Adsorption and degradation of the weak acid mesotrione in soil and environmental fate implications

The ability of soils to adsorb and degrade pesticides strongly influences their environmental fate. This paper examines the adsorption and degradation of a weak acid, a new herbicide mesotrione 12-[4-(methylsulfonyl)-2-nitrobenzoyl]-1,3-cyclohexanedione], in 15 different soils from Europe and the USA. Experiments were conducted to understand the influence of soil properties, covering a wide range of soil textures, soil pH values (4.4 to 7.5), and organic carbon contents (0.6 to 3.35%). Mesotrione adsorption (Kd values ranged from 0.13 to 5.0 L/kg) was primarily related to soil pH, and to a lesser extent by percent organic carbon (%OC). As soil pH rose. mesotrione Kd values got smaller as mesotrione dissociated from the molecular to anionic form. Mesotrione degradation (half-lives ranged from 4.5 to 32 d) was also related to soil pH, getting shorter as soil pH rose. Simple regression of mesotrione adsorption against soil pH and %OC and against degradation provided a close fit to the data. The correlation between mesotrione adsorption and degradation means that Kd and half-life values are only relevant for use in environmental fate assessment if these values are "paired" for the same soil pH and %OC. The implications were as illustrated for leaching, raising important issues about combining pesticide adsorption and degradation behavior in environmental fate assessments.     

Atrazine dissipation in s-triazine-adapted and nonadapted soil from Colorado and Mississippi: implications of enhanced degradation on atrazine fate and transport parameters

Soil bacteria have developed novel metabolic abilities resulting in enhanced atrazine degradation. Consequently, there is a need to evaluate the effects of enhanced degradation on parameters used to model atrazine fate and transport. The objectives of this study were (i) to screen Colorado (CO) and Mississippi (MS) atrazine-adapted and non-adapted soil for genes that code for enzymes able to rapidly catabolize atrazine and (ii) to compare atrazine persistence, Q(10), beta, and metabolite profiles between adapted and non-adapted soils. The atzABC and/or trzN genes were detected only in adapted soil. Atrazine's average half-life in adapted soil was 10-fold lower than that of the non-adapted soil and 18-fold lower than the USEPA estimate of 3 to 4 mo. Q(10) was greater in adapted soil. No difference in beta was observed between soils. The accumulation and persistence of mono-N-dealkylated metabolites was lower in adapted soil; conversely, under suboptimal moisture levels in CO adapted soil, hydroxyatrazine concentrations exceeded 30% of the parent compounds' initial mass. Results indicate that (i) enhanced atrazine degradation and atzABC and/or trzN genes are likely widespread across the Western and Southern corn-growing regions of the USA; (ii) persistence of atrazine and its mono-N-dealkylated metabolites is significantly reduced in adapted soil; (iii) hydroxyatrazine can be a major degradation product in adapted soil; and (iv) fate, transport, and risk assessment models that assume historic atrazine degradation pathways and persistence estimates will likely overpredict the compounds' transport potential in adapted soil.     

Retention and runoff losses of atrazine and metribuzin in soil

Minimizing herbicide runoff and mobility in the soil and thus potential contamination of water resources is a national concern. Metribuzin [4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazin-5(4H)-one] and atrazine [2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine] dynamics in surface soils and in runoff waters were studied on six 0.2-ha sugarcane (Saccharum spp.) plots of a Commerce silt loam (fine-silty, mixed, superactive, nonacid, thermic Fluvaquentic Endoaquept) during three growing seasons under different best management practices. Metribuzin was applied in the spring as a postemergence herbicide and atrazine was applied following winter harvest. Both herbicides were applied on top of the sugarcane rows as 0.6- or 0.9-m band width application, or broadcast application, where the entire area was treated. Maximum effluent concentrations were measured from the broadcast treatment and ranged from 600 to 1100 microg L(-1) for atrazine and 250 to 450 microg L(-1) for metribuzin. Atrazine runoff losses were highest for the broadcast treatment (2.8-11% of that applied) and lowest for the 0.6-m band treatment (1.9-7.6%), with a similar trend for metribuzin losses. Measured extractable herbicides from the surface soil exhibited a sharp decrease with time and were well described with a simple first-order decay model. For atrazine, estimates for the decay rate (lambda) were higher than for metribuzin. Results based on laboratory adsorption-desorption (kinetic-batch) measurements were consistent with field observations. The distribution coefficients (Kd) for atrazine exhibited stronger retention over time in comparison with metribuzin on the Commerce soil. Moreover, discrepancies between adsorption isotherm and desorption indicated slower release and that hysteresis was more pronounced for atrazine compared with metribuzin.     

A standardized approach for estimating the permeability of plastic films to soil fumigants under various field and environmental conditions

Minimizing atmospheric emissions of soil fumigants is critical for protecting human and environmental health. Covering the soil surface with a plastic tarp is a common approach to restrict fumigant emissions. The mass transfer of the fumigant vapors through the tarp is often the rate-limiting factor in fumigant emissions. An approach for standardizing measurements of film permeability is proposed that is based on determining the resistance (R) of films to diffusion of fumigants. Using this approach, values were determined for more than 200 film-chemical combinations under a range of temperature, relative humidity, and film handling conditions. Resistance to diffusion was specific for each fumigant/film combination, with the largest range of values observed for the fumigant chloropicrin. For each fumigant, decreased with increasing temperature. Changes in film permeability due to increases in temperature or field installation were generally less than a factor of five. For one film, values determined under conditions of very high relative humidity (approximately 100%) were at least 100 times lower than when humidity was very low (approximately 2%). This approach simplifies the selection of appropriate films for soil fumigation by providing rapid, reproducible, and precise measurements of their permeability to specific fumigants and application conditions.     

Fate of atrazine in sandy soil cropped with sorghum

A field study was conducted to determine the fate of atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) within the root zone (0 to 90 cm) of a sandy soil cropped with sorghum [Sorghum bicolor (L.) Moench] in Gainesville, Florida. Atrazine was uniformly applied at a rate of 1.12 kg ai. ha(-1) to a sorghum crop under moderate irrigation, optimum irrigation, and no irrigation (rainfed), 2 d after crop emergence. Bromide as a tracer for water movement was applied to the soil as NaBr at a rate of 45 kg Br ha(-1), 3 d before atrazine application. Soil water content, atrazine, and Br concentrations were determined as a function of time using soil samples taken from the root zone. Atrazine sorption coefficients and degradation rates were determined by depth for the entire root zone in the laboratory. Atrazine was strongly adsorbed within the upper 30 cm of soil and most of the atrazine recovered from the soil during the growing season was in that depth. The estimated half-life for atrazine was 32 d in topsoil to 83 d in subsoil. Atrazine concentration within the root zone decreased from 0.44 kg ai. ha(-1) 2 days after application (DAA) to 0.1 kg a.i. ha(-1) 26 DAA. Negligible amounts of atrazine (approximately 5 microg kg(-1)) were detected below the 60-cm soil depth by 64 DAA. Most of the decrease in atrazine concentration in the root zone over time was attributed to degradation. In contrast, all applied bromide had leached past the 60-cm soil depth during the same time interval.     

Measured concentrations of herbicides and model predictions of atrazine fate in the Patuxent River estuary

The environmental fate of herbicides in estuaries is poorly understood. Estuarine physical transport processes and the episodic nature of herbicide release into surface waters complicate interpretation of water concentration measurements and allocation of sources. Water concentrations of herbicides and two triazine degradation products (CIAT [6-amino-2-chloro-4-isopropylamino-s-triazine] and CEAT [6-amino-2-chloro-4-ethylamino-s-triazine]) were measured in surface water from four sites on 40 d from 4 Apr. through 29 July 19% in the Patuxent River estuary, part of the Chesapeake Bay system. Atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) was most persistent and present in the highest concentrations (maximum = 1.29 microg/L). Metolachlor [2-chloro-6'-ethyl-N-(2-methoxy-1-methylethyl)-o-acetoluidide], CIAT, CEAT, and simazine (1-chloro-3,5-bisethylamino-2,4,6-triazine) were frequently detected with maximum concentration values of 0.61, 1.1, 0.76, and 0.49 microg/L, respectively. A physical transport model was used to interpret atrazine concentrations in the context of estuarine water transport, giving estimates of in situ degradation rates and total transport. The estimated half-life of atrazine in the turbid, shallow upper estuary was t(1/2) = 20 d, but was much longer (t(1/2) = 100 d) in the deeper lower estuary. Although most (93%) atrazine entered the estuary upstream via the river, simulations suggested additional inputs directly to the lower estuary. The total atrazine load to the estuary from 5 April to 15 July was 71 kg with 48% loss by degradation and 31% exported to the Chesapeake Bay. Atrazine persistence in the estuary is directly related to river flows into the estuary. Low flows will increase atrazine residence time in the upper estuary and increase degradation losses.     

Photodegradation of selected herbicides in various natural waters and soils under environmental conditions

The photochemical degradation of herbicides belonging to different chemical groups has been investigated in different types of natural waters (ground, river, lake, marine) and distilled water as well as in soils with different texture and composition. Studied herbicides and chemical groups included atrazine, propazine, and prometryne (s-triazines); propachlor and propanil (acetanilides); and molinate (thiocarbamate). The degradation kinetics were monitored under natural conditions of sunlight and temperature. Photodegradation experiments were performed in May through July 1998 at low concentrations in water samples (2-10 mg/L) and soil samples (5-20 mg/kg), which are close to usual field dosage. The photodegradation rates of all studied herbicides in different natural waters followed a pseudo-first order kinetics. The half-lives of the selected herbicides varied from 26 to 73 calendar days in waters and from 12 to 40 d in soil surfaces, showing that the degradation process depends on the constitution of the irradiated media. The presence of humic substances in the lake, river, and marine water samples reduces degradation rates in comparison with the distilled and ground water. On the contrary, the degradation in soil is accelerated as the percentage of organic matter increases. Generally, the photodegradation process in soil is faster than in water. The major photodegradation products identified by using gas chromatography-mass spectrometry (GC-MS) techniques were the hydroxy and dealkylated derivatives for s-triazines, the dechlorinated and hydroxy derivative for the anilides, and the keto-derivative for the thiocarbamate, indicating a similar mode of degradation for each chemical category.     

Modeling concentration-dependent sorption-desorption hysteresis of atrazine in a loam soil

Nonequilibrium sorption plays an active role in the transport of organic contaminants in soil. We applied a two-stage, one-rate model (2S1R) and a new, nonlinear variant (2S1RN) of this model to examine the effects of wastewater irrigation on the sorption kinetics of atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) in soil. The models were applied to previously published sorption-desorption data sets, which showed pronounced deviations between sorption curves and desorption curves (sorption-desorption hysteresis). Moreover, the slopes of the desorption curves decreased with decreasing concentration. Different treatments had been used, and two experimental time steps (2 and 14 d) were used. Treatments considered were lipid removal, fulvic and humic acid removal, and untreated soil. The 2S1R model was unable to reproduce the observed type of hysteresis, but the 2S1RN model, which assumes that the sorption-desorption process follows a power function relationship, was able to reproduce the observed type of hysteresis. Visually, applying the new model improved the model fits in all test cases. Statistically, as tested by an extra sum of squares analysis, the new model performed significantly better in 50% of all test cases. According to an example simulation, the choice of the sorption model has a considerable impact on the prediction of atrazine transport in soil.     

Impact of environmental production conditions on productivity and efficiency: a case study of wheat farmers in Bangladesh

Environmental conditions significantly affect production, but are often ignored in studies analysing productivity and efficiency leading to biased results. In this study, we examine the influence of selected environmental factors on productivity and efficiency in wheat farming in Bangladesh. Results reveal that environmental production conditions significantly affect the parameters of the production function and technical efficiency, as well as correlates of inefficiency. Controlling for environmental production conditions improves technical efficiency by 4 points (p<0.01) from 86% to 90%. Large farms are more efficient relative to small and medium sized farms (p<0.01 and 0.05), with no variation among regions. Policy implications include soil fertility improvement through soil conservation and crop rotation, improvement in managerial practices through extension services and adoption of modern technologies, promotion of education, strengthening the research-extension link, and development of new varieties that have higher yield potential and are also suitable for marginal areas.     

RDX loss in a surface soil under saturated and well drained conditions

On military training ranges, low-order, incomplete detonations deposit RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) into surface soils. In this study, we evaluated RDX biodegradation in surface soils obtained from a military training range in Alaska. Two factors were compared: (i) soil water potential during the incubations; and (ii) the use of acetonitrile (ACN) as an RDX carrier to spike samples. Organic solvents have been used in laboratory studies to dissolve slightly water-soluble contaminants before addition to soil. We added ACN to obtain final soil ACN concentrations of 0 mg kg(-1) (0%), 1000 mg kg(-1) (0.1%) and 10 000 mg kg(-1) (1%). We then compared RDX attenuation in the soil under saturated and unsaturated conditions. RDX fell below the limit of detection within 3 wk of study initiation under the saturated condition. A maximum degradation rate of 0.15 mg RDX L(-1) d(-1) was measured. Under the unsaturated condition, 42% of the original RDX was still present at study termination (5 wk). The addition of acetonitrile at 0.1 or 1.0% had no affect on RDX loss in the saturated soil. In the unsaturated soil, however, ACN at 1.0% inhibited RDX loss by as much as 25%. These findings indicate that soil water potential and carrier solvent concentrations can impact the rate and extent to which RDX is attenuated in a surface soil.     

Employability of environmental science graduates in Australia

Since the 1970s, there has been a global proliferation of environmental courses. The types of courses are described, as are the structures, philosophies and objectives of courses which have stood the test of time. Employment of environmental graduates is discussed. The degree in Australian Environmental Studies (AES) from Griffith University is described and discussed with reference to pitfalls described in the literature. In Australia, there has been an increased demand for graduates in the environmental area. The trend in employers has been widening the field of potential recruits by keeping the degree specification broad and using the duty statements in the advertisements to specify the environmental skills and knowledge required. The number of graduates from AES has increased steadily since the course was established, and despite global and national trends of proliferation of environmental courses and graduates, survey results indicated that graduates from AES are professionally employed in a wide range of employment sectors, with female and male graduates being equally successful in obtaining employment.     

Predicting soil fumigant air concentrations under regional and diverse agronomic conditions

SOFEA (SOil Fumigant Exposure Assessment system; Dow AgroSciences, Indianapolis, IN) is a new stochastic numerical modeling tool for evaluating and managing human inhalation exposure potential associated with the use of soil fumigants. SOFEA calculates fumigant concentrations in air arising from volatility losses from treated fields for large agricultural regions using multiple transient source terms (treated fields), geographical information systems (GIS) information, agronomic specific variables, user-specified buffer zones, and field reentry intervals. A modified version of the USEPA Industrial Source Complex Short Term model (ISCST3) is used for air dispersion calculations. Weather information, field size, application date, application rate, application type, soil incorporation depth, pesticide degradation rates in air, tarp presence, field retreatment, and other sensitive parameters are varied stochastically using Monte Carlo techniques to mimic region and crop specific agronomic practices. Regional land cover, elevation, and population information can be used to refine source placement (treated fields), dispersion calculations, and risk assessments. This paper describes the technical algorithms of SOFEA and offers comparisons of simulation predictions for the soil fumigant 1,3-dichloropropene (1,3-D) to actual regional air monitoring measurements from Kern, California. Comparison of simulation results to daily air monitoring observations is remarkable over the entire concentration distribution (average percent deviation of 44% and model efficiency of 0.98), especially considering numerous inputs such as meteorological conditions for SOFEA were unavailable and approximated by neighboring regions. Both current and anticipated and/or forecasted fumigant scenarios can be simulated using SOFEA to provide risk managers and product stewards the necessary information to make sound regulatory decisions regarding the use of soil fumigants in agriculture.     

Industry Agreement Acts and environmental management in Australia

In Australia many major developments are authorized by agreements negotiated between companies and the state government and ratified by Parliament as Agreement Acts The means by which these are negotiated and ratified, their terms, and their legal status are thus of great importance to Australian resource and environmental management These aspects are examined, revealing a lessening of the tendency to provide special rights and privileges and a trend towards the inclusion of more resource and environmental management provisions in the Acts It is argued that major developments require special conditions beyond the scope of general laws in order to control their social and environmental side effects, and that Agreements Acts could be a valuable means to this end Ways of improving them from this point of view are discussed     

Review of studies on environmental impacts of recreation and tourism in Australia

The paper provides a review of available information on the impact of recreation and tourism on environments, particularly on vegetation and soil, in Australia, with an emphasis on forests. Efforts have been made to compare the current research and development situation in Australia with some overseas countries such as the United States and the United Kingdom. While many documents reveal that Australia has been experiencing an increasingly high level of recreation and tourism use in its environments, only limited studies of environmental impacts of recreation and tourism have been published. Compared with other developed countries, particularly the United Kingdom and the United States, Australia lags behind in undertaking research in this area. The results of these limited studies and some observations indicate that the most common recreational and tourist activities (such as bush walking, camping, horse-riding) can, if not well managed, adversely affect the values of Australian natural and semi-natural resources. Overall, they can affect the vegetation and other recreational sites physically and biologically. Physical effects include track formation, soil loss and/or compaction and an increase in fire frequency. Littering and water pollution are also seen as impacts associated with bush walking and camping. Biological effects include causing damage to vegetation, increasing risk of myrtle wilt disease and the spread of the soil pathogen,Phytophthora cinnamomi, as well as assisting weed dispersal. Based on the information reviewed, the authors suggest the following areas as priorities for future research into the environmental impact of recreation and tourism in Australia: determine the type of natural features that attract recreation use; determine the quantitative relationship between the impact and the level of recreation and tourism use for different activities within major vegetation habitats; ascertain site carrying capacity or environment thresholds for major vegetation habitats and recreation activities; and determine the impacts of recreation and tourism for major regions and major vegetation habitats where there have been considerable nature-based recreation and tourism activities.1998 Academic Press     

In vitro pesticide degradation in turfgrass soil incubated under open and sealed conditions

Degradation of selected pesticides was conducted in a turfgrass soil from a golf course under open (i.e., allowing gas exchange with atmosphere) and sealed systems. The time required for 50% of the initial dose of fenitrothion (O,O-dimethyl O-4-nitro-m-tolyl phosphorothioate), diazinon (O,O-dimethyl O-2-isopropyl-6-methylpyrimidin4-yl phosphorothioate), iprodione [3-(3,5-dichlorophenyl)-N-isopropyl-2,4-dioxo-imidazolidine-1-carboxamide], mecoprop [(RS)-2-(4-chloro-otolyloxy)propionic acid], and asulam (4-aminophenylsulfonyl-carbamate) to dissipate (half-life, t 1/2) was less than 2 wk under both conditions. The t 1/2 values of dithiopyr (S,S'-dimethyl 2-difluoromethyl-4-isobutyl-6-trifluoro-methylpyridine-3,5-dicarbothioate) were 324 and 185 d under the open and sealed conditions, respectively. The t 1/2 values of isoprothiolane (di-isopropyl 1,3-dithiolan-2-ylidene-malonate), flutolanil (alpha,alpha,alpha-trifluoro-3'-isopropoxy-o-toluanilide), and benefin (N-butyl-N-ethyl-alpha,alpha,alpha-trifluoro-2,6-dinitro-p-toluidine) under the open conditions were 154, 336, and 47 d, respectively. The t 1/2 values of these pesticides increased slightly under the sealed conditions. The t 1/2 values of terbutol (2,6-di-tert-butyl-4-methylphenyl N-methycarbamate) and one of the major degradation products, N-demethyl-terbutol (2,6-di-tert-butyl-4-methylphenyl carbamate), were 182 and 291 d under the open conditions and increased by six- and threefold under the sealed conditions, respectively. The degradation system under the sealed conditions could characterize the persistence of terbutol and N-demethyl-terbutol, which were the most persistent in the field.     

Small-scale spatial variability of atrazine and dinoseb adsorption parameters in an alluvial soil

Soil sorption processes largely control the environmental fate of herbicides. Therefore, accuracy of sorption parameters is crucial for accurate prediction of herbicide mobility in agricultural soils. A combined experimental and statistical study was performed to investigate the small-scale spatial variability of sorption parameters for atrazine and dinoseb in soils and to establish the number of samples needed to provide a value of the distribution coefficient (K(d)) next to the mean, with a given precision. The study explored sorption properties of the two herbicides in subsurface samples collected from four pits distributed along a transect of an alluvial soil; two to four samples were taken at about 30 cm apart at each sampling location. When considering all the data, the distribution coefficients were found to be normally and log-normally distributed for atrazine and dinoseb, respectively; the CVs were relatively high (close to 50% for dinoseb and 40% for atrazine). When analyzed horizon by horizon, the data revealed distribution coefficients normally distributed for both herbicides, whatever the soil layer, with lower CVs. The K(d) values were shown to vary considerably between samples collected at very short distance (a few centimeters), suggesting that taking a single soil sample to determine sorption properties through batch experiments can lead to highly unrepresentative results and to poor sorption/mobility predictions.     

Impact of land disturbance on the fate of arsenical pesticides

Increasing development of historic farmlands raises questions regarding the fate of pesticides applied when these land were in cultivation. We quantified As and Pb budgets in field soils in two orchards where arsenical pesticides were applied in the early 20th century and a third uncontaminated control field. Sequential extractions and X-ray analyses also were used to determine mineral phases. In addition, we measured metal loads in drainages adjacent to the fields and in two common macroinvertebrate taxa within the wetland at the outlet of the drainages. We find that the applied As and Pb have undergone little vertical redistribution; concentrations of As and Pb in the top 25 cm of contaminated orchard soils are higher than in the uncontaminated control field. However, none of the applied lead arsenate (PbHAsO4) remains in its original mineral phase. Instead, the metals are now primarily adsorbed onto fine silt and clay-sized amorphous oxides and organic matter. Further, physical erosion associated with tilling and replanting appears to have mobilized the fine-particulate-bound As and Pb in one orchard. The remobilized metals are found in sediments in the stream channel draining the tilled orchard. It is unclear if the As and Pb transported sediments are biologically active; average macroinvertebrate metal burdens in the wetland are not elevated above those observed elsewhere in the region. However, little of the mobilized metals may have reached the wetland. These results demonstrate that land use change can significantly impact the retention of arsenical pesticides.     

Anaerobic degradation of atrazine and metolachlor and metabolite formation in wetland soil and water microcosms

The half-lives, degradation rates, and metabolite formation patterns of atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) and metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamide] were determined in an anaerobic wetland soil incubated at 24 degrees C for 112 d. At 0, 7, 14, 28, 42, 56, and 112 d, the soil and water were analyzed for atrazine and metolachlor, and their major metabolites. The soil oxidation-reduction potential reached -200 mV after 14 d. Degradation reaction rates were first-order for atrazine in anaerobic soil and for metolachlor in the aqueous phase. Zero-order reaction rates were best fit for atrazine in the aqueous phase and metolachlor in anaerobic soil. In anaerobic soil, the half-life was 38 d for atrazine and 62 d for metolachlor. In the aqueous phase above the soil, the half-life was 86 d for atrazine and 40 d for metolachlor. Metabolites detected in the anaerobic soil were hydroxyatrazine and deethylatrazine for atrazine, and relatively small amounts of ethanesulfonic acid and oxanilic acid for metolachlor. Metabolites detected in the aqueous phase above the soil were hydroxyatrazine, deethylatrazine, and deisopropylatrazine for atrazine, and ethanesulfonic acid and oxanilic acid for metolachlor. Concentrations of metabolites in the aqueous phase generally peaked within the first 25 d and then declined. Results indicate that atrazine and metolachlor can degrade under strongly reducing conditions found in wetland soils. Metolachlor metabolites, ethanesulfonic acid, and oxanilic acid are not significantly formed under anaerobic conditions.     

气候环境试验设备温度参数数据处理方法的分析与探讨

不同的温度参数数据处理方法有不同的计算结果,本文针对检测与评定气候环境试验设备的技术性能中存在的问题,分析了三个标准(GB 11158-89、GB/T 5170.1-1995、JTM K 05-1991)的温度参数数据处理方法,比对了二组实际检测数据的计算结果,说明"绝对极值法"科学准确、简捷实用.