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1.
On the relation of herbicide adsorption and soil organic fraction Freundlich adsorption isotherms were measured for four herbicides (atrazine, terbuthylazine, chlorotoluron, isoproturon) and 24 soil horizons, which are typical of Schleswig-Holstein, northern Germany. The relationship between the adsorption constant (KFr) of a chemical and the fraction of organic carbon (fOC) of the soil horizons was evaluated. Chemical specific K'OC-values, that are independent of soil organic carbon fraction varied considerably for each herbicide (CV about 50%); therefore these values as well as KOC-values, that are determined by linear regression of KFr and fOC should be evaluated critically before application. K'OC- and KOC-values derived from experiments showed decreasing affinity of the herbicides to soil horizons in the order terbuthylazine > chlorotoluron > atrazine ? isoproturon. Calculation of KOC from KOW or water solubility of each herbicide, however, led to changes in the above mentioned ranking. Hence, especially KOW or water solubility based KOC-values may lead to false conclusions concerning chemical mobility. For atrazine, terbuthylazine and isoproturon Freundlich adsorption constants increased overproportionally with increasing organic carbon content of soils. The relationships between KFr and fOC therefore were described better by a non-linear equation (second order polynom) than by a linear approach. Contrary, for chlorotoluron a linear relation between KFr and fOC holds at least for the range of fOC investigated in this study.  相似文献   

2.
Dimethenamid [2-chloro-N-(2,4-dimethyl-3-thienyl)-N-(2-methoxy-1-methylethyl)acetamide] and flufenacet [N-(4-fluorophenyl)-N-(1-methylethyl)-2-(5-(trifluoromethyl)-1,3,4-thiadiazol-2-yl)oxy] were isolated by C-18 solid-phase extraction and separated from their ethanesulfonic acid (ESA) and oxanilic acid (OXA) degradates during their elution using ethyl acetate for the parent compound, followed by methanol for the polar degradates. The parent compounds were detected using gas chromatography-mass spectrometry in selected-ion mode. The ESA and OXA degradates were detected using high-performance liquid chromatography--electrospray mass spectrometry (HPLC-ESPMS) in negative-ion mode. The method detection limits for a 123-mL sample ranged from 0.01 to 0.07 microg/L. These methods are compatible with existing methods and thus allow for analysis of 17 commonly used herbicides and 18 of their degradation compounds with one extraction. In a study of herbicide transport near the mouth of the Mississippi River during 1999 and 2000, dimethenamid and its ESA and OXA degradates were detected in surface water samples during the annual spring flushes. For flufenacet, the only detections at the study site were for the ESA degradates in samples collected at the peak of the herbicide spring flush in 2000. The low frequency of detections in surface water likely is due to dimethenamid and flufenacet being relatively new herbicides. In addition, detectable amounts of the stable degradates have not been detected in ground water.  相似文献   

3.
The response of Scenedesmus spp. to three phenylureas, namely Maloran, Dicuran, and Patoran was investigated. Chloropyll (a) content, ratio of chlorophyll (a/b), growth rate and dry weight of algae tended to decrease as the concentration of herbicide in the bioassay media was increased. The inhibitory effect of the studied herbicides followed the order; Maloran > Dicuran > Patoran. At low concentration levels, patoran led to an increase in Chl. (a) content, Chl. (a/b) ratio and maximum growth rate. Uptake of the studied compounds by algal cells was at its maximum value in the presence of low herbicide concentrations and tended to decrease as the herbicide concentration was increased. Scenedesmus algal Cells were able to recover and attained their normal growth rate and morphological characteristics when the cells were transferred to a herbicide-free medium. The pH value of the algal media gradually increased as algal growth proceeded. In media containing inhibitory levels of phenylureas, the pH value was unchanged. Statistical analysis indicated that changes in Chl. (a) induced by the herbicides were significant.  相似文献   

4.
Event-based precipitation samples were collected during the main agricultural season (April-September) over 4 years (2000-2003) at one site in the Choptank River Watershed on the Delmarva Peninsula. The samples were analyzed for 19 agricultural pesticides to determine the contribution of wet deposition as a source of these compounds to the Chesapeake Bay and the factors affecting the temporal trends in deposition. Chlorothalonil was detected most frequently (92% samples) followed by metolachlor (66%) and endosulfans (49%). Although chlorothalonil is the single biggest contributor to pesticide flux (33-46%), pesticide wet deposition is dominated by herbicides (46-61%), with the greatest fluxes occurring during the time of herbicide application on corn and soybeans. The analysis suggests that the extent of wet deposition of herbicides depends on the timing of precipitation relative to herbicide application. The insecticide and fungicide flux was greater in years with above-average rainfall (2001 and 2003), suggesting that for these pesticides deposition flux is dependent on the total amount of rainfall in the agricultural season. The data indicate that the use of chlorpyrifos, an organophosphate insecticide which is on the Toxics of Concern list for the Bay, is on the increase. Total pesticide flux ranged from 90 microg/m2 (2001) to 180 microg/m2 (2000). Wet deposition can account for up to 10-20% of the annual loadings of pesticides to the Bay.  相似文献   

5.
The adsorption of herbicides on soil colloids is a major factor determining their mobility, persistence, and activity in soils. Solvent extraction could be a viable option for removing sorbed contaminants in soils. This study evaluated the extractability of three herbicides: 2,4 dichlorophenoxy-acetic acid (2,4-D), 4-chloro-2-methylphenoxypropanoic acid (mecoprop acid or MCPP), and 3,6-dichloro-2-methoxybenzoic acid (dicamba). Three solvents (water, methanol, and iso-propanol) and three methods of extraction (column, batch, and soxhlet) were compared for their efficiencies in removing the herbicides from three soils (loamy sand, silt loam, and silty clay). Both linear and non-linear Freundlich isotherms were used to predict sorption intensity of herbicides on soils subjected to various extraction methods and conditions. High Kdand Kfr, and low N values were obtained for all herbicides in silty clay soil by batch extraction. Methanol was the best solvent removing approximately 97% of all added herbicides from the loamy sand either by column or soxhlet extraction method. Isopropanol ranked second by removing over 90% of all herbicides by soxhelet extraction from all three soils. However, water was ineffective in removing herbicides from any of the soils using any of the three extracting procedures used in this study. In general, the extent of herbicide removal depended on soil type, herbicide concentration, extraction procedure, solvent type and amount, and extraction time.  相似文献   

6.
The straw on the soil in the green cane harvesting system acts as a physical barrier to the action of the pre-emergence herbicides. However, some herbicides have physico-chemical characteristics to pass through the straw in water solution. The aim was to evaluate the influence of different densities of sugarcane straw on the leaching of aminocyclopyrachlor in a tropical soil (Oxisol—Typic Hapludox) in a system of green cane harvesting. The experiment was carried out using glass columns filled with soil, with and without sugarcane straw (0, 5, 10, and 20 t ha?1) on the top of the soil. 14C-aminocyclopyrachlor was applied followed by 200 mm of simulated rain for 48 h. The herbicide was detected in all soil layers (0–30 cm), and in the leachate (>?30 cm), in small trace amounts (≤?0.21%) in all treatments, showing that aminocyclopyrachlor undergoes a high degree of leaching in the clayey soil. In the absence of straw, 39% of the herbicide remained in the upper layer (0–5 cm). In the presence of straw, the herbicide was distributed through the soil profile, mainly from 0 to 25 cm. Forty percent more herbicide was retained in the straw with 20 t ha?1 of sugarcane straw. Thus, it is concluded that the straw in high amounts retains aminocyclopyrachlor, but does not prevent it from reaching the soil; the high solubility of the herbicide and intense rainfall in a short period of time are factors that contribute to the herbicide passing through this barrier.  相似文献   

7.
The effect of light and temperature on the dissipation of four s-triazine herbicides (terbuthylazine, simazine, atrazine and prometryn) was studied in drinking and wastewaters during long-term laboratory incubation (4 months), and by comparing the results with those obtained in purified water (Milli-Q). Residues were analyzed by GC-NPD and confirmed by GC-MSD. A micro on-line method for isolating the herbicide residues was used. The results showed that temperature and light had a certain influence on the behaviour of the s-triazine herbicides. In drinking water, prometryn dissipated more rapidly than the other compounds under all laboratory conditions (t 1/2= 75–128 days), while atrazine showed the highest degree of persistence (t 1/2= 132–227 days). In general, atrazine was the least (t 1/2= 90–142 days) and simazine the most (t 1/2= 118–278 days) persistent compound in Milli-Q and wastewater. Only in the case of atrazine in drinking water was the remaining percentage at the end of the experiment higher than 50% (53–69%). Dissolved organic substances in wastewater (DOC, 53.3 mg l–1) appear to be particularly important in the photosensitization process. The time required to reach the maximum admissible concentration (MAC) according to European legislation (0.1 g l–1) ranged from 3 to 10 years for prometryn and atrazine, respectively, in drinking water depending on the used conditions.  相似文献   

8.
There is no data currently available on acidic pesticides in the drinking water of Greece, although considerable quantities of them are in use. In this study, the occurrence of the six most important acidic herbicides in the drinking water of Greece was investigated. The target compounds studied include four chlorophenoxy herbicides, namely mecoprop, dichlorprop, MCPA and 2,4-D, and two other acidic herbicides, i.e. bromoxynil and bentazone. Analysis was carried out at a concentration level of 100 ng L?1 using capillary gas chromatography-mass spectrometry (GC-MS) with selected ion monitoring (SIM). The method involved a pre-concentration with solid phase extraction and derivatization with pentafluorobenzyl bromide. Thirty-eight samples of drinking water from nine regions in Greece were screened. No herbicides were detected although fortification experiments with parallel water samples resulted in recovery rates better than 70%. The detection limits of the recovered compounds were found to be between 10 and 50 ng L?1.  相似文献   

9.
采用气相色谱-氮磷检测器（GC—NPD）方法,建立了同时测定土壤中13种三嗪类除草剂（脱乙基阿特拉津、莠去通、西玛津、莠去津、扑灭津、特丁津、敌草净、赛克津、西草净、莠灭净、扑草净、异丙净、甲氧丙净）残留量的方法。土壤样品用乙腈-水混合提取剂经超声波提取20min,弗罗里硅土（Florisil）固相萃取柱净化后,毛细管柱分离样品,NPD测定。结果表明,13种三嗪类除草剂在0．05-5．0mg·L^-1范围内线性关系良好,相关系数均大于0．999;添加回收率在72．7％～128．2％之间;相对标准偏差在0．4％～20．5％;方法的检出限在0．001-0．005mg·kg^-1之间。  相似文献   

10.
Ground and surface water contamination by herbicides applied to olive groves in Spain and other Mediterranean countries is demanding strategies to prevent and remediate the environmental problems repeatedly caused by such herbicides. In this study, six different organic cations (L-carnitine, spermine, hexadimethrine, tyramine, phenyltrimethylammonium, and hexadecyltrimethylammonium) were incorporated into Na-rich Wyoming montmorillonite (SWy-2) and Ca-rich Arizona montmorillonite (SAz-1) at two different loadings (50% and 100% of the cation exchange capacity of the clays) as a strategy to enhance the affinity of the clay minerals for three herbicides widely used in olive groves: terbuthylazine, diuron, and MCPA. The modified montmorillonites were characterized and tested as adsorbents of the herbicides through batch adsorption tests. At the experimental conditions used, some of the modified montmorillonites removed more than 95% of the herbicide initially present in aqueous solution, whereas the unmodified clays removed less than 15%. All three herbicides displayed very strong affinities for SAz-1 exchanged with hexadecyltrimethylammonium cations, particularly when these were incorporated at 100% of the cation exchange capacity of the clay mineral. Terbuthylazine and diuron also displayed very strong affinities for SWy-2 exchanged with L-carnitine and spermine, respectively. The chemical characteristics of the organic cation greatly influenced the adsorptive properties of the resultant organoclay. The herbicides were in general reversibly adsorbed by the modified clays. The results indicate that some of the tested modified clays could be suitable for the removal of the assayed herbicides from contaminated water and also as possible supports for the design of slow release formulations of such herbicides to attenuate their environmental impact when used in high-risk scenarios such as olive groves.  相似文献   

11.
Cloudwater samples have been collected for the first time at a high-elevation site in the US interior Southwest. Cloud samples were collected at the summit of Mt. Elden near Flagstaff, Arizona. The samples were analyzed for pH, ionic composition, trace metals, organic carbon content, and volatile organic compounds. All of the samples showed high pH values (5.12–6.66), which appear to be the result of soil/crustal acid-neutralizing components. Ammonium and nitrate were the dominant ionic species. Organic carbon concentrations ranged from 3 to 18 mg/l. Volatile aromatic compounds (toluene, ethylbenzene, and xylenes) were detected, although they did not contribute significantly to the dissolved organic matter (<1% of dissolved organic carbon). Still, their aqueous-phase concentrations were substantially higher than equilibrium partitioning from the gas phase would suggest. Metal concentrations were high when compared to other cloud studies in remote areas. Overall, with the exception of pH, the cloud chemistry showed marked inter-event variability. The source of the variability was investigated using NOAA HYSPLIT dispersion calculations. Like the cloud composition, the air mass back trajectories differed widely from event to event, and consistently, air masses that passed over highly urbanized areas had higher trace metal, organic, and ion concentrations than more pristine air masses.  相似文献   

12.
The effect of 25 herbicides and herbicide combinations, in amounts comparable to those used in agriculture, on microbial activity in two soil types was determined in the laboratory. Herbicides did not affect respiration, assayed by CO2 evolution and dehydrogenase activity, in either silty clay loam or loamy sand. Organic matter decomposition, determined by the amount of CO2 evolved and inorganic N formed from decomposing alfalfa tissue, was also not affected. Alteration in soil pH or moisture content did not affect herbicide action. Addition of herbicides 3 weeks before amendment, or fertilizer application, also did not influence herbicide activity. Selected herbicides (trifluralin, linuron, dinoseb) at concentrations 100-fold higher than the recommended rates did not affect alfalfa decomposition. Solubilization of Ca3(PO4)2 in soil was not affected by herbicides. S oxidation to SO2?4 in soil, however, was increased by most herbicides. In silty clay loam, 18 of the 25 herbicides and herbicide combinations increased S oxidation almost up to 3-fold. Results in loamy sand were similar. Dinoseb effectively reduced the algal population in loamy sand by more than 90%. Trifluralin, linuron, and metribuzin did not inhibit algal populations.  相似文献   

13.
In situ denitrification walls and biofilters made of wood chips are being implemented as innovative technologies for the removal of nitrates in tile drainage water from farms to reduce pollution of surface waters and the hypoxia problem in the Gulf of Mexico. Although fairly effective in removing nitrates, not much is known about the effectiveness of the biofilters in removal of herbicides, pesticides, and antibiotics in the drainage water. Using weathered wood chips obtained from an in situ denitrification wall, four common pollutants tested sorbed strongly to wood chips in the following order: enrofloxacin > monensin A > atrazine > sulfamethazine. Of the four chemicals tested, enrofloxacin was found to desorb the least by water extraction. The apparent hysteresis index for atrazine was found to be lower than that for enrofloxacin and sulfamethazine indicating greater sorption?Cdesorption hysteresis for atrazine than enrofloxacin and sulfamethazine. Consecutive steps of water desorption and organic solvent extraction indicated that more than 65% of the sorbed atrazine, 70% of sulfamethazine, 90% of enrofloxacin, and 80% of monensin A were retained in wood chips. Results of this study showed that wood chip denitrification walls or biofilters have an added benefit in retaining herbicides and antibiotics and therefore can act as a barrier to reduce pollution of surface water and groundwater.  相似文献   

14.
The occurence of organic priority pollutants in groundwater and surface water impacted by municipal landfill leachate was studied at the Orange County Landfill in Orange County, Florida. The results of the investigation were compared to existing data from two municipal landfills in Alachua County, Florida. The investigation in Orange County evaluated existing wells and surface water stations through sampling of groundwater, surface water, sediment, and aquatic biota. Very few organic priority pollutants were detected. The constituents most frequently found were volatile organic compounds, particularly aromatic organic constituents. Volatile organic compounds were detected in groundwater at total concentrations of less than 100 Μg L?1. Few base/neutral and acid extractable organic priority pollutants were detected. Data from the Alachua County landfills indicated the presence of volatile organic compounds in groundwater at both landfill sites but few organic priority pollutants in the base/neutral and acid extractable group were fouund. Any organic priority pollutants that were present in the solid waste as deposited were likely metabolized by microorganisms or otherwise degraded, sorbed on particulate matter, or diluted to such an extent as to be non-detected.  相似文献   

15.
Experimental plots within the Hubbard Brook Experimental Forest, NH, were treated with sodium trifluoroacetate (TFA) and lithium bromide (Br), to study the impact of TFA alone and in the presence of increased anion concentrations (e.g. acid deposition) on the soil solution chemistry of a northern hardwood forest soil. Trifluoroacetate is a major atmospheric degradation product of replacement compounds of chlorofluorocarbons (CFC) and Br is widely used as a hydrologic tracer. Calculated drainage losses via soil water flow were less than 60% of inputs, added during the summer, and TFA and Br were temporarily retained in the soil until fall. The initial indication of an acid input of the treatments (HTFA, HBr) in the Bs2 horizon, which reflects stream water chemistry as well, was an increase of base cations in the soil solution, decreasing the soil's acid neutralizing capacity. Thereafter, trifluoroacetate and Br concentrations peaked after the peak in base cations, synchronous with peaks in H+ and Al concentrations. Organic anions, nitrate and chloride played the major role in accompaning base cations out of the solum. Sulfate retention at soil adsorption sites was increased by the presence of TFA and Br, reducing its role as a mobile anion of base cations in this experiment. Relative retention of anions for the whole profile of this northern hardwood forest soil was estimated by correlation analyses and input-output balances in decreasing order on an equivalant basis: SO4 > TFA = Br ≥ Cl > NO3 > organic anions. Recovery from acid additions were recorded within several weeks after the treatments were stopped. Evaluating the impact of added chemical compounds to soils must be considered within the context of linkages among element cycles and pools.  相似文献   

16.
 The interactive effects of vermi-compost from sewage sludge and either the sulfonylurea herbicide, rimsulfuron, or the imidazolinone herbicide, imazethapyr, on some soil biochemical and microbiological properties were investigated. The herbicides were applied at field and 10-fold field rates. Both herbicides exerted a detrimental effect on soil microbial biomass and its biochemical properties. Even though the effect of both herbicides on soil microbial biomass was not detectable at the field rate, some significant influences on acid and alkaline phosphatase were observed. The higher rate of herbicide application impaired the observed microbial parameters to a greater degree. The detrimental effects seemed to be reduced by organic amendments. Among the studied microbial characteristics, the specific respiration quotient was particularly reliable and sensitive in determining the influence of herbicides on the soil microbial biomass. In this paper a new synthetic index, specific hydrolytic activity (qFDA), for assessing microbial activity in reply to xenobiotic treatments is proposed. Received: 31 May 1999  相似文献   

17.
Abstract

A field study was conducted to assess the fate and mobility of two commonly used herbicides, dicamba (3,6‐dichloro‐2‐methoxybenzoic acid), and picloram (4‐amino‐3,5,6, trichloro‐2 pyridinecarboxylic acid), in an irrigated pasture. The herbicides were applied at two application rates to four plots (two replicates) that contained soil‐water collectors. Herbicide concentrations as a function of depth and application rate were evaluated statistically to determine if replicate data could be combined. Results indicated dicamba concentration variations were low, suggesting the mean value of the replicate plots could be compared; however, picloram concentration variations were high, and the replicate plot data could not be combined. Half‐time values for herbicide disappearance (time required for herbicide concentration to diminish from its maximum to half maximum levels), calculated from the arithmetic mean of the logistic equations, were found to be useful in describing herbicide transport. Half‐time values were dependent upon application rate, collector depth, pesticide type, and plot location. Dicamba applied at the low application rate was detected at 15 and 30 cm depths only, and was not detected throughout the entire study period (467 days) at deeper depths. Significant differences occurred between plots receiving the high dicamba application rate, which was attributed to permeability differences that affected herbicide migration in the soil profile. Picloram half‐time values were also affected by soil organic carbon, which increased picloram adsorption. In general, differences in herbicide concentrations were observed within plots receiving the high picloram application rates, which was primarily attributed to spatial differences in hydraulic conductivity. Herbicide disappearance was most rapid at the shallow depth (e.g., 15 cm) within plots receiving lower herbicide application rates.  相似文献   

18.
Several volatile organic compounds associated with petroleum fuels (mainly alkylated benzenes) were extracted from spiked fish tissue samples with a stream of air, trapped on charcoal, eluted with a solvent, and analyzed by gas chromatography. These volatile compounds are among the most water-soluble components of crude oils and petroleum products, and they have been associated with tainting in fish tissues. Recoveries for these compounds were about 90% when spiked directly either onto traps or into fish tissues although naphthalene desorbed poorly from the charcoal; recoveries of this compound were about 50%. Relative standard deviations (RSD) for most recoveries of spiked samples were in the 2-10% range based on 6 samples analyzed in duplicate. However, when live fish were contaminated experimentally by adding the aromatic compounds to the aquarium water, the RSDs were higher (10-30%).  相似文献   

19.
The addition of organic amendments to soil increases soil organic matter content and stimulates soil microbial activity. Thus, processes affecting herbicide fate in the soil should be affected. The objective of this work was to investigate the effect of olive oil production industry organic waste (alperujo) on soil sorption-desorption, degradation, and leaching of diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] and terbuthylazine [N2-tert-butyl-6-chloro-N4-ethyl-1,3,5-triazine-2,4-diamine], two herbicides widely used in olive crops. The soils used in this study were a sandy soil and a silty clay soil from two different olive groves. The sandy soil was amended in the laboratory with fresh (uncomposted) alperujo at the rate of 10% w/w, and the silty clay soil was amended in the field with fresh alperujo at the rate of 256 kg per tree during 4 years and in the laboratory with fresh or composted alperujo. Sorption of both herbicides increased in laboratory-amended soils as compared to unamended or field-amended soils, and this process was less reversible in laboratory-amended soils, except for diuron in amended sandy soil. Addition of alperujo to soils increased half-lives of the herbicides in most of the soils. Diuron and terbuthylazine leached through unamended sandy soil, but no herbicide was detected in laboratory-amended soil. Diuron did not leach through amended or unamended silty clay soil, whereas small amounts of terbuthylazine were detected in leachates from unamended soil. Despite their higher sorption capacity, greater amounts of terbuthylazine were found in the leachates from amended silty clay soils. The amounts of dissolved organic matter from alperujo and the degree of humification can affect sorption, degradation, and leaching of these two classes of herbicides in soils. It appears that adding alperujo to soil would not have adverse impacts on the behavior of herbicides in olive production.  相似文献   

20.
A new bioassay method for measurement of herbicides in soil and water is reported in this paper. It is based on the effect of herbicides on the oxygen produced by photosynthesis and estimation of this oxygen by the bioluminescence system of photobacteria. The method was rapid and sensitive, being capable of estimating herbicide concentration of 2 parts/108 within an hour. The high specificity of the reaction allowed the technique to be used directly without any extraction or purification of the herbicide from samples.  相似文献   

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