Struktur-Aktivitätsbeziehungen (QSAR)

The correlation between the bioconcentration (BCF) of 20 pesticides and 3 PCB-congeners from two test soils in earthworms (Lumbricus terrestris) and the corresponding log K_ow was investigated. The relationship, expressed by the equation log BCF=a· log K_ow+b, did not show strong statistical correlation, especially for the soil with higher organic matter content. However, strong statistical correlation could be demonstrated between log BCF and log K_ow for both soils when the bioconcentration in earthworms was calculated on the basis of interstitial water instead of soil. The resulting equations represent a useful tool for assessing the bioaccumulation potential of organic chemical in soil.     

Regression models for some solute distribution equilibria in the terrestrial environment

Sorption coefficients (K_p) of several organochlorine insecticides (OCs) in volcanic ash silt from Central Java are presented.

Selected experimental and estimated octanol‐water partition coefficient (P) values are used to study log‐log regressions with K_p data collected from the literature (PAHs, chlorophenols, phenylureas, chloro‐s‐triazines, carbamates and organophosphorus insecticides) and those of the OCs determined in the present study. Leaching distances and bioactivities in soil are correlated with the K_p values of the pesticides, and with the organic matter and the water content of the soil.     

Adsorption and movement of carbaryl in soils: A verification of cosolvent theory and comparison of batch equilibrium and soil thin layer chromatography results

Batch equilibrium and soil thin layer chromatography (TLC) techniques were used to investigate the influence of different volume fractions of organic cosolvents (acetone and methanol) on the adsorption and movement of carbaryl in four different types of Indian soils. L-shaped isotherms were obtained for both the cosolvent–water mixtures at all f _s values and were in close agreement with the Freundlich equation. Higher adsorption was observed on F.R.I. soil (FSL) followed by Alampur soil (ASL), Kalai soil (KL), and Bhoran soil (BSL) at all f _s values for both the cosolvent systems as was anticipated from the K and K _D values. The K and K _D values also confirmed that carbaryl adsorption was higher in methanol–water mixture than acetone–water mixture and decreased with increasing f _s values. The frontal R _f values obtained from soil TLC studies were inversely proportional to the K and K _D values for both the cosolvent systems. The higher K and K _D values and lower R _f values in methanol–water mixtures relative to acetone–water mixtures for all the soils indicated that acetone had a greater potential for ground water contamination compared to methanol. The adsorption data were used to evaluate the cosolvent theory for describing adsorption of carbaryl in acetone–water and methanol–water mixtures. The aqueous phase partition coefficients, K _DW (mol g^?1), normalized with respect to f _oc for carbaryl was evaluated by extrapolating f _s → 0.     

Biokinetic modeling of heavy metals in earthworms

Studies concerning bioaccumulation kinetics and bioconcentration factor (BCF) of heavy metals like zinc (Zn), lead (Pb), chromium (Cr), cadmium (Cd), and copper (Cu) in earthworm Eudrilus eugeniae tissues including integument, gizzard, clitellum, and head region were undertaken. Calculated BCF, predicted K _ow, and predicted K _oc showed a significant correlation between heavy metals in different earthworm tissues, in substrate spiked with heavy metals. The regression coefficient (r ²) between heavy metal uptake concentration and exposure time varied between 0.73 and 0.99, indicating significant correlation. The K _oc was a maximum of 13.9016 in case of Cu and integument at an exposure time of 100 days and a minimum of 0.1114 in case of Cr with respect to head at the same exposure time. Earthworms accumulated heavy metals following chronic exposure to municipal solid waste containing heavy metals. BCF and uptake rate kinetics of heavy metals were calculated and showed increased values in head tissue followed by integument.     

Effect of insecticides alone and in combination with fungicides on nitrification and phosphatase activity in two groundnut (Arachis hypogeae L.) soils

The effect of selected pesticides, monocrotophos, chlorpyrifos alone and in combination with mancozeb and carbendazim, respectively, was tested on nitrification and phosphatase activity in two groundnut (Arachis hypogeae L.) soils. The oxidation of ammonical nitrogen was significantly enhanced under the impact of selected pesticides alone and in combinations at 2.5 kg ha⁻¹ in black soil, and furthermore, increase in concentration of pesticides decreased the rate of nitrification, whereas in the case of red soil, the nitrification was increased up to 5.0 kg ha⁻¹ after 4 weeks, and then decline phase was started gradually from 6 to 8 weeks of incubation. The activity of phosphatase was increased in soils, which received the monocrotophos alone and in combination with mancozeb up to 2.5 and 5.0 kg ha⁻¹, whereas the application of chlorpyrifos singly and in combination with carbendazim at 2.5 kg ha⁻¹ profoundly increased the phosphatase activity after 20 days of incubation, in both soils. But higher concentrations of pesticides were either innocuous or inhibitory to the phosphatase activity.     

Nuclear magnetic resonance studies of interactions between organic pollutants and soil components,a review

This article presents a short overview of selected recent papers using nuclear magnetic resonance (NMR) to investigate interactions between organic pollutants and soil components such as organic matter, clays, whole soils, and sediments. First, we describe solid state cross polarisation magic angle spinning (CP-MAS) experiments as the main tools to investigate covalent bonds. Second, we report NMR approaches allowing us to assess molecule mobility and to characterise non-covalent interactions. Those approaches include correlations between K _oc values and soil organic matter functions determined by CP-MAS, ²H NMR fingerprints, relaxation time measurements, ¹⁹F and ¹H high resolution (HR)-MAS experiments.     

Arachis hypogaea derived activated carbon steered remediation of Benzimidazole based fungicide adsorbed soils

Sorption characteristics of the Benzimidazole fungicide Carbendazim were assessed in seven different soils using batch equilibrium method and analysed by UV-Vis spectrophotometer. The values of adsorption co-efficient K_d ranged from 14.3 to 39.8?µg/mL depending upon unique physiochemical properties of soils. Negative values for Gibbs free energy (ΔG) proposed an exothermic and low interaction between Carbendazim and soil samples leading to physiosorption. Statistical analysis showed a negative correlation of soil pH and K_d (R²= ?0.80) and a positive correlation with organic matter (R^2?=?0.77). Activated carbon prepared from Arachis hypogaea (peanut shells) by acid activation for Carbendazim removal from soils was characterised by FTIR spectrometry, indicating the change in functional groups. The highest percentage removal observed was 70% in 5?ppm initial Carbendazim concentration while 65% in 7.5?ppm concentration. This method can be implied in agricultural soils as an efficient and cheap technique for removing the hazardous pesticides from the environment.     

Clam‐sediment accumulation factors for polychlorinated biphenyl congeners at a contaminated estuarine marsh

Clam‐sediment accumulation factors for hexa‐, hepta‐ and octa‐chlorobiphenyls were estimated at an intertidal marsh that has been contaminated with Aroclor 1268. Accumulation factors for PCB congeners with K _ow > 6.5 were in the range of 0.07–0.88, indicating that their uptake was hindered by steric factors, contamination levels, non‐equilibrium conditions and stronger affinity to sediment organic carbon. Biota‐sediment accumulation factors (BSAFs) were negatively correlated with log K _ow of superhydrophobic PCB congeners. BSAFs estimated based on 2,3,7,8‐TCDD equivalents of PCBs were 2‐fold greater than those derived from total PCB concentrations.     

Bioavailability of hydrophobic organic contaminants and quality of organic carbon

U.S. laws require that contaminant bioaccumulation potential be evaluated before dredged material can be recycled. Simple fugacity models, e.g. organic contaminant aqueous partition coefficient (K _oc)-derived theoretical bioaccumulation potential, are commonly used to estimate the partitioning of hydrophobic organic contaminants between sediment organic matter and organism lipid. K _oc-derived models, with or without the addition of a soot carbon term, did not accurately or consistently predict total polycyclic aromatic hydrocarbons (PAHs) and polychlorobiphenyls partitioning of eight sediments from ongoing dredging operations onto C₁₈-coated filter paper. These models also failed to predict the partitioning of individual PAHs from these eight sediments. These data underscore the trade-offs between the ease of using simple models and the uncertainty of predicted partitioning values.     

4种农药对土壤脱氢酶活性的影响

通过天王星、功夫、久效磷、氧化乐果4种农药对土壤脱氢酶活性的抑制性进行试验，确认了实验条件的影响因素，同时分析了不同农药用量、不同土样用量及不同培养时间对脱氢酶活性的影响。试验结果表明，4种农药在不同情况下对脱氢酶活性均有不同程度的抑制作用，表明了在本地区特有的农业环境条件下，农用化学物质可能会影响和破坏农业生态环境。     

Adsorption‐desorption hysteresis of α‐endosulfan in tropical soils using isotopic techniques

This study was designed to evaluate the adsorption‐desorption hysteresis of endosulfan (1,2,3,4, 7,7‐hexachlorobicyclo[2,2,1]‐2‐heptene‐5,6‐bisoxymethylene sulfite) in selected tropical soils. Two major tropical soils from Thailand were selected, Rangsit lowland soils (Rangsit series) and Phrabat upland soils (Pakchong series). The soil types were sub‐divided into plow soils, 0–20cm depth from the surface, and subsoils, 20–40cm depth. Adsorption was determined in 24h batch equilibrium, with five different concentrations of ¹⁴C endosulfan ranging from 1.04 to 16.64 ng/mg soils. Four successive desorption studies were performed continuously after three adsorption concentrations, 24h for each successive. Adsorption coefficient values (K _ads) as determined by Freundlich model ranged from 0.02 to 0.14 and found to be higher in Rangsit soils as expected when compared with Phrabat soils. Desorption was hysteresis in every desorption study. Desorption coefficient values (K _des) were higher than adsorption (K _des).     

pH dependence of copper adsorption in vineyard soils of Geneva

Copper adsorption by vineyard soils of the Geneva canton was evaluated by batch equilibration experiments in a pH range from 4 to 6. The adsorption curves fit significantly to Freundlich function log q = n log C + log K_f, where q is adsorbed Cu concentration on the solid phase and C is solution Cu concentration at the end of the equilibration time. Moreover, we found that Freundlich parameters n and log K_f are moderately correlated to pH, yielding the following equations: log K_f = 0.23 pH + 0.51 (R ² 0.59) and n = –0.12 pH + 1.06 (R ² 0.59). Such equations may be useful to predict Cu mobility for risk assessment studies.     

Biokonzentration von persistenten superlipophilen Chemikalien in aquatischen Organismen

According to generally accepted theory, persistent superlipophilic chemicals with logn-octanol/water partitioning coefficient (log K_ow) >6 and molecular sizes >9,5 Å, such as octachlorodibenzo-p-dioxin, decachlorobiphenyl, Mirex etc., do not significantly bioconcentrate in aquatic organisms from ambient water. In the light of new results and considerations, this hypothesis has to be revised. The most convincing argument against this hypothesis is that in all bioconcentration experiments with superlipophilic chemicals compound concentrations have been applied which exceeded water solubility by several orders of magnitude. In this paper we describe various methods how to determine bioconcentration (BCF) factors of superlipophilic compounds. As exemplified with octachlorodibenzo-p-dioxin and Mirex, BCF values evaluated by this means match well those calculated by QSARs for fish and mussels based on log K_ow and water solubility as well. As expected these BCF values exceed previous ones by several orders of magnitude. As practical consequences, we recommend for BCF evaluations of superlipophilic chemicals:

1. flow-through systems, kinetic method (OECD guideline No 305 E)
2. ambient concentrations≤water solubility.

*** DIRECT SUPPORT *** A00HP013 00002     

Sorption of cadmium(II) and copper(II) by soil humic acids: temperature effects and sorption heterogeneity

Sorption by humic acids is known to modify the bioavailability and toxicity of metals in soils and aquatic systems. The sorption of cadmium(II) and copper(II) to two soil humic acids was measured at pH 6.0 using ion-selective electrode potentiometric titration at different temperatures. Sorption reactions were studied with all components in aqueous solution, or with the humates in suspension. Adsorption reactions were described using a multiple site-binding model, and a model assuming a continuous log-normal distribution of adsorption constants. Adsorption of Cu²⁺ was more favourable than adsorption of Cd²⁺. The log-normal distribution model provided the closest fit to observations and allowed parameterisation of adsorption data using a mean adsorption constant (log K _μ). Sorption of Cd²⁺ to dissolved humic acids increased slightly in extent and sorption affinity with increasing temperature, but the effect was small (log K _μ 2.96–3.15). A slightly greater temperature effect occurred for sorption of Cd²⁺ to solid-phase humic acids (log K _μ 1.30–2.08). Sorption of copper(II) to both aqueous- and colloidal-phase humates showed more pronounced temperature dependence, with extent of sorption, and sorption affinity, increasing with increasing temperature (log K _μ 3.4–4.9 in solution and 1.4–4.5 in suspension). The weaker adsorption of Cd²⁺ than Cu²⁺, and smaller temperature effects for dissolved humates than suspended humates, suggested that the observed temperature effects had a kinetic, rather than thermodynamic, origin. For any metal-to-ligand ratio, free metal ion concentration, and by inference metal bioavailability, decreased with increasing temperature. The consistency of the data with kinetic rather than thermodynamic control of metal bioavailability suggests that equilibrium modelling approaches to estimating bioavailability may be insufficient.     

土壤水溶态铜对小白菜的毒害效应及其预测模型

土壤中铜(Cu)重金属的生物毒性/有效性主要取决于它们在土壤液相中含量和土壤溶液的性质。探寻土壤有效态Cu的生物毒害效应,表征量化其与土壤溶液性质关系,可为土壤Cu的环境风险评价提供参考。选取17种典型农田土壤,探讨了有效态Cu(土壤孔隙水以及CaCl_2浸提态)对小白菜生长的毒性效应及其预测模型。结果表明:土壤孔隙水中Cu对小白菜生长10%抑制的毒性阈值值(EC_(10))和50%抑制的毒性阈值(EC_(50)),最大值与最小值相差为14.7和14.6倍;同样,对于CaCl_2提取态Cu的EC_(10)和EC_(50),最大值与最小值相差12.7和7.7倍,表明土壤溶液性质对水溶性Cu对小白菜的毒性阈值影响很大。建立了土壤溶液的重要因子(溶解性有机碳、土壤溶液pH值、电导率、全硫含量、Ca~(2+)、Mg~(2+)、K~+、Na~+)和水溶性Cu阈值之间的多元回归关系,结果显示,土壤溶液性质可以较好地预测水溶性Cu对小白菜的毒性阈值。同时,土壤溶液中Mg~(2+)、K~+和S的含量是控制孔隙水中Cu对小白菜生长毒性的最重要因子,单一的S能分别解释34%的EC_(10)变异,K~+解释26%的EC_(50)变化。本研究结果可为陆地环境中水溶性Cu的风险评价提供基础。     

Metal partitioning in sediment pore water from the Ondo coastal region,Nigeria

Distribution and equilibrium partitioning of metals (Cd, Cu, Cr, Fe, Ni, Pb, Mn, and Zn) between pore water and surface sediments at the Ilaje coast of Ondo State, Nigeria, were studied. The Ilaje River can be one of the interesting research locations because of its economic nature and history of oil pollution. Seasonal variations were observed to investigate possible variations in the availability of metals for organisms throughout the year. The concentrations in both sediments and pore water during the dry and wet seasons were as follows: Cu?>?Fe???Mn?>?Pb?>?Ni?>?Cr?>?Cd?>?Zn. The pore water–sediment partition coefficient (K _p) showed that Zn and Cd were highly mobile while Fe and Cu have restricted mobility. Dissolved organic carbon (DOC) in pore water had a strong influence on mobility and bioavailability of all the metals (p?K _oc), increased levels of Fe and Cu were linked to lithological origin. Concentrations of Pb and Ni were associated with petroleum-related sources. The significance of the field-based techniques for ecotoxicological purposes is discussed.     

Persistence and dissipation of synthetic pyrethroid pesticides in red soils from the Yangtze River Delta area

Laboratory incubation trials were conducted to investigate the effects of several factors on the persistence as well as the dissipation of three synthetic pyrethroid pesticides in red soils obtained from the Yangtze River Delta region in China. The pyrethroids selected for investigation were cypermethrin, fenvalerate, and deltamethrin, which continue to be used extensively to control pests on farmland in the region despite the concern that they are highly toxic to certain vertebrate and mammalian species. Data from this exploratory study showed that the dissipation half-lives (T _1/2) tended to correlate with soil pH and soil organic matter contents, but not with soil cation-exchange capacity. The T _1/2 values were seen to be shorter in soil samples fertilized with glucose than without. The rates of pyrethroid dissipation also tended to increase with increasing initial soil concentration, but were largely unaffected by whether the pesticides were present in the soil separately or as a mixture. Another noteworthy observation is that microbial activity appeared to dominate the degradation process. Findings of this type could offer valuable clues for future research directions in reducing pesticide persistence in soil, which in turn could lead to the ultimate reduction of environmental pollution caused by pyrethroid application to farmland in the region. Project supported by Chinese Academy of Sciences (Project No. KSCX2-YW-N-038) and the National Key Basic Research Support Foundation (973), China (No. 2002CB4108010).     

Retention of 137cesium in acid sulphate soils of South Central Thailand

Adsorption and desorption of ¹³⁷Cs by acid sulphate soils from the Nakhon Nayok province, South Central Plain of Thailand located near the Ongkarak Nuclear Research Center (ONRC) were investigated using a batch equilibration technique. The influence of added limestone (12 and 18 tons ha^?1) on ¹³⁷Cs adsorption–desorption was studied. Based on Freundlich isotherms, both adsorption and desorption of ¹³⁷Cs were nonlinear. A large portion (98.26–99.97%) of added ¹³⁷Cs (3.7?×?10³?7.03?×?10⁵ Bq l^?1) was sorbed by the soils with or without added lime. The higher lime treatments, however, favoured stronger adsorption of ¹³⁷Cs as compared with soil with no lime, which was supported by higher K _ads values. The addition of lime, the cation exchange capacity and pH of the soil increased and hence favoured the stronger adsorption of ¹³⁷Cs. Acid sulphate soils with a high clay content, medium to high organic matter, high CEC, and predominant clay types consisting of a mixture of illite, kaolinite, and montmorillonite were the main soil factors contributing to the high ¹³⁷Cs adsorption capacity. Competing cations such as NH₄ ⁺, K⁺, Na⁺, Ca²⁺, and Mg²⁺ had little influence on ¹³⁷Cs adsorption as compared with liming, where a significant positive correlation between K _ads and soil pH was observed. The ¹³⁷Cs adsorption–desorption characteristics of the acid sulphate soils studied exhibited a very strong irreversible sorption pattern. Only a small portion (0.09–0.58%) of ¹³⁷Cs adsorbed at the highest added initial ¹³⁷Cs concentration was desorbed by four successive soil extractions. Results clearly demonstrated that Nakhon Nayok province acid sulphate soils have a high ¹³⁷Cs adsorption capacity, which limits the ¹³⁷Cs bioavailability.