Analysis of pesticide residues in Peninsular Malaysian waterways

The use of organochlorine pesticides has caused concern due to their effects on human health and the Malaysian aquatic ecosystem, particularly so in view of their persistent and bioaccumulative properties. Since the extent of organochlorine pesticide pollution in Malaysian waterways is unknown except for isolated instances, a systematic survey has now been carried out. Water samples from various rivers were extracted, cleaned up with Florisil and analysed for the individual organochlorine pesticides by gas chromatography (GC) with an electron capture detector (ECD). DDE, DDT and heptachlor were present in all the river water samples of the west coast of Peninsular Malaysia. Other organochlorine pesticides were also identified from the water samples. However, the levels of all these are still below criteria values for Malaysian aquatic life, indicating that organochlorine pesticide pollution is less of a problem than other organic or inorganic pollutants.     

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.     

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.     

Removal of atrazine and four organophosphorus pesticides from environmental waters by diatomaceous earth-remediation method

A new viable remediation technique based on the use of diatomaceous earth is proposed to improve the ecological system. Its ability to remove atrazine and the four organophosphorus pesticides parathion-methyl, chlorpyriphos, fenamiphos and methidathion from river and waste waters has been proven. A series of experiments including variable conditions, such as temperature, pH, contact time, pesticide concentration and adsorbent quantity, were performed to demonstrate the efficiency of pesticide removal from three different water samples. The batch experiments showed that diatomaceous earth was able to remove 95% of chlorpyriphos, 75% of methidathion and parathion-methyl and 55% of atrazine and fenamiphos from all types of waters tested. The individual adsorption of each pesticide on diatomaceous earth could be described by the Freundlich isotherm and a tentative adsorption mechanism was proposed. The Freundlich coefficient (Kf) and Freundlich constant (1/n) appeared to be closely related to the physicochemical properties (Kow, solubility) of the compounds. The actual results support the conclusion that diatomaceous earth has the potential to serve as an extractant in remediation techniques.     

The occurrence of glyphosate, atrazine, and other pesticides in vernal pools and adjacent streams in Washington, DC, Maryland, Iowa, and Wyoming, 2005–2006

Vernal pools are sensitive environments that provide critical habitat for many species, including amphibians. These small water bodies are not always protected by pesticide label requirements for no-spray buffer zones, and the occurrence of pesticides in them is poorly documented. In this study, we investigated the occurrence of glyphosate, its primary degradation product aminomethylphosphonic acid, and additional pesticides in vernal pools and adjacent flowing waters. Most sampling sites were chosen to be in areas where glyphosate was being used either in production agriculture or for nonindigenous plant control. The four site locations were in otherwise protected areas (e.g., in a National Park). When possible, water samples were collected both before and after glyphosate application in 2005 and 2006. Twenty-eight pesticides or pesticide degradation products were detected in the study, and as many as 11 were identified in individual samples. Atrazine was detected most frequently and concentrations exceeded the freshwater aquatic life standard of 1.8 micrograms per liter (microg/l) in samples from Rands Ditch and Browns Ditch in DeSoto National Wildlife Refuge. Glyphosate was measured at the highest concentration (328 microg/l) in a sample from Riley Spring Pond in Rock Creek National Park. This concentration exceeded the freshwater aquatic life standard for glyphosate of 65 microg/l. Aminomethylphosphonic acid, triclopyr, and nicosulfuron also were detected at concentrations greater than 3.0 microg/l.     

Concentrations of dissolved herbicides and pharmaceuticals in a small river in Luxembourg

Urban and agricultural areas affect the hydraulic patterns as well as the water quality of receiving drainage systems, especially of catchments smaller than 50 km(2). Urban runoff is prone to contamination due to pollutants like pesticides or pharmaceuticals. Agricultural areas are possible sources of nutrient and herbicide contamination for receiving water bodies. The pollution is derived from leaching by subsurface flow, as well as wash-off and erosion caused by surface runoff. In the Luxembourgish Mess River catchment, the pharmaceutical and pesticide concentrations are comparable with those detected by other authors in different river systems worldwide. Some investigated pesticide concentrations infringe current regulations. The maximum allowable concentration for diuron of 1.8 μg l(?-?1) is exceeded fourfold by measured 7.41 μg l(?-?1) in a flood event. The load of dissolved pesticides reaching the stream gauge is primarily determined by the amount applied to the surfaces within the catchment area. Storm water runoff from urban areas causes short-lived but high-pollutant concentrations and moderate loads, whereas moderate concentrations and high loads are representative for agricultural inputs to the drainage system. Dissolved herbicides, sulfonamides, tetracyclines, analgesics and hormones can be used as indicators to investigate runoff generation processes, including inputs from anthropogenic sources. The measurements prove that the influence of kinematic wave effects on the relationship between hydrograph and chemographs should not be neglected in smaller basins. The time lag shows that it is not possible to connect analysed substances of defined samples to the corresponding section of the hydrograph.     

Pesticide residues in river Yamuna and its canals in Haryana and Delhi, India

Yamuna, a prominent river of India covers an extensive area of 345,843 km(2) from Yamunotri glacier through six Indian states. Residues of organochlorine pesticides (OCPs) namely, isomers of HCH and endosulfan, DDT and its metabolites, aldrin, dieldrin, were analysed in water of river Yamuna along its 346 km stretch passing through Haryana-Delhi-Haryana and the canals originating from it. beta-HCH, p.p'-DDT, p.p'-DDE and p.p'-DDD had maximum traceability in test samples (95-100%) followed by gamma-HCH, alpha-HCH and o.p'-DDD (60-84%) and o.p'-DDT, delta-HCH and o.p'-DDE (7-30%) while aldrin, dieldrin, alpha and beta endosulfan remained below detection limits (BDL). The concentration of SigmaHCH and SigmaDDT at different sites of the river ranged between 12.76-593.49 ng/l (with a mean of 310.25 ng/l) and 66.17-722.94 ng/l (with a mean of 387.9 ng/l), respectively. In canals the values were found between 12.38-571.98 ng/l and 109.12-1572.22 ng/l for SigmaHCH and SigmaDDT, respectively. Water of Gurgaon canal and Western Yamuna canal contained maximum and minimum concentration, respectively both of SigmaHCH and SigmaDDT residues. Sources of these pesticides and suggested measures to check pesticide pollution of this major Indian river, keeping in view its vital link with life, are discussed in this paper.     

Pesticides residues in okra (non-target crop) grown close to a watermelon farm in Ghana

The study looked at the levels of pesticides in okra grown close to a watermelon farm herein referred to as a non-target crop. The watermelon received some pesticide application in the course of its cultivation, and the okra which was not meant to be sprayed was also affected by the pesticide. About 500 okra samples were collected for a period of 6 weeks and pesticides extracted with 1:1 n-hexane and dichloromethane which was analysed with Agilent 2222 GC/MS coupled with 389 auto-sampler. The results confirmed accumulation of significant levels of pesticides in the non-target crop (okra grown close to watermelon farm). Levels of organochlorine pesticides ranged from 3.10 to 7.60 μg/kg whilst the organophosphorus pesticides had levels ranging from 2.80 to 2016.80 μg/kg. The synthetic pyrethroid pesticide mean levels also ranged from 0.10 to 4.10 μg/kg and were below World Health Organization/Food and Agriculture Organization-recommended residue levels, and though not appearing to constitute a grave threat to life, their occurrence is a concern, and pre-emptive techniques must be developed to thwart the contaminations. Though the non- target crop was not treated directly with the pesticides, some level of contamination with organochlorine and organophosphorus pesticides persisted in the crops. It can be inferred that application of pesticides affected the adjoining crops, meaning that inter-cropping and mix-cropping might not be acceptable when one of the crops requires pesticide application. It is important for the farmers to be trained to ensure proper application of pesticide to minimise its impact on the health of consumers.     

Assessment of elemental contaminants in water and fish samples from Aba river

The elemental contaminants in water and fish samples from Aba river were studied. The elements studied were Zn, Ni, As, Hg, Co and Mn. Three water samples and three samples of different fish species were collected from different locations in the river. The water and fish samples were analysed for elemental contaminants using Atomic Absorption Spectrophotometer (AAS). The elemental toxicants Zn and Mn were identified in appreciable amounts in fresh fish species namely, Lates niloticus and Oriochronis niloticus, of mean values 8.012 ppm and 0.861 ppm, respectively. The analysis also shows arsenic concentration of mean value 0.01 ppm in Lates niloticus. The analysis of frozen fish samples purchased from the Waterside market located near the river shows Ni and Hg levels of mean values 0.83 ppm and 0.02 ppm, respectively. The levels of elemental contaminants As, Zn, Hg and Mn from the water samples have mean values 0.082 ppm, 11.284 ppm, 0.201 ppm and 1.024 ppm, respectively. There are five industries that discharge waste products into Aba river. In view of this, there is a need to determine the level of pollution of the river, since the inhabitants depend on the river for their drinking water, fishing and other domestic uses. This study is aimed at determining the level of heavy metal toxicants in fish and water samples from the river. The effect of these elemental contaminants and the associated health hazards were examined.     

Integration of multi-disciplinary geospatial data for delineating agroecosystem uniform management zones

The aim of this study was the development of analytical methods for the simultaneous determination of 25 selected pharmaceuticals, metabolites, and pesticides, belonging to the various chemical classes, in river sediments and their corresponding surface and ground water with the purpose of monitoring the contamination levels. The methods were based on the solid-phase extraction as the sample preparation method for water samples, and the ultrasonic solvent extraction for the sediment samples, followed by the liquid chromatography–tandem mass spectrometry. High recoveries were achieved for extraction from both water and sediment samples for the majority of analytes. Low limits of detection were achieved for all investigated compounds in the water sample (1–5 ng L^?1) as well as in the sediment (1–3 ng g^?1). Applicability of the developed methods was demonstrated by determination of pharmaceutical and pesticide residues in 30 surface water, 44 groundwater, and 5 sediment samples from the Danube River Basin in Serbia. Sixty percent of target compounds were detected in environmental samples. The most frequently detected analytes in river sediments were the pesticides dimethoate and atrazine, while carbamazepine and metamizole metabolites 4-AAA and 4-FAA were the most frequently found in water samples.     

乌江流域中上游水体中有机氯农药残留现状调查

采集了乌江流域中上游30个采样点的60个水样品,用液-液萃取对样品进行前处理,然后用GC-ECD测定有机氯农药含量,分析有机氯农药残留现状。结果表明,有机氯农药在样品中都有不同程度的检出,其中六六六、滴滴涕类物质的检出率分别为90.7%、46.9%,质量浓度为4.03~42.89 ng/L,同我国其它区域相比,乌江流域中上游水体中的有机氯含量处于中等水平,低于相应的标准限值。故就有机氯农药这类污染物在水中的含量来说,乌江流域中上游的水体是相对安全的。但由于这类污染物是持久性的,因此它们在水环境中的存在和影响也是不容忽视的。     

Monitoring of pesticide residues levels in fresh vegetable form Heibei Province,North China

In this study, 226 samples of seven types of domestic vegetables collected from several vegetable-growing regions in Hebei Province of China were tested for the presence of 38 different agricultural pesticides using a gas chromatograph equipped with electron capture and nitrogen phosphorus detectors. The aim of this study was to investigate the distribution of pesticides in main vegetables from Hebei Province. Results showed that, in 65.93 % of the samples, no residues were found, 31.42 % of the samples contained pesticide residues at or below the maximum residue levels (MRLs), and 2.65 % of the samples contained pesticide residues above MRL. The most frequently detected pesticides were acephate (31), followed by cyhalothrin (15), bifenthrin (8), omethoate (6), isazophos (6), dimethoate (5), chlorpyrifos (2), and malathion (1). Some (1.33 %) of the samples contained multiple residues. The results provide useful information on the current contamination status of a key agricultural area in North China, and points to the continuous monitoring and strict regulation of pesticide use on vegetables are necessary.     

气相色谱法测定土壤中37种有机磷农药残留

采用气相色谱法测定土壤中37种有机磷农药,当取样量为10 g时,37种有机磷农药方法检出限为0. 002～0. 015 mg/kg,测定下限为0. 008～0. 060 mg/kg。低含量加标样品中有机磷农药的加标回收率为72. 8%～104%,相对标准偏差为4. 2%～13. 8%;中含量加标样品中有机磷农药的加标回收率为71. 5%～101%,相对标准偏差为4. 3%～13. 5%;高含量加标样品中有机磷农药的加标回收率为74. 6%～109%,相对标准偏差为6. 8%～14. 6%。该方法灵敏度高、分离效果好、重现性好,能够满足土壤中37种有机磷农药残留检测的要求。     

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.     

Detection of toxic heavy metals and pesticide residue in herbal plants which are commonly used in the herbal formulations

Herbal formulations are getting popular throughout the world and commercialized extensively for various medicinal properties. WHO has emphasized the need for quality assurance of herbal products, including testing of heavy metals and pesticides residues. In view of WHO guidelines, single herbal drugs used in herbal formulations were collected from local market, for testing heavy metals and persistent pesticides residue. Therefore, in the present case, we have examined few local samples of certain herbs viz. Emblica officinalis, Terminalia chebula, Terminalia belerica, and Withania somnifera. The present studies were selected for estimation of four heavy metals namely Arsenic, Cadmium, Lead, and Mercury. Apart from these, pesticide residue Viz. Organochlorine pesticides, Organophosphorus pesticides, and Pyrethroids were analyzed in the four samples of single crude drugs. Heavy metals and pesticide residue were found below detection limits in all the samples.     

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.     

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.     

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.     

Occurrence of heavy metals in fish: a study for impact assessment in industry prone aquatic environment around Kolkata in India

A study was conducted during November 2005-October 2006 for determining the heavy metal contamination in surface water and sediments and giving prime thrust to determine the heavy metal concentrations fish samples collected from various points of the river Ganga at different time interval. Fish samples (viz., Channa marulius and Aorichthys seengala) were analyzed for heavy metals using standard laboratory procedures by AAS method. In impact points the annual average values for Cu, Cr, Cd, Pb and Zn were 0.15, 0.04, 0.03, 0.02 and 0.29 ppm, respectively. The concentrations of heavy metals in the riverine water collected from middle point had the order Zn > Cu > Cr > Cd > Pb. The data indicated that copper was maximally accumulated in the riverine sediments whereas least annual average concentration was obtained for lead. The trend of accumulation suggested deposition was maximum for zinc and minimum for cadmium in the muscles of both fish species. Only zinc has shown some significant seasonal variation in relation to metal deposition in fish muscles (minimum in monsoon and maximum in summer). The heavy metal contamination to fish may be due to indiscriminate discharge of polluted and untreated sewage sludge to the river. The heavy metal contents in fish at some places are alarming.