Assessing copper thresholds for phytotoxicity and potential dietary toxicity in selected vegetable crops

Copper pollution in soils is widespread, and its accumulation in crop products could pose a risk on human health. In this paper, bioavailability of added copper (Cu) and critical Cu concentrations in a vegetable garden soil was evaluated for Chinese cabbage (Brassica chinensis L.), pakchoi (Brassica chinensis L.), and celery (Apiumg graveolens L. var. dulce DC) based on human dietary toxicity. The availability of added Cu in the soil decreased with incubation time, and had minimal change after 10-12 weeks. After incubated for 12 weeks, about 60% of added Cu was not extractable by DTPA. The same crops were also grown in sand culture to determine their responses to solution Cu. Shoot growth was significantly inhibited at Cu concentrations above 10 mg kg(-1) in the solution or above 150 mg kg(-1) (DTPA-Cu) in the soil. The sensitivity of the crops to Cu toxicity differed among the three vegetable crops. Copper concentration in shoots and edible parts varied with Cu supply levels and type of the vegetables. Negative correlations (r=-0.90-0.99**) were noted between Cu concentration in shoots and fresh matter yields, but Cu concentrations in the edible parts were positively correlated with available and total Cu in the soil (r=0.91-0.99**). The critical tissue Cu concentrations at 10% shoot DM reduction were 19.4, 5.5, 30.9 mg kg(-1) for Chinese cabbage, pakchoi, and celery, respectively. Based on the threshold of human dietary toxicity for Cu (10 mg kg(-1)), the critical concentrations of total and available Cu in the soil were 430 and 269 mg kg(-1) for pakchoi, 608 and 313 mg kg(-1) for celery, and 835 and 339 mg kg(-1) for Chinese cabbage, respectively.     

填闲作物防治菜田土壤硝酸盐污染的研究进展

探讨了通过调整蔬菜生产的轮作结构 ,运用生物修复的原理 ,引入适宜的深根系填闲作物对深层土壤硝酸盐吸收利用 ,以避免硝酸盐进一步淋失 ,提高氮素的利用率的可行性。填闲作物应选择生长迅速、生物量大、氮素累积能力强的作物 ,在考虑填闲作物防治硝酸盐淋溶的同时 ,要兼顾其经济利用价值 ,并指出结合深根系的填闲作物进行合理轮作是蔬菜安全生产及可持续发展的途径之一     

Dieldrin uptake by vegetable crops grown in contaminated soils

The aim of these trials was to study the distribution of dieldrin in soil and its translocation to roots and the aerial parts of vegetable crops grown in greenhouses and fields. The main objectives were to characterize dieldrin accumulation in plant tissues in relation to the levels of soil contamination; uptake capability among plants belonging to different species, varieties and cultivars. The presence of the contaminant was quantified by gas chromatography-electron capture detector (GC-ECD) and confirmed by gas chromatography-mass spectrometer (GC-MS). The results showed a translocation of residues in cucurbitaceous fruits and flowers confirming that zucchini, cucumber and melon are crops with high uptake capability. The maximum level of dieldrin residue at 0.01 mg/kg was found to be a threshold value to safeguard the quality production of cucurbits. Tomato, lettuce and celery were identified as substitute crops to grow in contaminated fields.     

Biomassbed: a biological system to reduce pesticide point contamination at farm level

A potential method for cleaning water from point-source pollution by organic compounds is using biological reactors. In this study, four reactors were tested for their ability to retain and degrade pesticides. The pesticides tested were the insecticide chlorpyrifos, the fungicide metalaxyl and the herbicide imazamox. The reactors were filled with differing mixtures of vine-branch, citrus peel, urban waste and public green compost. The reactor volume was 188 l. Forced circulation of the contaminated solution was programmed to decontaminate the solution. Both retention and degradation of the compounds by the reactors was studied. Chlorpyrifos was the best retained, due to its physico-chemical characteristics, while only one substrate effectively retained metalaxyl and imazamox (citrus peel+urban waste compost). Degradation of the pesticides in the reactors was faster than published values for degradation in soil. The half-life of all pesticides in the reactors was less than 14 days, compared to literature values of 60-70 days in soil. The combined retention and fast degradation make the biofilter a feasible technique to reduce spill-related and point environmental contamination by pesticides. The technique is most effective against persistent pesticides, while for mobile pesticides, the efficiency can be improved with several passages of the contaminated solution through biofilters.     

我国有机磷农药废水的生化法处理研究进展

农药废水的污染已受到国内外环保工作者的重视 ,我国也不例外。各种处理方法层出不穷 ,而生化法是各处理方法中的重要方法 ,本文仅就我国生化法处理有机磷农药废水的研究进展作一概述     

Temperature dependence of gas-phase polycyclic aromatic hydrocarbon and organochlorine pesticide concentrations in Chicago air

The temperature dependence of gas-phase atmospheric concentrations of polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides measured in Chicago, IL between June and October 1995 were investigated using plots of the natural logarithm of partial pressures (ln P) vs. reciprocal mean temperatures (1/T). For the eight lowest molecular weight PAHs, temperature dependence was statistically significant (at the 95% confidence level) and temperature accounted for 23–49% of the variability in gas-phase concentrations. The relatively higher slopes for most of the PAHs suggested that volatilization from local sources and short-range transport influenced their concentrations. For pesticides, temperature dependence was statistically significant for DDD and for trans-nonachlor (at the 95% and 90% confidence levels), and was not statistically significant for the other five compounds (2–18% of the variability in their gas-phase concentrations). The relatively lower slopes for individual pesticides suggested that they have mostly non-urban and distant sources.Results of back trajectory analyses suggested that the region, southwest of Chicago, might be an important local or regional source sector for PAHs and organochlorine pesticides. No statistically significant relationship was observed between wind speed and PAH or pesticide concentrations. None of the variables (temperature, wind speed, wind direction, local and regional sources) could fully explain the variation in their concentrations measured in Chicago, therefore, this variation can be attributed to the combined effect of those factors.     

Changes in pesticide adsorption with time at high soil to solution ratios

Adsorption of six pesticides (2,4-D, dicamba, fluroxypyr, fluazifop-P, metsulfuron-methyl and flupyrsulfuron-methyl) in nine contrasting soils was measured using two techniques: (i) a classical batch method and (ii) a centrifugation method that allowed the measurement of adsorption at a realistic soil to solution ratio after one and seven days. Although the batch method gived significantly higher values of Kd than the centrifugation method for the more strongly sorbed molecules in the more sorptive soils, it tended to give lower adsorption coefficients compared to the centrifugation method when adsorption was lower. Discrepancies between the two methods were probably mainly due to the vigorous shaking applied in the batch technique that artificially enhances the availability of adsorption sites. This implies that shortly after application, more pesticide may be present in the soil solution and thus be available for degradation, plant uptake or leaching than will be predicted from adsorption coefficient determined using the batch method. Adsorption significantly increased between one and seven days and the extractability of total residues decreased with time. The increase in adsorption was not directly related to the level of adsorption although it was more important in soils containing more organic carbon (p=0.022). These results confirm the importance of time-dependent processes and the necessity to include them in risk assessment procedures. The centrifugation technique is a useful method to measure adsorption of pesticides at realistic soil moisture contents and seems to be an adequate technique to characterise the fraction of pesticide that is available for leaching at a given time after application.     

The frequency and causes of elevated concentrations of ozone at ground level at rural sites in north-west England

Ozone concentration data measured in 1977–1979 and 1981–1983 at rural sites in north-west England have been analysed in relation to elevated concentrations. Overall, concentrations exceed 60 ppb on 11.2% of days, 80 ppb on 4.2% of days and reach levels in excess of 100 ppb on 1.5% of days monitored. It is concluded that photochemical pollution is the most frequent cause of elevated concentrations, and that both long-range (continental) and middle-distance (U.K. urban) sources contribute. On a smaller percentage of days, elevated ozone levels arise from enhanced intrusions of stratospheric air associated with vigorous frontal activity. The meteorological situations associated with tropospheric photochemical ozone formation are summer anticyclonic conditions, in common with other observations in the U.K. and other parts of the world.     

Arsenic contaminated site at an abandoned copper smelter plant: waste characterization and solidification/stabilization treatment

A preliminary survey of an arsenic contaminated site from an abandoned copper smelting facility and feasibility study of using solidification/stabilization (S/S) process to treat the contaminant waste were undertaken. It was found that the waste, located in the three-flue gas discharge tunnels, contained 2-40% arsenic. The pH of the contaminated waste is extremely low (ranging from 1.8 to 3.6). The X-ray diffraction evidence indicates that the arsenic particles present in the flue gas mainly exist as As(III), or As(2)O(3). The total amount of arsenic contaminated waste is estimated to be 700 ton in the studied area. About 50% of the particle sizes are less than 2 mm. Arsenic is easily extracted from wastes with a variety of leaching solutions. In order to meet the arsenic leaching standard of the toxicity characteristic leaching procedure (TCLP), an extremely high cement dosage is required in the S/S process (cement/waste weight ratio>6). The waste with lower particle size having higher specific surface area exhibits somewhat positive effect on the S/S performance. The use of fly ash from municipal waste incinerators, in conjunction with the reduced amount of cement, is able to meet the TCLP arsenic and lead standards. The use of lime alone could meet the TCLP arsenic standard, but lead leaching concentrations exceeded leaching Pb standard. The results of semi-dynamic leaching tests of some solidified samples indicate higher accumulated arsenic leaching concentrations after only a few leachant renewals.     

Phytoavailability and fractionation of copper, manganese, and zinc in soil following application of two composts to four crops

Two experiments were conducted to evaluate the effect of compost addition to soil on fractionation and bioavailability of Cu, Mn, and Zn to four crops. Soils growing Swiss chard (Beta vulgaris var. cicla L.) and basil (Ocimum basilicum L.) were amended (by volume) with 0, 20, 40, and 60% Source-Separated Municipal Solid Waste (SS-MSW) compost, and dill (Anethum graveolens L.) and peppermint (Mentha X piperita L.) were amended with 0, 20, 40, and 60% of high-Cu manure compost (by volume). The SS-MSW compost applications increased the concentration of Cu and Zn in all fractions, increased Mn in acid extractable (ACID), iron and manganese oxides (FeMnOX), and organic matter (OM) fractions, but decreased slightly exchangeable-Mn. Addition of 60% high-Cu manure compost to the soil increased Cu EXCH, ACID, FeMnOX, and OM fractions, but decreased EXCH-Mn, and did not change EXCH-Zn. Addition of both composts to soil reduced bioavailability and transfer factors for Cu and Zn. Our results suggest that mature SS-MSW and manure composts with excess Cu and Zn could be safely used as soil conditioners for agricultural crops.     

The effect of vegetation on pesticide dissipation from ponded treatment wetlands: quantification using a simple model

Field data shows that plants accelerate pesticide dissipation from aquatic systems by increasing sedimentation, biofilm contact and photolysis. In this study, a graphical model was constructed and calibrated with site-specific and supplementary data to describe the loss of two pesticides, endosulfan and fluometuron, from a vegetated and a non-vegetated pond. In the model, the major processes responsible for endosulfan dissipation were alkaline hydrolysis and sedimentation, with the former process being reduced by vegetation and the latter enhanced. Fluometuron dissipation resulted primarily from biofilm reaction and photolysis, both of which were increased by vegetation. Here, greater photolysis under vegetation arose from faster sedimentation and increased light penetration, despite shading. Management options for employing constructed wetlands to polish pesticide-contaminated agricultural runoff are discussed. The lack of easily fulfilled sub-models and data describing the effect of aquatic vegetation on water chemistry and sedimentation is also highlighted.     

Organochlorine pesticide residuals in chickens and eggs at a poultry farm in Beijing, China

Chicken organs, animal feed, droppings, and ambient air were sampled at a farm in Beijing to determine the concentrations of hexachlorocyclohexane isomers (HCHs) and dichlorodiphenyltrichloroethane and metabolites (DDTs). Mean fresh weight concentrations of HCHs and DDTs were 0.122 ± 0.061 ng/g and 0.051 ± 0.038 ng/g in the muscles. These values are 1-2 orders of magnitude lower than those reported in China in 1980. Contaminated feed was the main source of HCHs and DDTs. Only 12.8% of HCH and 3.3% of DDT of the amount consumed were excreted. Accumulated quantities of HCHs and DDTs increased during growth. However, concentrations of HCHs and DDTs did not increase because of dilution from rapid growth. Based on the observed residual levels in mature chicken and the average diet of residents of China, the contributions from chicken and egg consumption to per capita daily intake of HCHs and DDTs were 487% and 88% of those of fish consumption.     

Zinc, copper and nickel concentrations in soil extracts and crops grown on four soils treated with metalloaded sewage sludges

Sludges containing high concentrations of zinc, copper or nickel and an uncontaminated sludge were added to two sandy loams (pH 6.5 and 7.1), a heavy clay (pH 6.3) and a calcareous clay (pH 7.8) to give ten sludge treatments for each soil. The mixtures were incubated fallow, cropped continuously with clover, or cropped with barley and red beet in rotation for 21 months. The quantity of added metal either in the soil solution or extracted by 0.1m CaCl(2) depended on the metal loading, pH and soil cation exchange capacity, and changed with time after mixing soils and sludges. Crop metal concentrations, and the occurrence of metal-induced yield reductions, also depended on soil properties as well as metal loading. The best chemical extractant for predicting plant metal concentrations was 0.1m CaCl(2).     

A comparison of predicted and measured levels of runoff-related pesticide concentrations in small lowland streams on a landscape level

Short-term pollution events via runoff are typical of streams in agricultural areas. Existing runoff models that simulate pesticide loss from agricultural fields require extensive input of information. There is thus a need for a simple model that can predict runoff-related pesticide concentrations in many streams on a landscape level when only limited data are available. To validate such a model, the runoff-related pesticide load of 18 small lowland streams was predicted with an extended version of the model "simplified formula for indirect loadings caused by runoff" (available from the Organisation for Economic Cooperation and Development, OECD). The authors suggest that the model presented here is suitable for use in routine exposure assessment of pesticides on a landscape level, as all input data (soil, slope, precipitation, pesticide application) are readily available from public authorities or could be generated by simple regional flood hydrograph curves. The predicted concentrations were compared with measured concentrations obtained by runoff-triggered sampling. Fungicides, insecticides and herbicides were detected in 17 streams, with max. concentrations measuring up to 29.7 microg/l for the fungicide azoxystrobin and 0.3 microg/l for the insecticide parathion-ethyl. Herbicides were detected in 16 streams, with max. concentrations between 13.7 and 1.2 microg/l. The linear regression between the predicted and measured concentrations (log-values) shows significant correlations for the following pesticides: azoxystrobin: r2=0.43; p=0.03; epoxiconazole: r2=0.71; por=0.5 microg/l).     

Catalytic oxidative treatment of diluted black liquor at mild conditions using copper oxide/cerium oxide catalyst.

Wet-air oxidation of diluted black liquor (chemical oxygen demand [COD] approximately 3250 to 14 500 mg/L) was performed at mild operating conditions (temperature = 388 to 423 K and total pressure = 0.6 MPa) in the presence of heterogeneous 60% copper oxide (CuO)/ 40% cerium oxide (CeO2) catalyst. Maximum COD reduction of 77.3% was obtained at 423 K at pH 3.0, which was marginally higher than that obtained at 413 K temperature (77.1%). In the acidic environment (pH < or = 3), most of the COD was removed in the form of settleable solids during the transient heating of the wastewater from room temperature to the desired one. The solid residue obtained after the reaction has a heating value of 20.1 MJ/kg, which is comparable with that of Indian coal. Thermal degradation kinetic determination suggested that thermal characteristics of the solid residue are well represented by a power law model with Agarwal and Sivasubramanian approximation (Safi et al., 2004).     

The transportation,time-dependent distribution of heavy metals in paddy crops

Sixteen experimenmtal plots (5 m x 6 m = 30 m2) were designed with four different levels of heavy metals (HMs) concentration in soil. The concentrations of heavy metals in soils, and paddy plant during the different periods of growth were investigated. A relationship between the total HM content in plants and the HM level in soil was found for a wide range of concentrations. The exchangeable fraction of HMs extracted with 1 M MgCl2 solution according to Tessier's method increased correlation with the dosage of supplemented HMs, then decreased as time went on. The time-related variation of exchangeable HMs in soil demonstrated that the amount of effective HMs taken up by paddy differed at various growth phases. The amount of HMs accumulated in different parts of paddy followed the order of root > stem > grain, leaf. The transportation potential of the HMs in paddy in present study followed the order of Zn, Cr > Cd, Cu > Pb. The HM content in root, stem and leaf of paddy plant (dry weight) was low at time of seedling. The concentration in the root increased sharply at time of tillering, decreased thereafter. The concentrations in stem and leaf reached the highest at time of tillering, then decreased, while rose slightly at following time.     

Environmental copper: Behaviour when involved in physical adsorption at several interfaces

From a literature-based assessment of the current knowledge about both the toxic or salutary properties of copper, this study focused on the determination, at 25 °C, of the interfacial properties of CuCl_2, either alone or in mixture with carbofuran used, here, as a model of organics and/or pesticide. The interfaces under study were: i) the air/solution interface and ii) the silica/solution interface. The former is considered as a path for volatilization, whereas the latter permits a modelling of physical adsorption upon solids, which is the first and unavoidable step in any adsorption process. One should note that it can also mimic adsorption on some sandy soils. Coadsorption was clearly identified as implicated in an enhancement of the surface content of both solutes at both interfaces. However, at the two interfaces under study, the way the surface became structured led to opposite adsorption mechanisms for the organic compounds and the salt. A rough theory about ionic adsorption is also proposed.     

The partitioning and modelling of pesticide parathion in a surfactant-assisted soil-washing system

Soil sorption of organic pollutants has long been a problematic in the soil washing process because of its durability and low water solubility. This paper discussed the soil washing phenomena over a wide range of parathion concentrations and several soil samples at various fractions of organic content (foc) levels. When parathion dosage is set below the water solubility, washing performance is stable for surfactant concentrations above critical micelle concentration (cmc) and it is observed that more than 90% of parathion can be washed out when dosage is five times lower than the solubility limit. However, such trends change when non-aqueous phase liquids (NAPL) is present in the system. Parathion extraction depends very much on the surfactant dosage but is not affected by the levels of foc in the system. In between the extreme parathion dosage, a two-stage pattern is observed in these boundary regions. Washing performance is first increased with additional surfactant, but the increase slows down gradually since the sorption sites are believed to be saturated by the huge amount of surfactant in the system. A mathematical model has included foc to demonstrate such behavior and this can be used as a prediction for extraction.     

农村生活污水处理设施省级管理体系探索——以浙江省为例

农村生活污水治理是我国提升农村人居环境行动的重要一环。在国家有关政策的推动下,近年来我国农村生活污水处理设施大量建成,但由于法规标准、管理保障机制等的相对滞后,影响了现有设施的长效运行,亟待探索并建立因地制宜的农村生活污水处理设施省级管理体系。浙江省作为全国首个全面开展农村生活污水治理并对其专门立法的省级行政区,经过十几年的摸索,初步形成了“以条例为抓手,以标准体系作指导,以运维管理体系作保障”较为完善的农村生活污水处理设施管理体系。详细梳理了浙江省农村生活污水处理设施的建设与运维管理发展历程,系统总结了浙江省在颁布条例、建立标准体系及运维管理保障机制方面取得的进步与积累的经验,提出了顶层设计先行、重视试点示范、政产学研深度融合3点建议,可为全国其他省(自治区、直辖市)农村生活污水治理工作的开展提供参考。     

The recovery of copper from a copper mine effluent in a hybrid flotation/microfiltration cell

A new hybrid process for cleaning wastewater, combining flotation and membrane microfiltration, was investigated. The hybrid process combined the advantages of both flotation and membrane separation: the flotation cell removed a large proportion of suspended solid particles, while the membrane module produced clean water permeate effluent. The hybrid cell performance has been studied in depth and reviewed in the current paper. The proof of concept for the hybrid solid/liquid separation process was investigated using an aqueous suspension of fine and ultra fine particles (synthetic adsorbents, ion exchangers). The feasibility of this combined process was investigated in the recovery of metal cations (copper) from a Bulgarian copper mine effluent.