Pesticide and Heavy Metals Residue in Wastewater, Soil and Plants in Wastewater Disposal Site Near Al-Lajoun Valley, Karak / Jordan

Disposal of raw wastewater and sludge creates thepotential for pesticides and heavy metal contamination. Afield study was conducted to determine the residueconcentration level of chlorinated pesticides and four heavymetals (Zn, Pb, Cu and Ni) in raw wastewater, soils andplants at Karak raw wastewater disposal site. The resultsindicated that the investigated area was heavily contaminatedwith various types of pesticides. The distribution of different pesticides in soils and wastewater was influencedby the solubility of these pesticides such that the higherthe solubility the more is present in water phase and viceversa. Vinclozoline was the dominant pesticide in most of thesamples. Some pesticides of which application is restrictedto be used in Jordan, such as DDT and its metabolites, weredetected in the investigated area.Heavy metals existed in relatively higher concentrationsin soils than in wastewater, which was due to the high pH ofthe wastewater enhancing its precipitation. Zinc was thehighest among the analyzed heavy metals in both wastewaterand soils.The residue level of both heavy metals and chlorinatedpesticides were highest at the emission source decreasinggradually with distance.     

Volatilization of trifluralin,atrazine, metolachlor,chlorpyrifos, alpha-endosulfan,and beta-endosulfan from freshly tilled soil

The volatile and soil loss profiles of six agricultural pesticides were measured for 20 days following treatment to freshly tilled soil at the Beltsville Agricultural Research Center. The volatile fluxes were determined using the Theoretical Profile Shape (TPS) method. Polyurethane foam plugs were used to collect the gas-phase levels of the pesticides at the TPS-defined critical height above a treated field. Surface-soil (0-8 cm) samples were collected on each day of air sampling. The order of the volatile flux losses was trifluralin > alpha-endosulfan > chlorpyrifos > metolachlor > atrazine > beta-endosulfan. The magnitude of the losses ranged from 14.1% of nominal applied amounts of trifluralin to 2.5% of beta-endosulfan. The daily loss profiles were typical of those observed by others for volatile flux of pesticides from moist soil. Even though heavy rains occurred from the first to third day after treatment, the majority of the losses took place within 4 days of treatment, that is, 59% of the total applied atrazine and metolachlor and >78% of the other pesticides. Soil losses generally followed pseudo-first-order kinetics; however, leaching due to heavy rainfall caused significant errors in these results. The portion of soil losses that were accounted for by the volatile fluxes was ordered as follows: alpha-endosulfan, 34.5%; trifluralin, 26.5%; chlorpyrifos, 23.3%; beta-endosulfan, 14.5%; metolachlor, 12.4%; and atrazine, 7.5%.     

Determination of multiresidues in rapeseed, rapeseed oil, and rapeseed meal by acetonitrile extraction, low-temperature cleanup, and detection by liquid chromatography with tandem mass spectrometry

A multiresidue method for determining pesticides in rapeseed, rapeseed oil, and rapeseed meal by use of liquid chromatography-tandem mass spectrometry is developed. Samples were extracted with acetonitrile or acidified acetonitrile and cleaned up by a 12 h freezing step. The recovery data were obtained by spiking blank samples at three concentration levels. The recoveries of 27 selected pesticides in rapeseed, rapeseed oil, and rapeseed meal were in the range of 70-118%, at the concentration level of 10 μg kg(-1), with intraday and interday precisions of lower than 22 and 27%, respectively. Linearity was studied between 2 and 500 μg L(-1) with determination coefficients (R(2)) of higher than 0.98 for all compounds in the three matrices. The limits of quantitation (LOQs) of pesticides in rapeseed, rapeseed oil, and rapeseed meal ranged from 0.3 to 18 μg kg(-1). The n-octanol-water partition coefficient showed more influence than water solubility in extracting pesticides by acetonitrile from matrices of high fat content. This method was successfully applied for routine analysis in commercial products.     

Effect of biobed composition, moisture, and temperature on the degradation of pesticides

Biobeds retain and degrade pesticides through the presence of a biobed mixture consisting of straw, peat, and soil. The effects of biobed composition, moisture content, and temperature on pesticide degradation were investigated in laboratory studies. Straw produced the main microbial activity in the biobed mixtures as strong positive correlations were observed between straw, respiration, and phenoloxidase content. Most pesticides investigated were dissipated by cometabolic processes, and their dissipation was correlated with respiration and/ or phenoloxidase content. More pesticides were more dissipated at biobed moisture levels of 60% water holding capacity (WHC) than at 30% and 90% WHC, while 20 degrees C gave higher dissipation rates than 2 and 10 degrees C. A straw:peat:soil ratio of 50:25:25% v/v is recommended in field biobeds since this produces high microbial activity and low pH, favorable for lignin-degrading fungi and phenoloxidase activity.     

Microwave-assisted extraction for the simultaneous determination of thiamethoxam, imidacloprid, and carbendazim residues in fresh and cooked vegetable samples

Microwave-assisted extraction (MAE) was carried out for the simultaneous determination of the insecticides thiamethoxam [(EZ)-3-(2-chloro-1,3-thiazol-5-ylmethyl)-5-methyl-1,3,5-oxadiazinan-4-ylidene(nitro)amine], imidacloprid [1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine], and the fungicide carbendazim (methyl benzimidazol-2-ylcarbamate) in vegetable samples. Five crop samples consisting of cabbage, tomatoes, chilies, potatoes, and peppers were fortified with the three pesticides and subjected to MAE followed by cleanup to remove coextractives prior to analysis by high-performance liquid chromatography. Using the selected microwave exposure time and power setting, the recoveries of the three pesticides from the fortified vegetable samples ranged from 68.1 to 106%. The corresponding recoveries for samples processed simultaneously but without microwave exposure ranged from 37.2 to 61.4%. The recoveries by MAE were comparable to those obtained by the conventional blender extraction technique. The precision of the MAE method was demonstrated by relative standard deviations of <7% for the three pesticides. The cooked cabbage and tomato samples showed no breakdown of the parent compounds, and the recoveries of three pesticides were comparable to those obtained with the uncooked samples.     

Isolation and concentration of organophosphorus pesticides from drinking water at the ng/L level, using macroreticular resin.

A screening method has been developed for determining organophosphorus pesticides at ng/L levels in drinking water. Sixteen organophosphorus pesticides, diazinon, diazinon-oxon, dimethoate, ronnel, beta-phosphamidon, methyl parathion, ethyl parathion, malathion, chlorpyrifos, fenitrothion, ruelene, methidathion, ethion, EPN, phosalone, and phosmet, were extracted by Amberlite XAD-2 resin from 100 and 200 L drinking water previously spiked with these pesticides. The pesticides were eluted from the XAD-2 resin with acetone-hexane (15+85). The concentrated extract was analyzed by gas chromatography using a nitrogen-phosphorus selective detector and by gas chromatography-mass spectrometry using selected ion monitoring. Recoveries at the 10 and 100 ng/L spiking levels were greater than 90%, except recoveries for dimethoate and phosphamidon were 37 and 42%, respectively. The analysis of 300 L Ottawa tap water showed no detectable amounts (less than 1 ng/L) of any of the 16 organophosphorus pesticides.     

Occurrence of Pesticides in Water, Sediments, and Fish Tissues in a Lake Surrounded by Agricultural Lands: Concerning Risks to Humans and Ecological Receptors

Lake Vela (Littoral Centre of Portugal) is considered a natural habitat with community interest and consequently was included in the Natura 2000 Network. However, this freshwater ecosystem has been potentially exposed to diffuse pollution generated by agricultural and livestock activities, which seriously compromise its ecological balance. As part of the Ecological Risk Assessment (ERA) proposed for Lake Vela, this study aimed to evaluate the occurrence of pesticides in different compartments: surface water, groundwater, sediments, and fish tissues. Moreover, to assess potential concerning effects on ecosystem and human health, the measured concentrations of pesticides were compared with regulatory and toxicological benchmarks. The results confirmed the presence of high concentrations of pesticides, including organochloride pesticides banned decades ago, in surface water, groundwater, and sediment. The measured concentrations of pesticides, compared with toxicological benchmarks, indicated that harmful effects are likely for aquatic species due to the presence of alachlor, aldrin, and dieldrin. Additionally, the concentrations of pesticides detected in groundwater were also above the recommended safety levels for drinking water, which constitutes a concern for the local population’s health. Results also showed an accumulation of alachlor in predator and benthic fish species which could represent a risk to human consumers and particularly to the regular fish predators (e.g., otters and birds). This study, as the first exposure characterization performed on the Lake Vela system, constitutes valuable and useful information for the ERA process. Although this preliminary assessment of risks should be continued and confirmed through a weight-of-evidence approach, it had already unraveled how concerning are the problems in this ecosystem and the urgency of implementing restoration measures to guaranty its sustainability. Furthermore, this study reinforces the importance of evaluating similar freshwater ecosystems that are also highly threatened by diffuse pollution.     

Occurrence,Degradation and Fate of Pesticides During Composting

This paper reviews the findings of research reported in the currently available literature regarding the occurrence and transformations of pesticides through the composting process and the use of compost. Part I summarizes the composting process, pesticides and mechanisms of pesticide degradation. Part II reviews research studies concerning the occurrence and fate of pesticides during composting. Investigations of pesticide residues in composting feedstocks and finished compost detected few of the target pesticides. The compounds that were found occurred at low concentrations. The majority of the compounds detected were insecticides in the organochlorine category, including chemicals that have been banned from use in the U.S. for many years. Generally, organophosphate and carbamate insecticides and most herbicides were rarely detected. Comparisons of pesticide concentrations before and after composting also showed organochlorine compounds to be most resistant to biodegradation during composting. With some exceptions, pesticides in other categories decomposed moderately well to very well. Studies that followed the mechanisms of degradation indicate that mineralization accounts for only a small portion of pesticide disappearance. Other prominent fates include partial degradation to secondary compounds, adsorption, humification, and volatilization. In general the research results suggest that the pattern of pesticide degradation during composting is similar to the degradation observed in soils. With a few important distinctions, composting can be considered a biologically active soil environment in which degradation is accelerated. However, as some studies noted, composting does not always speed the degradation of all pesticides. The nature of the pesticide, specific composting conditions and procedures, the microbial communities present, and the duration of composting affect the extent and the mechanisms of degradation.     

Acute Toxicity of Seven Selected Pesticides (Alachlor, Atrazine, Dieldrin, Diuron, Pirimiphos-Methyl, Chlorpyrifos, Diazinon) to the Marine Fish (Turbot, Psetta maxima)

The present study evaluated the short-term toxicity of seven selected pesticides: four insecticides (chlorpyrifos, dieldrin, diazinon and pirimiphos-methyl) and three herbicides (diuron, alachlor and atrazine). With this aim, a standard toxicity test with the highly sensitive early life stages (ELS) of a marine fish was used. The turbot, Psetta maxima, is abundant in shallow estuarine and costal habitats and is currently the most commonly cultivated fish species in Galicia, NW Spain. According to the turbot ELS test results, chlorpyrifos was the most toxic pesticide tested for both embryos and larvae and was followed in order of decreasing toxicity by dieldrin, pirimiphos-methyl, diazinon, alachlor, atrazine and diuron. Larvae were more sensitive than embryos to the seven pesticides. The median lethal concentrations of the selected pesticides during a 48- and a 96-h exposure for turbot embryos and larvae were, respectively (in micrograms per litre): chlorpyrifos, 116.6 and 94.65; dieldrin, 146 and 97; pirimiphos-methyl, 560 and 452; diazinon, 1,837 and 1,230; alachlor, 2,177 and 2,233; diuron, 10,076 and 7,826; and atrazine, 11,873 and 9,957. According to their acute toxicity, the insecticides were more toxic than the herbicides. Furthermore, all insecticides and herbicides appear to be teratogenic to turbot ELS.     

Pesticide residues in Lake Albufera, Valencia, Spain

Analysis of water samples from the lake in Albufera, Valencia, indicates that the pesticides molinate, benthiocarb, and fenitrothion do not reach levels that are lethal to fish.     

An assessment of potential pesticide transmission,considering the combined impact of soil texture and pesticide properties: A meta-analysis

Pesticides are widely employed as a cost-effective means of reducing the impacts of undesirable plants and animals. The aim of this paper is to develop a risk ranking of transmission of key pesticides through soil to waterways, taking into account physico-chemical properties of the pesticides (soil half-life and water solubility), soil permeability, and the relationship between adsorption of pesticides and soil texture. This may be used as a screening tool for land managers, as it allows assessment of the potential transmission risks associated with the use of specified pesticides across a spectrum of soil textures. The twenty-eight pesticides examined were differentiated into three groups: herbicides, fungicides and insecticides. The highest risk of pesticide transmission through soils to waterways is associated with soils containing <20% clay or >45% sand. In a small number of cases, the resulting transmission risk is not influenced by soil texture alone. For example, for Phenmedipham, the transmission risk is higher for clay soils than for silt loam. The data generated in this paper may also be used in the identification of critical area sources, which have a high likelihood of pesticide transmission to waterways. Furthermore, they have the potential to be applied to GIS mapping, where the potential transmission risk values of the pesticides can be layered directly onto various soil textures.     

Comparison of dieldrin, lindane, and DDT extractions from serum, and gas-liquid chromatography using glass capillary columns.

Rats were given an oral dose of 14C-labeled chlorinated pesticides to obtain serum containing p,p'-DDT, dieldrin, or lindane. Simple hexane and formic acid-hexane extraction methods, involving pretreatment of the serum with formic acid, were compared by radiometric and by paper chromatographic and gas chromatographic analysis. In vivo binding of chlorinated pesticides to constituents of the serum does not necessarily prohibit their isolation by simple hexane extractions, provided that the extraction is very vigorous and at least 5 min long. Stable emulsions were broken by cooling in liquid nitrogen or Dry Ice-acetone. The hexane extraction method described yields quantitative recovery of the pesticides studied, whereas the formic acid-hexane method is quantitative for p,p'-DDT, 93% for dieldrin, and 89% for lindane. Gas chromatographic comparison of both methods, using human serum, shows that the hexane method extracts 16% more beta-BHC, 7% more dieldrin and HCB, and 4% more p,p'-DDE from serum than does the formic acid-hexane method. The difference for p,p'-DDT is not significant. Gas chromatography with glass capillary columns and an all-glass solids injection system yielded detection limits as low as 15 fg. Data show that the use of an internal standard considerably improves the precision of quantitation.     

Multiresidue pesticide analysis of agricultural commodities using acetonitrile salt-out extraction, dispersive solid-phase sample clean-up, and high-performance liquid chromatography-tandem mass spectrometry

A multiresidue method analyzing 209 pesticides in 24 agricultural commodities has been developed and validated using the original Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) procedure and high performance liquid chromatography-positive electrospray ionization-tandem mass spectrometry (LC-MS/MS) analysis. Using solvent-only calibration standards (SOCSs) and matrix-matched calibration standards (MMCSs), it was demonstrated that a minimal concentration of 5-10 μg/kg (part per billion, ppb) of analytes in matrix is required for the consistent identification of targeted pesticides with two MRM transitions. Method performance was validated by the precision and accuracy results obtained from fortification studies at 10, 25, 100, and 500 ppb and MMCSs. The method was demonstrated to achieve an average recovery of 100 ± 20% (n = 4) for >75% of evaluated pesticides at the low fortification level (10 ppb) and improved to >84% at the higher fortification concentrations in all 24 matrices. Matrix effects in LC-MS/MS analysis were studied by evaluating the slope ratios of calibration curves (1.0-100 ng/mL) obtained from the SOCSs and MMCSs. Principal component analysis (PCA) of LC-MS/MS and method validation data confirmed that each matrix exerts its specific effect during the sample preparation and LC-MS/MS analysis. The matrix effect is primarily dependent on the matrix type, pesticide type and concentration. Some caution is warranted when using matrix matched calibration curves for the quantitation of pesticides to alleviate concerns on matrix effects. The QuEChERS method with LC-MS/MS was used to identify and quantitate pesticides residues, with concentrations ranging from 2.5 to >1000 ppb in a variety of agricultural samples, demonstrating fitness for screening and surveillance applications.     

Reduction of azinphos-methyl, chlorpyrifos, esfenvalerate, and methomyl residues in processed apples

McIntosh, Red Delicious, and Golden Delicious from two years of experimental spray programs using azinphos-methyl, chlorpyrifos, esfenvalerate, and methomyl were processed into frozen apple slices, applesauce, single-strength juice, and juice concentrate. Residue levels were expressed as micrograms per 150 g of apple or the equivalent amount of apple product to calculate the percentage change in these pesticides brought about by processing. Producing single-strength apple juice reduced azinphos-methyl, chlorpyrifos, esfenvalerate, and methomyl residues by 97.6, 100, 97.8, and 78.1%, respectively. Production of applesauce reduced all four compounds by >/=95%. Azinphos-methyl, chlorpyrifos, esfenvalerate, and methomyl residues were reduced in apple slices by 94.1, 85.7, 98.6, and 94.7%, respectively. Processing is shown to be very effective in reducing the levels of these pesticides.     

Influence of two insecticides, chlorpyrifos and quinalphos, on arginine ammonification and mineralizable nitrogen in two tropical soil types

Effects of seed treatments with chlorpyrifos [5 g of active ingredient (ai) kg(-1) of seed] and quinalphos (6.25 g of ai kg(-1) of seed) and standing crop treatments with chlorpyrifos (800 g of ai ha(-1)) and quinalphos (1000 g of ai ha(-1)) on arginine deamination and mineralizable nitrogen were monitored, in the sandy loam and loamy sand soils of two tropical semiarid fields, for three consecutive crop seasons. The arginine ammonification activity of rhizospheric microbes was inhibited after seed treatment with chlorpyrifos and quinalphos and their principal metabolites, 3,5,6-trichloro-2-pyridinol (TCP) and 3,5,6-trichloro-2-methoxypyridine (TMP) and 2-hydroxyquinoxaline and quinoxaline-2-thiol, respectively. Quinalphos produced transient inhibitions, whereas chlorpyrifos and its metabolites (TCP and TMP) exerted a greater inhibition in both loamy sand and sandy loam soils. Arginine ammonification by nonrhizospheric microbes was stimulated by standing crop treatments with both pesticides. In the loamy sand soil, the parent compounds stimulated rhizospheric N-mineralization, whereas the metabolites were inhibitory. However, nonrhizospheric N-mineralization was inhibited by both chlorpyrifos and quinalphos and stimulated by their metabolites. A higher magnitude of inhibition of arginine deamination in the loamy sand than in the sandy loam soil could be due to greater bioavailability of the pesticides in the former, resulting from lesser sorption of the pesticides due to alkalinity of the soil and its low content of clay and organic carbon. Although both pesticides affected mineralizable nitrogen, seed treatment with quinalphos and standing crop treatment with quinalphos and chlorpyrifos produced the most significant effects. The recommended doses of the pesticides not only efficiently controlled whitegrubs, which increased pod yields, but also left no residues in harvested kernels. They also caused no long-term inhibition of ammonification, which could have been of significant concern during the short crop period in semiarid areas where nitrogen determines plant productivity.     

Pesticide Residue Awareness among Students and Employees in the University of Jordan,Jordan

The objective of the current study was to examine the awareness of employees, students, and community at The University of Jordan about pesticides residue in food and whether they are interested to learn more about it. A questionnaire consisted of 28 questions in three sections was designed and included questions about the demographic characteristics and about the knowledge of the participants about pesticides and their residual limit. Results showed that young respondents with ages between 19–35 years old and with higher educational levels and scientific background were more knowledgeable in many aspects regarding pesticides and their residues, however, this study should be expanded to include higher numbers of respondents, from different universities in Jordan, and among different school backgrounds in order to be able to generalize the results.     

Extraction and cleanup of organochlorine, organophosphate, organonitrogen, and hydrocarbon pesticides in produce for determination by gas-liquid chromatography.

A rapid, multiresidue procedure utilizing the minimal cleanup necessary for gas-liquid chromatographic (GLC) analysis is presented. The samples are extraced with acetone and partitioned with methylene chloride-petroleum either to remove water. The organophosphorus and organonitrogen compounds are then quantitated by GLC, using a KCl thermionic detector. A Florisil cleanup of the extract is performed prior to the determination of organochlorine compounds by a GLC electron capture detector. Carbon-hydrogen compounds such as biphenyl and o-phenylphenol undergo the Florisil cleanup and may also be quantitated by GLC. Quantitative recoveries for 15 organophosphorus, 9 organochlorine, 5 organonitrogen, and 2 hydrocarbon pesticides show the range in polarities of pesticides recovered, from Monitor to biphenyl. The method is simple and fast with a great potential for the analysis of many more compounds.     

Occurrence and distribution of chemical pollutants in Lake Mariut,Egypt

Occurrence and distribution of organochlorine pesticides in the water of Lake Mariut, a brackish coastal Egyptian lake suffering from pollution, and their accumulation in the common fish Tilapia were studied. The major pesticides detected in the lake water were lindane, p,p′-DDE, o,p′-DDT, and p,p′-DDT. These compounds, except o,p′-DDT, were detected in the fish samples in exceedingly higher concentrations compared with those found in the lake water.     

Pesticides in River and Tap Water in a Rice Production Area of Niigata,Japan

Water samples collected in 1995 and 2007 from the Shinano and Agano rivers were examined to determine the types and concentrations of pesticides and their effects on tap water in typical rice production areas of Japan. Tap water originating from the Shinano River was also sampled in 2007, in Niigata City, Japan. Pesticides were present in the river and tap water throughout the year. Comparison of 13 pesticides common to both 1995 and 2007 series revealed that the frequency of individual pesticide occurrence and concentrations were decreasing. Riverine pesticides were classified into five groups according to the period of their appearance and changes in concentration. Pesticides were detected at the time of application to, and drainage from, paddy fields. Pesticide concentrations in tap water showed notable decline following rapid sand-filtration combined with granular activated carbon. The detection index (DI) for tap water and Shinano River water did not exceed a value of 1. Herbicides contributed most to the DI.

     

Optimized gel permeation chromatographic cleanup for soil, sediment, wastes, and oily waste extracts for determination of semivolatile organic pollutants and PCBs

A gel permeation chromatographic (GPC) method, used by the U.S. Environmental Protection Agency (USEPA), was modified for cleanup of soil, sediments, wastes, and oily wastes before determination of semivolatile organic pollutants. The modifications included new calibration procedures and control of the amount of material processed. The modifications were evaluated for soil and sediment matrixes in a 5-laboratory study where each laboratory processed a solution containing a phthalate, substituted phenols and benzenes, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), nitroaniline, and pesticides. With the exception of nitroaniline, analyte recoveries were 87-112%, with relative standard deviations (RSDs) of 6.7-26%. Soil samples containing PCBs and fortified with 6 pesticides at 0.7-4 micrograms/g were also analyzed by the 5 laboratories. The mean recovery of the 6 pesticides was 100% with a mean RSD of 16%. Mean RSD for the determination of total PCBs was 8.9%. An additional modification for the processing of wastes and high concentration waste samples was attempted; this involved GPC processing of sample extracts dissolved in 1 + 1 butyl chloride-methylene chloride. This modification did not improve recoveries of the semivolatile analytes. Finally, the modified GPC protocol was applied to PCB-contaminated reclaimed waste oils samples. Two GPC cleanup steps were used to separate PCBs from the waste oil samples before PCBs were determined by gas chromatography combined with electron-capture detection (GC/ECD).