Determination of biocides and pesticides by on-line solid phase extraction coupled with mass spectrometry and their behaviour in wastewater and surface water

This study focused on the input of hydrophilic biocides into the aquatic environment and on the efficiency of their removal in conventional wastewater treatment by a mass flux analysis. A fully automated method consisting of on-line solid phase extraction coupled to LC-ESI-MS/MS was developed and validated for the simultaneous trace determination of different biocidal compounds (1,2-benzisothiazoline-3-one (BIT), 3-Iodo-2-propynylbutyl-carbamate (IPBC), irgarol 1051 and 2-N-octyl-4-isothiazolinone (octhilinone, OIT), carbendazim, diazinon, diuron, isoproturon, mecoprop, terbutryn and terbutylazine) and pharmaceuticals (diclofenac and sulfamethoxazole) in wastewater and surface water. In the tertiary effluent, the highest average concentrations were determined for mecoprop (1010 ng/L) which was at comparable levels as the pharmaceuticals diclofenac (690 ng/L) and sulfamethoxazole (140 ng/L) but 1-2 orders of magnitude higher than the other biocidal compounds. Average eliminations for all compounds were usually below 50%. During rain events, increased residual amounts of biocidal contaminants are discharged to receiving surface waters.     

Perspectives of the chemical fate and toxicity of pesticides

Abstract

The wide‐spread use of pesticides in modern agriculture has created a need to investigate the chemical transformation of pesticides in plants and animals. This paper reviews the chemical and biochemical fate of various pesticides and other xenobiotics. Photochemical mechanisms appear to be the most common pathways for the abiotic transformation of these chemicals. Biotic transformation includes a large group of biochemical reactions which may result in either deactivation (detoxication) or activation (toxication) of bioactive compounds. The need for quality control in the production of pesticides is also discussed.     

Comparative study of accessibility of distinctive pesticides

Interactions of micro-contaminants with soil may play a crucial role in their environmental fate and possible harmful effects. Major goals of our investigations were to model the availability of widely used pesticides and characterize adsorption capabilities of distinctive soil types by the accomplishment of extensive comparative studies and application of several extraction methods. Environmental and biological relevance of these examinations is enhanced by the fact that intrinsic features and specific details of pesticide accessibility have not been revealed so far by a comparative approach. Five different experimental methods were assessed for modelling accessibility of five selected pesticides. The applied models for regaining the pesticides showed diverse efficiency in extraction capability in cases of the different soil types (sandy, brown forest and alluvial soils). The amounts of the obtained pesticides were determined by using gas-chromatography coupled to mass spectrometry (GC-MS) and high pressure liquid chromatography coupled to mass spectrometry (HPLC-MS). Accessibility of pesticides was also compared in cases of sterilized and real soil samples in order to estimate the extent of the influence of microflora. Aqueous extraction solvents proved to be suitable for accurate assessment of the accessible amounts of pesticides, as their effectivity was at least as high as that of the applied organic solvents. In our studies pesticide-soil interactions have comprehensively been characterized, and possible influences of environmental factors on the accessibility have also been revealed. Our study might be regarded as a tentative approach to model some significant circumstances playing key roles in pesticides' possible bioavailability.     

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.     

Organochlorine pesticide residues in sediments from the Uganda side of Lake Victoria

Organochlorine (OC) residues were analysed in 117 sediment samples collected from four bays of the Uganda side of Lake Victoria. The sediments were collected with a corer at a depth of 0-20 cm, and extracted for OC residues using a solid dispersion method. The extracts were cleaned using gel permeation chromatography and analysed for pesticide residues using a gas chromatograph (GC) equipped with an electron capture detector. The results were confirmed using a GC equipped with a mass spectrometer (MS). A total of 16 OC residues, most of them persistent organic pollutants (POPs) were identified and quantified. The OC residue levels were expressed on an oven dry weight (d.w.) basis. Endosulphan sulphate, in the range of 0.82-5.62 μg kg⁻¹d.w., was the most frequently detected residue. Aldrin and dieldrin were in the ranges of 0.22-15.96 and 0.94-7.18 μg kg⁻¹d.w., respectively. DDT and its metabolites lay between 0.11-3.59 for p,p′-DDE, 0.38-4.02 for p,p′-DDD, 0.04-1.46 for p,p′-DDT, 0.07-2.72 for o,p′-DDE and 0.01-1.63 μg kg⁻¹d.w. for o,p′-DDT. The levels of γ-HCH varied from 0.05 to 5.48 μg kg⁻¹d.w. Heptachlor was detected only once at a level of 0.81 μg kg⁻¹d.w., while its photo-oxidation product, heptachlor epoxide, ranged between non-detectable (ND) to 3.19 μg kg⁻¹d.w. Chlordane ranged from ND to 0.76 μg kg⁻¹d.w. Based on the threshold effect concentration (TEC) for fresh water ecosystems, aldrin and dieldrin were the only OCs that seemed to be a threat to the lake environment.     

Persistent organic pollutants associated to water fluxes and sedimentary processes in the Colorado River delta, Baja California, México

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were studied in sediment cores from two distinctive modern channels of the Colorado River (CR) delta. Their abundance and temporal changes are associated with flood-flows from the CR across the USA-Mexico border. The CR channel is directly exposed to river flood-flows while the Hardy River (HR) is a local channel derived mainly from agricultural runoff, geothermal effluents, and treated urban wastewater. Different headwater compositions and degrees of exposure to flood-flows appear to be the factors controlling the composition of persistent organic pollutants (POPs). Enrichment of OCPs (46 ng g⁻¹ dwt in HR and 4.37 ng g⁻¹ dwt in CR) occurred during or a few years after flooding. PCB-138 (4.2 ng g⁻¹ dwt) is enriched in HR suggesting its origin in dielectric oils from the geothermal power plant. PCB-28 (2.1 ng g⁻¹ dwt) in CR may be related with atmospheric input and/or re-deposition of upstream sediments. In surficial sediments (0-3 cm), only HR exceeds international sediment quality guidelines (4,4′-DDE = 8.16 ng g⁻¹ dwt and ΣDDT = 8.34 ng g⁻¹ dwt).     

Pesticide exposure and health conditions among orange growers in Southern Brazil

This study aimed to evaluate the exposure to pesticides through the biomarkers analysis, as well as life habits and use of Personal Protective Equipment (PPE) in a group of farmers who grow citrus in the Vale do Caí region, in Rio Grande do Sul, southern Brazil. The study population consisted of 73 volunteer farmers, 45 males and 28 females, aged between 13 and 69 years old. The control group consisted of 30 individuals who were not exposed to pesticides. Measures of urea, creatinine, aspartate aminotransferase (AST), alanine aminotransferase (ALT), gamma-glutamyltransferase (GGT), plasma cholinesterase (BChE) activity, and hematological parameters were analyzed. The study population also answered a structured questionnaire on life habits and health. The results showed that BChE activity was significantly lower in the exposed group than in the control group. AST, ALT, and creatinine were increased in the group of women exposed to pesticides when compared to the control group. GGT, urea, and hematological parameters did not show statistical differences for both male and female group. The most prevalent symptom reported by farmers after exposure to pesticides was headache. Furthermore, it was verified that the use of complete PPE is only made by 38% of the studied population.     

Effects of prevalent freshwater chemical contaminants on in vitro growth of Escherichia coli and Klebsiella pneumoniae

Many surface and ground waters in the continental US are contaminated with a variety of chemical pollutants, which are usually present in concentrations in the ppm and ppb range. The effects of these pollutants on coliform bacteria, which are prominent members of the aquatic flora, are poorly understood. Using a microtiter plate assay, isolates of Escherichia coli (from chicken intestine and fresh water), and an isolate of Klebsiella pneumoniae (from bovine milk) were exposed to varying concentrations of common pollutants over a 24 h period. The herbicides/pesticides simazine, atrazine, and diazinon; the VOCs trichloroethene and MTBE; the estrogens estradiol and estrone; and caffeine, all failed to inhibit bacterial growth at ppm levels. Only ethylene glycol, and the herbicide 2,4-D, significantly inhibited bacterial growth compared to controls. These results suggest that the replication of coliform bacteria in fresh waters is not adversely impacted by many common pollutants.     

Calibration of the Chemcatcher passive sampler for monitoring selected polar and semi-polar pesticides in surface water

Passive sampling is a powerful method for continuous pollution monitoring, but calibration experiments are still needed to generate sampling rates in order to estimate water concentrations for polar compounds. We calibrated the Chemcatcher device with an uncovered SDB-XC Empore disk as receiving phase for 12 polar and semi-polar pesticides in aquatic environments in flow-through tank experiments at two water flow velocities (0.135 m/s and 0.4 m/s). In the 14-day period of exposure the uptake of test substances in the sampler remained linear, and all derived sampling rates R(s) were in the range of 0.1 to 0.5 L/day. By additionally monitoring the release of two preloaded polar pesticides from the SDB-XC disks over time, very high variation in release kinetics was found, which calls into question the applicability of performance reference compounds. Our study expands the applicability of the Chemcatcher for monitoring trace concentrations of pesticides with frequent occurrence in water.     

Serum levels of organochlorine pesticides in healthy adults from five regions of Spain

The aim of this study was to measure of serum levels of p,p′-dichlorodiphenyl trichloroethane (p,p′-DDT), p,p′-dichlorodiphenyl dichlorethylene (p,p′-DDE), β-hexachlorocyclohexane (β-HCH), and hexachlorobenzene (HCB) in healthy adults in Spain. Furthermore, we also analyzed these levels according to dietary, other lifestyle factors and anthropometric characteristics. We measured the concentrations of such organochlorine pesticides (OCPs) in serum samples collected during 1992–1996 from 953 subjects aged 35–64 years, they were residents of five Spanish regions, they were randomly selected from the European Prospective Investigation into Cancer and Nutrition (EPIC) cohort. OCPs were determined by means of gas chromatography with electron-capture detection (GC-ECD). The most frequent compound found in serum was p,p′-DDE, present in 98% of the samples, followed by HCB and β-HCH, found in 89% and 77% of samples, respectively, while p,p′-DDT could be measured only in 26% of subjects. The geometric means of serum concentrations (ng/g lipid) were 822 for p,p′-DDE, 167 for β-HCH, and 379 for HCB. The concentrations of all OCPs were positively associated with age and body mass index, and decreased along the period of blood collection. No association was found between OCPs levels and dietary factors. The concentrations of p,p′-DDE and β-HCB were higher in Murcia, one of southern regions, most likely associated with intensive past use of pesticides related to agricultural practices, while higher levels of HCB were found in Navarra, located in the north, maybe due to industrial use rather than agricultural application.