Local physical habitat quality cloud the effect of predicted pesticide runoff from agricultural land in Danish streams

The combination of intensive agricultural activities and the close connectivity between land and stream emphasise the potential risk of pesticide exposure in Danish streams. Benthic macroinvertebrates are applied in the assessment of stream ecological status, and some sensitive species have been shown to respond strongly to brief pulses of pesticide contamination. In this study we investigate the impact of agriculturally derived pesticides on stream macroinvertebrate communities in Denmark. As a measure of toxic pressure we apply the Runoff Potential. We investigated a total of 212 streams. These were grouped into distinct classes according to the magnitude of pesticide contamination in the period from 2003-2006. A total of 24 different macroinvertebrate indices were applied to detect effects of pesticide runoff (e.g. the SPEAR-index and the number of EPT taxa). We found high predicted pesticide runoff in 39% of the streams, but we found no significant effect of predicted pesticide exposure on stream macroinvertebrate indices. We, additionally, examined the influence of a series of environmental parameters ranging from site scale to catchment scale on the macroinvertebrate community. Relative proportions of gravel, sand and silt in bed sediments explained most of the variation in macroinvertebrate indices as well as the upstream riparian habitat quality. We suggest that the Runoff Potential model overestimate pesticide runoff contamination in Danish streams due the presence of buffer strips enforced by Danish legislation. When pesticide runoff contamination is low to moderate, poor physical properties (indirectly related to agricultural activity) are the main impediment for the ecological quality of Danish streams.     

Pesticide occurrence and aquatic benchmark exceedances in urban surface waters and sediments in three urban areas of California, USA, 2008–2011

Urban pesticide use has a direct impact on surface water quality. To determine the extent of pesticide contamination, the California Department of Pesticide Regulation initiated a multi-area urban monitoring program in 2008. Water and sediment samples were collected at sites unaffected by agricultural inputs in three areas: Sacramento (SAC), San Francisco Bay (SFB), and Orange County (OC). Samples were analyzed for up to 64 pesticides or degradates. Multiple detections were common; 50 % of the water samples contained five or more pesticides. Statewide, the most frequently detected insecticides in water were bifenthrin, imidacloprid, fipronil, fipronil sulfone, fipronil desulfinyl, carbaryl, and malathion. Bifenthrin was the most common contaminant in sediment samples. Key differences by area: OC had more pesticides detected than SAC or SFB with higher concentrations of fipronil, whereas SAC had higher concentrations of bifenthrin. The most frequently detected herbicides were 2,4-D, triclopyr, dicamba, diuron, and pendimethalin. Key differences by area: OC and SFB had higher concentrations of triclopyr, whereas SAC had higher concentrations of 2,4-D and dicamba. Detection frequency, number of pesticides per sample, and pesticide concentration increased during rainstorm events. In water samples, all of the bifenthrin, malathion, fipronil, permethrin, and λ-cyhalothrin detections, and most of the fipronil sulfone and cyfluthrin detections were above their lowest US EPA aquatic benchmark. Diuron was the only herbicide that was detected above its lowest benchmark. Based on the number of pesticides and exceedances of aquatic benchmarks or the high number of sediment toxicity units, pesticides are abundant in California surface waters.     

Spatial Relationships Between Water Quality and Pesticide Application Rates in Agricultural Watersheds

Pesticide applications to agricultural lands in California, USA, are reported to a central data base, while data on water and sediment quality are collected by a number of monitoring programs. Data from both sources are geo-referenced, allowing spatial analysis of relationships between pesticide application rates and the chemical and biological condition of water bodies. This study collected data from 12 watersheds, selected to represent a range of pesticide usage. Water quality parameters were measured during six surveys of stream sites receiving runoff from the selected watershed areas. This study had three objectives: to evaluate the usefulness of pesticide application data in selecting regional monitoring sites, to provide information for generating and testing hypotheses about pesticide fate and effects, and to determine whether in-stream nitrate concentration was a useful surrogate indicator for regional monitoring of toxic substances. Significant correlations were observed between pesticide application rates and in-stream pesticide concentrations (p < 0.05) and toxicity (p < 0.10). In-stream nitrate concentrations were not significantly correlated with either the amount of pesticides applied, in-stream pesticide concentrations, or in-stream toxicity (all p > 0.30). Neither total watershed area nor the area in which pesticide usage was reported correlated significantly with the amount of pesticides applied, in-stream pesticide concentrations, or in-stream toxicity (all p > 0.14). In-stream pesticide concentrations and effects were more closely related to the intensity of pesticide use than to the area under cultivation.     

Levels, sources and spatiotemporal variation of nutrients and micropollutants in small streams of a Mediterranean River basin

In this study, nutrients, trace metals and priority pesticide compounds were investigated for the first time in water and sediment samples in streams of the Evrotas River basin (S.E. Greece) from 2006 to 2008. The most important sources of contamination were from the entry of pesticides and nutrients into surface waters and sediments as a result of the intensive agricultural activity as well as from the uncontrolled disposal of olive mill and citrus processing wastewaters. Aquatic risk assessment revealed that all insecticides detected showed high risk, suggesting adverse effects on the stream biota. Among the metals analyzed, Cr, Ni and Ba presented the highest concentrations in sediments, however, due to natural geological processes. Multivariate statistical techniques applied for data compression, exploration and interpretation proved to be useful tools for identifying the most critical pollutants affecting the surface water quality. The findings of this study suggest that the inclusion of streams with small catchment areas into WFD monitoring and assessment programs is essential, especially those of the Mediterranean region.     

AgInput: An Agricultural Nutrient and Pesticide Source Model

Agriculture can be a major nonpoint source (NPS) of nutrient and pesticide contamination in the environment. Available databases do not provide accurate and dynamic data on fertilizer and pesticide application, which limits the ability of complex watershed models to simulate contaminant loads into impaired water bodies. A model for estimating agricultural nutrient and pesticide input for watershed modeling has been developed. Climate, soils, and major agricultural operations are considered within the model, so that it can be adapted to any watershed or subregion within a watershed. The timing of the agricultural operations is a function of the weather data, providing realistic results at daily, monthly, or annual application rates. The model also predicts irrigation demand and biomass production, which can be used to calibrate the model. Model output can be used in any watershed model that considers agricultural land uses. Two case studies were evaluated, using grape vineyards in the Napa River and strawberry production in Newport Bay as examples. The predicted time to maturity corresponded well with actual data. Irrigation and fertilizer needs were very sensitive to weather input. Although the model can generate weather from long-term averages, the simulated results are best when at least observed precipitation and temperature are provided, to capture extreme events. The model has data for 98 crops and 126 pesticides, based on the California Department of Pesticide Regulation database. The databases are easily modifiable by the user to adapt them to local conditions. The output from AgInput is much needed for watershed modeling and for development of total maximum daily loads (TMDLs), based on realistic targets of irrigation, nutrient, and pesticide inputs. The model is available for free download at .     

Impacts of pesticides in a Central California estuary

Recent and past studies have documented the prevalence of pyrethroid and organophosphate pesticides in urban and agricultural watersheds in California. While toxic concentrations of these pesticides have been found in freshwater systems, there has been little research into their impacts in marine receiving waters. Our study investigated pesticide impacts in the Santa Maria River estuary, which provides critical habitat to numerous aquatic, terrestrial, and avian species on the central California coast. Runoff from irrigated agriculture constitutes a significant portion of Santa Maria River flow during most of the year, and a number of studies have documented pesticide occurrence and biological impacts in this watershed. Our study extended into the Santa Maria watershed coastal zone and measured pesticide concentrations throughout the estuary, including the water column and sediments. Biological effects were measured at the organism and community levels. Results of this study suggest the Santa Maria River estuary is impacted by current-use pesticides. The majority of water samples were highly toxic to invertebrates (Ceriodaphnia dubia and Hyalella azteca), and chemistry evidence suggests toxicity was associated with the organophosphate pesticide chlorpyrifos, pyrethroid pesticides, or mixtures of both classes of pesticides. A high percentage of sediment samples were also toxic in this estuary, and sediment toxicity occurred when mixtures of chlorpyrifos and pyrethroid pesticides exceeded established toxicity thresholds. Based on a Relative Benthic Index, Santa Maria estuary stations where benthic macroinvertebrate communities were assessed were degraded. Impacts in the Santa Maria River estuary were likely due to the proximity of this system to Orcutt Creek, the tributary which accounts for most of the flow to the lower Santa Maria River. Water and sediment samples from Orcutt Creek were highly toxic to invertebrates due to mixtures of the same pesticides measured in the estuary. This study suggests that the same pyrethroid and organophosphate pesticides that have been shown to cause water and sediment toxicity in urban and agriculture water bodies throughout California, have the potential to affect estuarine habitats. The results establish baseline data in the Santa Maria River estuary to allow evaluation of ecosystem improvement as management initiatives to reduce pesticide runoff are implemented in this watershed.     

Use of cluster and principal component analyses to profile areas in California where ground water has been contaminated by pesticides

An empirical approach to profiling areas of ground water contamination by pesticides was devised that did not rely upon determining the level of vulnerability between land areas and that did not assume any particular pathway for ground water contamination. Climatic and soil data were obtained for 1-square mile sections of land in California where pesticide residues had been found in well water samples and the detection was attributed to legal agricultural applications. These sections were designated as known contaminated (KC) sections. Climate and soil data were also obtained for sections which lacked either well sampling data or a positive pesticide detection. These sections were designated as candidate sections. Statistical procedures were used to cluster groups of KC sections first with respect to climate characteristics and then with respect to soil characteristics. Principal components analysis (PCA) was used to construct a statistical profile of soil variables for each cluster of KC sections. A method based on the PCA was developed to compare the similarity of soil profiles derived for each KC section cluster to individual candidate sections. Since the profiling scheme was based only on data from KC sections, candidate sections that did not match any KC cluster profile could only be considered dissimilar to contaminated sections, receiving a status of not-classified. This profiling method is flexible and it can be revised to incorporate updated well sampling information.     

Integrated approach for the quality assessment of freshwater resources in a vineyard area (South Portugal)

An integrated chemical and biological approach for the quality assessment of freshwater resources in a vineyard area of the ??Alentejo?? region (South Portugal) is presented. This includes analysis to 11 pesticide compounds and whole toxicity testing on algae and crustaceans. Simazine, terbuthylazine, terbutryn, desethylatrazine and chlorpyrifos were the most frequently detected pesticides in water collected from wells and drainage channels. Mixtures of up to three compounds in different qualitative combinations were also found. The quality standards for individual pesticides (0.1 ??g L^???1) and pesticides-total (0.5 ??g L^???1) were exceeded in some samples. However, their maximum concentrations were lower than the WHO guidelines, the USEPA health advisory values and the environmental quality standards for priority substances applicable to surface water. In five samples, the herbicides terbuthylazine and terbutryn and the insecticide chlorpyrifos did not pass the toxicity exposure ratio (TER) trigger values specified for aquatic organisms (algae, Daphnia and fish). Maximum toxic effects on Daphnia magna (100%) and Pseudokirchneriella subcapitata (82.56%) were determined in groundwater samples, while in surface water, no toxicity was observed. Concerning effects on Heterocypris incongruens in sediment samples collected at the drainage channels, mortality and growth inhibition values were below 38%. Pro-active management of the use of pesticides is recommended for implementing at the farm and catchment level to reduce inputs into ground- and surface water.     

Transport and fate of organochlorine pesticides in the River Wuchuan,southeast China

Persistent organic pollutants (POPs) such as chlorinated pesticides are of global concern due to their widespread occurrence, persistence, bioaccumulation and toxicity to animals and human. This paper summarises recent research on 18 chlorinated pesticides in an important catchment in China, by determining their concentrations and behaviour in water, sediment, soil and plants. The concentrations of the total pesticides were in the ranges 187-893 ng l(-1) in river water, 8.53-210 ng g(-1) dry weight in soil, 2.66-13.45 ng g(-1) dry weight in river sediment, and 651-2823 ng g(-1) dry weight in plants. The predominance of beta-HCH as the major isomer of HCHs in all water, soil, sediment and plant samples was clearly observed, due to beta-HCH's resistance to biodegradation. On average beta-HCH accounted for 44%, 53%, 50%, and 46% of the total HCH concentration in water, soil, sediment and plant, respectively. Of the DDTs, DDE accounted for 48%, 43%, 53%, 55% of the total DDT, which suggested that DDT had been transformed to its metabolites, DDE and DDD, of which DDE was the more stable. The chlorinated pesticide levels in the River Wuchuan were generally below the guideline values in China, but some sites displayed levels in excess of EC Environmental Quality Standards for HCHs and DDTs. The results therefore provide important information on the current contamination status of a key agricultural watershed in China, and point to the need for urgent actions to evaluate the long-term fate and toxicity of such persistent compounds and an appropriate remediation strategy.     

Effectiveness of wastewater management in rural areas of developing countries: a case of Al-Chouf Caza in Lebanon

Ghaggar, one of the major rivers of northern India originating in outer Himalayas and flowing through the state of Punjab, Haryana, and Rajasthan, is put to multiple uses. Along its course of 464 km, it receives discharge from various cities and runoff from agricultural lands. Punjab and Haryana are two predominantly agricultural states of India using substantial amounts of agrochemicals, yet there are no reports available in literature on the level of pesticides in the stretch of river Ghaggar through Punjab and Haryana. This is the first report on pesticide pollution of the river Ghaggar in Haryana. Water samples along the 230-km stretch of the river in Haryana were analyzed for the presence of organochlorine insecticide residues. While aldrin and dieldrin were below detection limits, both hexachlorocyclohexane (HCH) and dichlorodiphenyltrichloroethane (DDT) were traceable in all the water samples. High concentration of β-HCH among ΣHCH indicates old pollution source whereas predominance of p,p^′ -DDT among ΣDDT reflects its recent use in the catchment area of the river. The concentrations of HCH and DDT in all the samples were above the permissible limits prescribed by the European Commission Directive for drinking purposes.     

An analytical model for the assessment of pesticide exposure levels in soils and groundwater

The movement and degradation of pesticide residues in soils and groundwater are complex processes affected by soil physical, (bio)chemical, and hydrogeological properties, climatic conditions, and agricultural practices. This work presents a physically-based analytical model suitable for long-term predictions of pesticide concentrations in groundwater. The primary interest is to investigate the impact of soil environment, related physical and (bio)chemical processes, especially, volatilization, crop uptake, and agricultural practices on long-term vulnerability of groundwater to contamination by pesticides. The soil is separated into root and intermediate vadose zones, each with uniform properties. Transport in each soil zone is modeled on the basis of complete mixing, by spatial averaging the related point multiphase-transport partial differential equation (i.e., linear-reservoir models). Transport in the aquifer, however, is modeled by a two-dimensional advection-dispersion transport equation, considering adsorption and first-order decay rate. Vaporization in the soil is accounted for by assuming liquid-vapor phase partitioning using Henry's law, and vapor flux (volatilization) from the soil surface is modeled by diffusion through an air boundary layer. Sorption of liquid-phase solutes by crops is described by a linear relationship which is valid for first-order (passive) crop uptake. The model is applied to five pesticides (atrazine, bromacil, chlordane, heptachlor, and lindane), and the potential for pesticide contamination of groundwater is investigated for sandy and clayey soils. Simulation results show that groundwater contamination can be substantially reduced for clayey soil environments, where bio(chemical) degradation and volatilization are most efficient as natural loss pathways for the pesticides. Also, uptake by cross can be a significant mechanism for attenuating exposure levels in ground-water especially in a sandy soil environment, and for relatively persisting pesticides. Further, simulations indicate that changing agricultural practices can have a profound effect on vulnerability of groundwater to mobile and relatively persisting pesticides.     

江苏省茶园和农田土壤中拟除虫菊酯类农药残留与污染特征分析

于2018年4—6月采集了江苏省10个市的茶园和农田表层土壤样品,采用气相色谱-三重四级杆质谱仪分析样品中12种拟除虫菊酯类农药的质量比和组成。结果表明,江苏省茶园和农田土壤中广泛检出拟除虫菊酯类农药,总量分别为27.1~50.7,56.9~97.0 ng/g。研究区域的拟除虫菊酯类农药含量存在差异,但组成相近,均是高效氯氟氰菊酯和联苯菊酯的比例较高。与国内其他地区土壤相比,江苏省茶园和农田土壤中拟除虫菊酯含量处于中等水平。     

Organochlorine Pesticide Residues in Wheat and Drinking Water Samples from Jaipur, Rajasthan, India

The organochlorine pesticide contamination in dietary sources has caused serious threat to the human progeny. The present study was therefore conducted to evaluate the pesticide contamination in wheat flour and drinking water from Jaipur City, Rajasthan, India using Gas Chromatograph. All the wheat and water samples were found to be contaminated with various organochlorine pesticide residues of DDT and its metabolites, HCH and its isomers, heptachlor and its expoxide and aldrin. The amount of pesticide detected in wheat flour was higher than the permissible limits prescribed by WHO/FAO. In drinking water only a few pesticides exceeded the permissible limits. Seasonal variations of pesticides residues were also observed during the study period.     

Studies on urban drinking water quality in a tropical zone

Anthropogenic activities associated with industrialization, agriculture and urbanization have led to the deterioration in water quality due to various contaminants. To assess the status of urban drinking water quality, samples were collected from the piped supplies as well as groundwater sources from different localities of residential, commercial and industrial areas of Lucknow City in a tropical zone of India during pre-monsoon for estimation of coliform and faecal coliform bacteria, organochlorine pesticides (OCPs) and heavy metals. Bacterial contamination was found to be more in the samples from commercial areas than residential and industrial areas. OCPs like α,γ-hexachlorocyclohexane and 1,1 p,p-DDE {dichloro-2, 2-bis(p-chlorophenyl) ethene)} were found to be present in most of the samples from study area. The total organochlorine pesticide levels were found to be within the European Union limit (0.5 μg/L) in most of the samples. Most of the heavy metals estimated in the samples were also found to be within the permissible limits as prescribed by World Health Organization for drinking water. Thus, these observations show that contamination of drinking water in urban areas may be mainly due to municipal, industrial and agricultural activities along with improper disposal of solid waste. This is an alarm to safety of public health and aquatic environment in tropics.     

A multi-lysimeter investigation on the mobility and persistence of pesticides in the loam soil of the Fucino Plain (Italy)

In order to evaluate the impact of intensive horticulture on the water resources of the Fucino Plain, one of the most important agricultural settlements of Central Italy, the mobility and persistence in the soil of five commonly used pesticides was investigated by means of multi-lysimeter experiments. The fate of simazine, carbaryl, dicloran, linuron and procymidone was evaluated in the laboratory under experimental conditions simulating as closely as possible both pesticide application and irrigation practices required by the local crops. An efficient extraction procedure followed by chromatographic analysis, allowing the simultaneous determination of the applied chemicals, was used to monitor the pesticide residues in the soil columns as a function of time from application and depth. The experiment, carried out for about 60 days, revealed that soil contamination apparently involves only the surface layer since none of the investigated pesticides was detected at depths greater than 20-30 cm. However, the five pollutants exhibit a quite different behaviour that can be related to their physico-chemical properties.     

Levels and source of organochlorine pesticides in surface waters of Qiantang River, China

Qiantang River is a typical river used for drinking water source, flowing through agricultural area in east China. Surface water samples at 45 sampling sites from the river were collected and analyzed for 13 organochlorine pesticides (OCPs) during six surveys in 2 years of 2005–2006. Sediments, soils, farmland runoff water and dry/wet deposition of this region were also measured for their OCPs residue in order to know possible source of OCPs contamination. The total OCPs concentrations in surface water were 7.68–615.2 ng/l. β-HCH, δ-HCH, Aldrin, Heptachlor, Heptachlor epoxide are the major OCPs in water. The maximum levels of OCPs in water were found in July, while significantly lower OCP concentrations were measured in January. Significant linear correlation was found between the concentration of HCH and that of total 13 OCPs in water. The measured OCP concentrations in sediments, soils, farmland runoff water and dry/wet deposition are discussed in relation to concentrations and patterns found in the surface water. Comparison of OCP levels in sediments and soils led to conclusion that erosion of soil contribute significantly to the contamination of water. The OCPs dry and wet deposition to water body was estimated to 0.49 and 0.86 ton/year, respectively. The ratio of α/γ-HCH and (DDE+DDD)/∑DDT in environmental matrix indicated there probably existed new OCPs input of lindane and dicofol into the river.     

Monitoring and risk assessment of pesticides in a tropical river of an agricultural watershed in northern Thailand

The increasing application of pesticides in the uplands of northern Thailand has increased the transfer of pesticides to surface water. To assess the risk of pesticide use for stream water quality, we monitored the concentrations of seven pesticides (atrazine, dichlorvos, chlorpyrifos, dimethoate, chlorothalonil, (α-, β-) endosulfan, cypermethrin) frequently used in the Mae Sa watershed (77 km²) in water and sediment samples over a period of one and a half years (2007–2008). All investigated pesticides were recorded in the river. Chlorpyrifos was detected most often in water samples (75 % at the headwater station), while cypermethrin was most often found in riverbed (86 %) and in all suspended sediment samples. The highest concentrations of the pesticides were detected during the rainy season. About 0.002 to 4.1 % by mass of the applied pesticides was lost to surface water. The risk assessment was based on the risk characterization ratio (RCR). The RCRs of dichlorvos in water, (α-, β-) endosulfan, and cypermethrin in water and sediments were higher than unity indicating that they are likely to pose a threat to aquatic ecosystem. Finally, we discuss the role of sampling design on ecotoxicological risk assessment. Our study shows that pesticide contamination of surface waters is an environmental issue in the Mae Sa watershed and that measures need to be undertaken to reduce the loss of pesticides from soil to surface waters.     

Evaluation of soil contamination in intensive agricultural areas by pesticides and organic pollutants: south-eastern Spain as a case study

A comprehensive survey of the occurrence and fate of pesticides and organic contaminants in soils from an intensive agricultural area devoted to horticultural production in plastic-based greenhouses has been performed to determine if the operation under integrated pest management practices has contributed to reduce the levels of these compounds. Almería province (south-eastern Spain) was selected for the case study. 38 agricultural soil samples (each sample corresponds to an independent private greenhouse) of areas working under integrated pest management (IPM) programs have been analyzed in order to evaluate their contamination fate. Sampling was designed to cover an area of about 400 km(2). Pesticides, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), phenolic compounds and di-(2-ethylhexyl)phthalate (DEHP) were monitored. The obtained results were compared to other studies reported in Spain and Europe. Among relevant persistent pesticides, DDTs and endosulfans were mainly found and the results indicated historical application, although recent application of endosulfan was rarely detected. PAHs were also found but to a lesser extent and derived from pyrogenic sources. DEHP levels were considerably higher in comparison to the other monitored analytes. The evaluation revealed that despite the use of IPM programs, pesticide and organic contaminants are still being detected in this type of agricultural soil, although at relatively low concentration levels. In general, the contamination rate was similar or lower in comparison to other agricultural areas from nearby regions or countries. However, further monitoring studies should be carried out to establish the possible reduction in contamination by the selected compounds.