Laboratory-polluted soils: a methodological approach to establish equilibrium conditions for different metal chemical forms in soils

An approach based on the number of extractions performed over time was applied to study the time necessary to attain equilibrium conditions between the different chemical forms present in two natural soils laboratory-loaded with heavy metals (Cu(II), Pb(II), Zn(II)). The influence of some soil parameters, such as pH value, cation exchange capacity and organic matter content, on the equilibrium time was evidenced both by the different nature of the soils and by the treatment of soils with paper mill sludge. Equilibrium conditions were determined by studying the metal partitioning in the soil on a case by case basis. The behaviour of the three metals was not the same, and the conditions of equilibrium among the different chemical forms were the result of the amount of heavy metals added as well as of the nature of the soil.     

Community air monitoring for pesticides. Part 3: using health-based screening levels to evaluate results collected for a year

The CA Department of Pesticide Regulation (CDPR) and the CA Air Resources Board monitored 40 pesticides, including five degradation products, in Parlier, CA, to determine if its residents were exposed to any of these pesticides and, if so, in what amounts. They included 1,3-dichloropropene, acrolein, arsenic, azinphos-methyl, carbon disulfide, chlorpyrifos and its degradation product, chlorthalonil, copper, cypermethrin, diazinon and its degradation product, dichlorvos, dicofol, dimethoate and its degradation product, diuron, endosulfan and its degradation product, S-ethyl dipropylcarbamothioate (EPTC), formaldehyde, malathion and its degradation product, methyl isothiocyanate (MITC), methyl bromide, metolachlor, molinate, norflurazon, oryzalin, oxyfluorfen, permethrin, phosmet, propanil, propargite, simazine, SSS-tributylphosphorotrithioate, sulfur, thiobencarb, trifluralin, and xylene. Monitoring was conducted 3 days per week for a year. Twenty-three pesticides and degradation products were detected. Acrolein, arsenic, carbon disulfide, chlorpyrifos, copper, formaldehyde, methyl bromide, MITC, and sulfur were detected in more than half the samples. Since no regulatory ambient air standards exist for these pesticides, CDPR developed advisory, health-based non-cancer screening levels (SLs) to assess acute, subchronic, and chronic exposures. For carcinogenic pesticides, CDPR assessed risk using cancer potency values. Amongst non-carcinogenic agricultural use pesticides, only diazinon exceeded its SL. For carcinogens, 1,3-dichloropropene concentrations exceeded its cancer potency value. Based on these findings, CDPR has undertaken a more comprehensive evaluation of 1,3-dichloropropene, diazinon, and the closely related chlorpyrifos that was frequently detected. Four chemicals—acrolein, arsenic, carbon disulfide, and formaldehyde—sometimes used as pesticides were detected, although no pesticidal use was reported in the area during this study. Their presence was most likely due to vehicular or industrial emissions.     

Non-target effect of organic insecticides: effect of two plant extracts on soil microbial biomass and enzymatic activities in soil

Efficacious botanical derivatives can provide an alternative to synthetic pesticides for organic farming systems. However, there is lack of information regarding the side effects of organic pesticides on key soil ecological processes. In this study, we investigated the effects of aqueous extracts from Urginea maritima and Euphorbia myrsinites exhibiting translaminar and systemic activity against pests on microbial biomass and enzymatic activities in soil. Two grams of plant material was extracted with 100 ml of water and then diluted 1:100, 2:100, and 4:100 with distilled water. Diluted plant extracts were applied around hypocotyl of tomato by soil drench. The effect of both plant extracts on microbial biomass C, amount of total N and organic C, and enzymatic activity in soil was significant. After the last application, the highest microbial biomass C was determined in the lowest U. maritima concentration (U 1:100). Soils treated with the highest concentration of U. maritima (U 4:100) had always lower SMBC content than control soil. All concentrations of E. myrsinites decreased microbial biomass C by 18% to 27% compared to the control. Total nitrogen and organic carbon decreased in soils without (control) and with treated U. maritima extract from first application to last application. Phosphatase, urease, and β-glucosidase activities were monitored in plant extract-treated soils. Except U. maritima 1:100 treatments of second and fourth applications, the other treatments of plant extracts negatively affected enzymatic activity in soil. U. maritima and E. myrsinites plant extracts exhibited different effects on soil microbial biomass and activity, probably because of their different chemical contents.     

Community air monitoring for pesticides—part 2: multiresidue determination of pesticides in air by gas chromatography,gas chromatography–mass spectrometry,and liquid chromatography–mass spectrometry

Two multiresidue methods were developed to determine pesticides in air collected in California. Pesticides were trapped using XAD-4 resin and extracted with ethyl acetate. Based on an analytical method from the University of California Davis Trace Analytical Laboratory, pesticides were detected by analyzing the extract by gas chromatography–mass spectrometry (GC-MS) to determine chlorothalonil, chlorthal-dimethyl, cycloate, dicloran, dicofol, EPTC, ethalfluralin, iprodione, mefenoxam, metolachlor, PCNB, permethrin, pronamide, simazine, trifluralin, and vinclozolin. A GC with a flame photometric detector was used to determine chlorpyrifos, chlorpyrifos oxon, diazinon, diazinon oxon, dimethoate, dimethoate oxon, fonophos, fonophos oxon, malathion, malathion oxon, naled, and oxydemeton. Trapping efficiencies ranged from 78 to 92 % for low level (0.5 μg) and 37–104 % for high level (50 and 100 μg) recoveries. Little to no degradation of compounds occurred over 31 days; recoveries ranged from 78 to 113 %. In the California Department of Food and Agriculture (CDFA) method, pesticides were detected by analyzing the extract by GC-MS to determine chlorothalonil, chlorpyrifos, cypermethrin, dichlorvos, dicofol, endosulfan 1, endosulfan sulfate, oxyfluorfen, permethrin, propargite, and trifluralin. A liquid chromatograph coupled to a MS was used to determine azinphos-methyl, chloropyrifos oxon, DEF, diazinon, diazinon oxon, dimethoate, dimethoate oxon, diuron, EPTC, malathion, malathion oxon, metolachlor, molinate, norflurazon, oryzalin, phosmet, propanil, simazine and thiobencarb. Trapping efficiencies for compounds determined by the CDFA method ranged from 10 to 113, 22 to 114, and 56 to 132 % for 10, 5, and 2 μg spikes, respectively. Storage tests yielded 70–170 % recovery for up to 28 days. These multiresidue methods represent flexible, sensitive, accurate, and cost-effective ways to determine residues of various pesticides in ambient air.     

Assessment of Robinia pseudoacacia cultivations as a restoration strategy for reclaimed mine spoil heaps

Reforestation with black locust (Robinia pseudoacacia) is considered a successful technique that is often used for the reclamation of open-cast mine areas. An alternative reclamation technique could be the natural regeneration of vegetation with spontaneous grass species. In this study, we compared the concentrations of chemical and biochemical variables in soil samples taken under black locust canopy to those from sites covered by spontaneous grass vegetation (control samples) in a time sequence of spoil deposition (0–10 years), in order to assess which of the two reclamation techniques yields higher soil quality. Soil quality refers here to the ability of soils to function ecologically. This has a special interest since the main question for the restored soils is their capacity to perform a range of ecological functions under stress or disturbance. Furthermore, we aimed at identifying the effect of vegetation type on soil ecological succession. The effect of vegetation type on primary succession becomes apparent after 2 years of reclamation. R. pseudoacacia as a nitrogen-fixing plant enriched soil with organic and inorganic nitrogen and organic matter to a greater extent than the natural grasses. It also increased the amount of soil microbial biomass and the activity of alkaline phosphatase. However, the fact that black locust failed to enhance dehydrogenase activity and actually decreased the activity of urease, activities that represent specialized niche functions and therefore, are more vulnerable to stress or disturbance, suggests that the development of an indigenous grass community in combination with organic supplements might often be more appropriate for the reclamation of similar kinds of mine areas.     

Monitoring and risk assessment of pesticides in a tropical river of an agricultural watershed in northern Thailand

The increasing application of pesticides in the uplands of northern Thailand has increased the transfer of pesticides to surface water. To assess the risk of pesticide use for stream water quality, we monitored the concentrations of seven pesticides (atrazine, dichlorvos, chlorpyrifos, dimethoate, chlorothalonil, (α-, β-) endosulfan, cypermethrin) frequently used in the Mae Sa watershed (77 km²) in water and sediment samples over a period of one and a half years (2007–2008). All investigated pesticides were recorded in the river. Chlorpyrifos was detected most often in water samples (75 % at the headwater station), while cypermethrin was most often found in riverbed (86 %) and in all suspended sediment samples. The highest concentrations of the pesticides were detected during the rainy season. About 0.002 to 4.1 % by mass of the applied pesticides was lost to surface water. The risk assessment was based on the risk characterization ratio (RCR). The RCRs of dichlorvos in water, (α-, β-) endosulfan, and cypermethrin in water and sediments were higher than unity indicating that they are likely to pose a threat to aquatic ecosystem. Finally, we discuss the role of sampling design on ecotoxicological risk assessment. Our study shows that pesticide contamination of surface waters is an environmental issue in the Mae Sa watershed and that measures need to be undertaken to reduce the loss of pesticides from soil to surface waters.     

Effect of fertilizer application on soil heavy metal concentration

A large amount of chemicals is annually applied at the agricultural soils as fertilizers and pesticides. Such applications may result in the increase of heavy metals particularly Cd, Pb, and As. The objective of this study was to investigate the variability of chemical applications on Cd, Pb, and As concentrations of wheat-cultivated soils. Consequently, a study area was designed and was divided into four subareas (A, B, C, and D). The soil sampling was carried out in 40 points of cultivated durum wheat during the 2006–2007 periods. The samples were taken to the laboratory to measure their heavy metal concentration, soil texture, pH, electrical conductivity, cationic exchange capacity, organic matter, and carbonate contents. The result indicated that Cd, Pb, and As concentrations were increased in the cultivated soils due to fertilizer application. Although the statistical analysis indicates that these heavy metals increased significantly (P value < 0.05), the lead and arsenic concentrations were increased dramatically compared to Cd concentration. This can be related to overapplication of fertilizers as well as the pesticides that are used to replant plant pests, herbs, and rats.     

Microcosm studies on the air-soil exchange of hexachlorobenzene and polychlorinated biphenyls

Soils have an important role to play in supplying and receiving contaminants from the atmosphere, and in the global cycling of certain persistent organic pollutants (POPs). A microcosm study was conducted, in which some aspects of air-soil exchange likely to be important for the global cycling of POPs were simulated. HCB and PCBs were introduced into a sealed chamber, which contained soils of varying organic matter content, and in which soil mixing was a variable. Uptake of these compounds on to the soils was monitored over time. Subsequently, the primary chemical source was removed and further changes in the residues retained on the soils were monitored. The rates of uptake onto the different soil treatments are compared and the influence of the soil organic matter content and mixing evaluated. The implications for the global cycling of POPs are discussed.     

An analytical model for the assessment of pesticide exposure levels in soils and groundwater

The movement and degradation of pesticide residues in soils and groundwater are complex processes affected by soil physical, (bio)chemical, and hydrogeological properties, climatic conditions, and agricultural practices. This work presents a physically-based analytical model suitable for long-term predictions of pesticide concentrations in groundwater. The primary interest is to investigate the impact of soil environment, related physical and (bio)chemical processes, especially, volatilization, crop uptake, and agricultural practices on long-term vulnerability of groundwater to contamination by pesticides. The soil is separated into root and intermediate vadose zones, each with uniform properties. Transport in each soil zone is modeled on the basis of complete mixing, by spatial averaging the related point multiphase-transport partial differential equation (i.e., linear-reservoir models). Transport in the aquifer, however, is modeled by a two-dimensional advection-dispersion transport equation, considering adsorption and first-order decay rate. Vaporization in the soil is accounted for by assuming liquid-vapor phase partitioning using Henry's law, and vapor flux (volatilization) from the soil surface is modeled by diffusion through an air boundary layer. Sorption of liquid-phase solutes by crops is described by a linear relationship which is valid for first-order (passive) crop uptake. The model is applied to five pesticides (atrazine, bromacil, chlordane, heptachlor, and lindane), and the potential for pesticide contamination of groundwater is investigated for sandy and clayey soils. Simulation results show that groundwater contamination can be substantially reduced for clayey soil environments, where bio(chemical) degradation and volatilization are most efficient as natural loss pathways for the pesticides. Also, uptake by cross can be a significant mechanism for attenuating exposure levels in ground-water especially in a sandy soil environment, and for relatively persisting pesticides. Further, simulations indicate that changing agricultural practices can have a profound effect on vulnerability of groundwater to mobile and relatively persisting pesticides.     

Solid-phase microextraction coupled to gas chromatography-mass spectrometry for the study of soil adsorption coefficients of organophosphorus pesticides

A solid-phase microextraction-gas chromatography-mass spectrometry (SPME-GC-MS) method for the simultaneous determination of the organophosphorus pesticides (OPPs), phorate, diazinon, methyl-parathion, fenitrothion, malathion, fenthion, ethyl-parathion and methidathion, has been developed to study their soil/water distribution. The method was used in conjunction with a conventional 'batch equilibrium method' to assess the soil adsorption coefficients (Koc) of the target compounds in different soil samples with known organic carbon content. Contrary to traditional techniques, the present method is fast, solvent-free and highly sensitive, thus permitting the assessment of the Koc values of the target compounds even at low soil concentration levels, close to those encountered in real field contamination, where the Freudlich adsorption isotherms can be considered to be linear. The estimated Koc values were found to be in good agreement with those reported in the literature.     

The potential for anaerobic mineralisation of hydrocarbon constituents of oily drill cuttings from the North Sea seabed

The potential for natural attenuation of hydrocarbons in oily drill cuttings from the seabed beneath a North Sea oil platform was investigated. The study focused on the anaerobic degradation of n-hexadecane, n-octacosane and naphthalene using additions of 14C-labelled analogues to drill cuttings samples and was conducted under realistic seabed conditions (except pressure) over an 11-month period. No mineralisation of naphthalene was detected over this time period and mineralisation of octacosane represented only 0.5-1.5% of the added label. In contrast, mineralisation of hexadecane was 10-49% after 11 months of incubation. Selective inhibition of key functional bacterial groups revealed the key role of both sulfate reduction and methanogenesis in the degradation process. This study demonstrates the potential for natural attenuation of at least some hydrocarbon constituents of oily drill cuttings under realistic environmental conditions and highlights the involvement of a wide functional consortium in the natural attenuation process.     

Soil mineralization of two-phase olive mill wastes: effect of the lignocellulosic composition on soil C dynamics

The low degradation rate of two-phase olive mill wastes (TPOMW) during composting and after soil application is a characteristic feature of these materials. The aim of this work was to evaluate the relationship between the lignocellulosic fraction of TPOMW and the organic matter (OM) degradation rate in three agricultural soils amended with four TPOMW composting mixtures at different degree of stabilisation and prepared with different bulking agents and N sources. The mineralisation kinetics of TPOMW composting mixtures in soil reflected a large amount of slowly mineralisable C even in the starting mixtures (I and T1) where this fraction represented up to 85% of the total potentially mineralisable C pool. The effect of rich lignocellulosic composition was confirmed by the study of the DTS (50% dry TPOMW + 50% sheep manure) mixtures prepared with dry TPOMW, which had undergone partial degradation in a storage pond for one year before composting. These DTS samples showed a more similar kinetic behaviour in soil than the more transformed composting mixtures as reflected in the principal component analysis (PCA) diagram, where they were grouped in the same quadrant dominated by the lignin/holocellulose ratio. Soils amended with mature composts evolved very low amounts of C (between 2 and 6% of the added C) after two months of incubation, which highlights the suitability of these materials as a suitable C source for the soil to promote long term soil C stabilisation.     

呼伦贝尔地区草原表层土壤中总有机碳与有机质初探

通过非分散红外线吸收法测定呼伦贝尔地区具有代表性的16个草原表层土壤(0~20 cm)中总有机碳、溶解性有机碳,使用重铬酸钾容量法测定有机质,并对其总有机碳与有机质水平及两者相关性进行了分析。初步分析了造成各样品之间总有机碳水平差异的原因。结果表明,只以打草场作为利用方式的土壤总有机碳含量较常年放牧场的总有机碳含量高。从草原类型和土壤类型上看,草甸草原总有机碳含量明显高于典型草原,黑钙土总有机碳含量明显高于栗钙土。综上,过度放牧会使草原土壤总有机碳大量释放。总有机碳含量与有机质含量有显著正相关性,相关系数达到0.902。     

Effects of organic amendments and irrigation waters on the physical and chemical properties of two calcareous soils in Bahrain

The present investigation studies the effects of cow and chicken manure and sewage sludge at different rates of addition and with two irrigation waters of different salinities on two major calcareous soils in Bahrain. The aim was to quantify potential improvements in soil quality, the accumulation of trace metals, and quality of leachates.From the pot experiments it was found that soil waterholding capacity did not change significantly after addition of organic amendments, except in the case of sewage sludge. Total organic carbon and total Kjeldhal nitrogen content increased in the 0–5 cm layer. Low salinity water and sewage applications improved aggregate stability. Extractable phosphorus was enhanced by the chicken manure treatment more than others. Addition of different organic amendments did not affect exchangeable cations. pH values did not show appreciable changes and soils were neutral. Trace metals studied were present at non-toxic levels in the 0–5 cm layer. Zinc and copper were the only metal showing a tendency to leach to the lower soil layer. In all cases metal levels in the surface layer were proportional to the quantities added in the amendments and their levels in the leachate were very low.     

江苏省茶园和农田土壤中拟除虫菊酯类农药残留与污染特征分析

于2018年4—6月采集了江苏省10个市的茶园和农田表层土壤样品,采用气相色谱-三重四级杆质谱仪分析样品中12种拟除虫菊酯类农药的质量比和组成.结果表明,江苏省茶园和农田土壤中广泛检出拟除虫菊酯类农药,总量分别为27.1～50.7,56.9～97.0 ng/g.研究区域的拟除虫菊酯类农药含量存在差异,但组成相近,均是高...     

大气痕量有机硫化物的光电离色谱法测定及硫酸铵在湿浸土壤中释放有机硫化物的研究

采用国产光电离色谱仪(GC-PID)对有机硫化物:乙基硫醇,二甲基硫,二甲基二硫进行了分离分析,其最小检知量在亚微克/升级,并对北京郊区的某些天然源环境样品进行了有机硫化物浓度的测定,实验数据证实,在鸡场,猪场,水稻田与塑料蔬菜大棚等环境大气中含有机硫化物。研究了硫酸铵作为氮肥加入到水浸土壤中后,由于缺氧而生成有机硫化物的现象,观察了其对有机硫化物的释放规律及硫酸铵与葡萄糖分别作为硫源与碳源对有机硫化物生成的影响,实验结果认为:硫酸铵在五种不同类型的水浸土壤中(环境温度25℃),均可解离释放出有机硫化物,随其在土壤中加入量的增多,释放气中的有机硫浓度增加,二甲基硫的释放量最大。     

Assessment of the effects of Cr, Cu, Ni and Pb soil contamination by ecotoxicological tests

This study aimed to assess soil quality by chemical and ecotoxicological investigations and to check the correspondence between soil metal concentrations and ecotoxicity. For these purposes, surface soils collected at four adjacent roadside urban parks and at a former industrial area were characterized for C/N, organic matter content, texture, and pH. Cr, Cu, Ni and Pb, chosen among the most representative soil metal contaminants, were measured as total content and as available and water soluble fractions. In addition, the total concentrations of the investigated metals were used to calculate two chemical indices: the contamination and the potential ecological risk factors. The toxicity of the investigated soils was evaluated by an ecotoxicity test battery carried out on both soil samples (Vibrio fischeri, Heterocypris incongruens and Sinapis alba) and elutriates (Vibrio fischeri, Daphnia magna and Selenastrum capricornutum). The findings, both by the chemical and ecotoxicological approaches, would suggest that the soils with high metal contamination pose ecological risks. On the other hand, moderately metal contaminated soils did not exclude soil ecotoxicity. In fact, toxic effects were also highlighted in soils with low metal content, toxicity being affected by metal availability and soil characteristics. Moreover, the results suggest the importance of using a battery of tests to assess soil ecotoxicity.     

Evaluation of soil contamination in intensive agricultural areas by pesticides and organic pollutants: south-eastern Spain as a case study

A comprehensive survey of the occurrence and fate of pesticides and organic contaminants in soils from an intensive agricultural area devoted to horticultural production in plastic-based greenhouses has been performed to determine if the operation under integrated pest management practices has contributed to reduce the levels of these compounds. Almería province (south-eastern Spain) was selected for the case study. 38 agricultural soil samples (each sample corresponds to an independent private greenhouse) of areas working under integrated pest management (IPM) programs have been analyzed in order to evaluate their contamination fate. Sampling was designed to cover an area of about 400 km(2). Pesticides, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), phenolic compounds and di-(2-ethylhexyl)phthalate (DEHP) were monitored. The obtained results were compared to other studies reported in Spain and Europe. Among relevant persistent pesticides, DDTs and endosulfans were mainly found and the results indicated historical application, although recent application of endosulfan was rarely detected. PAHs were also found but to a lesser extent and derived from pyrogenic sources. DEHP levels were considerably higher in comparison to the other monitored analytes. The evaluation revealed that despite the use of IPM programs, pesticide and organic contaminants are still being detected in this type of agricultural soil, although at relatively low concentration levels. In general, the contamination rate was similar or lower in comparison to other agricultural areas from nearby regions or countries. However, further monitoring studies should be carried out to establish the possible reduction in contamination by the selected compounds.     

Pesticide residue level in tea ecosystems of Hill and Dooars regions of West Bengal, India

In the present study we quantified the residues of organophosphorus (e.g. ethion and chlorpyrifos), organochlorine (e.g. heptachlor, dicofol, alpha-endosulfan, beta-endosulfan, endosulfan sulfate) and synthetic pyrethroid (e.g. cypermethrin and deltamethrin) pesticides in made tea, fresh tea leaves, soils and water bodies from selected tea gardens in the Dooars and Hill regions of West Bengal, India during April and November, 2006. The organophosphorus (OP) pesticide residues were detected in 100% substrate samples of made tea, fresh tea leaves and soil in the Dooars region. In the Hill region, 20% to 40% of the substrate samples contained residues of organophosphorus (OP) pesticides. The organochlorine (OC) pesticide residues were detected in 33% to 100% of the substrate samples, excluding the water bodies in the Dooars region and 0% to 40% in the Hill region. The estimated mean totals of studied pesticides were higher in fresh tea leaves than in made tea and soils. The synthetic pyrethroid (SP) pesticide residues could not be detected in the soils of both the regions and in the water bodies of the Dooars. Sixteen percent and 20% of the made tea samples exceeded the MRL level of chlorpyrifos in Dooars and Hill regions respectively. The residues of heptachlor exceeded the MRL in 33% (April) and 100% (November) in the Dooars and 40% (April) and 20% (November) in the Hill region. Based on the study it was revealed that the residues of banned items like heptachlor and chlorpyrifos in made tea may pose health hazards to the consumers.     

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.