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1.
Pesticide transport through the unsaturated zone is a function of chemical and soil characteristics, application, and water recharge rate. The fate and transport of 82 pesticides and degradates were investigated at five different agricultural sites. Atrazine and metolachlor, as well as several of the degradates of atrazine, metolachlor, acetochlor, and alachlor, were frequently detected in soil water during the 2004 growing season, and degradates were generally more abundant than parent compounds. Metolachlor and atrazine were applied at a Nebraska site the same year as sampling, and focused recharge coupled with the short time since application resulted in their movement in the unsaturated zone 9 m below the surface. At other sites where the herbicides were applied 1 to 2 yr before sampling, only degradates were found in soil water. Transformations of herbicides were evident with depth and during the 4-mo sampling time and reflected the faster degradation of metolachlor oxanilic acid and persistence of metolachor ethanesulfonic acid. The fraction of metolachlor ethanesulfonic acid relative to metolachlor and metolachlor oxanilic acid increased from 0.3 to >0.9 at a site in Maryland where the unsaturated zone was 5 m deep and from 0.3 to 0.5 at the shallowest depth. The flux of pesticide degradates from the deepest sites to the shallow ground water was greatest (3.0-4.9 micromol m(-2) yr(-1)) where upland recharge or focused flow moved the most water through the unsaturated zone. Flux estimates based on estimated recharge rates and measured concentrations were in agreement with fluxes estimated using an unsaturated-zone computer model (LEACHM).  相似文献   

2.
Occurrence and fate of 45 pesticides and 40 pesticide degradates were investigated in four contrasting agricultural settings--in Maryland, Nebraska, California, and Washington. Primary crops included corn at all sites, soybeans in Maryland, orchards in California and Washington, and vineyards in Washington. Pesticides and pesticide degradates detected in water samples from all four areas were predominantly from two classes of herbicides--triazines and chloroacetanilides; insecticides and fungicides were not present in the shallow ground water. In most samples, pesticide degradates greatly exceeded the concentrations of parent pesticide. In samples from Nebraska, the parent pesticide atrazine [6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine] was about the same concentration as the degradate, but in samples from Maryland and California atrazine concentrations were substantially smaller than its degradate. Simazine [6-chloro-N,N'-diethyl-1,3,5-triazine-2,4-diamine], the second most detected triazine, was detected in ground water from Maryland, California, and Washington. Metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide] rarely was detected without its degradates, and when they were detected in the same sample metolachlor always had smaller concentrations. The Root-Zone Water-Quality Model was used to examine the occurrence and fate of metolachlor at the Maryland site. Simulations accurately predicted which metolachlor degradate would be predominant in the unsaturated zone. In analyses of relations among redox indicators and pesticide variance, apparent age, concentrations of dissolved oxygen, and excess nitrogen gas (from denitrification) were important indicators of the presence and concentration of pesticides in these ground water systems.  相似文献   

3.
Rainfall samples were collected during the 2003 and 2004 growing seasons at four agricultural locales across the USA in Maryland, Indiana, Nebraska, and California. The samples were analyzed for 21 insecticides, 18 herbicides, three fungicides, and 40 pesticide degradates. Data from all sites combined show that 7 of the 10 most frequently detected pesticides were herbicides, with atrazine (70%) and metolachlor (83%) detected at every site. Dacthal, acetochlor, simazine, alachlor, and pendimethalin were detected in more than 50% of the samples. Chlorpyrifos, carbaryl, and diazinon were the only insecticides among the 10 most frequently detected compounds. Of the remaining pesticide parent compounds, 18 were detected in fewer than 30% of the samples, and 13 were not detected. The most frequently detected degradates were deethylatrazine; the oxygen analogs (OAs) of the organophosphorus insecticides chlorpyrifos, diazinon, and malathion; and 1-napthol (degradate of carbaryl). Deethylatrazine was detected in nearly 70% of the samples collected in Maryland, Indiana, and Nebraska but was detected only once in California. The OAs of chlorpyrifos and diazinon were detected primarily in California. Degradates of the acetanilide herbicides were rarely detected in rain, indicating that they are not formed in the atmosphere or readily volatilized from soils. Herbicides accounted for 91 to 98% of the total pesticide mass deposited by rain except in California, where insecticides accounted for 61% in 2004. The mass of pesticides deposited by rainfall was estimated to be less than 2% of the total applied in these agricultural areas.  相似文献   

4.
Permeable zerovalent iron (Fe0) barriers have become an established technology for remediating contaminated ground water. This same technology may be applicable for treating pesticides amenable to dehalogenation as they move downward in the vadose zone. By conducting miscible displacement experiments in the laboratory with metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide; a chloroacetanilide herbicide] under unsaturated flow, we provide proof-of-concept for such an approach. Transport experiments were conducted in repacked, unsaturated soil columns attached to vacuum chambers and run under constant matrix potential (-30 kPa) and Darcy flux (approximately 2 cm d(-1)). Treatments included soil columns equipped with and without a permeable reactive barrier (PRB) consisting of a Fe0-sand (50:50) mixture supplemented with Al2(SO4)3. A continuous pulse of 14C-labeled metolachlor (1.45 mM) and tritiated water (3H2O) was applied to top of the columns for 10 d. Results indicated complete (100%) metolachlor destruction, with the dehalogenated product observed as the primary degradate in the leachate. Similar results were obtained with a 25:75 Fe0-sand barrier but metolachlor destruction was not as efficient when unannealed iron was used or Al2(SO4)3 was omitted from the barrier. A second set of transport experiments used metolachlor-contaminated soil in lieu of a 14C-metolachlor pulse. Under these conditions, the iron barrier decreased metolachlor concentration in the leachate by approximately 50%. These results provide initial evidence that permeable iron barriers can effectively reduce metolachlor leaching under unsaturated flow.  相似文献   

5.
The Acetochlor Registration Partnership (ARP) conducted a 7-yr ground water monitoring program at a total of 175 sites in seven states: Illinois, Indiana, Iowa, Kansas, Minnesota, Nebraska, and Wisconsin. While acetochlor [2-chloro-N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)-acetamide] was the primary focus, the analytical methods also quantified alachlor [2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)-acetamide], atrazine [6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine], metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)-acetamide], and two classes of soil degradates for acetochlor, alachlor, and metolachlor. Ground water samples were collected monthly for five years and quarterly for two additional years. All samples were analyzed for the presence of parent herbicides, and degradates were monitored during the last three years. Parent acetochlor was detected above 0.1 microg L(-1) in three or more samples at just seven sites. Alachlor and metolachlor were also rarely detected, but atrazine was detected in 36% of all samples analyzed. Even more widespread were the tertiary amide sulfonic acid (ethanesulfonic acid, ESA) degradates of acetochlor, alachlor, and metolachlor, which were detected at 81, 76, and 106 sites, respectively. The other class of monitored soil degradates (oxanilic acid, OXA) was detected less frequently, at 26, 16, and 63 sites for acetochlor OXA, alachlor OXA, and metolachlor OXA, respectively. The geographic distribution of detections did not follow the pattern originally expected when the study began. Rather than being a function primarily of soil texture, the detection of these herbicides in shallow ground water was related to site-specific factors associated with local topography, the occurrence of surface water drainage features, irrigation practices, and the vertical positioning of the well screen.  相似文献   

6.
There is a current need to simulate leaching and runoff of pesticide from rice (Oryza sativa L.) paddies for assessing environmental impacts on a valuable agricultural system. The objective of this study was to develop a model for determining predicted environmental concentration (PEC) in soil, runoff, and ground water through the linkage of two models, rice water quality model (RICEWQ) and vadose zone transport model (VADOFT), to simulate pesticide fate and transport within a rice paddy and underlying soil profile. Model performance was evaluated with a field data set obtained from a 2-yr field experiment in 1997 and 1998 in northern Italy. The predictions of amount of pesticide running off from the paddy field and accumulating in the paddy sediment were in agreement with measured values. Leaching into the vadose zone accounted for approximately 19% of the applied dose, but only a small amount of chemical (<0.1%) was predicted to reach ground water at a 5-m depth due to sorption and transformation in the soil. The permeability of the soil and the water management practices in the paddy field were shown to have a strong influence on pesticide fate. These factors need to be well characterized in the field if model predictions are to be successful. The combined model developed in this work is an effective tool for exposure assessments for soil, surface water, and ground water, in the particular conditions of rice cultivation.  相似文献   

7.
ABSTRACT: Since 1991, the U.S. Geological Survey has been conducting the National Water Quality Assessment (NAWQA) Program to determine the quality of the Nation's water resources. In an effort to obtain a better understanding of why pesticides are found in shallow ground water on a national scale, a set of factors likely to affect the fate and transport of two herbicides in the subsurface were examined. Atrazine and metolachlor were selected for this discussion because they were among the most frequently detected pesticides in ground water during the first phase of the NAWQA Program (1993 to 1995), and each was the most frequently detected compound in its chemical class (triazines and acetanilides, respectively). The factors that most strongly correlated with the frequencies of atrazine detection in shallow ground‐water networks were those that provided either: (1) an indication of the potential susceptibility of ground water to atrazine contamination, or (2) an indication of relative ground‐water age. The factors most closely related to the frequencies of metolachlor detection in ground water, however, were those that estimated or indicated the intensity of the agricultural use of metolachlor. This difference is probably the result of detailed use estimates for these compounds being available only for agricultural settings. While atrazine use is relatively extensive in nonagricultural settings, in addition to its widespread agricultural use, metolachlor is used almost exclusively for agricultural purposes. As a result, estimates of agricultural applications provide a less reliable indication of total chemical use for atrazine than for metolachlor. A multivariate analysis demonstrated that the factors of interest explained about 50 percent of the variance in atrazine and metolachlor detection frequencies among the NAWQA land‐use studies examined. The inclusion of other factors related to pesticide fate and transport in ground water, or improvements in the quality and accuracy of the data employed for the factors examined, may help explain more of the remaining variance in the frequencies of atrazine and metolachlor detection.  相似文献   

8.
Pesticide leaching through variably thick soils beneath agricultural fields in Morgan Creek, Maryland was simulated for water years 1995 to 2004 using LEACHM (Leaching Estimation and Chemistry Model). Fifteen individual models were constructed to simulate five depths and three crop rotations with associated pesticide applications. Unsaturated zone thickness averaged 4.7 m but reached a maximum of 18.7 m. Average annual recharge to ground water decreased from 15.9 to 11.1 cm as the unsaturated zone increased in thickness from 1 to 10 m. These point estimates of recharge are at the lower end of previously published values, which used methods that integrate over larger areas capturing focused recharge in the numerous detention ponds in the watershed. The total amount of applied and leached masses for five parent pesticide compounds and seven metabolites were estimated for the 32-km2 Morgan Creek watershed by associating each hectare to the closest one-dimensional model analog of model depth and crop rotation scenario as determined from land-use surveys. LEACHM parameters were set such that branched, serial, first-order decay of pesticides and metabolites was realistically simulated. Leaching is predicted to be greatest for shallow soils and for persistent compounds with low sorptivity. Based on simulation results, percent parent compounds leached within the watershed can be described by a regression model of the form e(-depth) (a ln t1/2-b ln K OC) where t1/2 is the degradation half-life in aerobic soils, K OC is the organic carbon normalized sorption coefficient, and a and b are fitted coefficients (R2 = 0.86, p value = 7 x 10(-9)).  相似文献   

9.
Millions of tons of agricultural fertilizer and pesticides are applied annually in the USA. Due to the potential for these chemicals to migrate to groundwater, a study was conducted in 2004 using field data to calculate water budgets, rates of groundwater recharge and times of water travel through the unsaturated zone and to identify factors that influence these phenomena. Precipitation was the only water input at sites in Indiana and Maryland; irrigation accounted for about 80% of total water input at sites in California and Washington. Recharge at the Indiana site (47.5 cm) and at the Maryland site (31.5 cm) were equivalent to 51 and 32%, respectively, of annual precipitation and occurred between growing seasons. Recharge at the California site (42.3 cm) and Washington site (11.9 cm) occurred in response to irrigation events and was about 29 and 13% of total water input, respectively. Average residence time of water in the unsaturated zone, calculated using a piston-flow approach, ranged from less than 1 yr at the Indiana site to more than 8 yr at the Washington site. Results of bromide tracer tests indicate that at three of the four sites, a fraction of the water applied at land surface may have traveled to the water table in less than 1 yr. The timing and intensity of precipitation and irrigation were the dominant factors controlling recharge, suggesting that the time of the year at which chemicals are applied may be important for chemical transport through the unsaturated zone.  相似文献   

10.
Abstract: Groundwater transport often complicates understanding of surface‐water contamination. We estimated the regional flux of nitrate and selected herbicides from groundwater to nontidal headwater streams of the Atlantic Coastal Plain (New Jersey through North Carolina) based on late‐winter or spring base‐flow samples from 174 streams. Sampled streams were selected randomly, and flux estimates are based on resulting population estimates rather than on empirical models, which have been used previously for similar estimates. Base‐flow flux in the estimated 8,834 headwater streams of the study area are an estimated 21,200 kg/day of nitrate (as N) and 5.83, 0.565, and 20.7 kg/day of alachlor, atrazine, and metolachlor (and selected degradates), respectively. Base‐flow flux of alachlor and metolachlor is <3% of the total base‐flow flux of those compounds plus degradates. Base‐flow flux of nitrate and herbicides as a percentage of applications is typically highest in well‐drained areas and lowest in areas with abundant poor drainage and anoxic conditions. In Coastal Plain watersheds of Albemarle and Pamlico Sounds, <2% of applied nitrogen reaches headwater streams as base flow. On the Delmarva Peninsula part of the Chesapeake Bay watershed, however, more than 10% of such applications are transported through groundwater to streams, and base‐flow nitrate flux represents 70% of total nitrogen flux in headwater streams.  相似文献   

11.
12.
ABSTRACT: A three‐dimensional fractured medium flow model was developed for the Bear Creek Valley (BCV) S‐3 site of the Oak Ridge Reservation (ORR) using SWIFT III. The numerical modeling for this site focused on a conceptual model established through the analysis of heterogeneous geologic units and matrix fracture properties of the subsurface in the BCV area. The SWIFT III modeling analysis was based on the previous modeling studies that used MODFLOW and MODPATH. A rigorous calibration was obtained first by comparing simulated results with the existing data on ground water levels and then by comparing pumping test results with the simulated ground water levels. A satisfactory agreement between observed and simulated results was obtained. The calibrated model was used to determine sustained yield from a ground water interceptor trench. Different withdrawal rates were used to simulate the performance of the trench for the sustained withdrawal of ground water.  相似文献   

13.
ABSTRACT: A previous modeling study used the Generalized Watershed Loading Functions (GWLF) model to simulate stream‐flow, and nutrient and sediment loads to Cannonsville Reservoir from the West Branch Delaware River (WBDR). We made several model revisions, calibrated key parameters, and tested the original GWLF model and a revised GWLF model using more recent data. Model revisions included: addition of unsaturated leakage between unsaturated and saturated subsurface reservoirs; revised timing of sediment export; inclusion of urban sediments and dissolved nutrients; tracking of particulate nutrients from point sources; and revised timing of septic system loads. The revision of sediment yield timing resulted in significant improvements in monthly sediment and particulate phosphorus predictions as compared to the original model. Addition of unsaturated leakage improved hydrologic predictions during low flow months. The other model changes improve realism without adding significant model complexity or data requirements. Goodness of fit of revised model predictions versus stream measurements, as measured by the Nash‐Sutcliff coefficient of model efficiency, exceeded 0.8 for streamflow‐0.7 for sediment yield and dissolved nitrogen (N) and 0.6 for particulate and dissolved phosphorus (P). The revised GWLF model, with limited calibration, provides reasonable estimates of monthly streamflow, and nutrient and sediment loads in the Cannonsville watershed.  相似文献   

14.
Cultural management practices that reduce the off-site transport of herbicides applied to row crops are needed to protect surface water quality. A soybean [Glycine max (L.) Merr.] field study was conducted near Stoneville, MS on Sharkey clay to evaluate row spacing (50 cm vs. 100 cm) effects on metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(methoxy-1-methylethyl) acetamide] transport. One day after the foliar application of metolachlor to 2.03 m wide by 2.43 m long plots, 60 mm h(-1) of simulated rainfall was applied until 25 min of runoff was generated per plot. The calculated mass of metolachlor intercepted by the soybean foliage was greater in narrow-row than wide-row soybean, 0.39 kg ha(-1) vs. 0.23 kg ha(-1), respectively. Field and laboratory studies indicated that less than 2% of the metolachlor intercepted by the soybean foliage was available for foliar wash-off 1 d after application. Antecedent soil water content at the start of the simulations was lower in narrow-row soybean. In turn, there was a 1.7-fold greater time to runoff on narrow-row plots. The greater time to runoff likely contributed to lower metolachlor concentration in runoff from narrow-row plots. Cumulative metolachlor losses were significantly greater in wide-row than narrow-row soybean, 3.7% vs. 2.2%, respectively. Findings indicate that narrow-row planting systems may reduce metolachlor runoff following a post-emergence application.  相似文献   

15.
A numerical simulation model of pesticide runoff through vegetative filer strips (PRVFS) was developed as a tool for investigating the effects of pesticide transport mechanisms on VFS design in dormant-sprayed orchard. The PRVFS model was developed applying existing theories such as kinematic wave theory and mixing zone theory for pesticide transport in the bare soil area. For VFS area, the model performs flow routing by simple mass accounting in sequential segments and the pesticide mass balance by considering pesticide washoff and adsorption processes on the leaf, vegetative litter, root zone and soil. Model sensitivity analysis indicated that pesticide transfer from surface soil to overland flow and pesticide washoff from the VFS were important mechanisms affecting diazinon transport. The VFS cover ratio and rainfall intensity can be important design parameters for controlling diazinon runoff using inter-row VFS in orchard. The PRVFS model was validated using micro-ecosystem simulation of diazinon transport for 0, 50 and 100% VFS cover conditions. The PRVFS model is shown to be a beneficial tool for evaluating and analyzing possible best management practices for controlling offsite runoff of dormant-sprayed diazinon in orchards during the rainy season.  相似文献   

16.
Probabilistic capture zones are combined with a regression model and used as buffer zones around wells for Tobit regression analysis to predict contaminant concentration of groundwater in an agricultural region. A backward transport equation, which is a mathematical model based on the physical processes of solute transport, is used to delineate probabilistic capture zones. The probabilistic capture zone defines the area where contaminant discharge can have a direct influence, with pertinent probability, on the quality of groundwater pumped from a well. Tobit regression analysis is used to find the relationship between independent regression variables and a dependent variable, which is contaminant concentration in this study. The capture zone and the regression are combined into a model, and its applicability for prediction of nitrate concentration is tested in a small agricultural basin in Chuncheon, Korea, which is occupied mainly by vegetation fields, orchards, and small barns. Three cases of Model 1, Model 2, and Model 3 are compared in which buffer zones are circles, capture zones with probability over 0.1, and capture zones divided into sections with different probabilities, respectively. The resulting regression model describes nitrate concentration in terms of selected independent variables. When the concentrations are calculated with the model, the best fit with the observed concentrations was in Model 3. This result supports the applicability of the method proposed in this study to prediction of contaminant concentration of groundwater.  相似文献   

17.
The main physical and chemical controls on nitrogen (N) fluxes between the root zone and the water table were determined for agricultural sites in California, Indiana, Maryland, Nebraska, and Washington from 2004 to 2005. Sites included irrigated and nonirrigated fields; soil textures ranging from clay to sand; crops including corn, soybeans, almonds, and pasture; and unsaturated zone thicknesses ranging from 1 to 22 m. Chemical analyses of water from lysimeters and shallow wells indicate that advective transport of nitrate is the dominant process affecting the flux of N below the root zone. Vertical profiles of (i) nitrogen species, (ii) stable isotopes of nitrogen and oxygen, and (iii) oxygen, N, and argon in unsaturated zone air and correlations between N and other agricultural chemicals indicate that reactions do not greatly affect N concentrations between the root zone and the capillary fringe. As a result, physical factors, such as N application rate, water inputs, and evapotranspiration, control the differences in concentrations among the sites. Concentrations of N in shallow lysimeters exhibit seasonal variation, whereas concentrations in lysimeters deeper than a few meters are relatively stable. Based on concentration and recharge estimates, fluxes of N through the deep unsaturated zone range from 7 to 99 kg ha(-1) yr(-1). Vertical fluxes of N in ground water are lower due to spatial and historical changes in N inputs. High N fluxes are associated with coarse sediments and high N application rates.  相似文献   

18.
ABSTRACT: Field data collected from the Feitsui Reservoir in Taiwan indicate that the water is at a stage between mesotrophic and eutrophic. Recent measurements such as total phosphorus, chlorophyll a and Secchi depth levels suggest that the water quality has been declining. A two‐dimensional, laterally averaged, finite difference hydrodynamic and water quality model was used to simulate the water quality in the Feitsui Reservoir in an effort to determine sound water quality management strategies. The model was calibrated and verified using data collected in 1996 and 1997. The calibrated model was used to simulate algal biomass (in terms of chlorophyll a) levels under various wasteload reduction scenarios. Model results show that 50 percent reduction of the total phosphorus load will improve the existing water quality, shifting the trophic status from eutrophic/mesotrophic to oligotrophic. The modeling effort has yielded valuable information that can be used by decision makers for the evaluation of different management strategies of reducing watershed nutrient loads.  相似文献   

19.
Abstract: Quantifying the hydrologic responses to land use/land cover change and climate variability is essential for integrated sustainable watershed management in water limited regions such as the Loess Plateau in Northwestern China where an adaptive watershed management approach is being implemented. Traditional empirical modeling approach to quantifying the accumulated hydrologic effects of watershed management is limited due to its complex nature of soil and water conservation practices (e.g., biological, structural, and agricultural measures) in the region. Therefore, the objective of this study was to evaluate the ability of the distributed hydrologic model, MIKE SHE to simulate basin runoff. Streamflow data measured from an overland flow‐dominant watershed (12 km2) in northwestern China were used for model evaluation. Model calibration and validation suggested that the model could capture the dominant runoff process of the small watershed. We found that the physically based model required calibration at appropriate scales and estimated model parameters were influenced by both temporal and spatial scales of input data. We concluded that the model was useful for understanding the rainfall‐runoff mechanisms. However, more measured data with higher temporal resolution are needed to further test the model for regional applications.  相似文献   

20.
Abstract: The Soil and Water Assessment Tool (SWAT) has been applied successfully in temperate environments but little is known about its performance in the snow‐dominated, forested, mountainous watersheds that provide much of the water supply in western North America. To address this knowledge gap, we configured SWAT to simulate the streamflow of Tenderfoot Creek (TCSWAT). Located in central Montana, TCSWAT represents a high‐elevation watershed with ~85% coniferous forest cover where more than 70% of the annual precipitation falls as snow, and runoff comes primarily from spring snowmelt. Model calibration using four years of measured daily streamflow, temperature, and precipitation data resulted in a relative error (RE) of 2% for annual water yield estimates, and mean paired deviations (Dv) of 36 and 31% and Nash‐Sutcliffe (NS) efficiencies of 0.90 and 0.86 for monthly and daily streamflow, respectively. Model validation was conducted using an additional four years of data and the performance was similar to the calibration period, with RE of 4% for annual water yields, Dv of 43% and 32%, and NS efficiencies of 0.90 and 0.76 for monthly and daily streamflow, respectively. An objective, regression‐based model invalidation procedure also indicated that the model was validated for the overall simulation period. Seasonally, SWAT performed well during the spring and early summer snowmelt runoff period, but was a poor predictor of late summer and winter base flow. The calibrated model was most sensitive to snowmelt parameters, followed in decreasing order of influence by the surface runoff lag, ground water, soil, and SCS Curve Number parameter sets. Model sensitivity to the surface runoff lag parameter reflected the influence of frozen soils on runoff processes. Results indicated that SWAT can provide reasonable predictions of annual, monthly, and daily streamflow from forested montane watersheds, but further model refinements could improve representation of snowmelt runoff processes and performance during the base flow period in this environment.  相似文献   

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