Spatial and temporal analysis of pesticides concentrations in surface water: pesticides atlas

Dutch water boards have a well-established program for monitoring pesticide contamination of surface waters. These monitoring data have been processed into a graphic format accessible online and designed to provide insight into pesticide presence in Dutch surface waters and trends over time: the Pesticides Atlas (http://www.pesticidesatlas.nl). With this tool one can easily get maps of where a pesticide is being measured and where it might possibly constitute an environmental problem over the years. Presently, results of the periods 1997/1998 until 2005/2006 are available at the level of individual active ingredients. At a national level, the percentage of pesticides concentrations that exceed the maximum tolerable risk has declined 30% to 38% over the years 2003/2004 compared with 1997/1998. This means that surface water quality in the Netherlands has improved with respect to pesticides, however there are still many locations at which the measured concentrations exceed the environmental quality standards. The results on linking land use to pesticides concentrations were shown to assist in optimization of monitoring programs. By developing the present Internet tool, many new opportunities for environmental risk assessment and risk management were identified, e.g. optimization of monitoring strategies and communication to policymakers.     

有机磷农药残留检测技术研究进展

综述了近年来有机磷农药残留检测技术的研究进展,其检测方法主要有色谱法、降解酶法、化学发光技术和生物传感技术.详细介绍了几种生物传感器(如酶传感器、微生物传感器、免疫传感器、压电传感器、纳米传感器和液晶型化学传感器)在有机磷农药检测中的应用,并展望了这一领域的发展趋势.     

Raman and SERS spectra of thiamethoxam and the Ag3–thiamethoxam complex: an experimental and theoretical investigation

Dutch water boards have a well-established program for monitoring pesticide contamination of surface waters. These monitoring data have been processed into a graphic format accessible online and designed to provide insight into pesticide presence in Dutch surface waters and trends over time: the Pesticides Atlas (http://www.pesticidesatlas.nl). With this tool one can easily get maps of where a pesticide is being measured and where it might possibly constitute an environmental problem over the years. Presently, results of the periods 1997/1998 until 2005/2006 are available at the level of individual active ingredients. At a national level, the percentage of pesticides concentrations that exceed the maximum tolerable risk has declined 30% to 38% over the years 2003/2004 compared with 1997/1998. This means that surface water quality in the Netherlands has improved with respect to pesticides, however there are still many locations at which the measured concentrations exceed the environmental quality standards. The results on linking land use to pesticides concentrations were shown to assist in optimization of monitoring programs. By developing the present Internet tool, many new opportunities for environmental risk assessment and risk management were identified, e.g. optimization of monitoring strategies and communication to policymakers.     

Weak Governmental Institutions Impair the Management of Pesticide Import and Sales in Zanzibar

Poor pesticide handling practices and risk-awareness among African farmers puts human health and the environment at risk. To investigate information available to farmers in Zanzibar (Tanzania), an interview study was conducted with retailers, and governmental pesticide importation to Zanzibar was examined. Pesticide retailers in Zanzibar did not have the necessary knowledge to safely handle or to advise farmers on proper use of pesticides. Licensed shop owners were rarely found in the shops; instead, untrained personnel were employed to sell the pesticides. Implementation of the legislation was weak, mainly due to lack of surveillance by governmental institutions. Poor governmental importation practices and unregulated private imports indicate serious weakness in the management of pesticide importation in Zanzibar. The situation calls for increased attention on the monitoring of pesticide importation and sales to protect the health of farmers and retailers, as well as the environment.     

Application of automated mass spectrometry deconvolution and identification software for pesticide analysis in surface waters

A new approach to surface water analysis has been investigated in order to enhance the detection of different organic contaminants in Nathan Creek, British Columbia. Water samples from Nathan Creek were prepared by liquid/liquid extraction using dichloromethane (DCM) as an extraction solvent and analyzed by gas chromatography mass spectrometry method in scan mode (GC-MS scan). To increase sensitivity for pesticides detection, acquired scan data were further analyzed by Automated Mass Spectrometry Deconvolution and Identification Software (AMDIS) incorporated into the Agilent Deconvolution Reporting Software (DRS), which also includes mass spectral libraries for 567 pesticides. Extracts were reanalyzed by gas chromatography mass spectrometry single ion monitoring (GC-MS-SIM) to confirm and quantitate detected pesticides. Pesticides: atrazine, dimethoate, diazinone, metalaxyl, myclobutanil, napropamide, oxadiazon, propazine and simazine were detected at three sampling sites on the mainstream of the Nathan Creek. Results of the study are further discussed in terms of detectivity and identification level for each pesticide found. The proposed approach of monitoring pesticides in surface waters enables their detection and identification at trace levels.     

Review of advances in the thin layer chromatography of pesticides: 2008-2010

Techniques and applications of thin layer chromatography (planar chromatography) for the separation, detection, qualitative and quantitative determination, and preparative isolation of pesticides and their metabolites and other related compounds are reviewed for the period from November 1, 2008 to November 1, 2010. Analyses are described for a variety of samples types and pesticide classes. In addition to references on residue analysis, studies such as pesticide structure-retention relationships, identification and characterization of plant pesticides and synthesized pesticides, metabolism, degradation, mobility, identification of biomarkers for detection of herbicide effects in plants, and lipophilicity are covered.     

Review of advances in the thin layer chromatography of pesticides: 2008–2010

Techniques and applications of thin layer chromatography (planar chromatography) for the separation, detection, qualitative and quantitative determination, and preparative isolation of pesticides and their metabolites and other related compounds are reviewed for the period from November 1, 2008 to November 1, 2010. Analyses are described for a variety of samples types and pesticide classes. In addition to references on residue analysis, studies such as pesticide structure-retention relationships, identification and characterization of plant pesticides and synthesized pesticides, metabolism, degradation, mobility, identification of biomarkers for detection of herbicide effects in plants, and lipophilicity are covered.     

Novel approaches for remediation of pesticide pollutants

The use of synthetic pesticides has become an indispensable tool in agriculture for the control of pests. Therefore, the search for remedies and techniques for decontamination and detoxification of a pesticide-contaminated environment has become an important part of the research. Currently, bioremediation seems to be one of the most environmentally safe and cost-effective methods. In nature, the existence of abundant material resources can be used to degrade the environmental pesticide pollutants. At present, a number of microorganisms, capable of degrading pesticides, have been isolated and characterised. For insects, insecticide resistance-associated esterases have been purified and characterised from several insect species, and a new family of cytochrome P450 apparently associated with insecticide resistance in the tobacco budworm, was discovered. Generally, two bioremediation approaches have been used one directly based on microorganisms, and the other involved in isolated enzymes. For the former, in addition to using natural microorganism strains, with genetic techniques certain desirable biodegradation pathways from different organisms are brought together in a single host. However, because of their own limits, especially problems associated with releasing genetically altered microorganisms into the environment, the strategy based on enzymes seems more feasible. In the long term, collaborations between microbiologists, biochemists, and engineers will become increasingly important to efficiently dispose of the pesticide pollutants.     

Application of Automated Mass Spectrometry Deconvolution and Identification Software for Pesticide Analysis in Surface Waters

A new approach to surface water analysis has been investigated in order to enhance the detection of different organic contaminants in Nathan Creek, British Columbia. Water samples from Nathan Creek were prepared by liquid/liquid extraction using dichloromethane (DCM) as an extraction solvent and analyzed by gas chromatography mass spectrometry method in scan mode (GC-MS scan). To increase sensitivity for pesticides detection, acquired scan data were further analyzed by Automated Mass Spectrometry Deconvolution and Identification Software (AMDIS) incorporated into the Agilent Deconvolution Reporting Software (DRS), which also includes mass spectral libraries for 567 pesticides. Extracts were reanalyzed by gas chromatography mass spectrometry single ion monitoring (GC-MS-SIM) to confirm and quantitate detected pesticides. Pesticides: atrazine, dimethoate, diazinone, metalaxyl, myclobutanil, napropamide, oxadiazon, propazine and simazine were detected at three sampling sites on the mainstream of the Nathan Creek. Results of the study are further discussed in terms of detectivity and identification level for each pesticide found. The proposed approach of monitoring pesticides in surface waters enables their detection and identification at trace levels.     

Development and field validation of an indicator to assess the relative mobility and risk of pesticides in the Lourens River catchment,South Africa

A GIS based pesticide risk indicator that integrates exposure variables (i.e. pesticide application, geographic, physicochemical and crop data) and toxicity endpoints (using species sensitivity distributions) was developed to estimate the Predicted Relative Exposure (PREX) and Predicted Relative Risk (PRRI) of applied pesticides to aquatic ecosystem health in the Lourens River catchment, Western Cape, South Africa. Samples were collected weekly at five sites from the beginning of the spraying season (October) till the beginning of the rainy season (April) and were semi quantitatively analysed for relevant pesticides applied according to the local farmers spraying programme. Monitoring data indicate that physicochemical data obtained from international databases are reliable indicators of pesticide behaviour in the Western Cape of South Africa. Sensitivity analysis identified K_OC as the most important parameter influencing predictions of pesticide loading derived from runoff. A comparison to monitoring data showed that the PREX successfully identified hotspot sites, gave a reasonable estimation of the relative contamination potential of different pesticides at a site and identified important routes of exposure (i.e. runoff or spray drift) of different pesticides at different sites. All pesticides detected during a monitored runoff event, were indicated as being more associated with runoff than spray drift by the PREX. The PRRI identified azinphos-methyl and chlorpyrifos as high risk pesticides towards the aquatic ecosystem. These results contribute to providing increased confidence in the use of risk indicator applications and, in particular, could lead to improved utilisation of limited resources for monitoring and management in resource constrained countries.     

The status of pesticide pollution in surface waters (rivers and lakes) of Greece. Part I. Review on occurrence and levels

This review evaluates and summarizes the results of long-term research projects, monitoring programs and published papers concerning the pollution of surface waters (rivers and lakes) of Greece by pesticides. Pesticide classes mostly detected involve herbicides used extensively in corn, cotton and rice production, organophosphorus insecticides as well as the banned organochlorines insecticides due to their persistence in the aquatic environment. The compounds most frequently detected were atrazine, simazine, alachlor, metolachlor and trifluralin of the herbicides, diazinon, parathion methyl of the insecticides and lindane, endosulfan and aldrin of the organochlorine pesticides. Rivers were found to be more polluted than lakes. The detected concentrations of most pesticides follow a seasonal variation, with maximum values occurring during the late spring and summer period followed by a decrease during winter. Nationwide, in many cases the reported concentrations ranged in low ppb levels. However, elevated concentrations were recorded in areas of high pesticide use and intense agricultural practices. Generally, similar trends and levels of pesticides were found in Greek rivers compared to pesticide contamination in other European rivers. Monitoring of the Greek water resources for pesticide residues must continue, especially in agricultural regions, because the nationwide patterns of pesticide use are constantly changing. Moreover, emphasis should be placed on degradation products not sufficiently studied so far.     

Detection limits can influence the interpretation of pesticide monitoring data in Canadian surface waters

Water quality monitoring programs rely on residue data that are frequently left censored, due to some observations occurring below the Method Detection Limit (MDL). Our objective was to determine the influence the MDL has on the interpretation of pesticide residues in surface waters. Water samples from tributaries in southern and central Ontario were collected by Environment Canada from 2003 to 2008 and were analyzed for 27 pesticides, with MDLs that averaged 7.02 ng⁻¹ L (range 0.39-25.1 ng⁻¹ L). We then simulated MDLs ranging from 25 to 1700 ng⁻¹ L, to determine the impact this would have on the reporting of pesticide concentrations and detections. The mean number of pesticides detected simultaneously declined with increasing, i.e. less sensitive MDLs, from 5.02 pesticides (native MDL) to 0.08 pesticides detected (MDL < 1700 ng⁻¹ L). We compared the proportion of sites where pesticides were detected in surface waters under five MDL scenarios for 13 selected pesticides. The proportions decreased sharply with increasing MDLs. We calculated detection probabilities in an effort to compensate for higher MDLs using maximum likelihood; while adjusting for detection probabilities generally improved estimates of the presence of pesticides, as the MDLs increased the ability to compensate for detection probabilities deteriorated and became unviable at high MDLs. Depending on the method of substitution for observations below MDL (replacement with ½ × or 0 × MDL), the mean and median pesticide residues became increasingly over- and underestimated, respectively, at higher MDLs. Although monitoring programs that are focused on exceedences of water quality guidelines may not require low MDLs, the achievable goals of monitoring programs oriented towards other ecological and toxicological objectives may be limited by higher MDLs.     

Monitoring of organochlorine pesticides residues in green mussels (Perna viridis) from the coastal area of Thailand

The utilization of organochlorine pesticides for pest control chemical has been of great interest on residue contamination from biological organisms in the environment. Green mussel (Perna viridis) samples were monitored as bioindicators for assessment of the water quality in coastal waters along the Gulf of Thailand. Thirty-six samples were collected from 12 stations during 1997-1999 and analysed for 26 organochlorine pesticide compounds. This paper focuses on the contamination of organochlorine pesticide residues in green mussel (P. viridis) during 1997-1999. The limit of detection of all organochlorine pesticides compounds was at the range of 0.1-8.3 ng g(-1) wet weight and recovery 75-95%. The concentration of organochlorine pesticides residues in green mussel was lower than the maximum residue limit for aquatic animals as recommended by the Ministry of Public Health of Thailand. The trend of organochlorine pesticide residue contamination in this area decreased from 1989 to 1999.     

Green pre-concentration techniques during pesticide analysis in food samples

The ever-increasing demand for determining pesticides at low concentration levels in different food matrices requires a preliminary step of pre-concentration which is considered a crucial stage. Recently, the parameter of “greenness” during sample pre-concentration of pesticides in food matrices is as important as selectivity in order to avoid using harmful organic solvents during sample preparation. Developing new green pre-concentration techniques is one of the key subjects. Thus, to reduce the impact on the environment during trace analysis of pesticides in food matrices, new developments in pre-concentration have gone in three separate directions: the search for more environmentally friendly solvents, miniaturization and development of solvent-free pre-concentration techniques. Eco-friendly solvents such as supercritical fluids, ionic liquids and natural deep eutectic solvents have been developed for use as extraction solvents during pre-concentration of pesticides in food matrices. Also, miniaturized pre-concentration techniques such as QuEChERS, dispersive liquid–liquid micro-extraction and hollow-fiber liquid-phase micro-extraction have been used during trace analysis of pesticides in food samples as well as solvent-free techniques such as solid-phase micro-extraction and stir bar sorptive extraction. All these developments which are aimed at ensuring that pesticide pre-concentration in different food matrices is green are critically reviewed in this paper.     

Review of advances in the thin layer chromatography of pesticides: 2012–2014

Publications reporting techniques and applications of thin layer chromatography (planar chromatography) for the separation, detection, qualitative, and quantitative determination, and preparative isolation of pesticides and their metabolites are reviewed for the period from November 1, 2012 to November 1, 2014. Analyses are described for a variety of sample types and pesticide classes. In addition to references on residue analysis, studies such as pesticide structure – retention relationships, identification and characterization of natural and synthesized pesticides, metabolism, bioactivity, degradation, soil mobility, and lipophilicity are covered.     

The implications of US Government policy on the development and use of biopesticides

Biopesticides developed and used in the future will emerge against the backdrop of the environmental effects associated with the use of conventional pesticides and government policies designed to control these effects. In the final analysis, farmers' choices on pesticides will be influenced by the prevailing costs and benefits of conventional pesticides and their alternatives, including biopesticides. The outlook for pesticide use is complicated, though some directions can be perceived. There are a number of factors that will serve potentially to impact pesticide use, which in turn will affect the development of biopesticides. These include pesticide regulation, the FAIR Act, the crops planted, the management of ecologically based systems, and consumer demand for 'green' products.     

Review of advances in the thin layer chromatography of pesticides: 2006–2008

Applications of thin layer chromatography and high performance thin layer chromatography for the separation, detection, qualitative and quantitative determination, and preparatire isolation of pesticides and their metabolites are reviewed for the period from July 1, 2006 to November 1, 2008. Analyses are described for a variety of sample types and pesticide classes. In addition to references on residue and formulation analysis, studies such as pesticide-structure relationships, identification and characterization of plant pesticides, metabolism, degradation, mobility, and lipophilicity are covered. Future prospects for pesticide thin layer chromatography are also considered.     

Application of various methods to determine the lipophilicity parameters of the selected urea pesticides as predictors of their bioaccumulation

Different lipophilicity procedures including a newly developed (based on O?cik's equation) was applied in order to compare various urea pesticides with herbicidal and also insecticidal activity, such as monolinuron, chlorotoluron, diuron, isoproturon, linuron, dimefuron, diflubenzuron, teflubenzuron and lufenuron. Lipophilicity parameters (R_MWS and R_MW0) of nine examined pesticides were determined on the chromatographic plates RP-8F₂₅₄ with the use of methanol–water as a mobile phase_. Similarity analysis enabled to group all examined pesticides depending on their lipophilic character and allowed to perform a more objective comparison of different lipophilicity parameters obtained for investigated compounds by means of thin-layer chromatography and by the use of computational methods. It was stated that with the number of fluorine in examined pesticides, the lipophilic character of insecticides and also their tendency to bioaccumulation in the living systems increases noticeably. The results of this work confirmed that a new procedure for determining the lipophilicity parameter (R_MW0) by O?cik's equation could be a suitable tool in the prediction of pesticide bioaccumulation in living system and may be used as an indicator in design of new urea pesticides, which will be safe for humans and the environment.     

Assessment and review of organochlorine pesticide pollution in Kyrgyzstan

The current study describes the preliminary assessment and securing activities of the largest and most hazardous POPs-contaminated sites in Kyrgyzstan. In 2010, cattle died and population were found with high pesticide levels in blood, human milk, and placenta. In the first phase of the study, a historic assessment of the pesticide dumping at the landfill/dump sites have been conducted. In the second phase, soil analysis for organochlorine pesticides in the areas of the pesticide disposal sites, the former pesticides storehouses, agro-air strips, and the cotton-growing fields were conducted. By this assessment, a first overview of the types and sources of pollution and of the scale of the problem is compiled including information gaps. From major pesticides used, DDT, DDE, and HCH were measured in the highest concentrations. With the limited analytical capacity present, a reasonable risk assessment could be performed. This paper also reports on practical risk reduction measures that have been carried out recently at the two major pesticide disposal sites with support of a Dutch environmental engineering company, an international NGO (Green Cross Switzerland) and local authorities from the Suzak region within an UN project. Local population living near the sites of the former pesticide storehouses and agro-airstrips are advised not to cultivate vegetables and melons or to raise cattle on these areas. Instead, it is recommended to grow technical crops or plant trees. Further recommendations on monitoring and assessment is given including the suggestion to consider the findings in the National Implementation Plan of Kyrgyzstan.     

Prospects and limitations of phytoremediation for the removal of persistent pesticides in the environment

The environmental problems that have arisen from the use of persistent pesticides in the past, and potential sources of further contamination have been discussed. The potential and limitations of phytoremediation for removal of pesticides in the environment have been reviewed. The enzymatic processes in plants that are known to be involved in phytodegradation of pesticides, and possibilities for enhancing them have also been discussed.