Multi-residues analysis of pre-emergence herbicides in fluvial sediments: application to the mid-Garonne River

Contamination of man and ecosystems by pesticides has become a major environmental concern. Whereas many studies exist on contamination from agriculture, the effects of urban sources are usually omitted. Fluvial sediment is a complex matrix of pollutants but little is known of its recent herbicide content. This study proposes a method for a fast and reliable analysis of herbicides by employing the accelerated solvent extractor (ASE). The aim of the study is to show the impact of a major town (Toulouse) on the herbicide content in the river. In this study, three herbicide families (i.e.s-triazine, substituted ureas and anilides) were analysed in fluvial sediment fractions at 11 sampling sites along the mid-Garonne River and its tributaries. River water contamination by herbicides is minor, except for at three sites located in urban areas. Among the herbicidal families studied, urban and suburban areas are distinguished from rural areas and were found to be the most contaminated sites during the study period, a winter low-water event. The herbicide content of the coarse sediment fractions is about one third of that found in the fine fractions and usually ignored. The distribution of pesticide concentrations across the whole range of particle sizes was investigated to clarify the role of plant remains on the significant accumulation in the coarse fractions.     

The effects of pesticide mixtures on degradation of pendimethalin in soils

Most agronomic situations involve a sequence of herbicide, fungicide, and insecticide application. On the other hand, use of pesticidal combinations has become a standard practice in the production of many agricultural crops. One of the most important processes influencing the behavior of a pesticide in the environment is its degradation in soil. It is known that due to several pesticide applications in one vegetation season, the pesticide may be present in mixtures with other pesticides or xenobiotics in soil. This study examines the role which a mixture of chemicals plays in pesticide degradation. The influence of other pesticides on the rate of pendimethalin (PDM) degradation in soil was measured in controlled conditions. Mixtures of PDM with mancozeb or mancozeb and thiamethoxam significantly influenced the degradation of pendimethalin under controlled conditions. The second type of mixtures, with metribuzin or thiamethoxam, did not affect the behavior of pendimethalin in soil. Also, we determined the influence of water content on the rate of pendimethalin degradation alone in two soils and compared it to the rate in three pesticide mixtures. We compared two equations to evaluate the predictors of the rate of herbicide dissipation in soil: the first-order kinetic and the non-linear empirical models. We used the non-linear empirical model assuming that the degradation rate of a herbicide in soil is proportional to the difference of the observed concentration of herbicide in soil at time and concentration of herbicide in the last day of measurement.     

Fate and movement of atrazine, cyanazine, metolachlor and selected degradation products in water resources of the deep Loess Hills of Southwestern Iowa, USA

The environmental fate and movement of herbicides widely used for weed control in corn are assessed for a deep loess soil in southwestern Iowa. Beginning in the early 1980s, the herbicide-based weed control program emphasized the application of atrazine (ATR) or cyanazine (CYN) and metolachlor (MET) for both broadleaf and grass control. Between 1992 and 1995, concentrations of ATR, desethylatrazine (DEA), desisopropylatrazine (DIA), CYN and MET were measured in rainwater, both shallow and deep vadose zone water, and well water. Results show that the frequency of herbicide detections and the range and distribution of occurrences are dependent upon both landscape position and temporal inputs of recharge water from rainfall. Generally, DIA was observed more frequently and in higher mean concentration in well water than DEA, while DEA was observed more frequently than DIA in vadose zone groundwater. A chromatographic analogy is suggested to explain the occurrence patterns observed for both parent herbicide and degradation products within the unsaturated zone water. Analysis of rainwater samples collected during this time also revealed low concentrations of ATR, CYN and MET, with the timing of the detections indicative of non-local transport. Results show that the deep loess soil conducts both water and agricultural chemicals relatively rapidly and as such represents a production system which is vulnerable to contamination of shallow groundwater by herbicide-derived chemicals. Results also illustrate the importance of including major herbicide degradation products in water resource impact assessment studies.     

Fluroxypyr biodegradation in soils by multiple factors

Fluroxypyr (4-amino-3,5-dichloro-6-fluoro-2-pyridinyl-1-methylheptyl ester) is a widely used herbicide for controlling weeds, fungi, and insects. However, extensive use of the herbicide has led to its high accumulation in ecosystems and contamination to soils and crops. Environmental behaviors and fate of herbicides are dependent on many physiochemical and biological factors. Whether fluroxypyr is significantly affected and how it is degraded under the environmental conditions is largely unknown. The present study investigated the effects of soil microbe, soil type, dissolved organic matter (DOM), temperature, soil moisture, and surfactant on fluroxypyr degradation in soils. Application of DOM derived from sludge and straw to fluroxypyr-contaminated soils increased degradation of fluroxypyr. Environmental factors such as temperature, moisture, soil microbe and soil type could affect the rate of fluroxypyr dissipation. Also, the microorganism affected the degradation of fluroxypyr. Analysis by gas chromatography-mass revealed that the reaction in soils might include the removal of 1-methylheptyl ester to generate fluroxypyr acid (4-amino-3,5-dichloro-6-fluoro-2-pyridiny). Our results provided initial data that a set of biological and physiochemical factors coordinately regulates the decay of fluroxypyr in soils.     

Occurrence and behaviour of organophosphorus insecticides in the River Wuchuan,southeast China

Organophosphorus (OP) insecticides are used worldwide, yet their persistence in the environment is not well understood. This paper summarises recent research on 17 OP insecticides in the River Wuchuan, an important catchment in China, by determining their concentrations in water, soil, sediment and plants by gas chromatography with flame photometric detection (GC-FPD). The concentrations of the total OP insecticides ranged from 92.77 to 229 ng l-1 in river water, 1.61 to 9.93 ng g-1 dry weight in soil, 1.24 to 7.56 ng g-1 dry weight in sediment and 75.28 to 326 ng g-1 dry weight in plants. There was a relatively high abundance of methamidophos, dichlorvos, malathion, omethoate and dimethoate in all water, soil, sediment and plant samples. On average, these five compounds collectively accounted for 64%, 71%, 71% and 54% of the total OP insecticide concentration in water, soil, sediment and plants, respectively, which was similar to the composition of OP insecticides in application formulations used in our study area and in China as a whole. The results therefore reflect the application pattern to some extent, and suggest that the sources of the OP insecticides are mainly from current usage. When compared with other areas, the levels of OP insecticides in the River Wuchuan were moderate. The animal and human risks from exposure to OP insecticides in water and plants were evaluated against relevant threshold values. The results therefore provide important information on the current contamination status of a key agricultural watershed in China, and point to the need for urgent action to control the use of some excessively applied and potentially persistent agrochemicals, such as methamidophos, omethoate and dimethoate.     

水上事故溢油运动轨迹与环境归宿预测模型的研究进展

以事故溢油在水面上的运动轨迹和环境归宿为研究对象,重点对溢油水下分散过程、岸边黏附及受水流冲刷下油膜质量衰减过程、水体悬浮物对石油黏附/吸附量的预测模型研究成果,以及目前日益受到关注的河流溢油模型的研究进展进行归纳总结。对比分析了不同预测模型结构功能差异和适用性问题,为不同环境条件下溢油事故的后预警、后预测提供模型选择依据和技术支持。最后就溢油模型尚存的一些问题及未来发展的方向进行了探讨。     

Atrazine Transport Within a Coastal Zone in Southeastern Puerto Rico: a Sensitivity Analysis of an Agricultural Field Model and Riparian Zone Management Model

Agrichemical runoff from farmland may adversely impact coastal water quality. Two models, the Agricultural Policy/Environmental eXtender (APEX) and the Riparian Ecosystem Management Model (REMM), were used to evaluate the movement of the herbicide atrazine to the Jobos Bay National Estuarine Research Reserve from adjacent fields. The reserve is located on Puerto Rico’s southeast coast. Edge-of-field atrazine outputs simulated with the APEX were routed through a grass-forest buffer using the REMM. Atrazine DT₅₀ (half-life) values measured in both field and buffer soils indicated that accelerated degradation conditions had developed in the field soil due to repeated atrazine application. APEX simulations examined both the measured field and buffer soil atrazine DT₅₀ and the model’s default value. The use of the measured field soil atrazine degradation rate in the APEX resulted in 33 % lower atrazine transport from the field. REMM simulations indicated that the buffer system had the potential to reduce dissolved atrazine transport in surface runoff by 77 % during non-tropical storm events by increasing infiltration, slowing transport, and increasing time for pesticide degradation. During a large runoff event due to a tropical storm that occurred close to the time of an atrazine application, the REMM simulated only a 37 % reduction in atrazine transport. The results indicate that large storm events soon after herbicide application likely dominate herbicide transport to coastal waters in the region. These results agree with water quality measurements in the reserve. This study demonstrated the sensitivity of these models to variations in DT₅₀ values in evaluating atrazine fate and transport in the region and emphasizes that the use of measured DT₅₀ values can improve model accuracy.     

Transport and fate of organochlorine pesticides in the River Wuchuan,southeast China

Persistent organic pollutants (POPs) such as chlorinated pesticides are of global concern due to their widespread occurrence, persistence, bioaccumulation and toxicity to animals and human. This paper summarises recent research on 18 chlorinated pesticides in an important catchment in China, by determining their concentrations and behaviour in water, sediment, soil and plants. The concentrations of the total pesticides were in the ranges 187-893 ng l(-1) in river water, 8.53-210 ng g(-1) dry weight in soil, 2.66-13.45 ng g(-1) dry weight in river sediment, and 651-2823 ng g(-1) dry weight in plants. The predominance of beta-HCH as the major isomer of HCHs in all water, soil, sediment and plant samples was clearly observed, due to beta-HCH's resistance to biodegradation. On average beta-HCH accounted for 44%, 53%, 50%, and 46% of the total HCH concentration in water, soil, sediment and plant, respectively. Of the DDTs, DDE accounted for 48%, 43%, 53%, 55% of the total DDT, which suggested that DDT had been transformed to its metabolites, DDE and DDD, of which DDE was the more stable. The chlorinated pesticide levels in the River Wuchuan were generally below the guideline values in China, but some sites displayed levels in excess of EC Environmental Quality Standards for HCHs and DDTs. The results therefore provide important information on the current contamination status of a key agricultural watershed in China, and point to the need for urgent actions to evaluate the long-term fate and toxicity of such persistent compounds and an appropriate remediation strategy.     

profiling areas of ground water contamination by pesticides in california: phase ii – evaluation and modification of a statistical model

A well sampling study was conducted to evaluate anempirical approach to classifying areasof land in California as vulnerable to ground watercontamination by pesticides (Troiano et al., 1994). Wells were sampled from sections of land that had noprevious detections of pesticideresidues. The sections had been classified into vulnerablesoil clusters or into a not-classified groupusing a procedure based on Principal Components Analysis(PCA). Grape, citrus, and olive growingareas of Fresno and Tulare Counties were targeted, areas wherepre-emergence herbicide residues hadbeen detected in well water. Overall, herbicide residues weredetected in 75 of 176 sampled wells, ahigh frequency of detection in relation to results fromprevious targeted well sampling studies. Sinceresidues were also detected in the not-classified group, theclassification procedure was modified usingan approach based on Canonical Variates Analysis (CVA). Moresections were classified intovulnerable soil clusters with the CVA approach than with thePCA method. Data from two otherexplanatory variables, depth to ground water and amount ofpesticide used per section, were includedto illustrate how additional information can be incorporatedinto this approach of identifying vulnerable areas.     

New procedures for simultaneous determination of mesotrione and atrazine in water and soil. Comparison of the degradation processes of mesotrione and atrazine

A method for the determination of residues of mesotrione, atrazine and its degradation products: deethylatrazine, hydroxyatrazine, deisopropylatrazine, desethyldesisopropylatrazine in a variety of water and soil matrices has been developed. Mesotrione is a new selective herbicide for use in corn, which has been substituted for atrazine, which has been banned in European Union countries since 2007. Although atrazine has not been used for three vegetative periods, it is still detected in the environment. The analysis was conducted by means of ultra-high-pressure liquid chromatography with ultraviolet detection and liquid chromatography with diode array detection. The procedures for analyte separation from water and soil matrices were also established. The optimal conditions for solid-phase extraction (SPE) were determined. The recoveries were compared with that obtained by means of SPE. Method fortification recoveries from water samples averaged 78–97% and for soil 80–97% depending on the analyte and type of sample. The limits of detection were 0.04–0.61 μg/L for water samples and for soil samples 0.02–0.88 μg/g. The soil samples were collected in spring 2009 from three different fields with water samples being made from effluents from these fields. Samples collection was conducted in the day of mesotrione (Callisto 100SC) application and then done weekly, until the mesotrione concentration was below the limit of quantification. The results enabled the monitoring of mesotrione degradation in soil and its permeability into surface waters; simultaneously, the same studies were conducted for atrazine.     

Simulation of soil loss processes based on rainfall runoff and the time factor of governance in the Jialing River Watershed,China

Jialing River is the largest tributary in the catchment area of Three Gorges Reservoir, and it is also one of the important areas of sediment yield in the upper reaches of the Yangtze River. In recent years, significant changes of water and sediment characteristics have taken place. The "Long Control" Project implemented since 1989 had greatly changed the surface appearance of the Jialing River Watershed (JRW), and it had made the environments of the watershed sediment yield and sediment transport change significantly. In this research, the Revised Universal Soil Loss Equation was selected and used to predict the annual average amount of soil erosion for the special water and sediment environments in the JRW after the implementation of the "Long Control" Project, and then the rainfall–runoff modulus and the time factor of governance were both considered as dynamic factors, the dynamic sediment transport model was built for soil erosion monitoring and forecasting based on the average sediment yield model. According to the dynamic model, the spatial and temporal distribution of soil erosion amount and sediment transport amount of the JRW from 1990 to 2007 was simulated using geographic information system (GIS) technology and space-grid algorithm. Simulation results showed that the average relative error of sediment transport was less than 10% except for the extreme hydrological year. The relationship between water and sediment from 1990 to 2007 showed that sediment interception effects of the soil and water conservation projects were obvious: the annual average sediment discharge reduced from 145.3 to 35 million tons, the decrement of sediment amount was about 111 million tons, and decreasing amplitude was 76%; the sediment concentration was also decreased from 2.01 to 0.578 kg/m³. These data are of great significance for the prediction and estimation of the future changing trends of sediment storage in the Three Gorges Reservoir and the particulate non-point source pollution load carried by sediment transport from watershed surface.     

Arsenic distribution in water/sediment system of Sevojno

Arsenic is a toxic and carcinogenic element. Its toxicity depends on its oxidation state and its concentration. The aim of this paper is to determine, for the first time, the concentration levels of arsenic in water and sediment during the spring/summer period of 2009 in Sevojno, a region in West Serbia with a long industrial tradition, as well as to determine the model of arsenic distribution in water/sediment system and the level of its compatibility with the existing theoretical model. Adsorption is a continual process in the environment. It plays a very important role in the transport and fate of pollutants, especially in sediment. The adsorption of arsenic was examined using the Freundlich adsorption isotherm.     

Empirical evaluation of spatial and non-spatial European-scale multimedia fate models: results and implications for chemical risk assessment

Multimedia environmental fate models are commonly-applied tools for assessing the fate and distribution of contaminants in the environment. Owing to the large number of chemicals in use and the paucity of monitoring data, such models are often adopted as part of decision-support systems for chemical risk assessment. The purpose of this study was to evaluate the performance of three multimedia environmental fate models (spatially- and non-spatially-explicit) at a European scale. The assessment was conducted for four polycyclic aromatic hydrocarbons (PAHs) and hexachlorobenzene (HCB) and compared predicted and median observed concentrations using monitoring data collected for air, water, sediments and soils. Model performance in the air compartment was reasonable for all models included in the evaluation exercise as predicted concentrations were typically within a factor of 3 of the median observed concentrations. Furthermore, there was good correspondence between predictions and observations in regions that had elevated median observed concentrations for both spatially-explicit models. On the other hand, all three models consistently underestimated median observed concentrations in sediment and soil by 1-3 orders of magnitude. Although regions with elevated median observed concentrations in these environmental media were broadly identified by the spatially-explicit models, the magnitude of the discrepancy between predicted and median observed concentrations is of concern in the context of chemical risk assessment. These results were discussed in terms of factors influencing model performance such as the steady-state assumption, inaccuracies in emission estimates and the representativeness of monitoring data.     

Monitoring of selected veterinary antibiotics in environmental compartments near a composting facility in Gangwon Province, Korea

Many studies have been recently reported that veterinary antibiotics released into the environment have a detrimental effect on humans such as the occurrence of antibiotic-resistant bacteria. However, only limited information is available regarding to the release of antibiotics in environmental compartments in Korea. Objectives of this study were to evaluate the concentrations of antibiotics in water, sediment, and soil adjacent to a composting facility in Korea and to determine the dilution effects of antibiotics when released into the environment. Seven antibiotics of chlortetracycline, oxytetracycline, tetracycline, sulfamethazine, sulfamethoxazole, sulfathiazole, and tylosin were evaluated by high-performance liquid chromatography?Ctandem mass spectrometry following pretreatment using solid-phase extraction to clean the samples. Results showed that the highest concentration of each antibiotic in both aqueous and solid samples was detected from a site adjacent to the composting facility. We also found that the studied water, sediment, and soil samples are contaminated by veterinary antibiotics throughout comparison with studies from other countries. However, relatively lower concentrations of each antibiotic were observed from the rice paddy soil located at the bottom of the water stream. Further research is necessary to continuously monitor the antibiotics release into ecosystems, thereby developing an environmental risk assessment.     

Estimation of suspended sediment concentration in rivers using acoustic methods

Acoustic Doppler current meters (ADV, ADCP, and ADP) are widely used in water systems to measure flow velocities and velocity profiles. Although these meters are designed for flow velocity measurements, they can also provide information defining the quantity of particulate matter in the water, after appropriate calibration. When an acoustic instrument is calibrated for a water system, no additional sensor is needed to measure suspended sediment concentration (SSC). This provides the simultaneous measurements of velocity and concentration required for most sediment transport studies. The performance of acoustic Doppler current meters for measuring SSC was investigated in different studies where signal-to-noise ratio (SNR) and suspended sediment concentration were related using different formulations. However, these studies were each limited to a single study site where neither the effect of particle size nor the effect of temperature was investigated. In this study, different parameters that affect the performance of an ADV for the prediction of SSC are investigated. In order to investigate the reliability of an ADV for SSC measurements in different environments, flow and SSC measurements were made in different streams located in the Aegean region of Turkey having different soil types. Soil samples were collected from all measuring stations and particle size analysis was conducted by mechanical means. Multivariate analysis was utilized to investigate the effect of soil type and water temperature on the measurements. Statistical analysis indicates that SNR readings ob tained from the ADV are affected by water temperature and particle size distribution of the soil, as expected, and a prediction model is presented relating SNR readings to SSC mea surements where both water temperature and sediment characteristics type are incorporated into the model. The coefficients of the suggested model were obtained using the multivariate anal ysis. Effect of high turbidity conditions on ADV performance was also investigated during and after rain events.     

新疆图木舒克地区土壤盐渍化空间分布特征

土壤盐渍化已成为影响图木舒克地区农业生产与生态环境的重要因素。本文以0~150 cm深度范围内土壤和地下水为研究对象,利用实际野外调查与数据统计分析的方法,研究得出:①强盐渍化主要分布于距离河流与渠道较远的地下水浅埋深区域,在纵向上表层聚盐现象明显,盐渍土类型随着土壤层深度加大从亚氯-亚硫酸盐渍土变为亚硫酸盐渍土。②土壤易溶盐含量与地下水化学类型在平面分布上吻合程度较高、与潜水矿化度呈正的高度相关性、与潜水埋藏深度呈负的中度相关性、沿潜水径流方向各层土壤盐渍化减弱。③当地下水埋深较浅时,潜水通过毛细管将易溶盐带入土壤表层,形成表层土壤盐渍化;地下水埋藏较深时,易溶盐分会随着降水淋滤和灌溉冲洗不断降低,地表盐渍化减弱。中、轻度盐渍化区域应控制灌溉用水矿化度,重度盐渍化及盐土区域可在建立排水系统的基础上采用泡田洗盐法。     

Quantification and source identification of polycyclic aromatic hydrocarbons in sediment, soil, and water spinach from Hanoi, Vietnam

Polycyclic aromatic hydrocarbons (PAHs) were quantified in sediment, soil, and plant material from Hanoi, Vietnam, and an aquatic production system in peri-urban Hanoi. The sum of the concentration of 16 US-EPA priority PAHs ( summation PAH16) ranged between 0.44 and 6.21 mg kg(-1) dw in sediment and between 0.26 and 1.35 mg kg(-1) dw in soil, with decreasing concentrations from the urban area to the peri-urban area, indicating contributions from urban and industrial sources. Double plots of diagnostic source ratios indicate that PAHs originate from mixed petrogenic and pyrogenic sources, the latter being predominant. The predominance of low molecular weight (LMW) PAHs in the sediment samples suggests that petrogenic sources are more prevalent in the water environment than in the soil. In contrast, high molecular weight (HMW) PAHs dominated in water spinach which probably reflects the plant's uptake of particle-bound PAHs that originate from pyrogenic sources.     

Soil erosion and sediment fluxes analysis: a watershed study of the Ni Reservoir,Spotsylvania County,VA, USA

Anthropogenic forces that alter the physical landscape are known to cause significant soil erosion, which has negative impact on surface water bodies, such as rivers, lakes/reservoirs, and coastal zones, and thus sediment control has become one of the central aspects of catchment management planning. The revised universal soil loss equation empirical model, erosion pins, and isotopic sediment core analyses were used to evaluate watershed erosion, stream bank erosion, and reservoir sediment accumulation rates for Ni Reservoir, in central Virginia. Land-use and land cover seems to be dominant control in watershed soil erosion, with barren land and human-disturbed areas contributing the most sediment, and forest and herbaceous areas contributing the least. Results show a 7 % increase in human development from 2001 (14 %) to 2009 (21.6 %), corresponding to an increase in soil loss of 0.82 Mg ha^-1 year^-1 in the same time period. ²¹⁰Pb-based sediment accumulation rates at three locations in Ni Reservoir were 1.020, 0.364, and 0.543 g cm^-2 year^-1 respectively, indicating that sediment accumulation and distribution in the reservoir is influenced by reservoir configuration and significant contributions from bedload. All three locations indicate an increase in modern sediment accumulation rates. Erosion pin results show variability in stream bank erosion with values ranging from 4.7 to 11.3 cm year^-1. These results indicate that urban growth and the decline in vegetative cover has increased sediment fluxes from the watershed and poses a significant threat to the long-term sustainability of the Ni Reservoir as urbanization continues to increase.     

土壤侵蚀的环境磁学监测方法

依据土壤、沉积物磁性理论,河流或湖泊的悬移物和沉积物记载了其产地的磁信息,根据它们的磁性参数可以追踪其来源及分布范围;根据表土磁性增强现象,可以采用土壤剖面磁性变化方法来判断土壤侵蚀程度;另外,应用“磁性示踪剂”也是研究土壤侵蚀的有效手段。文章就这方面的国内外研究进展情况加以阐述,并对该方法的优缺点及发展前景提出看法。     

Contamination by lead in sediments at Toledo River,hydrographic basin of PARANÁ III

Due to intense agricultural and industrial activities, the environment has been affected by increasing amounts of pollutants, such as lead, a toxic heavy metal. When introduced to the environment, toxic metals are distributed and incorporated into the liquid medium, sediments, and aquatic biota; bioaccumulating. This research aimed to identify and quantify the levels of toxic metals present in the waters and sediments of Toledo River, compare the obtained results with legislation and other studies, as well as to evaluate the possible pollutant sources of the water body. Six water and sediment samples were taken at seven strategic sites. The concentrations of Cu, Zn, Fe, Mn, Cd, Pb, and Cr in water were compared to the maximum limits established by Brazilian legislation IN CONAMA No. 357/05, for class II fresh waters. The sediment samples were submitted to nitroperchloric digestion, and then the total concentrations of the metals were determined by flame atomic absorption spectrometry (FAAS). The toxicological quality of the Toledo River has been considerably affected by the activities carried out in its surroundings, such as extensive areas of agriculture, pig farming and industrial areas, causing concentrations of Cd, Fe, and mainly Pb, which is observed at concentrations higher than value allowed by the legislation.