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At least 235 records · Page 13Linked to original sources
PubMed2000

Biodegradation of atrazine in sand sediments and in a sand-filter.

The potential of a microbial consortium for treating waters contaminated with atrazine was considered. In conventional liquid culture, atrazine and its two dealkylated by-products were equally metabolised by the microbial consortium. Transient production of hydroxyatrazine was observed during atrazine catabolism, indicating that the catabolic pathway was similar to the one reported for isolates capable of atrazine mineralisation. This consortium was then inoculated to sediments sampled from an artificial recharge site. These sediments were contaminated by atrazine and diuron and exhibited only a slow endogenous herbicide dissipation. Inoculated microorganisms led to extensive atrazine degradation and survived for more than 10 weeks in the sediments. A rudimentary bioreactor was then setup using a soil core originating from the same recharge site. Degrading microorganisms rapidly colonised the core and expressed their degrading activity. The efficiency of the bioreactor was improved in the presence of spiked environmental surface waters. Atrazine degraders thus possibly benefited from the other organic sources in developing and expressing their activity. The microbial consortium did not initially exhibit the capacity to degrade diuron, which was used as reference compound. No change in this characteristic was detected throughout the study.

Atrazine↗
PubMed1986

Mapping of the triazine binding site to a highly conserved region of the QB-protein.

A number of herbicide classes, including the s-triazines and ureas (atrazine, diuron) inhibit photosynthetic electron transport via a direct interaction with the QB-protein. This protein, also known as the 32-kDa protein or herbicide binding protein, is believed to bind the plastoquinone QB, which functions as the second stable electron acceptor at the reducing side of Photosystem II. The site of covalent attachment of the photoaffinity herbicide analog azido-[14C]atrazine to the QB-protein of spinach chloroplast thylakoid membranes has been determined. Two amino acid residues are labeled; one residue is methionine-214, the other lies between histidine-215 and arginine-225. Both residues are within a region of the amino acid sequence which is highly conserved between the QB-protein and the L and M reaction center proteins of Rhodopseudomonas capsulata and R. sphaeroides. This region includes the site of a mutation which results in diuron resistance in Chlamydomonas reinhardi (valine-219). However, this region is well removed from point mutations at phenylalanine-255 (which gives rise to atrazine resistance in C. reinhardi) and at serine-264, (which results in extreme atrazine resistance in C. reinhardi and naturally occurring weed biotypes). The patterns of labeling and mutation imply that the quinone and herbicide binding site is formed by at least two protein domains.

Affinity Labels↗
PubMed1995

Trace determination of herbicides in estuarine waters by liquid chromatography-high-flow pneumatically assisted electrospray mass spectrometry.

High-flow pneumatically assisted electrospray (ESP) was applied to the characterization of triazine (atrazine, simazine, ametryne, cyanazine, deethylatrazine and deisopropylatrazine), phenylurea (chlortoluron++, isoproturon, diuron, linuron and diflubenzuron) and other priority herbicides (alachlor, metolachlor). In LC-ESP-MS the [M+Na]+ ion was used as the base peak in most cases, with the exception of chlorotriazines, which showed [M+H]+ as the base peak. When LC-TSP-MS was used, [M+H]+ was the base peak for many of the pesticides, with the exception of linuron and diflubenzuron, which showed [M+NH4]+ as the base peak. The ESP results were compared with those obtained with thermospray (TSP). LC-TSP-MS offered greater sensitivity for triazines than phenylurea herbicides, whereas the use of LC-ESP-MS offered an enhancement in sensitivity for phenylurea herbicides. As regards the fragmentation obtained using both techniques, ESP offered a considerable amount of structural information for the different chlorotriazines studied when the extraction voltage was increased from 20 to 40 V. Liquid-liquid extraction with dichloromethane was used for the trace enrichment of the different herbicides in estaurine water samples from the Elorn river (France). The presence of the different triazine metabolites, atrazine, simazine, metolachlor, isoproturon and diuron was confirmed by both LC-MS techniques.

Chromatography, High Pressure Liquid↗
PubMed2005

Phytotoxicity of surface waters of the Thames and Brisbane River estuaries: a combined chemical analysis and bioassay approach for the comparison of two systems.

The Thames Estuary, UK, and the Brisbane River, Australia, are comparable in size and catchment area. Both are representative of the large and growing number of the world's estuaries associated with major cities. Principle differences between the two systems relate to climate and human population pressures. In order to assess the potential phytotoxic impact of herbicide residues in the estuaries, surface waters were analysed with a PAM fluorometry-based bioassay that employs the photosynthetic efficiency (photosystem II quantum yield) of laboratory cultured microalgae, as an endpoint measure of phytotoxicity. In addition, surface waters were chemically analysed for a limited number of herbicides. Diuron, atrazine and simazine were detected in both systems at comparable concentrations. In contrast, bioassay results revealed that whilst detected herbicides accounted for the observed phytotoxicity of Brisbane River extracts with great accuracy, they consistently explained only around 50% of the phytotoxicity induced by Thames Estuary extracts. Unaccounted for phytotoxicity in Thames surface waters is indicative of unidentified phytotoxins. The greatest phytotoxic response was measured at Charing Cross, Thames Estuary, and corresponded to a diuron equivalent concentration of 180 ng L(-1). The study employs relative potencies (REP) of PSII impacting herbicides and demonstrates that chemical analysis alone is prone to omission of valuable information. Results of the study provide support for the incorporation of bioassays into routine monitoring programs where bioassay data may be used to predict and verify chemical contamination data, alert to unidentified compounds and provide the user with information regarding cumulative toxicity of complex mixtures.

Australia↗
PubMed2004

Pesticide uses and transfers in urbanised catchments.

An investigation on herbicide uses in two semi-urban catchments was performed simultaneously with sampling campaigns at six stations inside both watersheds from April to July 1998. Urban uses of herbicides exceeded agricultural uses, and transfer coefficients were also higher in urban areas. Therefore, the most used product in urban areas (diuron) was by far the most contaminating product. Householders accounted for 30% of all uses. The highest measured diuron concentration in water surface was 8.7 microg l(-1) due to its use on impervious surfaces. Compared to EEC standards for drinking water production (0.1 microg l(-1)), it is clear that suburban uses of herbicides may severely endanger drinking water production from river water.

Cities↗
PubMed2006

Determination of commonly used polar herbicides in agricultural drainage waters in Australia by HPLC.

The present study describes the application of different extraction techniques for the preconcentration of ten commonly found acidic and non-acidic polar herbicides (2,4-D, atrazine, bensulfuron-methyl, clomazone, dicamba, diuron, MCPA, metolachlor, simazine and triclopyr) in the aqueous environment. Liquid-liquid extraction (LLE) with dichloromethane, solid-phase extraction (SPE) using Oasis HLB cartridges or SBD-XC Empore disks were compared for extraction efficiency of these herbicides in different matrices, especially water samples from contaminated agricultural drainage water containing high concentrations of particulate matter. Herbicides were separated and quantified by high performance liquid chromatography (HPLC) with an ultraviolet detector. SPE using SDB-XC Empore disks was applied to determine target herbicides in the Murrumbidgee Irrigation Area (NSW, Australia) during a two-week survey from October 2005 to November 2005. The daily aqueous concentrations of herbicides from 24-h composite samples detected at two sites increased after run-off from a storm event and were in the range of: 0.1-17.8 microg l(-1), < 0.1-0.9 microg l(-1) and 0.2-17.8 microg l(-1) at site 1; < 0.1-3.5 microg l(-1), < 0.1-0.2 microg l(-1) and < 0.2-3.2 microg l(-1) at site 2 for simazine, atrazine and diuron, respectively.

Chromatography, High Pressure Liquid↗
PubMed2004

Monitoring of estrogens, pesticides and bisphenol A in natural waters and drinking water treatment plants by solid-phase extraction-liquid chromatography-mass spectrometry.

A multi-residue analytical method has been developed for the determination of various classes of selected endocrine disruptors. This method allows the simultaneous extraction and quantification of different estrogens (estradiol, estrone, estriol, estradiol-17-glucuronide, estradiol diacetate, estrone-3-sulfate, ethynyl estradiol and diethylstilbestrol), pesticides (atrazine, simazine, desethylatrazine, isoproturon and diuron), and bisphenol A in natural waters. In the method developed, 500 ml of water are preconcentrated on LiChrolut RP-18 cartridges. Further analysis is carried out by liquid chromatography-mass spectrometry (LC-MS) using atmospheric pressure chemical ionisation (APCI) in the positive ion mode for determination of pesticides and electrospray in the negative ionisation mode for determination of estrogens and bisphenol A. Recoveries for most compounds were between 90 and 119%, except for bisphenol A (81%) and diethylstilbestrol (70%), with relative standard deviations below 20%. Limits of detection ranged between 2 and 15 ng/l. The method was used to study the occurrence of the selected pollutants in surface and groundwater used for abstraction of drinking water in a waterworks and to evaluate the removal efficiency of the different water treatments applied. Water samples from the river, the aquifer, and after each treatment stage (sand filtration, ozonation, activated carbon filtration and post-chlorination) were taken monthly from February to August of 2002. The presence in river water of atrazine, simazine, diuron and bisphenol A were relatively frequent at concentrations usually below 0.1 microg/l. Lower levels, below 0.02 microg/l, were usual for isoproturon. Estrone-3-sulfate and estrone were detected occasionally in the river. Most of the compounds were completely removed during the water treatment, especially after activated carbon filtration.

Benzhydryl Compounds↗
PubMed2005

Influence of pH on pesticide sorption by soil containing wheat residue-derived char.

Field burning of crop residues incorporates resulting chars into soil and may thus influence the environmental fate of pesticides in the soil. This study evaluated the influence of pH on the sorption of diuron, bromoxynil, and ametryne by a soil in the presence and absence of a wheat residue-derived char. The sorption was measured at pHs approximately 3.0 and approximately 7.0. Wheat char was found to be a highly effective sorbent for the pesticides, and its presence (1% by weight) in soil contributed >70% to the pesticide sorption (with one exception). The sorption of diuron was not influenced by pH, due to its electroneutrality. Bromoxynil becomes dissociated at high pHs to form anionic species. Its sorption by soil and wheat char was lower at pH approximately 7.0 than at pH approximately 3.0, probably due to reduced partition of the anionic species of bromoxynil into soil organic matter and its weak interaction with the carbon surface of the char. Ametryne in its molecular form at pH approximately 7.0 was sorbed by char-amended soil via partitioning into soil organic matter and interaction with the carbon surface of the char. Protonated ametryne at pH approximately 3.0 was substantially sorbed by soil primarily via electrostatic forces. Sorption of protonated ametryne by wheat char was also significant, likely due not only to the interaction with the carbon surface but also to interactions with hydrated silica and surface functional groups of the char. Sorption of ametryne by char-amended soil at pH approximately 3.0 was thus influenced by both the soil and the char. Environmental conditions may thus significantly influence the sorption and behavior of pesticides in agricultural soils containing crop residue-derived chars.

Absorption↗
PubMed2006

Photochemical oxidation processes for the elimination of phenyl-urea herbicides in waters.

Four phenyl-urea herbicides (linuron, chlorotoluron, diuron, and isoproturon) were individually photooxidized by monochromatic UV radiation in ultra-pure aqueous solutions. The influence of pH and temperature on the photodegradation process was established, and the first-order rate constants and quantum yields were evaluated. The sequence of photodecomposition rates was: linuron>chlorotoluron>diuron>isoproturon. The simultaneous photooxidation of mixtures of the selected herbicides in several types of waters was then performed by means of UV radiation alone, and by UV radiation combined with hydrogen peroxide. The types of waters used were: ultra-pure water, a commercial mineral water, a groundwater, and a lake water. The influence of the independent variables in these processes - the presence or absence of tert-butyl alcohol, types of herbicide and waters, and concentration of hydrogen peroxide - were established and discussed. A kinetic study was performed using a competitive kinetic model that allowed various rate constants to be evaluated for each herbicide. This kinetic model allows one to predict the elimination of these phenyl-urea herbicides in contaminated waters by the oxidation systems used (UV alone and combined UV/H2O2). The herbicide concentrations predicted by this model agree well with the experimental results that were obtained.

Herbicides↗
PubMed2004

Herbicides implicated as the cause of severe mangrove dieback in the Mackay region, NE Australia: consequences for marine plant habitats of the GBR World Heritage Area.

Herbicides, particularly diuron, were correlated with severe and widespread dieback of the dominant mangrove, Avicennia marina (Forsk.) Vierh. var. eucalyptifolia (Val.) N.C. Duke (Avicenniaceae), its reduced canopy condition, and declines in seedling health within three neighbouring estuaries in the Mackay region of NE Australia. This unusual species-specific dieback, first observed in the early 1990s, had gotten notably worse by 2002 to affect >30 km(2) of mangroves in at least five adjacent estuaries in the region. Over the past century, agricultural production has responded well to the demands of increasing population with improvements in farm efficiency assisted by significant increases in the use of agricultural chemicals. However, with regular and episodic river flow events, these chemicals have sometimes found their way into estuarine and nearshore water and sediments where their effects on marine habitats have been largely unquantified. Investigations over the last three years in the Mackay region provide compelling evidence of diuron, and possibly other agricultural herbicides, as the most likely cause of the severe and widespread mangrove dieback. The likely consequences of such dieback included declines in coastal water quality with increased turbidity, nutrients and sediment deposition, as well as further dispersal of the toxic chemicals. The implications of such findings are immense since they describe not only the serious deterioration of protected and beneficial mangrove habitat but also the potential for significant direct and indirect effects on other highly-valued estuarine and marine habitats in the region, including seagrass beds and coral reefs of the Great Barrier Reef lagoon. This article reviews all key findings and observations to date and describes the essential correlative and causative evidence.

Animals↗
PubMed2004

Effects of Photosystem II inhibiting herbicides on mangroves--preliminary toxicology trials.

Mangroves are sensitive to the root application of Photosystem II inhibiting herbicides and Avicennia marina is more sensitive than other mangroves tested. Seedlings of four mangrove species, including two salt-excreting species (A. marina and Aegiceras corniculatum) and two salt-excluding species (Rhizophora stylosa and Ceriops australis) were treated with a range of concentrations of the herbicides diuron, ametryn and atrazine. Assessment of responses required the separation of seedlings into two groups: those that had only their roots exposed to the herbicides through the water (A. marina and R. stylosa) and those that had both roots and leaves exposed to herbicides through the water (A. corniculatum and C. australis). Salt-excreting species in each group were more susceptible to all herbicide treatments than salt-excluding species, indicating that root physiology was a major factor in the uptake of toxic pollutants in mangroves. Submergence of leaves appeared to facilitate herbicide uptake, having serious implications for seedling recruitment in the field. Each herbicide was ranked by its toxicity to mangrove seedlings from most damaging to least effective, with diuron>ametryn>atrazine. The relative sensitivity of A. marina found in these pot trials was consistent with the observed sensitivity of this species in the field, notably where severe dieback had specifically affected A. marina in the Mackay region, north eastern Australia.

Adaptation, Physiological↗
PubMed2006

Application of a GIS-AF/RF model to assess the risk of herbicide leaching in a citrus-growing area of the Valencia Community, Spain.

We integrated an index-based attenuation factor/retardation factor (AF/RF) model into a GIS to evaluate the risk of leaching of the most frequently applied herbicides (glyphosate, diuron, diquat, bromacil, simazine, linuron, terbuthylazine, and terbumeton) used in citrus orchards of the Valencia Community, Spain. The GIS-model system was applied to a region of 33,800 ha located near Valencia City. The soil and climate data required by the model were stored in an Arc/Info GIS in which the model algorithms were integrated using the AML programming language. A graphical user interface was developed to facilitate the use of the GIS-model system. The resulting simulation maps indicate that terbumeton, bromacil, and simazine herbicides have the highest risk of leaching because of their high mobility and low K(oc) (32-158 mg l(-1)). The remaining herbicides are strongly adsorbed by clay particles and organic matter, thus minimising the risk of leaching through the soil profile and into groundwater. The obtained ranking of the leaching potential of analysed herbicides is as follows, from highest to lowest risk: terbumeton>bromacil>simazine>terbuthylazine>diuron>linuron>glyphosate>diquat.

Agriculture↗
PubMed2006

Effects of various pesticides on human 5alpha-reductase activity in prostate and LNCaP cells.

Certain pesticides are able to disturb the sex steroid hormone system and to act as antiandrogens. While the different underlying mechanisms remain unclear, inhibition of 5alpha-reductase, the enzyme which is indispensable for the synthesis of DHT and thus normal masculinization, appears to be one of the sensitive targets for endocrine disruption. We therefore tested several endocrine disrupters with antiandrogenic effects in vivo for their influence on 5alpha-reductase activity in two different test systems: (a) an enzyme assay with human Lymph Node Carcinoma of Prostate (LNCaP) cells and (b) an enzyme assay with human prostate tissue homogenate. The selected pesticides and industrial compounds were monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT), triphenyltin (TPT), diuron, fenarimol, linuron, p,p'DDE, prochloraz and vinclozolin. The synthetic androgen methyltestosterone and the synthetic antiandrogen flutamide, as well as the 5alpha-reductase inhibitor finasteride served as control compounds. The effect of the organotin compounds DBT, TBT and TPT on enzyme activity was approximately the same in both test systems, with IC(50) values ranging between 2.7 and 11.2 microM, while in prostate tissue, methyltestosterone and prochloraz proved to be stronger inhibitors (IC(50) values of 1.9 and 12.4 microM) than in LNCaP cells (IC(50) values of 13.2 and 53.2 microM). The inhibitory impact of finasteride was approximately 130 times stronger in prostate tissue than in LNCaP cells. Fenarimol, flutamide, linuron and p,p'DDE inhibited 5alpha-reductase activity only at very high concentrations (IC(50)> or =24 microM) in prostate homogenates, and not at all in LNCaP cells. On average, the IC(20) values were 3.5 times lower than the IC(50) values. Diuron, MBT and vinclozolin exerted no effect in either of the test systems. The finding of pesticides acting as 5alpha-reductase inhibitors might be of clinical relevance. As a screening tool for putative ED, the tissue assay is the more practical and sensitive method. However, the cell assay can, to some extent, reflect particular cell processes since the living cell is able to compensate moderate toxicological effects of the ED on cell viability, and possibly also their impact on 5alpha-reductase activity.

3-Oxo-5-alpha-Steroid 4-Dehydrogenase↗
PubMed2000

Monitoring of priority pesticides and other organic pollutants in river water from portugal by gas chromatography-mass spectrometry and liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

Gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS) were optimized and applied for the trace-level determination of 42 priority pesticides and 33 priority organic pollutants from European Union Directive EC 76/464. First, off-line solid-phase extraction of 200 ml of river water using an OASIS solid-phase extraction cartridge, followed by GC-MS was used. Next, selected samples that were positive to GC-MS were analyzed by LC-APCI-MS in order to detect further polar byproducts or to improve the determination of previously detected polar analytes. The transformation products of triazine pesticides like deethylatrazine (DEA) and deisopropylatrazine (DIA) and compounds such as diuron and several chlorophenols were positively identified by LC-APCI-MS. The present methodology has also been used for searching for new analytes not included in the EC 76/464 list, like Irgarol, DEA and DIA. In addition it was applied to target pollutants in 43 river water samples from Portugal during a pilot survey from April to July 1999. Atrazine followed by simazine and 2,4,6-trichlorophenol were the most ubiquitous compounds detected in this area. The levels detected of the different compounds were in the range of: 0.01-2.73 microg/l, 0.05-0.74 microg/l, 0.02-1.65 microg/l, 0.02-5.43 microg/l, 0.01-0.40 microg/l, 0.01-0.26 microg/l, 0.02-0.61 microg/l, 0.01-3.90 microg/l, 0.01-1.24 microg/l, 0.02-2.3 microg/l, 0.01-0.13 microg/l and 0.01-0.5 microg/l for atrazine, simazine, terbuthylazine, alachlor, metolachlor, Irgarol, propanil; tributhylphosphate, diuron, 2,4,6-trichlorophenol, deisopropylatrazine and deethylatrazine, respectively.

Atmospheric Pressure↗
PubMed2002

High-performance liquid chromatographic determination of phenylureas by photochemically-induced fluorescence detection.

A HPLC method, using photochemically-induced fluorescence detection, is described for the separation and determination of four phenylurea herbicides including diuron, isoproturon, linuron and neburon. A post-column photoreactor, consisting of a reactor knitted around a 4 W xenon lamp, has been included between the column and the detector, in order to transform the non-fluorescent herbicides into fluorophors. The influence of mobile phase composition, flow-rate, pH, and buffer concentration has been studied. An acetonitrile-buffer solution of potassium phosphate dibasic of pH 7 and 0.01 M concentration (60:40, v/v), was selected as optimum. For the fluorimetric detection, optimal excitation/emission wavelengths 324/403, 301/433, 335/411 and 326/385 nm were selected for the determination of diuron, isoproturon, linuron and neburon, respectively. The detection limits ranged between 0.07 and 0.46 microg/ml, according to the compound.

Buffers↗
PubMed1999

Simultaneous determination of antifouling herbicides in marina water samples by on-line solid-phase extraction followed by liquid chromatography-mass spectrometry.

Solid-phase extraction (SPE) coupled on-line with either liquid chromatography-diode array detection (LC-DAD) or liquid chromatography-atmospheric pressure chemical ionization mass spectrometry was applied to the simultaneous analysis of several antifouling herbicides such as diuron, TCMTB (2-thiocyanomethylthiobenzothiazole), Irgarol and chlorothalonil in seawater samples. SPE was carried out on polymeric cartridges (PLRP-s) after the percolation of 100 ml of seawater sample, with recoveries ranging from 96 to 111% for the antifouling compounds. LC-MS detection was used in negative and positive ion mode. In positive ion mode, additional structural information for diuron and Irgarol was obtained by increasing the fragmentor voltage, thus permitting the unequivocal identification of these compounds in environmental waters. Method detection limits were in the range of 0.005 microg/l. This methodology was also compared to LC-DAD in terms of selectivity and sensitivity. Finally, the method was evaluated for the analysis of environmental seawater samples, from the Ebre Delta area and Masnou marina, in Catalonia (Spain).

Chromatography, Liquid↗
PubMed2000

Effects of selected herbicides on cytokine production in vitro.

To evaluate possible deleterious effects of commonly used herbicides on leukocytes, cytokine production was selected as a sensitive indicator. After in vitro exposure of human peripheral blood mononuclear cells from normal donors, the production of all 3 cytokines tested--interferon-gamma (a type 1 cytokine), interleukin-5 (a type 2 cytokine) and tumor necrosis factor-alpha (an inflammatory cytokine)--was impaired by up to 70, 50 and 70% respectively in a concentration-dependent manner in cultures exposed to atrazine (0.03-3 microM in 1% dimethylsulfoxide, DMSO). The effect paralleled that seen with dexamethasone, a known immunosuppressive agent. Other pesticides also dissolved in DMSO--mecoprop, simazine or MCPA (each up to 1 microM)--or dissolved in phosphate-buffered saline--diuron (up to 1 microM), isoproturon (up to 3 microM), metoxuron (up to 8 microM) or metamitron (up to 80 microM)--showed no concentration-related effects on cytokine production. There was, however, an inhibition of IFN-gamma and TNF-alpha production by simazine, metoxuron and mecoprop and of all three cytokines tested by diuron. MCPA (0.01 and 0.1 microM) stimulated the production of TNF-alpha. Thus, exposure to herbicides leading to plasma levels in the micromolar range induces imbalance in cytokine production.

Culture Media, Serum-Free↗
PubMed2002

Effects of new antifouling compounds on the development of sea urchin.

Tributyltin oxide (TBTO) has been used worldwide in marine antifouling paints as a biocide for some time. However, it produced toxic effects, especially in marine water/sediment ecosystems. Consequently, its use in antifouling paints has been prohibited in many countries. In this study, the toxicity of alternative and/or new antifouling biocides compared with TBTO is assessed by a biological method. The effects of these chemicals on marine species have not been well studied. This paper assesses, comparatively, the effects of eight biocides on sea urchin eggs and embryos. The chemicals assessed were TBTO, Irgarol 1051, M1 (the persistent degradation product of Irgarol), Diuron, zinc pyrithione, 'KH101', 'Sea-Nine 211', and copper pyrithione. For these chemicals, toxicity appears to be in the order zinc pyrithione > Sea-Nine 211 > KH101 > copper pyrithione > TBTO > Diuron approximately = Irgarol 1051 > M1. Here, we show that zinc pyrithione, Sea-Nine 211, KH101, and copper pyrithione are much more toxic to sea urchins than TBTO or the other chemicals.

Animals↗