Integrated assessment of the impacts of agricultural drainwater in the Salinas River (California,USA)

The Salinas River is the largest of the three rivers that drain into the Monterey Bay National Marine Sanctuary in central California. Large areas of this watershed are cultivated year-round in row crops and previous laboratory studies have demonstrated that acute toxicity of agricultural drainwater to Ceriodaphnia dubia is caused by the organophosphate (OP) pesticides chlorpyrifos and diazinon. In the current study, we used a combination of ecotoxicologic tools to investigate incidence of chemical contamination and toxicity in waters and sediments in the river downstream of a previously uncharacterized agricultural drainage creek system. Water column toxicity was investigated using a cladoceran C. dubia while sediment toxicity was investigated using an amphipod Hyalella azteca. Ecological impacts of drainwater were investigated using bioassessments of macroinvertebrate community structure. The results indicated that Salinas River water downstream of the agricultural drain is acutely toxic to Ceriodaphnia, and toxicity to this species was highly correlated with combined toxic units (TUs) of chlorpyrifos and diazinon. Laboratory tests were used to demonstrate that sediments in this system were acutely toxic to H. azteca, which is a resident genus. Macroinvertebrate community structure was moderately impacted downstream of the agricultural drain input. While the lowest macroinvertebrate abundances were measured at the station demonstrating the greatest water column and sediment toxicity and the highest concentrations of pesticides, macroinvertebrate metrics were more significantly correlated with bank vegetation cover than any other variable. Results of this study suggest that pesticide pollution is the likely cause of laboratory-measured toxicity in the Salinas River samples and that this factor may interact with other factors to impact the macroinvertebrate community in the system.     

城市河流水质常规评价技术研究

运用综合水质标识指数法,对我国河流水质评价面临的关键技术问题,包括水质评价方法、水质评价项目,水质级别评价,水环境功能区达标评价、水质定性评价、河流及水系整体水质比较、水质随时间和空间变化等作了明确界定,并介绍了在上海河流水质评价中的应用。     

Two sampling strategies for an overview of pesticide contamination in an agriculture-extensive headwater stream

Two headwaters located in southwest France were monitored for 3 and 2 years (Auvézère and Aixette watershed, respectively) with two sampling strategies: grab and passive sampling with polar organic chemical integrative sampler (POCIS). These watersheds are rural and characterized by agricultural areas with similar breeding practices, except that the Auvézère watershed contains apple production for agricultural diversification and the downstream portion of the Aixette watershed is in a peri-urban area. The agricultural activities of both are extensive, i.e., with limited supply of fertilizer and pesticides. The sampling strategies used here give specific information: grab samples for higher pesticide content and POCIS for contamination background noise and number of compounds found. Agricultural catchments in small headwater streams are characterized by a background noise of pesticide contamination in the range of 20–70 ng/L, but there may also be transient and high-peak pesticide contamination (2000–3000 ng/L) caused by rain events, poor use of pesticides, and/or the small size of the water body. This study demonstrates that between two specific runoff events, contamination was low; hence the importance of passive sampler use. While the peak pesticide concentrations seen here are a toxicity risk for aquatic life, the pesticide background noise of single compounds do not pose obvious acute nor chronic risks; however, this study did not consider the risk from synergistic “cocktail” effects. Proper tools and sampling strategies may link watershed activities (agricultural, non-agricultural) to pesticides detected in the water, and data from both grab and passive samples can contribute to discussions on environmental effects in headwaters, an area of great importance for biodiversity.     

Barrage fishponds,a funnel effect for metal contaminants on headwater streams

Fishponds are man-made shallow water bodies that are still little studied because of their small size. They represent high value ecosystems, both environmentally (biodiversity hotspot) and economically (fish production). They can have a high place on the hydrographic network, so their influence on water quality is of first importance for rivers and water bodies located downstream and monitored under the Water Framework Directive. These small water bodies can be a source of contaminants during draining period or an efficient buffer for pesticides. We wanted to evaluate whether these ponds could also be a remediation tool against metals by following the annual evolution of upstream/downstream flows. Cadmium, copper, lead and zinc concentrations were quantified in the dissolved phase upstream and downstream of three ponds, each one having a specific agricultural environment (traditional or organic). Metal concentration was quantified in sediments and water. For the dissolved phase, the predictive non-effect concentration was often exceeded, suggesting an environmental risk. Results highlighted also greater quantity of metals at the downstream of the pond compared to the upstream, suggesting remobilization into the ponds or direct cross-sectional contributions from the watershed (e.g. runoff from crops) or even remobilization. Regarding sediments, minimal contamination was shown but a high mineralogical variability. No buffer effect of ponds, which could reduce the risk of acute or chronic toxicity, was detected.

     

Modification of chemical oxygen demand monitoring in the Yellow River, China, with a high content of sediments.

This paper presents a modification of chemical oxygen demand (COD) monitoring giving a better indication of the pollution level compared with the conventional COD method for rivers with a high content of sediments. The correlation between the sediment organic carbon and COD was investigated using sediments sampled in the middle Yellow River, China. Partitioning of the sediment organic carbon between the water and sediment phases was also investigated using batch experiments, with the sediment concentration varying from 20 to 400 g/L. As a result, the COD modification equations are proposed for both turbid water (mixture of water and sediment) and supematant water (filtrate using a 0.45-microm membrane). The modified COD in turbid water and supernatant water could be 40 and 10% less than the monitored COD values, respectively. These results may have a significant influence on the assessment of water quality class in the Yellow River.     

Distribution and fate of organochlorine pesticide residues in sediments from the selected rivers in Taiwan

The contamination of organochlorine pesticides (OCPs) in sediments from selected rivers in Taiwan was investigated to evaluate the pollution potentials and hazard in river sediments. Da-han River and Erh-jen River were selected as the target rivers due to their serious pollution. A total of 40 surface sediment samples were collected at five sampling stations along the rivers. Results showed that the concentrations of various pesticides in sediments were in the range of 0.57-14.1 ng/g for sigmaHCH, 0.05-0.15 ng/g for aldrin, 0.12-5.8 ng/g for dieldrin, 0.22-0.64 for endrin, 0.24-6.37 ng/g for endosulfan and 0.21-8.81 ng/g for EDDT (p,p'-DDD, p,p'-DDE, p,p'-DDT). Among the OCPs, sigmaHCH, endosulfan and sigmaDDT were the most dominant compounds in the river sediments. Endosulfan sulfate was the most frequent detected compound in the sediments from the selected rivers. Also, sigmaDDT, dieldrin and beta-HCH were in abundance. Different contamination patterns between the selected river sediments were also observed. Da-han River was mainly contaminated with endosulfan sulfate and sigmaDDT. Whereas the main pesticides in Erh-jen River were beta-HCH and sigmaDDT. Among the cyclodiene compounds, dieldrin was in abundance in most of the sediments. Moreover, the frequencies of detection of the metabolites were higher than those of parent compounds, depicting that the sediments have contaminated for a long time. The results obtained in this study showed that there still exist a variety of OCP residues in the river sediments in Taiwan.     

Ecological risk assessment for aquatic species exposed to contaminants in Keelung River, Taiwan

An ecological risk assessment was conducted for Keelung River in northern Taiwan. The objective of this study was to assess the risk to fish, aquatic insects, and benthic macroinvertebrates associated with chemical-of-potential-concern (COPC) in the river and to rank ecological risk for these chemicals. The protection of at least 95% of the species 90% of the time from acute and chronic COPC exposures was the defined assessment endpoint. Nine inorganic and organic contaminants were selected to evaluate the impact to aquatic community in the Keelung River. The quotient method served as screen level estimation of risk. The Aquatic Ecological Risk Assessment model was used to analyze exposure and ecological effects and to estimate community level risk. The logarithmic regression model between probability and lethal concentration was established. The combined risks of multiple chemicals were evaluated under assumption of additive risk. The results indicated that zinc and copper pose higher risk among metals. Ammonia, copper, and zinc posed virtually all of the risk, while organic COPCs posed a negligible risk. Potential ecological risk from ammonia exposure was greatest. The probability of more than 5% of the species being affected by acute or chronic toxicity of COPCs is about 100%. In average (50% of the time), 99% of the species would be affected by acute toxicity of COPCs, and about all the species would be affected by chronic toxicity of COPCs. Uncertainties in this assessment were associated with variability in ecosystem stressors, exposure data, ecological effect data, and risk characterization.     

Levels and spatial distribution of chlorophenols - 2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol in surface water of China

The chlorophenol pollutants (CPs) have been reported to occur at relatively high concentrations in some Chinese waters. To map the distribution of CPs in the surface water throughout China, samples were collected from over 600 sites in the seven major watersheds and three drainage areas. The samples were analyzed for the representative CPs including 2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol. In general, it was observed that 2,4-dichlorophenol and 2,4,6-trichlorophenol were more frequently detected at higher concentrations in the rivers of North China compared with those of South China. High concentration sites of 2,4-dichlorophenol and 2,4,6-trichlorophenol mainly occurred in the Yellow River, Huaihe River, and Haihe River watersheds, while pentachlorophenol contamination mainly occurred in the Yangtze River watershed. The pentachlorophenol was the most ubiquitous CPs being detected in 85.4% of samples (median=50.0ngl(-1); range <1.1-594.0ngl(-1)), 2,4-dichlorophenol was detected in 51.3% (median=5.0ngl(-1); range <1.1-19960.0ngl(-1)) and the 2,4,6-trichlorophenol was detected in 54.4% of water samples (median=2.0ngl(-1), range <1.4-28650.0ngl(-1)). The results of this investigation indicated that 2,4-dichlorophenol and 2,4,6-trichlorophenol contaminations of Yellow River, Huaihe River, and Haihe River watersheds were of particular concern, while the pentachlorophenol contamination mainly occurred in the Yangtze River watershed. These results showed that CPs contamination in the surface water of China was similar to other places of the world.     

Bioassay-directed chemical analysis of River Elbe surface water including large volume extractions and high performance fractionation

A bioassay-directed fractionation and identification (toxicity identification evaluation procedure) was performed on extracts of 10 1 River Elbe water samples. The experimental method included a SDB-1 solid phase extraction followed by RP-HPLC fractionation and subfractionation. Chemical analysis by GC-MS as well as acute toxicity testing using a luminescent bacteria assay were conducted in the respective fractions. Many substances were identified, among which were pesticides and pharmaceuticals, but many compounds remained unknown.     

Assessment of water quality and toxicity of polluted Rivers Fez and Sebou in the region of Fez (Morocco)

Water quality assessment in the region of Fez based on the physicochemical and ecotoxicological investigations is presented. The results indicate that sites located close to the most urbanized and industrialized areas are severely impaired. The major water quality problems are: low dissolved oxygen (DO), high turbidity, organic matter and ammonia contents, severe chromium and copper pollution and high acute and chronic toxicity. This results in the loss of the aquatic life which is still flourishing in the Fez River upstream from the Fez Medina. Remote sites downstream show signs of physicochemical recovery. However, even there, bioassays showed significant acute and chronic toxicity. Well water in the region of Fez has moderately poor water quality with nitrate and metal enrichments. Use of water for drinking or for agriculture from the rivers or from some wells without treatment may expose the population to health risk.     

Organochlorine pesticide distribution in an organic production system for cow's milk in Chiapas,Mexico

The objective of this study was to evaluate the presence of organochlorine pesticides in samples of forage, soil, water, and milk in four units of an organic production system for cow´s milk (samples of forage, milk, soil, and water) in Tecpatan, Chiapas, Mexico. The organochlorine pesticides were extracted from forage, soil and water based on the USEPA (2005) guideline and from milk based on the IDF 1991 guideline. The pesticides were identified and quantified by gas chromatography with electron capture detector (CG-ECD). In general, the highest average concentration of total pesticides was found in the samples of milk and forage (311 ± 328 and 116.5 ±77 ng g^?1 respectively). Although, the production systems analyzed are organic, organochlorine pesticides were detected in all environmental samples (forage, soil, water, and organic milk). Although no values surpassed the defined limits of Mexican and International regulation it is advisable that a monitoring program of contaminants in these production systems is continued.     

Fate and assessment of persistent organic pollutants in water and sediment from Minjiang River Estuary,Southeast China

Persistent organochlorine compounds were analyzed in surface water, porewater and surficial sediment samples from Minjiang River Estuary, which is the first large river in Fujian Province, Southeast of China. The total concentrations of 18 organochlorine pesticides were 214.4-1819, 4541-13,699 ng/l, 28.79-52.07 ng/g in surface water, porewater and sediments (dry weight) respectively, and those of 21 polychlorinated biphenyls (PCBs) in the three phases were: 203.9-2473, 3192-10,855 ng/l, 15.14-57.93 ng/g respectively. The results showed that the concentrations of these selected organochlorine pesticides and PCBs in porewater were higher than those in surface water. It may be due to the fact that these organic hydrophobic pollutants tend to stay in the sediments, and then re-suspend from the sedimentary phase to the upper water. We have analyzed the distribution characteristics of individual organochlorine pesticide components and PCBs, and found that alpha-HCH, DDE, Heptachlor, Endosulfan II, Methoxychlor were the most common organochlorine pesticides contaminants. Considering the groups of HCHs (HCHs=alpha-HCH+beta-HCH+gamma-HCH+delta-HCH) and DDTs (DDTs=DDT+DDD+DDE), the predominance of beta-HCH, DDE in all water, porewater and sediment samples was clearly observed. This observation suggested that beta-HCH was resistant to biodegradation and the DDTs had been transformed to its metabolites, DDE and DDD, of which DDE that was more un-degradable. The PCB congeners containing 3-6 chlorines had the great preponderance in the three phase. These results were compared with those present in other estuaries and harbors. A risk assessment was evaluated for the persistent organic pollutants in the Minjiang River Estuary.     

Application of semipermeable membrane device for assessing toxicity in drinking water

Semipermeable membrane devices (SPMDs) mimic passive diffusive transport of bioavailable hydrophobic organic compounds through biological membranes and their partitioning between lipids and environmental levels. Our study was developed on a surface water treatment plant based in Turin, Northern Italy. The investigated plant treats Po River surface water and it supplies about 20% of the drinking water required by Turin city (about one million inhabitants). Surface water (input) and drinking water (output) were monitored with SPMDs from October 2001 to January 2004, over a period of 30 days. The contaminant residues, monthly extracted from SPMDs by dialysis in organic solvent, were tested with the Microtox^TM acute toxic test and with the Ames mutagenicity test. Same extracts were also analyzed with gaschromatography—mass spectrometry technique in order to characterise the organic pollutants sampled, especially Polycyclic Aromatic Hydrocarbons (PAHs).

Although the PAHs mean concentration is about one hundred times lower in the output samples, the mean toxic units are similar in drinking and surface water.

Our data indicate that the SPMD is a suitable tool to assess the possible toxicity in drinking water.     

PAH desorption from sediments with different contents of organic carbon from wastewater receiving rivers

Background and aim  

Many rivers have to receive treated or untreated wastewater as the main water sources in the world, especially in the countries facing with water shortage. For instance, the Haihe and Huaihe River Basin, which are among areas facing crises for water resources in China, receive 33,400 million tons of wastewater per year. As the sediment has large capacity for sorbing hydrophobic organic pollutants such as polycyclic aromatic hydrocarbons (PAHs), it can act as a natural repository for the contaminants. This means pollutants can release into water phase again under some conditions, such as resuspension, sediment dredging, etc. The objective of this research was to study the trends of PAH release from sediments in rivers receiving much wastewater, such as Yongding New River (YD), Northsewer (NS), and Southsewer (SS) from Haihe River Basin. These rivers received most of the wastewater from Tianjin, China and merge into Bohai Bay finally.     

Microtox testing of pentachlorophenol in soil extracts and quantification by capillary electrochromatography (CEC)--a rapid screening approach for contaminated land

An approach to rapid soil testing which involved the use of simple solvent extraction methods was developed. The analytes of interest were priority pollutants of low water solubility which could not be readily removed from the soil using water. Direct toxicity testing of the soil samples by Microtox showed a high background toxicity which prevented realistic toxicity data from being obtained for the contaminants present. A range of different extraction solutions was used in an attempt to extract the contaminants while eliminating the matrix effects of the soil. It was necessary that the solvents selected for extraction of the soil samples were not of significant toxicity, as this could potentially mask the toxic effects of any compounds extracted from the soil. The extraction efficiencies of solvent systems were evaluated using pentachlorophenol (PCP) as a model compound of known toxicity in the Microtox assay. A rapid and cost-effective method was developed in order to determine the amount of PCP recovered from the soil by the extraction solvents employed. This method consisted of a solid phase extraction (SPE) step followed by quantification using capillary electrochromatography (CEC). Recoveries were greater when a higher proportion of organic solvent (methanol) was used in the extraction process, and lowest when water was used. An extraction based on water could provide information on the potential for leaching of contaminants from the soil into nearby water bodies in an environmental setting. An organic solvent extraction method could indicate how much toxicity soil-dependent organisms might be exposed to through ingestion. Extraction based on 50% (v/v) methanol in water was considered to be the most suitable overall extraction solution for soil screening, given that this permitted extraction of the water-insoluble compound PCP at a level which was clearly toxic in the Microtox assay while also retaining the capability to extract water-soluble contaminants.     

Herbicide levels in rivers draining two prairie agricultural watersheds (1984)

A monitoring survey was conducted during 1984 on the Ochre and Turtle Rivers, which flow into Dauphin Lake in western Manitoba, Canada, to determine levels of the herbicides MCPA, diclofop-methyl, dicamba, bromoxynil, 2,4-D, triallate and trifluralin which were widely used in each watershed. Triallate concentrations exceeded 4 ng/L in 50% and 10% of the 21 samples taken from each of the Turtle and Ochre River, respectively, during the period March to October 1984. Trifluralin concentrations exceeded 3 ng/L in 14% and 10% of the samples from the respective rivers. Maximum concentrations did not exceed 25 ng/L and were unrelated to changes in river flow. Bromoxynil and diclofop were detected in the Turtle River, at concentrations of 113 and 476 ng/L, respectively, following a major high water event in late June, but were undetectable (less than 2 and 12 ng/L, respectively) at other sampling times. Dicamba and 2,4-D were detectable throughout most of the sampling period in both rivers at low levels (less than 100 ng/L). High levels of dicamba and 2,4-D (5476 and 2568 ng/L respectively) were found in water from the Turtle River prior to the high water event event possibly caused by spraying of ditches or rights-of-way near the river. Discharges (grams/year) of all seven herbicides monitored in the study represented less than 0.1% of the amounts estimated to be used in each watershed. Unit loadings (mg/ha/year) of 2,4-D and dicamba were similar to those reported for Southern Ontario streams in the mid-1970's. The results indicate that herbicide contamination of Manitoba streams draining agricultural areas is generally low except when major runoff occurs during the application period in May and June.     

Contamination levels of selected organochlorine and organophosphate pesticides in the Selangor River, Malaysia between 2002 and 2003

In Malaysia, rivers are the main source of public water supplies. This study was conducted from 2002 to 2003 to determine the levels of selected organochlorine and organophosphate pesticides in the Selangor River in Malaysia. Surface water samples have been collected seasonally from nine sites along the river. A liquid-liquid extraction followed by gas chromatography-mass spectrometry technique was used to determine the trace levels of these pesticide residues. The organochlorine pesticides detected were lindane, heptachlor, endosulfan, dieldrin, endosulfan sulfate, o,p'-DDT, p,p'-DDT, o,p'-DDE and p,p'-DDE whereas for organophosphate pesticides, they were chlorpyrifos and diazinon. At the river upstream where a dam is located for public water supply, incidents of pesticide levels exceeding the European Economic Community Directive of water quality standards have occurred. Furthermore, the wetland ecosystems located at the downstream of the river which houses the fireflies community is being threatened by occasional pesticide levels above EPA limits for freshwater aquatic organisms. The occurrence of these residual pesticides in the Selangor River can be attributed to the intense agriculture and urban activity.     

Temporal variability in particle-associated pesticide exposure in a temporarily open estuary, Western Cape, South Africa

This study assesses the risk of current-use pesticides in a temporarily open estuary in South Africa by developing probabilistic risk estimates. Particle-associated pesticides (chlorpyrifos, prothiofos, cypermethrin, fenvalerate, endosulfan and p,p-DDE) and physicochemical parameters (salinity, temperature, flow, and total organic content (TOC)) were measured in the Lourens River estuary (Western Cape) twice a month over a period of two years and equilibrium partitioning theory was applied to calculate concentrations of pesticides in the water. The 90th percentile concentrations of pesticides associated to suspended particles and the calculated concentrations in water were 34.0microg kg(-1) and 0.15microg l(-1) for prothiofos, 19.6microg kg(-1) and 0.45microg l(-1) for chlorpyrifos and 18.6microg kg(-1) and 0.16microg l(-1) for endosulfan. Highest average concentrations were found around the summer season due to higher application rates and as a result of the low flow during this season. Species sensitivity distribution indicated a 1.5-2.8 times higher toxicity (hazardous concentration HC5) for marine organisms compared to freshwater organisms. The calculated concentrations in the water exceeded all threshold values suggested by international water guidelines. Chlorpyrifos and endosulfan posed the highest acute risk to the Lourens River estuary. No sufficient toxicity data and threshold values were found for prothiofos.     

Pesticides in the surface waters of the Camanducaia River watershed,Brazil

Abstract

Camanducaia River is part of the Piracicaba watershed responsible for pumping water into the Cantareira System, which is one of the main water sources for the metropolis of São Paulo and Campinas, Brazil. Intensive use of pesticides and hilly topography represents a situation of high risk for river water contamination. Therefore, water samples from 12 locations were collected along the Camanducaia River and its tributaries, over a period of 4?mo during the rainy season, and analyzed by GC-MS/MS or UPLC- MS/MS for the presence of 46 pesticides. Seven pesticides (fipronil, methyl parathion, metolachlor, atrazine, carbofuran, diuron, and simazine) were positively detected. Only atrazine (the most frequently detected) and diuron were present at concentrations above the limit of quantification of the analytical method (0.32 and 0.57?μg L^?1 for atrazine and diuron, respectively). Pesticides detection frequency was higher than expected for a river system where only 11.8% of the land area is under agriculture. The vulnerability of the Camanducaia basin to pesticide contamination is attributed to the high annual precipitation (> 1.5?m y^?1 in the headwaters), associated with topographical features (steep terrain) and soil types that favor surface runoff, which has been exacerbated by poor soil management practices.     

Pesticide residues in rivers of a Brazilian Rain Forest Reserve: assessing potential concern for effects on aquatic life and human health

Pesticide residues in water, sediment, and fish samples from rivers of a Brazilian Rain Forest Reserve were measured in November 1998, March 1999, and January 2000. Concentrations of the individual pesticides were compared to ecotoxicological benchmarks based on acute toxicity tests, and to regulatory guidelines to determine the potential concern for effects on aquatic life and human health. Pesticides and metabolites were detected at all 7 sites surveyed. Residues of a total of 27 pesticides or metabolites were found in water and/or sediment samples and fish have accumulated some of the most persistent of these residues. Measured concentrations in water and sediment indicated concern for preservation of aquatic fauna. Several pesticides in water were above levels for drinking water recommended by Brazilian and/or European Union authorities, indicating also a concern for human health.