable water. However, peak metaldehyde levels have been persistently detected in raw water and reducing them to these limits has proven challenging and costly, in particular when using conventional treatment. In line with the EU Water Framework Directive, a more suitable approach and one adopted by the local water company, Anglian Water Services Ltd., would require moving towards mitigating pollution at source, preferably through participative action with multiple stakeholders in the agricultural industry. Initial findings demonstrate the potential of product substitution for reducing metaldehyde levels in surface waters. Reviewing Anglian Water's “Slug it Out” trial, we discuss key learnings derived from their experiences and make recommendations about the potential of the catchment approach to address the wider pesticide challenge.
... The DWQS for pesticides in the EU is based on the 'precautionary principle' (Bourguignon 2016). The DWQS for individual pesticides (0.1 µg/l) was a surrogate for zero when it was first introduced in 1980 (Dolan et al. 2013). It remained unchanged in the 1998 revision and was regarded by Dolan et al. (2013) to be still consistent with the precautionary principle. ...
... The DWQS for individual pesticides (0.1 µg/l) was a surrogate for zero when it was first introduced in 1980 (Dolan et al. 2013). It remained unchanged in the 1998 revision and was regarded by Dolan et al. (2013) to be still consistent with the precautionary principle. No changes to the DWQS for pesticides are planned in the revised Directive (European Commission 2018). ...
Pesticide pollution has raised public concern in Denmark due to potential negative health impacts and frequent findings of new substances after a recent expansion of the groundwater monitoring programme. Danish drinking water comes entirely from groundwater. Both the raw groundwater and the treated drinking water are regularly monitored, and the chemical analyses are reported to a publicly available national database (Jupiter). Based on these data, in this study we (1) provide a status of pesticide content in drinking water supplied by public waterworks in Denmark and (2) assess the proportion of Danish households exposed to pesticides from drinking water. ‘Pesticides’ here refers also to their metabolites, degradation and reaction products. The cleaned dataset represents 3004 public waterworks distributed throughout the country and includes 39 798 samples of treated drinking water analysed for 449 pesticides (971 723 analyses total) for the period 2002–2019. Of all these chemical analyses, 0.5% (n = 4925) contained a quantified pesticide (>0.03 μg/l). Pesticides were found at least once in the treated drinking water at 29% of all sampled public waterworks for the period 2002–2019 and at 21% of the waterworks for the recent period 2015–2019. We estimate that 56% of all Danish households were potentially exposed at least once to pesticides in drinking water at concentrations of 0.03–4.00 μg/l between 2002 and 2019. However, in 2015–2019, the proportion of the Danish households exposed to pesticides (0.03–4.00 μg/l) was 41%. The proportion of Danish households potentially exposed at least once to pesticides above the maximum allowed concentration (0.1 μg/l) according to the EU Drinking Water Directive (and the Danish drinking water standard) was 19% for 2002–2019 and 11% for 2015–2019. However, the maximum concentrations were lower than the World Health Organization’s compound-specific guidelines. Lastly, we explore data complexity and discuss the limitations imposed by data heterogeneity to facilitate future epidemiological studies.
... Countries have started including these pollutants which have adverse effects with little amounts in their regulations. One of those regulations was set by European Union (EU) in 1980 [8] for individual pesticides as 0.1 μg/L which is maximum allowable concentration and retained as they were in 1998 [9] for drinking water at the point of supply [10]. This regulation is then translated to Turkish and started being effective in Turkey, as Turkey is in the process of becoming a full-member of EU. ...
... These improvements in analytical techniques together with starting occurrence of different pollutants in water bodies result in detection of more pollutants in water samples [27,28]. On the other hand, the limits set by EU especially in terms of the pesticides are precautionary and does not reflect the progress in recent years for detecting and quantifying these chemicals in water [10]. These precautionary levels can be explained with the knowledge gap about the effects of mixture of these chemicals [29,30]. ...
Monitoring and assessment of surface drinking water resources is vital for human life. As it is known, many diseases are caused by contaminated waters. Surface water resources quality was classified in terms of treatment potential by using 41 conventional parameters in Turkey. It is not insufficient to take these conventional parameters into account alone due to the fact that there exist new developments in application of varying level of different chemicals generated as part of daily activities. The main objective of this study is to recommend some changes for the water resources quality classification of Turkey by investigating the No Observed Adverse Effect Limit (NOAEL) and Lowest Observed Adverse Effect Level (LOAEL) classifications of different pollutants. These pollutants are associated with highest and lowest doses at which there was not an observed toxic or adverse effect, respectively. This new evaluation scheme will allow integration of new pollutants, i.e., micropollut-ants, and monitoring as per the findings of this study. A detailed site-specific monitoring was also undertaken by collecting samples from 283 of surface water locations at four times during the year across Turkey. The results obtained in this study indicate that, even if there is a pressure in terms of micropollutants in surface water resources of Turkey, the problem in terms of conventional parameters are more dominated and the water quality problems in Turkey have been exacerbated in terms of microbiological indicators such as total coliform, fecal coliform and fecal streptococcus. It is also important to note that the heavy metal concentrations originated from the site-specific geological formation were detected in the surface drinking water resources of Turkey.
... Thus glyphosate is generally considered as a safe pesticide and unlikely to cause acute toxicity in animals and human beings in normal doses (Song et al., 2012;Sribanditmongkol et al., 2012;Szepanowski et al., 2019). The European Commission for environment setup a Drinking Water Directive which considered 0.1 mg/L of glyphosate as a maximum allowable concentration (MAC) in drinking water (Dolan et al., 2013) while the United State Environment Protection Agency (USEPA) defined 700 mg/L of glyphosate as a maximum contamination level (MCL) (Larsen et al., 2012). Both MAC and MCL represent the maximum permissible concentrations in drinking water and are considered as non-observable adverse effect levels of glyphosate. ...
... The WHO recognized glyphosate as one of the safest pesticides which is unlikely to cause acute toxicity in normal utilisation with an oral LD 50 value in rodents being several thousand times higher than MAC and MCL, the maximum permissible concentrations in drinking water recommended by Environmental Protection authorities of EU and USA (Dolan et al., 2013;Larsen et al., 2012;Song et al., 2012). Neurotoxicity of glyphosate has been reported in human beings (Ait Bali et al., 2017;Shaw, 2017;Zheng et al., 2018), rodents (Cattani et al., 2014(Cattani et al., , 2017Gallegos et al., 2016;Hern andez-Plata et al., 2015;Joaquim et al., 2014;Roy et al., 2016) and NSCs cultures (Coullery et al., 2016). ...
The developing nervous system is highly vulnerable to environmental toxicants especially pesticides. Glyphosate pesticide induces neurotoxicity both in humans and rodents, but so far only when exposed to higher concentrations. A few studies, however, have also reported the risk of general toxicity of glyphosate at concentrations comparable to allowable limits set up by environmental protection authorities. In vitro data regarding glyphosate neurotoxicity at concentrations comparable to maximum permissible concentrations in drinking water is lacking. In the present study, we established an in vitro assay based upon neural stem cells (NSCs) from the subventricular zone of the postnatal mouse to decipher the effects of two maximum permissible concentrations of glyphosate in drinking water on the basic neurogenesis processes. Our results demonstrated that maximum permissible concentrations of glyphosate recognized by environmental protection authorities significantly reduced the cell migration and differentiation of NSCs as demonstrated by the downregulation of the expression levels of the neuronal ß-tubulin III and the astrocytic S100B genes. The expression of the cytoprotective gene CYP1A1 was downregulated whilst the expression of oxidative stresses indicator gene SOD1 was upregulated. The concentration comparable to non-toxic human plasma concentration significantly induced cytotoxicity and activated Ca²⁺ signalling in the differentiated culture. Our findings demonstrated that the permissible concentrations of glyphosate in drinking water recognized by environmental protection authorities are capable of inducing neurotoxicity in the developing nervous system.
... This contamination occurs mainly through industrial wastewater discharges, leaching, surface run-off and deposition from aerial applications [3]. The maximum allowed concentration of total pesticides according to the European Union Directives and Regulations for drinking water hygiene is 0.1 μg/L [4]. Methomyl is one of different types of pesticides according to chemical structure. ...
... In equilibrium analysis, Langmuir [3] and Freundlich [4] models are the most frequently employed isotherm models for studying frequently employed isotherm models for studying the behavior and system of adsorption. Langmuir and Freundlich isotherms for the studied system at different temperatures are presented in Figures 8 and 9, respectively. ...
Peanut shells-derived activated carbons (ACPNS) with different chemical characteristics, appropriate for the removal of methomyl
pesticide in aqueous solutions are prepared. The steam activated carbon is obtained from the carbonized peanut shells in the presence
of nitrogen in the temperature range from 973 to 1173K. The carbonized peanut shells are, further, chemically activated using NaOH
and ZnCl2. The structure of the ACPNS was characterized by N2 adsorption at 77K, scan electron microscopy and FTIR. B.E.T methods
are used to deduce the effective surface areas. The parameters (such as initial pH, temperature, etc) affecting the adsorption capacity
of peanut shells-derived activated carbons toward methomyl removal from aqueous solutions are investigated using batch experiments.
The study of kinetic models including pseudo first order and pseudo second-order are carried out. Adsorption isotherms are investigated.
Equilibrium adsorption data fitted the Langmuir adsorption isotherm well with R2> 0.9980. The maximum adsorption capacities of peanut
shells-derived activated carbons for the removal of methomyl, are calculated. The thermodynamic parameters including ΔG°, ΔH° and
ΔS° for the adsorption processes of methomyl on the ACPNS were calculated, and the negative value of ΔG° indicated the spontaneous
nature of adsorption. The prepared peanut shells derived activated carbons are successfully applied to the removal of methomyl pesticide
from different water samples with a recovery % > 95 and a RSD< 3%. The mechanism of adsorption is proposed.
... A more thorough understanding of the impacts of pesticides in drinking water on human health and the ecosystem will be possible due to the work being carried out with effective pesticide pollution monitoring in real-time [71]. Many inquiries were made for people to comprehend and properly establish the health hazards based on scientific evidence [72]. In research for appropriate pesticide use and cutting-edge pest control techniques, the analytical confirmation of low amounts of pesticides is crucial [27]. ...
This study highlights the impact of formal agricultural practices and their adverse effect on the deterioration of underground water quality, with special emphasis on toxic elements, including pesticides, herbicides, fungicides, plasticizer accumulation and heavy-metal contamination. A comprehensive study was conducted at various recently developed societies of Sadiqabad that were formerly used for agricultural purposes. Ten various societies were selected, and three samples from each society were collected from different regions of these areas. Data regarding the physicochemical properties, metal contamination and accumulation of pesticide residues were determined using standard protocols. The results revealed that almost all the physicochemical properties of water samples selected from these sites were close to the WHO’s recommended limits. The range for physicochemical properties was pH (6.4–7.7), electrical conductivity (168–766 µ S cm−1), turbidity (6–17 NTU), total hardness (218–1030 mg L−1), chloride contents (130–870 mg L−1) and phosphate contents (2.55–5.11 mg L−1). Among heavy metals, lead and arsenic concentrations in all sampling sites were found to be above the recommended limits. The decreasing pattern in terms of water-quality deterioration with respect to physicochemical properties was FFT > USM > CRH > UCS > CHS > MAH > FFC > CGA > GIH > AGS. Overall, 95 different kinds of toxic elements, including pesticides, herbicides, plasticizer, etc., were detected in the groundwater samples. The toxic compounds in the groundwater were categorized into pesticides, herbicides, plasticizer, plant growth regulators, fungicides, acaricides and insecticides. Most of these parameters showed peak values at the Fatima Fertilizer Company area and Chief Residencia Housing Society. Pesticide contamination showed that water-filtration plants have a big positive impact on the drinking quality of water. Proper monitoring of the pesticides must be performed, as the majority of the pesticides showed low priority. The monitoring method of the pesticides needs to be updated so that the occurrence of recently authorized pesticides is demonstrated.
... For example, in the USA, the EPA established a maximum allowed value of 0.7 µg mL −1 [27], while most of the European countries imposed more restrictive values, with a value below 0.0005 µg mL −1 , and even a trend towards banning GLY use. Nevertheless, most of the concentrations found in the environment are above established limits [19,28]. [18,19]. ...
Herbicides with glyphosate (GLY) as an active ingredient (a.i.) are increasingly used, and GLY is currently the most used herbicide in the world. Consequently, its residues have often been found in aquatic ecosystems. Investigating how this substance affects aquatic species is a priority in ecotoxicology research, especially in fish, as they can absorb and concentrate toxins. In this sense, a critical review was performed, synthesizing data from the peer-reviewed bibliography, reporting on the toxicity of exposure to pure GLY and glyphosate-based herbicides (GBHs), using zebrafish as an animal model. The concentrations of this herbicide that induced toxic effects are highly variable, with some exceeding the limits determined by regulatory agencies. Globally, relevant toxic effects have been reported in zebrafish, namely, teratogenic effects incompatible with life, which translates directly into an increase in reported zebrafish mortality. Neurotoxicity, genotoxicity, changes in energy metabolism and oxidative stress, and immune and hormonal system dysfunction with an impact on fish reproduction were also described. In conclusion, both GLY and GBHs may induce damage to zebrafish, compromising their survival, reproduction, and maintenance. These results may be valid and applied to other fish species and aquatic ecosystems.
... Therefore, it is crucial to monitor pesticide use to minimize its impact on water resources (Li and Jennings, 2017). The MCL for glyphosate in drinking water before posing a risk to human health is considered 700 μg/L in the USA, 500 μg/L in Brazil, and 280 μg/L in Canada, while in Europe, the acceptable concentration in drinking water is less than 0.1 μg/L and the tolerable risk is reported to be 77 μg/L (EFSA, 2015;Dolan et al., 2013). Overall, the studies assessed over the last seven years showed that glyphosate was commonly detected in drinking water below the maximum allowable limits established by the USA but above those of the EU and the United Kingdom (Gunarathna et al., 2018;Panis et al., 2022;Klaimala et al., 2022). ...
Glyphosate is a broad-spectrum and one of the most widely used herbicides in the world, which has led to its high environmental dissemination. In 2015, the International Agency for Research on Cancer stated that glyphosate was a probable human carcinogen. Since then, several studies have provided new data about the environmental exposure of glyphosate and its consequences on human health. Thus, the carcinogenic effects of glyphosate are still under debate. This work aimed to review glyphosate occurrence and exposure since 2015 up to date, considering studies associated with either environmental or occupational exposure and the epidemiological assessment of cancer risk in humans. These articles showed that residues of the herbicide were detectable in all spheres of the earth and studies on the population showed an increase in the concentration of glyphosate in biofluids, both in the general population and in the occupationally exposed population. However, the epidemiological studies under review provided limited evidence for the carcinogenicity of glyphosate, which was consistent with the International Agency for Research on Cancer classification as a "probable carcinogen".
... The value of 0.1 μg/L (a surrogate zero) was consistent with the precautionary principle when it was originally set in 1980. It is not based on an (eco)toxicological threshold of concern, nor mixtures thereof (Dolan et al., 2013). Notice that for non-relevant metabolites there are currently no agreed values. ...
Groundwater monitoring is the highest tier in the leaching assessment of plant protection products in the EU. The European Commission requested EFSA for a review by the PPR Panel of the scientific paper of Gimsing et al. (2019) on the design and conduct of groundwater monitoring studies. The Panel concludes that this paper provides many recommendations; however, specific guidance on how to design, conduct and evaluate groundwater monitoring studies for regulatory purposes is missing. The Panel notes that there is no agreed specific protection goal (SPG) at EU level. Also, the SPG has not yet been operationalised in an agreed exposure assessment goal (ExAG). The ExAG describes which groundwater needs to be protected, where and when. Because the design and interpretation of monitoring studies depends on the ExAG, development of harmonised guidance is not yet possible. The development of an agreed ExAG must therefore be given priority. A central question in the design and interpretation of groundwater monitoring studies is that of groundwater vulnerability. Applicants must demonstrate that the selected monitoring sites represent realistic worst-case conditions as specified in the ExAG. Guidance and models are needed to support this step. A prerequisite for the regulatory use of monitoring data is the availability of complete data on the use history of the products containing the respective active substances. Applicants must further demonstrate that monitoring wells are hydrologically connected to the fields where the active substance has been applied. Modelling in combination with (pseudo)tracer experiments would be the preferred option. The Panel concludes that well-conducted monitoring studies provide more realistic exposure assessments and can therefore overrule results from lower tier studies. Groundwater monitoring studies involve a high workload for both regulators and applicants. Standardised procedures and monitoring networks could help to reduce this workload.
... There is no recommended value for glyphosate residue in drinking water; however, the EU standard for any pesticide in drinking water is 0.1 µg L −1 . [12] This is, without a doubt, a significant challenge for a portable water treatment facility. In light of the rising reports of glyphosate in the aquatic environment, it has been claimed that the cost of building the required equipment to remove herbicides from drinking water may be £1.0 billion, with annual operating expenses of £50-100 million in the UK. ...
The selective removal of one ligand in mixed‐ligand MOFs upon thermolysis provides a powerful strategy to introduce additional mesopores without affecting the overall MOF structure. By varying the initial ligand ratio, MOFs of the MIL‐125‐Ti family with two distinct hierarchical pore architectures are synthesized, resembling either large cavities or branching fractures. The performance of the resulting hierarchically porous MOFs is evaluated toward the adsorptive removal of glyphosate (N‐(phosphonomethyl)glycine) from water, and the adsorption kinetics and mechanism are examined. Due to their strong affinity for phosphoric groups, the numerous Ti–OH groups resulting from the selective ligand removal act as natural anchor points for effective glyphosate uptake. The relationships between contact duration, glyphosate concentration, and adsorbent dosage are investigated, and the impact of these parameters on the effectiveness of glyphosate removal from contaminated water samples is examined. The introduction of additional mesopores has increased the adsorption capacities by nearly 3 times with record values exceeding 440.9 mg g⁻¹, which ranks these MOFs among the best‐reported adsorbents.
... These agrochemicals break down quickly in the environment (e.g., soil, sediment, water), but some are quite persistent and bio-accumulative, hence, harming water quality with substantial environmental repercussions [58]. A more thorough understanding of the impacts of pesticides on drinking water and human health and the ecosystem will be possible due to the work being carried out regarding effective real-time pesticide pollution monitoring [59,60]. In the search for legal pesticide usage and cutting-edge pest control techniques, the analytical determination of low amounts of pesticides is crucial [61]. ...
The supply of clean drinking water is essential for a healthy life, but access to safe and healthy drinking water has become a key issue worldwide, especially in developing nations such as Pakistan. This research work focused on investigating the suitability of groundwater by measuring quality parameters, identification of pesticide pollutants, and health risk analysis in adults and children due to the consumption of groundwater in recently developed housing societies of the Gujranwala district, Punjab, Pakistan. Drinking water samples (n = 200) were collected from electric water pumps and analyzed by in situ testings following the Standard American Public Health Association (APHA) methods. Pesticides and plasticizers detection was carried out using gas chromatography-mass spectrometry (GC/MS). Results showed that the concentrations of dissolved Cr and Pb at more than 20% of sampling sites exceeded the allowable limit of the World Health Organization (WHO). However, the measured Physico-chemical attributes and concentrations of Fe and Zn did not exceed their respective permissible limits. The most abundant pollutants detected were plasticizers (30); followed by herbicides (21); fungicides, acaricides, and insecticides (16); and various types of plant growth regulators (7). Differential patterns for the hazard quotient (HQ) and hazard indices (HI) were observed, which were above the WHO limits. The decreasing order of the hazard quotient was Cl > Zn > Mg > Cr > Pb for both adults and children. In crux, the quality
of water is poor for drinking purposes and the safety and well-being of residents in the recently developed housing societies of the study area may be at risk. Hence, it is important to implement a plan for water quality management, and regular monitoring (periodic testing of qualitative and quantitative attributes) of the water quality to overcome health-related issues.
... The herbicide is mainly applied to rice fields, which results in surface water, groundwater, and soil contamination [3][4][5]. Propanil has been detected at concentrations up to 3.6 mg/l in water [5], while the acceptable level of propanil in drinking water is 0.1 μg/l [6]. ...
The herbicide propanil has been widely applied in Vietnam and around the world to control weeds. In this study, Acinetobacter baumannii DT isolated from soil was used to determine propanil degradation. Degradation experiments were carried out with condensed cells at 109 CFU/ml with both free and immobilized forms of the bacteria. Propanil degradation rates by bacteria immobilized in alginate were higher than those of free cells at the same concentrations. The degradation curve as a function of concentration fit well to the degradation kinetics described by the Edwards model with a maximum degradation of 0.034±0.003 mM/h for free cells and 0.053±0.005 mM/h for immobilized cells. Moreover, the immobilized bacteria could tolerate higher propanil concentrations and degrade propanil in a well-known herbicide more effectively compared to the freely suspended bacteria. These results demonstrate that A. baumannii DT immobilized in alginate is suitable for degradation of propanil in herbicides.
... Up to midland, the highest MPPA concentration (871 ng L -1 ) was recorded at RR13 in July ( Table 2). Note that as already mentioned, this station also showed the maximum concentrations and appeared to be an (statistical) outlier with respect to its concentrations of GLYP, GLUF, and AMPA (relative to those measured in the other stations), and even over the thresholds recommended by published EU regulations (Dolan et al., 2013). Indeed, it is noted here that the RR13 station ( Fig. 1) is close to the Nhue and Day tributaries of the main Red River stream in the Hanoi region, where both the water and sediment compartments have recently been reported to suffer from extreme pesticide pollution (Hoai et al., 2011(Hoai et al., , 2010. ...
... Regulatory agencies have established different maximum allowed concentrations for GP in drinking water. In the European Union, for example, the total permitted concentration for pesticides is 0.5 μg L −1 and 0.1 μg L −1 is the maximum allowed for each pesticide, its relevant metabolites, and its decomposition and reaction products (Dolan et al. 2013). In the USA, GP levels are tolerated up to 700 μg L −1 (EPA 2020), while in Brazil, the concentration of GP and AMPA together may not exceed 500 μg L −1 (Ministry of Health 2017). ...
South American agriculture focuses on extensive cereal and oilseed production destined mainly for the international market, followed by the horticultural production that takes place near urban centres. Extensive agriculture involves the use of fertilizers and pesticides for pest control. Among the latter, glyphosate-based herbicides (GBHs) are the most commercialized. In recent years, the increasing appearance of glyphosate (GP)-resistant weeds has led to the repeated application of higher doses of these products. Residual levels of the herbicides and their metabolites have therefore been reported in the environment, as well as toxic effects in animals and humans. The natural ability of bacteria and fungi to transform organic compounds in the environment has shown great potential to bioremediate GP in the soil. Some fungal species isolated from pesticide-contaminated sites are especially promising for this purpose, thanks to their enzymatic activity and their fast growth under optimal conditions. The present article offers an overview of the situation in Argentina regarding the use of GP. It also summarizes the data available which show a growing need to develop GP bioremediation strategies in the soil, based on the isolation of GP-degrading microorganisms adapted to water shortage conditions, such as fungi.
... The European Union (EU) standards of drinking water safety levels follow the precautionary principle in environmental science (Kriebel et al., 2001), and are considered a reference for human health and environmental protection. According to the EU Drinking Water Directive, the sum of the maximum allowable concentration of pesticides in drinking water is 0.1 µg/L (Dolan et al., 2013). Despite this, pesticide levels in drinking water are commonly above the EU preconized limits because of their capacity for persistence in the environment. ...
Pesticides, which are associated with endocrine dysfunction, immunological dysregulation, and cancer, are widespread sources of drinking water contamination. The state of Paraná has a population of 11 million, is the second largest grain producer in Brazil and is a leading consumer of pesticides. In this study, we analyzed the extent of drinking water contamination from 11 proven, probable, or potentially carcinogenic pesticides (alachlor, aldrin-dieldrin, atrazine, chlordane, DDT-DDD-DDE, diuron, glyphosate-AMPA, lindane-γ-HCH, mancozeb-ETU, molinate, and trifluralin) in 127 grain-producing municipalities in the state of Paraná. Extensive contamination of drinking water was found, including legacy pesticides such as aldrin-dieldrin (mean 0.047 ppb), DDT-DDD-DDE (mean: 0.07), chlordane (mean: 0.181), and lindane-HCH (mean: 2.17). Most of the municipalities were significantly above the maximum limits for each one of the currently allowed pesticides (67% for alachlor, 9.44% for atrazine, 96.85% for diuron, 100% for glyphosate-AMPA, 80.31% for mancozeb-ETU, 91.33% for molinate, and 12.6% for trifluralin). Ninety-seven percent of municipalities presented a sum of all pesticides at levels significantly above (189.84 ppb) the European Union preconized limits (
... Therefore, Brazilian water presents a mixture composed of toxic substances above the maximum limit allowed by Brazilian legislation, which is highly permissive. Europe standards are reference for drinking water safety, and if considering the maximum limits recommended by the European Union Directive about the highest levels authorized for each pesticide (0.1 ppb) or the sum of the levels of each substance in water for human consumption (maximum of 0.5 ppb), the water currently consumed by the Brazilian population would be unfit for human consumption (Dolan et al., 2013;EU, 2020). ...
... The international consensus is growing for the restored management of water and its quality. The European Union (EU) has set, through the Drinking Water Directive (DWD) (EU, DWD, 1998), the maximum admissible concentration (MAC) of pesticides for environmental and drinking water of 0.1 µg L −1 (for a single compound) and 0.5 µg L −1 (for the total pesticides) (Dolan et al., 2013). ...
This paper describes a simple, quick, and solvent-free multi-residue method to determine 90 pesticides in groundwater samples from 30 different chemical groups. The extraction was carried out by solid-phase microextraction in direct immersion mode (DI-SPME) using a polydimethylsiloxane/divinylbenzene fiber (65 µm thickness) followed by GC–MS detection. The main parameters affecting the DI-SPME process were studied in detail: temperature, NaCl addition, stirring rate, and extraction time. The validation parameters as linearity, precision (repeatability and reproducibility), and accuracy were evaluated. The limits of quantification (LOQs) were in the range of 0.009–0.976 µg L⁻¹. The analytes recoveries in groundwater samples varied from 60 to 120% and were appropriate for this type of water. The validated analytical method was successfully applied to the analysis of groundwater from wells located in agricultural sites in the municipality of Cadereyta Jimenez in Nuevo Leon, Mexico. The pesticides p, p’-DDT, bifenthrin, 2,4’-D ethylhexyl ester, and aldrin were below the LOQs in 73% of the analyzed samples. Oxyfluorfen and fenoxycarb were quantified at 0.08 and 0.2 µg L⁻¹, respectively. Fenoxycarb was above the maximum allowable concentration of 0.1 µg L⁻¹ for drinking water established by the European Union.
... Allowable Concentration (MAC) in drinking water [87]. Similarly, the USA Environmental Protection Agency (USEPA) has permitted 700 µgL -1 of glyphosate as the Maximum Contamination Level (MCL) in drinking water [88]. ...
... The restrictive value imposed by the European Union, based on the precautionary principle, which anticipates the potential risks of using glyphosate, would have been useful and important at the time it was legislated. However, the authors suggest its review because of the increase in studies on the toxicity of pesticides worldwide (Dolan et al. 2013). Mesnage et al. (2014) and Abrasco (2019) highlight that there is a risk to health when ingesting water/food contaminated by glyphosate, and the precautionary principle should preponderate in order to guarantee the integrity of the population (Torretta et al. 2018;Abrasco 2019). ...
The indiscriminate use of glyphosate is one of the main agricultural practices to combat weeds and grasses; however, its incorrect application increases soil and water contamination caused by the product. This situation is even more critical due to its great versatility for use in different cultivars and at lower prices, making it the most used pesticide in the world. Nevertheless, there is still a lack of in-depth studies regarding the damage that its use may cause. Therefore, this review focused on the analysis of environmental impacts at the soil–water interface caused by the use of glyphosate. In this sense, studies have shown that the intensive use of glyphosate has the potential to cause harmful effects on soil microorganisms, leading to changes in soil fertility and ecological imbalance, as well as impacts on aquatic environments derived from changes in the food chain. This situation is similar in Brazil, with the harmful effects of glyphosate in nontarget species and the contamination of the atmosphere. Therefore, it is necessary to change this scenario by modifying the type of pest control in agriculture, and actions such as crop rotation and biological control.
... The measured GLYP concentrations in the river stream region (RR-1, 2, and 7) were significantly over the European regulation for its limitation in drinking water [16] . No GLYP was detected in water samples collected at the river mouth (sampling RR-8 and RR-9). ...
A new green method for trace level quantification of four herbicides, glyphosate (GLYP), glufosinate (GLUF), and their main metabolites, aminomethylphosphonic acid (AMPA) and 3-(methyl-phosphinico)-propionic acid (MPPA), was developed. The purification step without any derivatization was conducted by solid-phase extraction using Chelex-100 resin in the Fe (III) form, followed by elution with 5% NH4OH. The four analytes were quantified by ultra-high-performance liquid chromatography coupled to tandem mass spectrometry. The developed extraction method was validated on five fresh and sea water matrices with mean recoveries ranging from 80.1% to 109.4% (relative standard deviation < 20%). The extraction conditions were evaluated and certified for the high applicability of the extraction method too. The limits of detection (ng/L) in the five water matrices were in ranges 0.70 – 4.0, 2.4 – 3.9, 1.8 – 4.7, and 1.6 – 4.0 for GLYP, AMPA, GLUF, and MPPA, respectively. The method was successfully applied to detect the four compounds in surface waters sampled along the Red River Delta region in July 2019. The highest concentrations were detected at 565, 1 330, 234, and 871 ng/L for GLYP, AMPA, GLUF, and MPPA, respectively. These results showed the potential capacity of this new method for convenient monitoring of herbicides and their metabolites in the diverse natural water system.
... Ce seuil, fixé à l'époque au seuil de détection du matériel analytique, est maintenant discuté par certains auteurs. Il est par exemple jugé trop bas lorsque comparé aux normes en vigueur aux Etats-Unis ou encore en Australie (Dolan et al., 2013) mais reconnu comme ayant un effet bénéfique pour la santé des européens pour qui 50% de Chapitre I : Synthèse bibliographique l'eau consommée provient des eaux souterraines, d'où l'importance de surveiller de près la qualité de cette ressource (Völker and Borchardt 2019;Gunnarsdottir et al., 2020). ...
De nombreux herbicides ciblent une enzyme végétale aussi retrouvée chez des organismes dits « non-cibles » tels que les microorganismes. Ce travail de thèse vise à établir la preuve de concept que les gènes microbiens codant l’enzyme ciblée ou l’activité de l’enzyme elle-même peuvent servir de marqueur d’impact écotoxicologique des herbicides dans les sols. L’enzyme HPPD (4-hydroxyphénylpyruvate dioxygénase) et le gène du même nom, cible des herbicides bêta-tricétones, sont sujets d’étude. Des études in silico montrent que le gène hppd est présent dans de nombreux genres bactériens et un couple d’amorces ciblant une majorité des séquences décrites a été dessiné. Ce dernier a servi à mesurer l’abondance, la composition et la diversité de la communauté bactérienne hppd de microcosmes de sols exposés à la sulcotrione ou à sa formulation commerciale, le Decano®. Les mêmes mesures sont réalisées sur des champs agricoles traités avec des ?-tricétones pendant une année. A l’échelle de la communauté, aucun effet des herbicides n’est décelable, renforçant leur réputation « eco-friendly ». Au niveau enzymatique, des études de docking moléculaire montrent que les herbicides se lient plus fortement à l’HPPD de certaines souches. Le bioessai développé soutient cette observation : les ?tricétones ont un effet variable sur l’activité HPPD en fonction de la souche considérée. La tembotrione inhibe plus fortement l’activité HPPD de Bacillus cereus ATCC14579 et Shewanella oneidensis MR-1 que la sulcotrione et la mésotrione. A l’avenir, ce bioessai pourrait être utilisé comme marqueur d’exposition des sols aux herbicides ?-tricétones dans une optique d’évaluation du risque par les autorités.
... The maximum permissible concentration of a single pesticide has been set to 0.1 μg L −1 by the European Union. Thus, the evolution of real-time on-site novel methods for monitoring of pollutants in drinking water has been enforced [3]. Among all the classes of pesticides and insecticides, carbamates are widely used against pests because they display quick action and a moderate persistence in the environment. ...
In the present work, the adsorption of carbaryl (CBL) on the modified graphene substrates has been studied by density functional theory (DFT) for the purpose of water remediation. Carbaryl is a carbamate pesticide used worldwide and has been reported as a potential carcinogen. It has been found that CBL adsorption on pristine graphene is endothermic and highly unfavorable. Further results show that the introduction of vacancy defects and Pt clusters significantly improves the reactivity of the graphene substrates towards the carbaryl molecule. The electron density difference plots give overview of the adsorption behavior of CBL and partial density of states (PDOS) give insights into the magnetic character exhibited by substrates after decorating with the cluster. This study reveals the suitability of Pt-decorated graphene substrates as adsorbents for the removal of CBL pesticide.
... Other studies have linked OPs with oxidative stress and possible genotoxicity [9] , however, long-term studies are required to confirm this. In the European union, pesticides in drinking water are currently regulated by the Drinking Water Directive using a maximum allowable concentration of 0.1 μg/l [61] . ...
The growing interest in nanomaterials with advanced optoelectronic properties has promoted the advancement of biosensors with various applications. In the environmental field, the need for rapid detection of pollutants in water sources has opened the door to fluorescent biosensors. These systems are quite sensitive and simple. Nanomaterials such as carbon dots (CD), quantum dots (QD), gold nanoparticles, nanoclusters, graphene (G), graphene oxide (GO), transition metal dialcogens (TMDC) and organometallic frameworks (MOF), have been used in the development of fluorescent detection systems. They are usually based on the Förster resonance energy transfer (FRET) quenching principle. Nanomaterials can be bioconjugated with molecules such as antibodies, enzymes or aptamers, to achieve specific detection of the target pollutant, even in real samples. This review conducts a critical analysis of the operating principle of different nanomaterial-based fluorescent biosensors. We discuss the detection of substances of high concern like heavy metals, pesticides, and so-called emerging contaminants. The advantages and disadvantages of the methods are discussed, as well as recommendations for future approaches and a possible massification of these systems.
... Diazinon is widely used pesticide and often is found in surface and groundwater. According to the Drinking Water Directive, pesticide concentration in drinking water should be below 0.1 μg/L (Dolan et al., 2013). Therefore, because of their toxic and carcinogenic nature of pesticide, their removal from the environment is quite significant as well as the reduction of pesticide use (Farmany et al., 2016). ...
Adsorption of diazinon from aqueous solution was studied by using cross-linked Chitosan/Carbon Nanotube (CHN-CNT) in a fixed-bed column. The cross linked CHN-CNT with 2.5% of MWCNT was prepared with a protected crosslinking method. The effects of the initial concentration of diazinon, bed-height, and flow rate on the adsorption of diazinon onto the cross linked CHN-CNT were investigated. The highest bed capacity of 29.47 mg/g was obtained at the initial concentration of 50 mg/L, flow rate of 10.5 mL/min, and fixed bed-height of 4 cm. Three models, namely Bohart-Adams, Thomas, and Yoon-Nelson, were investigated to predict the breakthrough curves and to determine the characteristic parameters. The experimental data were well fitted with the Yoon-Nelson model, indicating that it was suitable for continuous adsorption of diazinon onto cross-linked CHN-CNT in a fixed-bed column. The findings of this study revealed that the cross-linked CHN-CNT not only has a simple synthesis method and good strength but also adsorbs the diazinon well.
... These arise as a result of the EU's WFD, which mandates the maximum permissible concentration of pesticides in drinking water (0.1µg/l for a single pesticide, 0.5µg/l for total pesticides) (Dolan et al. 2013). Despite this legislation, FOrum for Co-ordination of pesticide fate models and their USe (FOCUS) predict a metaldehyde concentration of 28.8µg/l at day 0 of an average northern-European surface water pollution event, decreasing to 21.8µg/l after 28 days (FOCUS 2001) (Appendix: Figure 8.1.) ...
Pesticides are a fundamental tool of modern agriculture used to reduce crop damage and increase yield, however, are frequently lost from arable land to the detriment of aquatic biodiversity and water security. During July 2019 the UK High Court halted a ban on one molluscicide, metaldehyde, on legal grounds however, over 20 years since its emergence, the impacts of metaldehyde upon real-world non-target aquatic faunal communities remain unstudied. Therefore, as metaldehyde use is likely to continue for the foreseeable future, this study aimed to assess the legacy of metaldehyde use in five UK lowland rivers via a range of mesocosm simulations and analysis of long-term ecological records. Results indicated that existing biomonitoring metrics were ineffective at detecting metaldehyde pollution, likely as acute effects and differences between detected and control sites highlighted the limited significance of metaldehyde in driving non-target aquatic faunal communities. Mesocosm simulations support this with the concentrations required to cause mortality being significantly higher than those observed in test rivers. Sites affected by chronic metaldehyde pollution displayed differences in community composition which may have occurred as a result of changes in trophic interactions, however, a strong correlation between metaldehyde and other agricultural pollutants prevented the drawing of more authoritative conclusions. All analyses highlight the increased significance of orthophosphate in driving the entire faunal community, and phosphorus in driving the mollusc community, relative to metaldehyde. Overall, it was determined that metaldehyde concentrations observed in the real world were unlikely to cause compositional shift over any time period, with the observed differences likely due to more significant agricultural pollutants. Therefore, the halted ban upon metaldehyde use likely poses a limited threat to non-target aquatic faunal communities. Further research is, however, required to determine the residency and degradation of metaldehyde within aquatic environments in order to better inform future policy decisions.
... However, in some instances their use has raised concerns for human health, food and drinking water resource safety (World Health Organization and United Nations Environment Programme, 1990;Nicolopoulou-Stamati et al., 2016;Deng et al., 2019) and more widely in terms of unintended environmental effects (van der Werf, 1996;Carvalho, 2017;Wood and Goulson, 2017). The use of pesticides is heavily regulated in some regions (Karabelas et al., 2009;Handford et al., 2015), such as Europe where the European Union Water Framework Directive 2000/60/EC mandates a maximum permissible concentration of pesticides in drinking water of 0.1 mg/ L for a single pesticide (Dolan et al., 2013). ...
The use of pesticides has historically helped improve agricultural productivity, although their continued use may have unforeseen effects upon the natural environment when not applied appropriately. Metaldehyde is a commercial pesticide widely used to reduce crop losses resulting from terrestrial mollusc damage. However, following precipitation and runoff it frequently enters waterbodies with largely unknown consequences for aquatic fauna. This study represents one of the first attempts to examine its potential effects on aquatic macroinvertebrate communities at sites known to have experienced elevated metaldehyde concentrations alongside unaffected control sites. In addition, a series of laboratory exposures specifically examined the effects of metaldehyde on the survivorship of non-target aquatic mollusc species. When the entire aquatic macroinvertebrate community and aquatic mollusc community were considered, limited differences were observed between metaldehyde affected and control sites based on field data. Laboratory exposures highlighted that for the molluscs examined, gastropods (Bithynia tentaculata, Planorbis planorbis, Radix balthica and Potamopyrgus antipodarum) had a greater tolerance to metaldehyde than bivalves (Sphaerium corneum and Corbicula fluminea). However, the concentrations required to reduce survivorship of all species wee much greater than those ever recorded historically under field conditions. The results suggest that the differences in the community composition recorded between sites exposed to elevated metaldehyde concentrations and control sites were probably due to nutrient loading (N and P from agricultural fertilizers) rather than metaldehyde. However, these results do not negate wider concerns regarding metaldehyde use, particularly issues caused when ingested by vertebrate wildlife, livestock or children and pets in domestic settings.
... Elements that are brought in by humans as part of agricultural practice are foreign to the system and can significantly change the qualitative and quantitative composition of water. The most common organic compounds that are found in water include phenols, humic components, hydrocarbons, and surfactants (Dolan, 2013;Dolan et al., 2013). If the amount of these substances goes beyond the permissible level, the water quality will deteriorate to the point when it becomes not safe to drink; the observations include the change of colour, taste, and odour as well as the presence of foam (Blackstock et al., 2010). ...
The problem of drinking water quality assessment and the impact of agricultural practices on it is relevant these days. A certain select area can serve as a convenient model object in the investigation. This work aims to assess the effect of agricultural practices on the quality of drinking water. The qualitative and quantitative composition of drinking water consumed by the habitants of Vladivostok, Russian Federation, was investigated in 2018. A total of 1000 samples were collected from wells, small rivers, channels located nearby the wastewater treatment facilities, from a river flowing near fields and livestock farms, and from a river with the minimal anthropogenic impact. To evaluate the drinking water suitability, the following parameters were addressed: the mineral level, hardness, alkalinity, permanganate oxidation, and the concentration of various salts and ions, specifically Ca2+, Cl–, SO4, HCO3, NO2, Mg2+, P, and NH4-N. The concentration of organic compounds is affected by two factors, water temperature and pH. The mineral level in water near the farmland is 1.7-3 times higher than the norm (p ≤ 0.05). Intermediate results (i.e., elevation of 1.5 times) were obtained for wells and small rivers (p ≤ 0.05). In the preserve, all parameters are close to normal value. Thereby, almost all substances under study demonstrate elevation of at least 2-20 times. The reason for this situation is the human factor.
... For regulatory process, conservative assumptions (e.g., the precautionary principle) can effectively deal with data gaps and uncertainties to derive environmental quality standards. For example, the EU adopted the precautionary approach according to its policy principles before toxicological information was available, regulating each pesticide as 0.1 mg L À1 in drinking water (Li and Jennings, 2018;Dolan et al., 2013). To overcome this issue, it is suggested that a dynamic modeling network should be further developed to improve the simulated outcomes from the information collected by regulatory and environment agencies at each level of the cattle-related food industry. ...
To help countries worldwide regulate agricultural soil standards for organic contaminants, this study developed the pastoral-based chemical lifecycle management (PBCLM) modeling framework, which comprehensively models the bottom-up causation of the chemicals’ lifecycle at each level of the cattle industry and delivers top-down regulatory strategies. The lifecycle models for a total of 308 hydrophobic organic contaminants were constructed. The results indicated that the octanol-water partitioning coefficient (log KOW) values had the greater impact on the unit-legal-limit-based concentrations for contaminants at the producer level (i.e., grass) or higher. In addition, the analysis of the weather variables indicated that pastoral farming in warmer and drier places might lead to the bioaccumulation of more contaminants. By comparing the reference legal limits that were derived by the PBCLM, current soil standards might not be effective in protecting human health or harmonizing downstream food regulations. The PBCLM can help regulatory agencies better promulgate soil regulations to ensure sustainable agriculture.
... Drinking water companies regularly monitor drinking-, surface-and groundwater quality for the occurrence of pesticides and their metabolites, using routine target chemical analysis. Proactive monitoring, including newly authorized pesticides, can signal potential risks (Dolan et al., 2013(Dolan et al., , 2014. Several factors influence the potential risks of a pesticide for drinking water production. ...
We determined pesticide occurrence in groundwater and surface water sources used for drinking water production in The Netherlands, using both routine monitoring data from Dutch drinking water companies and by studying the presence of newly authorized pesticides in drinking water sources.
An analytical LC-MS/MS method was developed for 24 recently authorized pesticides, selected based on their mobility and persistence, and applied in a Dutch/Belgian ground- and surface water monitoring campaign. 15 of these pesticides were detected, including seven in concentrations above the water quality standard from the Water Framework Directive. Two neonicotinoids were detected in highest concentrations: acetamiprid (1.1 μg/L) and thiamethoxam (0.4 μg/L).
The routine monitoring data was collected over 2010–2014 in The Netherlands, covering 408 pesticides and 52 metabolites. 63 pesticides and 6 metabolites were prioritized according to their presence in groundwater, surface water and drinking water. The vast majority of the pesticides in routine monitoring has not been detected or only in low concentrations.
Overall, the study shows that pesticides are of major concern in drinking water sources across the Netherlands. In two third of the abstraction areas pesticides and/or metabolites have been detected. In one third of the abstraction areas pesticide and/or metabolites concentration exceeded water quality standards according to the Water Framework Directive. The results emphasize that monitoring should focus on priority pesticides, since the vast majority of the pesticides has a low priority. The occurrence of recently authorized pesticides in drinking water sources demonstrates the importance to keep routine monitoring methods up to date.
... Despite this, the reproducibility of retention time coupled with the selectivity of detection allowed a high precision of the measurements of the compounds, and their detection limits (Table 6) were much lower than those indicated by the European Community (0.1 μg/L). 95 Recently Hajazimi et al. 96 determined flavonols and phenolic acids by HPLC with coulometric array detection in berries common in Nordic diet. ...
... Given the impact of pesticide residues on the environment and human health, several priority lists comprising maximum contam- inant levels (MCLs) have been established by the US environmental protection agency (US EPA) and EU regulations [1][2][3][4] to monitor the quality of drinking, surface, and ground water. Today, several offi- cial techniques [2,3], including liquid-liquid extraction (LLE) and solid phase extraction (SPE), are available for determination of con- taminants (e.g. ...
The aim of the current study is the establishment of Green Analytical Chemistry strategies for water analysis by elimination/reduction of hazardous chemicals, energy consumption, and waste generation throughout the entire analytical workflow. The first approach introduced in this manuscript consists of addition of water to a sampling vessel that contains a thin film microextraction (TFME) device, followed by removal of the device after equilibration, and subsequent quantification of the extracted components by thermal desorption GC/MS. In this approach, namely the in-bottle TFME approach, analyte-loss associated errors that stem from analyte adherence to glass surfaces and/or degradation are avoided as extraction occurs in situ, while analytes are isolated from a complex matrix that contains degradation agents (bacteria, oxidizing or reducing species, etc.). This procedure also circumvents the splitting of original samples into sub-samples. The second approach involves the use of portable TFME devices that facilitate on-site extraction of compounds, therefore eliminating the use of collection vessels, a factor known to potentially introduce errors into analysis. The herein described procedure involves attachment of the TFME device to drill accessories, analyte extraction via direct immersion into sampled site, and subsequent on-site instrumental analysis, which is carried out with the use of a portable GC/MS containing an appropriate thermal desorption interface, or alternatively, by transferring the membrane to the laboratory for bench-top GC/MS analysis. To facilitate a better understanding of the processes governing the developed approaches, modeling by COMSOL Multiphysics® software was performed. The findings of this study were applied for further method optimization, and the optimized developed methods were then applied for on-site surface water analyses. Finally, the greenness of the developed methods was evaluated with use of the eco-scale assessment, with obtained scores compared to that of the US EPA 8270 method.
... In the United States, a maximum contaminant level (MCL) is derived for a single pesticide, based on the available toxicological evidence and an analysis of the costs and health benefits associated to the proposed MCL (EPA, 2016). Alternatively, in the European Union, almost all pesticides approved for use are subject to the same maximally allowable concentration (MAC) of 0.1 µg/L, which is supposed to function as a precautionary-based "surrogate zero" level (Dolan, Howsam, Parsons, & Whelan, 2013). Similar differences can be observed between 1 0272-4332/18/0100-0001$22.00/1 C 2018 The Authors Risk Analysis published by Wiley Periodicals, Inc. on behalf of Society for Risk Analysis. ...
Why do countries regulate, or prefer to regulate, environmental health risks such as radiofrequency electromagnetic fields and endocrine disruptors differently? A wide variety of theories, models, and frameworks can be used to help answer this question, though the resulting answer will strongly depend on the theoretical perspective that is applied. In this theoretical review, we will explore eight conceptual frameworks, from different areas of science, which will offer eight different potential explanations as to why international differences occur in environmental health risk management. We are particularly interested in frameworks that could shed light on the role of scientific expertise within risk management processes. The frameworks included in this review are the Risk Assessment Paradigm, research into the roles of experts as policy advisors, the Psychometric Paradigm, the Cultural Theory of Risk, participatory approaches to risk assessment and risk management, the Advocacy Coalition Framework, the Social Amplification of Risk Framework, and Hofstede's Model of National Cultures. We drew from our knowledge and experiences regarding a diverse set of academic disciplines to pragmatically assemble a multidisciplinary set of frameworks. From the ideas and concepts offered by the eight frameworks, we derive pertinent questions to be used in further empirical work and we present an overarching framework to depict the various links that could be drawn between the frameworks.
... The work with effective monitoring pollution status of pesticides in real time will provide reliable data for degradation dynamics and transfer law of the pesticides and provide more understanding the effects of pesticides in valuable drinking water on human health and the environments. Many questions were asked that people would understand the health risks based on scientific data and to appropriately establish them (Dolan et al. 2016). The analytical confirmation of low levels of pesticides plays a critical role in the studies for legitimate pesticide use and advanced pest management technologies. ...
This work investigated drinking water contamination by 11 commonly used herbicides in sugarcane production areas in Guangxi, China. The work developed an analytical method for determination of these herbicides in environmental waters. This work studied herbicide residues in drinking water in Guangxi, China. The maximum residues and percent of detects were: (0.091 µg/L, 29.2%, atrazine), (0.018 µg/L, 8.3%, ametryne), (0.188 µg/L, 8.3%, aetolaehlor), (0.139 µg/L, 4%, simazine), (0.585 µg/L, 62.5%, atrazine), (0.311 µg/L, 33.3%, acetochlor), (0.341 µg/L, 58.3%, ametryne), (1.312 µg/L, 29.2%, metolachlor), (0.088 µg/L, 4.2%, alachlor), (0.127 µg/L, 14.3%, atrazine), and (0.453 µg/L, 7.1%, metolachlor), respectively. The results demonstrated that agricultural herbicides were detected in all water samples, including tap, surface and groundwater samples. Since the residues are generally below the safe limits established by the government authorities, the monitored 11 herbicides do not significantly affect the quality of the human environment. This work will provide scientific understanding of pesticide residues in drinking water standards in terms of its consistency with precautionary human health and environmental safety.
... Both populations and the governments have great concern for conservation of the environment and biodiversity, but major nations with large ecological and economic importance, such as Brazil and the USA, are not consistent in pursuit of these objectives, establishing laws mostly focused on lethal concentrations for humans. In contrast, the Europe Union (E.U.) has more restrictive laws, based on the precautionary principle (Belt, 2003;EC, 2016), than American countries (Dolan et al., 2013). While U.S.A. and Brazil establishes high limits for glyphosate (700 and 65 μg l −1 respectively), E.U. countries establish a concentration of 0·1 μg l −1 for individual pesticides, provided the cumulative total does not exceed 0·5 μg l −1 (Junior & Santos, 2002). ...
Environmental relevant concentrations of glyphosate-based herbicide as 50 μg l −1 , 300 μg l −1 and 1800 μg l −1 can affect sperm quality of yellowtail tetra fish Astyanax lacustris. Viability of sperm cells was impaired at 300 μg l −1 , a concentration that is within legal limits in U.S.A. waterbodies, while motility was impaired at 50 μg l −1 , which is the more stringent limit set in Brazilian law. Therefore, environment protection agencies must review regulations of glyphosate-based herbicides on water bodies.
... The variations between jurisdictions are well known and arise from different motivations and methods for regulation. For example, the EU took a precautionary approach (in accordance with the principles of its environmental policy) before toxicological data was available, attempting to regulate each pesticide and its metabolites as 0.1 mg/L and a maximum total pesticide concentration of 0.5 mg/L, plus additional, more stringent MCLs were regulated for certain pesticides (0.03 mg/L), irrespective of toxicity (Dolan et al., 2013). ...
... Thus, aquatic communities are potentially exposed to glyphosate formulations via several different pathways (Geyer et al., 2016). None of the observed concentrations of glyphosate exceeded the maximum acceptable value (280 mg l À1 ), according to the Argentine legislation, and are also within the recommended levels for Australia (1000 mg l À1 ), Canada (280 mg l À1 ), Japan (4000 mg l À1 ) and the USA (700 mg l À1 ) (Hamilton et al., 2003); however, they were higher than the more stringent level established by the European Community (0.1 mg l À1 ) (Dolan et al., 2013). The presence of glyphosate in the reservoir Paso de las Piedras and other recreational water bodies should warn us about the possibility of human exposure to this chemical, by direct contact or ingestion. ...
... However, because of their high toxicity, bioaccumulation and environmental persistence, pesticides in coastal environment such as seawater, sediment and marine products, pose a risk of undesirable health effects [1,2]. According to the US Environmental Protection Agency and the European Union, the maximum allowed concentrations for individual pesticides and total pesticides in drinking water are 0.1 μg·L −1 and of 0.5 μg·L −1 [3,4]. Moreover, quantitative determination of pesticides at ultra-trace levels is very difficult to carry out because the high salinity of the samples matrix causes false-positive results. ...
The authors have developed a method for simultaneous quantification of several charged pesticides (as shown for amitrole, simazine, trichlorfon and bisultap). It is based on the use of a reduced graphene oxide-modified screen-printed electrode (RGO-SPE) and combines electrokinetic trapping (EKT) and surface-enhanced Raman scattering (SERS). When a 50 μL droplet containing negatively charged RGO and positively charged gold nanorods is placed on the SPE, the RGO and gold nanorods are selectively attracted on the surface of the SPE during EKT. This leads to the formation of sandwich-type hybrid substrates. The resulting substrates also contain Raman “hot spots” among the high-density gold nanorods. This, along with the excellent adsorption performance of RGO, makes it an excellent SERS substrate for on-site detection of the charged pesticides. The method is highly reproducible and long-term stable. The spot-to-spot variation of the intensity of the SERS is <15%, and the performance of SERS activity is maintained over a period of 6 weeks. The method works over a wide range of concentrations (0.5 nM to 4 μM) for charged pesticides under optimal conditions, with a sub-nanomolar detection limit (at a signal to noise ratio of 3). The EKT-SERS method requires only microliter volumes and takes only minutes for completion. Therefore, the method provides high sensitivity for detection while preserving the selectivity and stability required for reliable quantitative analysis.
Graphical abstractA method combining electrokinetic trapping and SERS can be used for simultaneous detection of charged pesticides in a drop of seawater.
... 662 In the EU, pesticides in drinking water are currently regulated by the Drinking Water Directive, which stipulates the maximum allowable concentration of 0.1 μg/L per pesticide or 0.5 μg/L for the total pesticide concentration. 663 2,4-Dichlorophenoxyacetic acid (2,4-D) embodies one of the most frequently applied herbicides in agriculture. It is a synthetic plant growth regulator, structurally and functionally akin to auxin. ...
We review the progress achieved during the recent five years in immunochemical biosensors (immunosensors) combined with nanoparticles for enhanced sensitivity. The initial part introduces antibodies as classic recognition elements. The optical sensing part describes fluorescent, luminescent, and surface plasmon resonance systems. Amperometry, voltammetry, and impedance spectroscopy represent electrochemical transducer methods; electrochemiluminescence with photoelectric conversion constitutes a widely utilized combined method. The transducing options function together with suitable nanoparticles: metallic and metal oxides, including magnetic ones, carbon-based nanotubes, graphene variants, luminescent carbon dots, nanocrystals as quantum dots, and photon up-converting particles. These sources merged together provide extreme variability of existing nanoimmunosensing options. Finally, applications in clinical analysis (markers, tumor cells, and pharmaceuticals) and in the detection of pathogenic microorganisms, toxic agents, and pesticides in the environmental field and food products are summarized.
Glyphosate (GLY), the preeminent herbicide utilized globally, is known to be exposed to the environment and population on a chronic basis. Exposure to GLY and the consequent health risks are alarming public health problems that are attracting international attention. However, the cardiotoxicity of GLY has been a matter of dispute and uncertainty. Here, AC16 cardiomyocytes and zebrafish were exposed to GLY. This study found that low concentrations of GLY lead to morphological enlargement of AC16 human cardiomyocytes, indicating a senescent state. The increased expression of P16, P21, and P53 following exposure to GLY demonstrated that GLY causes senescence in AC16. Moreover, it was mechanistically confirmed that GLY-induced senescence in AC16 cardiomyocytes was produced by ROS-mediated DNA damage. In terms of in vivo cardiotoxicity, GLY decreased the proliferative capacity of cardiomyocytes in zebrafish through the notch signaling pathway, resulting in a reduction of cardiomyocytes. It was also found that GLY caused zebrafish cardiotoxicity associated with DNA damage and mitochondrial damage. KEGG analysis after RNA-seq shows a significant enrichment of protein processing pathways in the endoplasmic reticulum (ER) after GLY exposure. Importantly, GLY induced ER stress in AC16 cells and zebrafish by activating PERK-eIF2α-ATF4 pathway. Our study has thus provided the first novel insights into the mechanism underlying GLY-induced cardiotoxicity. Furthermore, our findings emphasize the need for increased attention to the potential cardiotoxic effects of GLY.
E1, E2, E3, and EE2 are types of estrogens that need to be federally regulated in waterbodies in the United States. Absence of regulation has led to untreated releases from wastewater treatment plants of estrogen from natural human excretion and releases from animal feeding operations (AFOs) eluding proper waste management. Estrogens have been detected in drinking water, which has caused concerns over human health as there is little research
evaluating the health risks. Due to there being no evidence supporting negative impacts on human health, there is no justification for regulation under current Safe Drinking Water Act
provisions. However, as guided by the precautionary principle, current laws could be amended to utilize preventative measures since there is no certainty that exposure to estrogenic drinking
water is harmless. Exposure also proves to be an issue for aquatic life and potentially other species. Thus, I argue that E1, E2, E3, and EE2 must be listed as pollutants under the Clean Water Act and increased regulations on AFOs must be implemented.
Glyphosate is currently the herbicide with the highest use worldwide for weed control. It has been detected in different water sources, including drinking water, which could be generating potential damage to human health. In the Metropolitan Area of Cúcuta, intensive rice cultivation is predominant, and as it grows in flooded areas, the use of herbicides has greater contact with water bodies, which are used as sources of supply. Based on this, the concentration of glyphosate was quantified in five sampling points of surface and drinking water of the Pamplonita and Zulia rivers, using UV-Vis spectrophotometry, establishing that the concentration found in drinking water (216 and 204.5 µg/L) was below the maximum allowable limits of countries such as the United States, Canada, and Australia and above those of the European Union and the United Kingdom. Once the occurrence was identified, the removal capacity of glyphosate was evaluated using membrane technology through reverse osmosis (RO) and nanofiltration (NF) in a pilot plant, for which response surface optimization models were implemented, and 100% removals were obtained, with repeatability close to 1% with respect to other reported investigations, highlighting that the NF process was more efficient even though the molecular weight of glyphosate was below the limit of the membrane. In contrast, it was determined that, according to the concentrations found in the drinking water supplied to the Metropolitan Area of Cúcuta, this has a low risk according to the guidelines for drinking water quality in Canada and a moderate risk according to the World Health Organization (WHO). The conventional systems currently used for water purification are insufficient to remove traces of contaminants such as herbicides. Therefore, it is necessary to implement new technologies.
Background
Water is polluted day by day with biological and chemical toxins that can pose a serious threat to human health, animals and ecosystems. The regular identification and monitoring of biological and chemical toxins in water resources is the first step of the preventive method. The devices used in traditional detection methods such as adsorption and chromatography combined with mass spectrometry are not easy to transport for analysis and involve laborious preliminary sample preparation steps. However, the developments in nanosensors prepared with nanomaterials provide solutions to these challenges. Nanomaterials such as gold nanoparticles, graphene and quantum dots are often preferred for the surface preparation of plasmonic nanosensors for the selective, sensitive and label-free detection of very low concentrations of pollutants in water.
Methods
There are different plasmonic nanosensors such as electrochemical, colorimetry and optical sensors prepared using different nanomaterials for the determination of environmental pollutants. These different detection nanosensors also have many advantages and disadvantages. In this review, the use of different nanomaterials in different types of plasmonic nanosensors for the determination of environmental pollutants, their modification and their effects on performance in terms of signal enhancement will also be discussed.
Results:
When the studies in the literature are examined, although many articles have been published on the detection of pollutants in water, the number of publications specific to nanomaterial-based plasmonic nanosensors for detection is quite limited. In this review, we focused on the use of different nanomaterials in the preparation of nanosensor surfaces for the detection of environmental pollutants, and the preparation, optimization, experimental analysis and application areas of different plasmonic nanosensors made in the literature for detection methods
Conclusion:
Recent developments in plasmonic nanosensors, nanomaterials such as gold nanoparticles, graphene and quantum dots provide ultra-sensitive detection at the molecular level, leading to extraordinary developments. Nanomaterials have important plasmonic properties and are preferred for the selective, sensitive and label-free detection of very low water pollutant concentrations. In studies conducted in the literature, it has been observed that environmental pollutants such as toxin, bacteria, heavy metal ions, pesticides, especially in water, are determined and analyzed. In these review, it was observed that the sensitive and selective properties of nanomaterial-based nanosensors yielded results with low detection limits. The current review includes developments and application-oriented progress of nanomaterial-based plasmonic nanosensors, especially for the detection and quantification of various pollutants and environmental pollutants in water.
In river catchments used as drinking water sources, high pesticide concentrations in abstracted waters require an expensive treatment step prior to supply. The acid herbicide 2-methyl-4-chlorophenoxyacetic acid (MCPA) is particularly problematic as it is highly mobile in the soil-water environment following application. Here, an agri-environmental scheme (AES) was introduced to a large-scale catchment (384 km²) to potentially reduce the burden of pesticides in the water treatment process. The main measure offered was contractor application of glyphosate by weed wiping as a substitute for boom spraying of MCPA, supported by educational and advisory activities. A combined innovation applied in the assessment was, i) a full before-after-control-impact (BACI) framework over four peak application seasons (April to October 2018 to 2021) where a neighbouring catchment (386 km²) did not have an AES and, ii) an enhanced monitoring approach where river discharge and MCPA concentrations were measured synchronously in each catchment. During peak application periods the sample resolution was every 7 h, and daily during quiescent winter periods. This sampling approach enabled flow- and time-weighted concentrations to be established, and a detailed record of export loads. These loads were up to 0.242 kg km⁻² yr⁻¹, and over an order of magnitude higher than previously reported in the literature. Despite this, and accounting for inter-annual and seasonal variations in river discharges, the AES catchment indicated a reduction in both flow- and time-weighted MCPA concentration of up to 21% and 24%, respectively, compared to the control catchment. No pollution swapping was detected. Nevertheless, the percentage of MCPA occurrences above a 0.1 μg L⁻¹ threshold did not reduce and so the need for treatment was not fully resolved. Although the work highlights the advantages of catchment management approaches for pollution reduction in source water catchments, it also indicates that maximising participation will be essential for future AES.
Since being introduced as an alternative to the solid-phase microextraction (SPME) fiber format, thin-film microextraction (TFME) has been employed in various gas and liquid chromatography (GC and LC) applications. TFME solves a number of the analytical challenges related to sample preparation and sample introduction, in addition to allowing the integration of different analytical procedures into one step. The key feature of TFME is its greater extraction phase surface area and volume. These characteristics enable improved extraction kinetics, which in turn increases the amount of analytes that can be extracted. Furthermore, TFME's greater extraction phase surface area and volume provide much higher sensitivity in both the pre-equilibrium and equilibrium extraction regimes while maintaining similar equilibrium times. The protocol presented in this paper provides a detailed sequence of TFME optimization steps that can be applied in the development of TFME-GC methods for water applications.
Pesticides are pollutants of high concern in drinking water. Several approaches aimed to promote pesticide risk management in drinking water have been brought forward by diverse ways, however, these methods usually take too many indicators into consideration, which are complex and non-universal. In this study, a more focused and data driven ranking model was proposed for the purpose of development of the priority control list in drinking water. By determining three parameters including the total health risks of dietary exposure pathways, drinking water contribution rates, and the drinking water health risks, pesticides could be divided into four categories including the priority control list, secondary control list, candidate control list, and non-regulatory list. As a case study, the proposed model was implemented for 23 pesticides detected in drinking water from 36 major cities across China during two major science and technology program for water pollution control and treatment. Totally 13 kinds of pesticides including carbofuran, dicofol, chlorpyrifos, 2,4-D, acetochlor, deltamethrin, dimethoate, heptachlor, parathion, hexachlorobenzene, DDT, hexachlorocyclohexane and atrazine are selected for priority control, methyl parathion, dichlorvos and chlorothalonil are recommended for secondary control, butachlor and malathion are classified into candidate control list, and fenobucarb is suggested to be removed from the pesticide control list.
This article describes an optical method based on the association of surface plasmon resonance (SPR) with chitosan (CS) film and its nanocomposites, including zinc oxide (ZnO) or graphene oxide (GO) for glyphosate detection. CS and CS/ZnO or CS/GO thin films were deposited on an Au chip using the spin coating technique. The characterization, morphology, and composition of these films were performed by Fourier-transform infrared spectroscopy (FTIR), atomic force microscopy (AFM), and contact angle technique. Sensor preparation conditions including the cross-linking and mobile phase (pH and salinity) were investigated and thoroughly optimized. Results showed that the CS/ZnO thin-film composite provides the highest sensitivity for glyphosate sensing with a low detection limit of 8 nM and with high reproducibility. From the Langmuir-type adsorption model and the effect of ionic strength, the adsorption mechanisms of glyphosate could be controlled by electrostatic and steric interaction with possible formation of 1:1 outer-sphere surface complexes. The selectivity of the optical method was investigated with respect to the sorption of glyphosate metabolite (aminomethylphosphonic acid) (AMPA), glufosinate, and one of the glufonisate metabolites (3-methyl-phosphinico-propionic acid) (MPPA). Results showed that the SPR sensor offers a very good selectivity for glyphosate, but the competition of other molecules could still occur in aqueous systems.
Detection of organophosphate pesticides is indispensable to improve the quality of the water and therefore required by the European Union law. Here, we propose a novel architecture of a pesticide biosensor where the enzyme and the electrode are placed into neighboring zones in the stripe form. This separation permits to use the optimal conditions for their immobilization resulting in undisrupted mechanical stability of the biosensor. The enzyme, acetylcholinesterase, generates thiocholine which is further oxidized at the carbon nanoparticles film electrode, exhibiting high electrocatalytic activity. The whole device was tested as a biosensor for malaoxon employing a wild or recombinant acetylcholinesterase. The latter allowed for incubation time decrease down to 10 minutes and lowered the detection limit to 0.25 nM. Moreover, the encapsulated enzyme activity was visualised by a scanning electrochemical microscopy.
Metaldehyde is extensively used worldwide as a contact and systemic molluscicide for controlling slugs and snails in a wide range of agricultural and horticultural crops. Contamination of surface waters due to run-off, coupled with its moderate solubility in water, has led to increased concentration of the pesticide in the environment. In this study, for the first time, rapid analysis (<~1 minute) of metaldehyde residues in water is demonstrated using paper spray mass spectrometry (PS-MS). The observed precursor molecular ions of metaldehyde were confirmed from tandem mass spectrometry (MS/MS) experiments by studying the fragmentation patterns produced via collision-induced dissociation. The signal intensity ratios of the most abundant MS/MS transitions for metaldehyde (177 → 149 for protonated ion) and atrazine (221 → 179) were found to be linear in the range 0.01 to 5 ng/mL. Metaldehyde residues were detectable in environmental water samples at low concentration (LOD < 0.1 ng/mL using reactive PS-MS), with a relative standard deviation <10% and an R² value >0.99, without any pre-concentration/separation steps. This result is of particular importance for environmental monitoring and water quality analysis providing a potential means of rapid screening to ensure safe drinking water.
The ‘precautionary principle’, as formulated in the 1992 Rio Declaration on Environ ment and Development, calls for regulatory action in the face of serious environmental risks even in the absence of full scientific certainty. This paper traces negotiation of the principle at the Rio Conference, and its history in Europe from 1969 Swedish legislation to the latest directives of the European Union. As illustrated by recent court cases from Germany and France, in particular (on nuclear power plants, electro magnetic fields, and genetically modified organisms), judicial interpretation of the principle has tended to be restrictive. Future law making in this field is likely to focus on public access to environmental risk information, and on the development of new ‘right to know’ instru ments such as mandatory product labelling and transnational pollutant release inven tories, an area where Europe can still learn from North American experience.
In situations of serious uncertain risk, precautionary assessment, decision‐making and control may be inevitable. In this paper, the long and wide‐ranging debate about the precautionary principle (PP) is surveyed in comparison to parallel developments of classical risk analysis. The ‘new risks’ provoking precaution typically are complex, often extensive in space and time, socially diverse, supposedly unlikely but highly uncertain, and potentially catastrophic. Classical risk analysis falls short of grasping such ill‐defined problems validly enough for effective policy support. Similarly, the ‘prudent’ PP is criticised for its vagueness, multiple meanings and lack of practical elaboration. Despite their differences, however, risk‐analytic and precautionary‐principled approaches seem to be converging. On the way towards a decision‐theoretic exposition (see follow‐up paper), an integrative circumscription of the PP is proposed, which comprises 10 key issues for further elaboration. Logically, the ‘pessimistic’ PP is contrasted with its ‘optimistic’ counterpart, the venture principle (VP), which may be equally rational and/or inevitable in particular uncertain decision situations.
Rational decision theory could be more fully exploited for the prudent management of uncertain‐risk situations. After an integrative circumscription of the precautionary principle (PP), 10 key issues are discussed covering assessment, decision and control. In view of this, a variety of decision‐theoretic considerations are explored. ‘Sufficient evidence’ for precautionary action is treated as a diagnostic decision in the framework of signal detection theory. Thus, an assessment about ‘danger’ versus ‘no danger’ should depend on prior probability, evidence strength and the relative seriousness of false‐positive versus false‐negative outcomes. From an illustrated survey of simple and more complex decision rules, it appears that ‘precaution’ may be variously expressed via, for example, maximin utility, minimax regret, maximin expected utility and maximising expected utility‐minus‐regret. Logically, serious uncertain risk (against modest benefits) may provoke a precautionary approach – under the PP. In contrast, however, an uncertain ‘great opportunity’ (against modest costs) may elicit a venturous approach – following the venture principle (VP). Thus, the PP amounts to a basic attitude rather than a normative principle, whose practical application hinges on straightforward albeit uncertain decision variables. Decision postponement, temporal discounting and risk–risk tradeoffs are summarily reviewed. General conclusions are drawn and some suggestions for policy‐making and further research are proposed.
“Non-relevant metabolites” are those degradation products of plant protection products (PPPs), which are devoid of the targeted toxicities of the PPP and devoid of genotoxicity. Most often, “non-relevant metabolites” have a high affinity to the aquatic environment, are very mobile within this environment, and, usually, are also persistent. Therefore, from the point of drinking water hygiene, they must be characterized as “relevant for drinking water” like many other hydrophilic/polar environmental contaminants of different origins. “Non-relevant metabolites” may therefore penetrate to water sources used for abstraction of drinking water and may thus ultimately be present in drinking water.
Diffuse pesticide pollution is a problem for the environment, but it also presents a challenge for water companies managing treatment infrastructure to produce potable water. The legal framework for this context has three main components: that dealing with pesticides and pesticide use, that dealing with environmental water quality and that dealing with drinking water quality. The study set out to identify, interpret and assess the impact of the legal framework related to this challenge. The study found that the current policy and legislation do not provide a coordinated legal framework and some changes are warranted. For example the Water Framework Directive (WFD) sets environmental quality standards for some, but not all, pesticides. Article 7 provides special protection of water bodies used as sources for drinking water supply, but it is not clear whether the UK will achieve full compliance by 2015. This is a problem for water companies planning investment, because the WFD and Drinking Water Directive remain legally distinct. Further uncertainty arises from the application of Regulation (EC) 1107/2009 and the extent that restricted availability of pesticides will drive changes in agricultural practice and pesticide use.
The paper covers an integral risk concept consisting of a criteria-based risk evaluation, a novel proposal for risk classification and corresponding risk management strategies aimed at an analytic-deliberative approach in risk regulation. For this purpose, technical and scientific as well as social scientific concepts were integrated into a single conceptual framework. Eight criteria were selected for evaluating risks: probability of occurrence, extent of damage, incertitude, ubiquity, persistency, reversibility, delay effect and potential of mobilization. With respect to these criteria, six risk classes were formed in which risks may exceed thresholds determined by deliberative action. Effective and practicable management strategies were deduced for each risk class. The characterization and classification of risks provide a knowledge base for designing risk policies and class-specific management strategies. Three major management categories were identified: risk-based, precautionary and discursive strategies. In deliberative processes actors need to agree on norms and procedures to manage risks. If the results reflect the agreement of previous discourse procedures, political decisions become more legitimate. Because the risk evaluation, risk classification and management strategies are based on the concept of analytic-deliberative processes, the essential requirements for an effective and democratic risk policy are met.
The safety of 2,4-D to farm and forestry workers, commercial applicators and the general public has been of continuing concern because certain epidemiological studies of groups potentially exposed to 2,4-D have suggested a relationship between 2,4-D use and increased risk of soft tissue sarcoma, Hodgkin's disease or non-Hodgkin's lymphoma. This review on 2,4-D is unique in that the approach taken was to integrate data from worker exposure studies, whole animals, metabolic and other relevant laboratory studies with the epidemiological findings to assess the extent to which there is scientific support for the hypothesis that 2,4-D exposure is associated with any increased risk of human cancer.
The case-control epidemiological studies that have been the source of the cancer risk hypothesis are inconclusive. Problems in assessing exposure based on patients' memories make these studies difficult to interpret. Cohort studies of exposed workers do not generally support the specific hypothesis that 2,4-D causes cancer. Taken together, the epidemiological studies provide, at best, only weak evidence of an association between 2,4-D and the risk of cancer.
Importantly, the cancer hypothesis is not supported by other data. A critical evaluation of the exposure data indicates that exposure to 2,4-D in user groups is intermittent and much lower than the doses tested chronically in long-term animal studies that have not shown evidence of tumor induction. Moreover, the structure of 2,4-D does not suggest it would be a carcinogen. 2,4-D is a simple organic acid, that is largely excreted unchanged, and there is no evidence that it is metabolized to critically reactive metabolites or accumulates in tissues. This evidence is supported by a large body of negative studies on genotoxicity, which taken together with the metabolic studies, clearly indicates that 2,4-D is highly unlikely to be a genotoxic carcinogen. Furthermore, 2,4-D has no known hormonal activity and does not induce proliferative changes in any tissue or organ, indicating that it does not possess any of the characteristics of non-genotoxic animal carcinogens. Thus the available mechanistic studies provide no plausible basis for a hypothesis of carcinogenicity.
In this review, data relating to potential neurotoxicity, immunotoxicity and reproductive toxicity also were evaluated. There is no evidence that 2,4-D adversely affects the immune system and neurotoxic and reproductive effects only have been associated with high toxic doses that would not be encountered by 2,4-D users.
Historical exposures to 2,4-D by user groups, particularly farmers, forestry workers and commercial applicators, would be higher than those sustained under present rigorous standards for application which involve the use of protective clothing and other measures to reduce exposure. Proposed label changes indicate that in the future exposures will be even further reduced. Viewed in this context, the available data indicate that the potential public health impact of 2,4-D, including the risk of human cancer, was negligible in the past and would be expected to be even smaller in the present and future.
We defend the precautionary principle against five common charges, namely that it is ill-defined, absolutist, and a value judgement, increases risk-taking, and marginalizes science. We argue, first, that the precautionary principle is, in principle, no more vague or ill-defined than other decision principles and like them it can be made precise through elaboration and practice. Second, the precautionary principle need not be absolutist in the way that has been claimed. A way to avoid this is through combining the precautionary principle with a specification of the degree of scientific evidence required to trigger precaution, and/or with some version of the de minimis rule. Third, the precautionary principle does not lead to increased risk-taking, unless the framing is too narrow, and then the same problem applies to other decision rules as well. Fourth, the precautionary principle is indeed value-based, but only to the same extent as other decision rules. Fifth and last, the precautionary principle is not unscientific other than in the weak sense of not being exclusively based on science. In that sense all decision rules are unscientific.
Given that the precautionary principle has never been defined in the EC Treaty, the EC jurisdictions have been playing a key role in determining the status as well as the scope of that principle. Although scholars have hitherto been paying heed to the case law on food safety, the literature has become a little thinner when one considers environmental case law. This article attempts to set the scene to explain how the precautionary principle can be invoked in different judiciary procedures at the EU level.
Few policies for risk management have created more controversy than the precautionary principle. A main problem is the extreme number of different definitions and interpretations. Almost all definitions of the precautionary principle identify "scientific uncertainties" as the trigger or criterion for its invocation; however, the meaning of this concept is not clear. For applying the precautionary principle it is not sufficient that the threats or hazards are uncertain. A stronger requirement is needed. This article provides an in-depth analysis of this issue. We question how the scientific uncertainties are linked to the interpretation of the probability concept, expected values, the results from probabilistic risk assessments, the common distinction between aleatory uncertainties and epistemic uncertainties, and the problem of establishing an accurate prediction model (cause-effect relationship). A new classification structure is suggested to define what scientific uncertainties mean.
"This paper introduces the field of mixture toxicity and the challenges in regulating pesticide mixtures. Even though pesticides are unique chemical stressors designed to have biological activity that can affect a number of nontarget species, they are intentionally placed into the environment in large quantities. Currently, methods and terminology for evaluating mixture toxicity are poorly established. The most common approach used is the assumption of additive concentration, with the concentrations adjusted for potency to a reference toxicant. Using this approach, the joint action of pesticides that have similar chemical structures and modes of toxic action can be predicted. However, this approach and other modeling techniques often provide little insight into the observed toxicity produced by mixtures of pesticides from different classes. Particularly difficult to model are mixtures that involve a secondary toxicant that changes the toxicokinetics of a primary toxicant. This may result in increased activation or a change in the persistence of the primary toxicant within the organism and may be responsible for a several-fold increase or decrease in toxicity. At present, the ecological effects caused by mixtures of pesticides are given little consideration in the regulatory process. However, mixtures are being considered in relation to human health in the pesticide registration process, setting a precedent that could be followed for ecological protection. Additionally, pesticide mixtures may be regulated through toxicity testing of surface water under the Clean Water Act. The limits of our basic knowledge of how mixtures interact are compromising both these avenues for regulating mixtures. We face many challenges to adequately protecting the environment from mixture toxicity; these challenges include understanding the interactions of toxicants within an organism, identifying the mixtures that most commonly occur and cause adverse effects, and developing a regulatory structure capable of minimizing environmental impacts."
The California Department of Pesticide Regulation (CDPR) and the United States Environmental Protection Agency (USEPA) performed dietary exposure assessments for endosulfan in 1998 and 2002, respectively. Results of the USEPA assessment showed an increased risk for the population sub-group "Children 1-6 years" (>100% of the Population Adjusted Dose [PAD]). USEPA then required registrants to satisfy database uncertainties by performing subchronic neurotoxicity and developmental neurotoxicity studies and, based on the results, USEPA decreased the Food Quality Protection Act (FQPA, 1996) Safety Factor from 10x to 1x. Additionally, several tolerances on commodities consumed in quantity by children were cancelled in 2006. CDPR re-evaluated the dietary risk initially performed in 1998 after review of these same studies. Based on a review of the revised USEPA tolerances, decreased usage, decreased consumption, cancellations, and prior health protective margins of exposure (MOEs>100), CDPR determined that it was not necessary to redo the 1998 exposure assessment. In 2007, USEPA conducted a new human health risk assessment for endosulfan combining food+drinking water residues that characterized dietary risk as %PAD=([Exposure/PAD]x100). For all relevant USEPA population sub-groups, the %PADs were<100% (health protective benchmark).
A literature review covering the last 14 yr has been performed in the field of combination toxicology and human risk assessment from exposure to chemical mixtures, with special emphasis on mixtures of pesticides at low doses, that is, at levels likely to occur in human diet and environment. Despite a large body of knowledge in the field of risk assessment methodologies for exposure to chemical and pesticide mixtures, there is no single methodological approach in "combination toxicology" and health risk assessment of chemical mixtures, and therefore professional judgment is still required. Generally, the dose or response additivity approach that may be applied to evaluate potential risk for chemical mixtures in human toxicology overestimates the risk of a combination of chemicals. The recent endocrine disrupter issue demonstrated the difficulty of reproducibility of data when testing environmental toxicants at very low levels, and the need for more basic work in this field. The use of integrated methodological approaches may provide more reliable predictive data in the risk assessment of chemical mixtures in future. Yet data have demonstrated that exposure to a combination of compounds does not cause effects stronger than the ones of their most active component, provided components are present at low concentration levels, like acceptable daily intake (ADI) or reference dose (RfD) levels, well below their respective no-observed-adverse-effect levels (NOAELs). Although it has been demonstrated that a combination of compounds with the same target organ and the same or very similar mechanisms of action may cause additive or synergistic effects, the chance of such effects will most likely diminish with decreasing exposure levels to such combinations. Synergism and antagonism may both occur at the same time at different organs or targets in the same organism. However, and despite some exceptions, it has been demonstrated that interaction between components is not a common event at low levels of human exposure such as those that may occur through pesticides residues in food or drinking water. The introduction of a special safety factor as a standard for mixtures in addition to those normally used for deriving ADIs, RfDs, or minimal risk levels is not supported by data. It can be concluded from our review that, as a general rule, exposure to mixtures of pesticides at low doses of the individual constituents does not represent a potential source of concern to human health.
Methyl parathion is an organophosphorus (OP) insecticide with insecticidal properties derived from acetylcholinesterase (AChE) inhibition; this same property is also the root of its toxicity in humans. Poisoning with methyl parathion leads to cholinergic overstimulation with signs of toxicity including sweating, dizziness, vomiting, diarrhea, convulsions, cardiac arrest, respiratory arrest, and, in extreme cases, death. Reports of methyl parathion intoxication, usually seen only in field pesticide applicators, have increased throughout the United States as a result of unauthorized application of methyl parathion inside homes. The health concerns of the use of methyl parathion have resulted in cancellation of its use in most food crops in the United States. This review examines the well-documented neurotoxicity of methyl parathion as well as effects on other organ systems.
Uncertainty factors are used in the development of drinking-water guidelines to account for uncertainties in the database, including extrapolations of toxicity from animal studies and variability within humans, which result in some uncertainty about risk. The application of uncertainty factors is entrenched in toxicological risk assessment worldwide, but is not applied consistently. This report, prepared in collaboration with Health Canada, provides an assessment of the derivation of the uncertainty factor assumptions used in developing drinking-water quality guidelines for chemical contaminants. Assumptions used by Health Canada in the development of guidelines were compared to several other major regulatory jurisdictions. This assessment has revealed that uncertainty factor assumptions have been substantially influenced by historical practice. While the application of specific uncertainty factors appears to be well entrenched in regulatory practice, a well-documented and disciplined basis for the selection of these factors was not apparent in any of the literature supporting the default assumptions of Canada, the United States, Australia, or the World Health Organization. While there is a basic scheme used in most cases in developing drinking-water quality guidelines for nonthreshold contaminants by the jurisdictions included in this report, additional factors are sometimes included to account for other areas of uncertainty. These factors may include extrapolating subchronic data to anticipated chronic exposure, or use of a LOAEL instead of a NOAEL. The default value attributed to each uncertainty factor is generally a factor of 3 or 10; however, again, no comprehensive guidance to develop and apply these additional uncertainty factors was evident from the literature reviewed. A decision tree has been developed to provide guidance for selection of appropriate uncertainty factors, to account for the range of uncertainty encountered in the risk assessment process. Recent development of a series of "decision trees" by WHO to derive chemical specific adjustment factors for inter- and intraspecies variability may present an opportunity for a more systematic approach for the identification of evidence-based uncertainty factors.
By any measure, European Community (EC) water policy has been very poorly implemented by the Member States, and lacks self-consistency in some key respects and a sound scientific foundation. The conventional wisdom is that policies decided collectively tend towards the lowest common denominator of state preferences. But recent experience in the water sector suggests that directives decided by unanimity are nonetheless extremely difficult to reform once they become embedded in national political systems, even when they create enormous political problems for Member States and are outdated scientifically. Taking as an example the United Kingdom (UK) government’s handling of the directives on bathing and drinking water, this article shows how institutions have gradually hemmed in decision-makers, locking states into a policy trajectory that most now regard as sub-optimal in key respects.
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