Shifts in herbicide tolerance in paddy field periphyton following herbicide application

Herbicide susceptibility was examined in various algal strains isolated from herbicide-treated and untreated paddy fields. Diatom strains showed obvious tolerance to the herbicides simetryn and pretilachlor irrespective of herbicide exposure, while the susceptibility of green algae mostly reflected their history of herbicide exposure. Cross-resistance was also induced in some algae. Rapid development of herbicide tolerance indicated that the tolerance seemed to be conferred by tolerant strains already present in the communities. Thus, changes in genetic composition within a population seem to be the main mechanism by which paddy periphyton gain herbicide tolerance.     

Adsorption of sugar beet herbicides to Finnish soils

Three sugar beet herbicides, ethofumesate, phenmedipham and metamitron, are currently used on conventional sugar beet cultivation, while new varieties of herbicide resistant (HR) sugar beet, tolerant of glyphosate or glufosinate-ammonium, are under field testing in Finland. Little knowledge has so far been available on the adsorption of these herbicides to Finnish soils. The adsorption of these five herbicides was studied using the batch equilibrium method in 21 soil samples collected from different depths. Soil properties like organic carbon content, texture, pH and partly the phosphorus and oxide content of the soils were tested against the adsorption coefficients of the herbicides. In general, the herbicides studied could be arranged according to their adsorption coefficients as follows: glyphosate>phenmedipham>ethofumesate approximately glufosinate-ammonium>metamitron, metamitron meaning the highest risk of leaching. None of the measured soil parameters could alone explain the adsorption mechanism of these five herbicides. The results can be used in model assessments of risk for leaching to ground water resulting from weed control of sugar beet in Finland.     

Effects of simetryne on growth of various freshwater algal taxa

The sensitivity of 56 algal strains, representing 7 taxonomic groups to the triazine herbicide, simetryne, was examined using EC50 values for growth. There was a wide range of values from 6.5 to 1500 microg litre(-1). The Volvocales (Chlorophyceae, Chlorophyta) and Cyanophyceae (Cyanophyta) as a whole were the most sensitive, whereas the Desmidiales (Charophyceae, Chlorophyta) and Bacillariophyceae (Chromophyta) were the most tolerant, although sensitivity differed among strains of a single species. Sensitive and tolerant species were both isolated from samples collected at the same site. The results suggest that changes in species composition and relative abundance will occur when herbicides are applied in natural habitats.     

Population dynamics of Digitaria spp submitted to selection pressure by herbicides in sugarcane crop

The objective of this research was to study population dynamics of the weed crabgrass, genus Digitaria, submitted to selection pressure by herbicides currently applied in sugarcane crops in Brazil. In the first experiment two crabgrass species (Digitaria nuda and Digitaria ciliaris) and eight herbicide treatments applied in preemergence were used, and control percentage was evaluated at 7, 14, and 21 days after herbicide application (DAA). In the second experiment the level of tolerance through dose-response curve was determined for the species D. nuda and D. ciliaris, to the herbicides imazapyr, tebuthiuron, ametryne, and metribuzin. All the herbicides studied were efficient in controlling D. ciliaris, however, for D. nuda the best results were obtained only with ametryne, metribuzin, and isoxaflutole. The relation (T/S) between the rate required to reduce plant dry biomass (GR50) at 21 DAA of D. nuda and D. ciliaris was 16 for imazapyr and 6.3 for tebuthiuron, showing differential susceptibility of species; however for ametryne the rate T/S of 1.1 showed that D. nuda was not tolerant to this herbicide. For metribuzin, at 1.92 kg a.i. ha(-1), reduction of dry biomass was 80 and 90% to D. nuda and D. ciliaris, respectively. Even being controlled by metribuzin, D. nuda presented a higher level of tolerance to this herbicide, what was confirmed by the relationship T/S 14.4. As general conclusion of the research, it can be stated that the species D. nuda is more tolerant to ALS inhibiting herbicides and substituted urea, when compared with D. ciliaris; probably, D. nuda was selected by repetitive use of these herbicides.     

Toxicity of chlorinated phenoxyacetic acid herbicides in the experimental eukaryotic model Saccharomyces cerevisiae: role of pH and of growth phase and size of the yeast cell population

The inhibitory effect of the herbicides 2-methyl-4-chlorophenoxyacetic acid (MCPA) and 2,4-dichlorophenoxyacetic acid (2,4-D) in Saccharomyces cerevisiae growth is strongly dependent on medium pH (range 2.5-6.5). Consistent with the concept that the toxic form is the liposoluble undissociated form, at values close to their pK(a) (3.07 and 2.73, respectively) the toxicity is high, decreasing with the increase of external pH. In addition, the toxicity of identical concentrations of the undissociated acid form is pH independent, as observed with 2,4-dichlorophenol (2,4-DCP), an intermediate of 2,4-D degradation. Consequently, at pH values above 3.5 (approximately one unit higher than 2,4-D pK(a)), 2,4-DCP becomes more toxic than the original herbicide. A dose-dependent inhibition of growth kinetics and increased duration of growth latency is observed following sudden exposure of an unadapted yeast cell population to the presence of the herbicides. This contrasts with the effect of 2,4-DCP, which essentially affects growth kinetics. Experimental evidences suggest that the acid herbicides toxicity is not exclusively dependent on the liposolubility of the toxic form, as may essentially be the case of 2,4-DCP. An unadapted yeast cell population at the early stationary-phase of growth under nutrient limitation is significantly more resistant to short-term herbicide induced death than an exponential-phase population. Consequently, the duration of growth latency is reduced, as observed with the increase of the size of the herbicide stressed population. However, these physiological parameters have no significant effect either on growth kinetics, following growth resumption under herbicide stress, or on the growth curve of yeast cells previously adapted to the herbicides, indicating that their role is exerted at the level of cell adaptation.     

Atrazine and metolachlor residues in brookston Cl following conventional and conservation tillage culture

Atrazine and metolachlor are extensively used in Ontario, Canada for control of broadleaf weeds and annual grasses in corn. Conservation tillage may alter the physical and biological environment of soil affecting herbicide dissipation. The rate of dissipation of these two herbicides in soil from conventional, ridge and no-tillage culture was followed. Herbicide dissipation was best described by first order reaction kinetics. Half life, the time for herbicide residues to dissipate to half their initial concentration, was unaffected by tillage. Half life for atrazine and metolachlor was similar and ranged from 31 to 66 d. The rate of dissipation decreased in dry years when soil moisture content was low. In a dry year, herbicide residues during the growing season were significantly greater on ridge tops than in the other tillage treatments. However, after harvest no differences in herbicide residues were detected among tillage treatments. Residues of atrazine (6 to 9% of applied) and metolachlor (4 to 6%) were detected in soil before planting a year after application. De-ethyl atrazine, the primary degradation product of atrazine, increased in concentration during the growing season with the greatest concentrations measured at harvest and in years when atrazine dissipated fastest. De-ethyl atrazine one year after application accounted for about 12% of the remaining triazine residue. These herbicide residues would not be phytotoxic to subsequent crops but are a potential source for leaching to ground and surface waters.     

Dissipation and runoff transport of metazachlor herbicide in rapeseed cultivated and uncultivated plots in field conditions

The environmental fate of metazachlor herbicide was investigated under field conditions in rapeseed cultivated and uncultivated plots, over a period of 225 days. The cultivation was carried out in silty clay soil plots with two surface slopes, 1 and 5 %. The herbicide was detectable in soil up to 170 days after application (DAA), while the dissipation rate was best described by first-order kinetics and its half-life ranged between 10.92 and 12.68 days. The herbicide was detected in the soil layer of 10–20 cm from 5 to 48 DAA, and its vertical movement can be described by the continuous stirred tank reactor (CSTR) in series model. Relatively low amounts of metazachlor (less than 0.31 % of the initial applied active ingredient) were transferred by runoff water. More than 80 % of the total losses were transferred at the first runoff event (12 DAA), with herbicide concentrations in runoff water ranging between 70.14 and 79.67 μg L⁻¹. Minor amounts of the herbicide (less than 0.07 % of the initial applied active ingredient) were transferred by the sediment, with a maximum concentration of 0.57 μg g⁻¹ (12 DAA), in plots with 5 % inclination. Finally, in rapeseed plants, metazachlor was detected only in the first sampling (28 DAA) at concentrations slightly higher than the limit of quantification; when in seeds, no residues of the herbicide were detected.

     

Pollution-induced community tolerance (PICT) and seasonal variations in the sensitivity of phytoplankton to atrazine in nanocosms.

Algae communities exposed to a herbicide like atrazine (PS II inhibitor) are expected to be selected and to be more tolerant to the herbicide than unexposed communities (pollution-induced community tolerance, PICT). The PICT may be an ecotoxicological tool for detecting this selective action of chronic pollution, and this method has been applied to several toxicants in experimental systems and in field studies. But the detection of PICT with PS II inhibitors has sometimes been variable. This work was done to study the long-term effects of exposure to atrazine (10 microg/l) and the PICT responses of phytoplankton communities in repeated outdoor nanocosms. Phytoplankton communities were sampled in Lake Geneva at different periods of the year and the effects of atrazine were analysed by studying community structure, biomass and primary production, and by measuring tolerance to atrazine in a short-term physiological test based on 14C incorporation. We find that PICT is a sensitive method for measuring effects. Even atrazine concentrations causing little restructuring induced tolerance in most of our experiments. But the short- and long-term responses of phytoplankton to atrazine varied between experiments, probably due to the initial compositions of the communities and environmental factors associated with seasonal parameters. The selection and detection steps of PICT to atrazine thus vary greatly with environmental conditions and the physiological adaptations of algae to the herbicide. To monitor risk assessment in aquatic systems, PICT studies applied to algae, must be investigated in the light of seasonal contaminations and seasonal events and successions.     

除草剂阿特拉津(Atrazine)的环境行为综述

阿特拉津（２－氯－４－乙胺基－６－异丙氨基－１，３，５，－三氮苯）是目前应用广泛的化学除草剂之一。在世界许多国家和地区的地表水和地下水中已检出了阿特拉津的残留物。阿特拉津对人类的威胁究竟有多大，已成为目前研究的热点。本文从阿特拉津的检测方法、动力学性质、生化性质及风险评估四个方面进行了综述，并提出了自己的观点。     

An unconventional approach to studying the reaction kinetics of the Fenton's oxidation of 2,4-dichlorophenoxyacetic acid

The Fenton's oxidation kinetics of herbicide 2,4-D at various [Fe(II)] and [H(2)O(2)] combinations was investigated and modelled through an unconventional approach. The reaction kinetics of 2,4-D degradation demonstrated a two-stage pattern of decay, where a very fast reactive stage was followed by a retardation stage due to the depletion of oxidants and to the competitive side-reactions of the intermediates (including 2,4-dichlorophenol, chlorohydroquinone and 2,6-dichlororesorcinol). A model characterized by two newly established constants, the initial decay rate and the maximum oxidative capacity, was proposed and proven capable of describing the two-stage process, which cannot easily be described by conventional first- or second-order kinetics approaches.     

Effects of metsulfuron-methyl on the microbial population and enzyme activities in wheat rhizosphere soil

The effects of metsulfuron-methyl, a sulfonylurea herbicide, on the wheat soil microorganisms were evaluated by the methods of microbial inoculation culture, and the activities of three enzymes were measured using the colorimetric method. The tolerant microorganisms that can resist 500 microg x g(-1) metsulfuron-methyl in the counting culture medium were studied specially. Metsulfuron-methyl distinctly inhibited the common aerobic heterotriphic bacteria, but the effects on common fungi and common actinomycete were not evident. In the meantime, the number of tolerant fungi increased greatly in the rhizosphere after the application of metsulfuron-methyl in contrast to the significant decrease of the amount of tolerant actinomycete. It indicates that fungi might turn into the dominant microbial type and actinomycete is the sensitive factor in the soil polluted by sulfonylurea residues. The population of aromatic compounds-decomposing bacteria, aerobic azotobacter, and nitrite bacteria all increased in the earlier period, but the aerobic azotobacter decreased rapidly in number 30 days later, and the amount of nitrite bacteria also showed a temporary decrease with time 15 days later. However, the denitrifying bacteria just began to increase significantly after the crops had grown for 50 days. The amount of sulfur-oxidizing bacteria gradually decreased with the growth of crops, and so were the sulfate-reducing bacteria after metsulfuron-methyl application. To all types of microorganisms, there were more microbes in rhizosphere samples than those in nonrhizosphere except aerobic azotobacter. It means the growth of wheat root system can stimulate the growth of most microorganisms. The activities of hydrogen peroxidase and polyphenol oxidase in soil samples after metsulfuron-methyl application were notably lower than those in the control, and the difference of the activities between the samples of rhizosphere and nonrhizosphere was evident. On the contrary, the activity of dehydrogenase was not inhibited by the application of metsulfuron-methyl, and the rhizosphere effect was not obvious either.     

Kinetics of nitrosation of the herbicide glyphosate.

The herbicide glyphosate was nitrosated by third-order kinetics to N-nitrosoglyphosate. The nitrosation at 25 degrees C was maximum at the reaction pH of 2.5 and had a pH-dependent rate constant of 2.43 M-2 sec-1. An activation energy of 9.5 kcal mole-1 also suggested that glyphosate is nitrosated very readily. Thiocyanate increased the rate 4.6 fold. The possibility of using these results to predict the formation of N-nitrosoglyphosate under normal agricultural practice is discussed.     

Effects of Metsulfuron-Methyl on the Microbial Population and Enzyme Activities in Wheat Rhizosphere Soil

The effects of metsulfuron-methyl, a sulfonylurea herbicide, on the wheat soil microorganisms were evaluated by the methods of microbial inoculation culture, and the activities of three enzymes were measured using the colorimetric method. The tolerant microorganisms that can resist 500 μ g·g^?1 metsulfuron-methyl in the counting culture medium were studied specially. Metsulfuron-methyl distinctly inhibited the common aerobic heterotriphic bacteria, but the effects on common fungi and common actinomycete were not evident. In the meantime, the number of tolerant fungi increased greatly in the rhizosphere after the application of metsulfuron-methyl in contrast to the significant decrease of the amount of tolerant actinomycete. It indicates that fungi might turn into the dominant microbial type and actinomycete is the sensitive factor in the soil polluted by sulfonylurea residues. The population of aromatic compounds–decomposing bacteria, aerobic azotobacter, and nitrite bacteria all increased in the earlier period, but the aerobic azotobacter decreased rapidly in number 30 days later, and the amount of nitrite bacteria also showed a temporary decrease with time 15 days later. However, the denitrifying bacteria just began to increase significantly after the crops had grown for 50 days. The amount of sulfur-oxidizing bacteria gradually decreased with the growth of crops, and so were the sulfate-reducing bacteria after metsulfuron-methyl application. To all types of microorganisms, there were more microbes in rhizosphere samples than those in nonrhizosphere except aerobic azotobacter. It means the growth of wheat root system can stimulate the growth of most microorganisms. The activities of hydrogen peroxidase and polyphenol oxidase in soil samples after metsulfuron-methyl application were notably lower than those in the control, and the difference of the activities between the samples of rhizosphere and nonrhizosphere was evident. On the contrary, the activity of dehydrogenase was not inhibited by the application of metsulfuron-methyl, and the rhizosphere effect was not obvious either.     

Functional redundancy and food web functioning in linuron-exposed ecosystems

An extensive data set describing effects of the herbicide linuron on macrophyte-dominated microcosms was analysed with a food web model to assess effects on ecosystem functioning. We showed that sensitive phytoplankton and periphyton groups in the diets of heterotrophs were gradually replaced by more tolerant phytoplankton species as linuron concentrations increased. This diet shift--showing redundancy among phytoplankton species--allowed heterotrophs to maintain their functions in the contaminated microcosms. On an ecosystem level, total gross primary production was up to hundred times lower in the treated microcosms but the uptake of dissolved organic carbon by bacteria and mixotrophs was less sensitive. Food web efficiency was not consistently lower in the treated microcosms. We conclude that linuron predominantly affected the macrophytes but did not alter the overall functioning of the surrounding planktonic food web. Therefore, a risk assessment that protects macrophyte growth also protects the functioning of macrophyte-dominated microcosms.     

Glyphosate adsorption in soils compared to herbicides replaced with the introduction of glyphosate resistant crops

Use of glyphosate resistant crops was helpful in addressing observed increases in environmental contamination by herbicides. Glyphosate is a broad-spectrum herbicide, and its behaviour-as well as that of other herbicides-in soils is an important consideration for the overall environmental evaluation of genetically resistant crop introduction. However, few data have been published comparing glyphosate behaviour in soil to that of the herbicides that would be replaced by introduction of glyphosate resistant crops. This work compares glyphosate adsorption in soil with that of other herbicides frequently used in rape (trifluralin and metazachlor), sugarbeet (metamitron) and corn (sulcotrione). Herbicide adsorption was characterised in surface soils and in the complete soils profiles through kinetics and isotherms using batch equilibration methods. Pedological and molecular structure factors controlling the adsorption of all five herbicides were investigated. Glyphosate was the most strongly adsorbed herbicide, thus having the weakest potential for mobility in soils. Glyphosate adsorption was dependent on its ionisable structure in relation to soil pH, and on soil copper, amorphous iron and phosphate content. Trifluralin adsorption was almost equivalent to glyphosate adsorption, whereas metazachlor, metamitron and sulcotrione adsorption were lower. Trifluralin, metazachlor and metamitron adsorption increased with soil organic carbon content. Sulcotrione was the least adsorbed herbicide in alkaline soils, but its adsorption increased when pH decreased. Ranking the adsorption properties among the five herbicides, glyphosate and trifluralin have the lowest availability and mobility in soils, but the former has the broadest spectrum for weed control.     

The sensitivity of early 20th century cultivars of wheat to air pollution

The effects of a mixture of SO(2) and NO(2) at a concentration of 0.08 to 0.10 ppm (in microg m(-3): 164-205 for NO(2); 229-286 for SO(2)) were tested for four weeks on two old varieties of winter wheat, Little Joss and Holdfast, introduced in 1908 and 1938, respectively, grown in simulated autumn conditions. After two weeks, root dry weights of both varieties were significantly decreased but, although there was some leaf necrosis, shoot dry weights were unaltered. After a further two weeks, the dry weights of the shoots as well as the roots were significantly decreased. These effects, amounting to a combined 40% decrease in total dry weight, were greater than those in identical experiments carried out with the present day variety Avalon, in which the decrease was 20%. The results suggest that the modern cultivar Avalon is more tolerant of SO(2) and NO(2) than Little Joss and Holdfast, which were grown many years ago.     

Biotransformation and antioxidant enzymes of Lumbriculus variegates as biomarkers of contaminated sediment exposure

In this study the black worm Lumbriculus variegatus was tested for suitability as biomonitor for moderately contaminated sediments. The response capacity of the biotransformation system phase II enzyme glutathione-S-transferase (GST) and the oxidative defense enzyme catalase (CAT) to contaminated sediment and atrazine was investigated to establish them as sensitive biomarkers. To get an integrated view on the enzyme activity kinetics, increasing concentrations of the herbicide atrazine were applied to stimulate GST response, and relationship between enzyme activity and herbicide concentration was observed at various exposure durations. Furthermore, animals were exposed for up to 1 week to sediments of four typical urban river sections with high anthropogenic impact. L. variegatus was capable to accomplish the environmental stress and the selected enzymes showed elevation. Significant changes of GST (membrane-bound and soluble) were detected after at least 4 days of exposure to atrazine and contaminated sediments. Although CAT increase could be observed already after 1 day of exposure to sediments, an exposure time of one week is considerable for accurate interpretation of the enzymatic response. The clear enzymatic response of especially the membrane-bound GST indicated charges with organic lipophilic substances at all sampling sites.     

On the way to cyanobacterial blooms: impact of the herbicide metribuzin on the competition between a green alga (Scenedesmus) and a cyanobacterium (Microcystis)

The hypothesis that exposure to a common and widely applied photosynthesis-inhibiting herbicide, metribuzin, would alter the outcome of the competitive battle between susceptible green algae (Scenedesmus obliquus) and tolerant cyanobacteria (Microcystis aeruginosa) was tested. In a long-term (17 d) experiment, Scenedesmus and Microcystis populations as well as mixtures that started with different inoculum composition (i.e. 3:1, 1:1 and 1:3 Scenedesmus:Microcystis) were grown in the absence or presence of metribuzin (100 microg l-1). In the absence of metribuzin, Scenedesmus was competitively superior and out-competed Microcystis regardless the initial composition of the mixed communities. However, this competitive outcome was reversed completely in the presence of metribuzin, where despite growth inhibition Microcystis became dominant. Hence, photosynthesis-inhibiting herbicides may not only affect algal community structure, but also provide cyanobacteria founder populations a window for dominance and thus play an important role in promoting cyanobacteria blooms.     

Mortality response and LC50 values for juvenile and adult crayfish, Procambarus clarkii exposed to Thiodan (insecticide), Treflan, MSMA, Oust (herbicides) and Cutrine-Plus (algicide)

Toxicities of three herbicides (Treflan, MSMA and Oust), an algicide (Cutrine-plus) and an insecticide (Thiodan) to juvenile (3.0-3.4 cm) and adult (9.0-10.0 cm) crayfish, Procambarus clarkii, were determined by 96 h static bioassays. Freshly prepared 0.01% and 1.0% aqueous stock solutions of these pesticides were diluted to desired concentrations. Mortalities were recorded each day up to 96 h. Aged tap-water was used for preparing all test solutions. Per cent mortalities were analyzed for linear regression and LC(50) values were computed by probit analysis. LC(50) values for juvenile P.clarkii in the descending order of toxicity were: 24 ppb Thiodan, 13 ppm Treflan, 101 ppm MSMA, 461 ppm Cutrine-plus, 12,174 ppm Oust; and for adults these values were: 423 ppb Thiodan, 26 ppm Treflan, 1019 ppm MSMA and 2945 ppm Cutrine-plus. No LC(50) values for adult crayfish could be computed for Oust herbicide which caused no mortalities up to 60,000 ppm concentration. Comparing the overall toxicities of these pesticides, Thiodan was the most toxic to all crayfish; followed by Treflan, MSMA, Cutrine-plus and Oust. Oust was more than 1/2 million times less toxic than Thiodan to juvenile crayfish. Published LC(50) values indicate that freshwater crayfish are more tolerant than marine decapods, Crangon septemspinosa and Mysidopsis bahia, to Thiodan insecticide and Treflan herbicide.     

Phototransformation of clodinafop-propargyl

Photodegradation of the herbicide clodinafop-propargyl was investigated on glass surface under sunlight and UV light. Four photoproducts were identified by NMR, IR, and MS. Major photolysis products were 2-[(5-chloro-3-fluoro-2-pyridyloxy) phenoxy] propanoic acid and prop-2-ynyl-2-[(5-chloro-3-hydroxy-2-pyridyloxy) phenoxy] propanoate, while minor were ethyl 2-[(5-chloro-3-fluoro-2-pyridyloxy) phenoxy] propanoate and 1-hydroxypropanyl-2-[(5-chloro-3-fluoro-2-pyridyloxy) phenoxy] propanoate. Rate of photodegradation followed first-order kinetics with significant correlation coefficient. The major photoproducts were observed in maximum quantity on the 7th and 10th day and further degraded within 15-20 days.