An integrated approach for assessing the migration behavior of chlorpyrifos and carbaryl in the unsaturated soil zone

Chlorpyrifos (O, O-diethyl O-3,5,6-trichloropyridin-2-yl phosphorothioate) and carbaryl (1-naphthyl methylcarbamate) are often applied concurrently as insecticides in food production. The aim of this study was to research their migration behavior in a real environment. We researched the leaching of both pesticides by setting up field lysimeters on a farm with the typical soil used in fruit production today. In order to analyze the variables involved in this process, we performed complementary adsorption studies, we performed complementary adsorption studies using batches and undisturbed soil laboratory columns for both compounds. The results for pesticide transport through the lysimeters showed that less than 1% of chlorpyrifos was recovered in the leachates, while almost 17% was recovered for carbaryl. Having completed the experiment in undisturbed laboratory columns, soil analysis showed that chlorpyrifos mainly remained in the first 5 cm, while carbaryl moved down to the lower sections. These results can be explained in view of the sorption coefficient values (K_D) obtained in horizons A and B for chlorpyrifos (393 and 184 L kg^?1) and carbaryl (3.1 and 4.2 L kg^?1), respectively. By integrating the results obtained in the different approaches, we were able to characterize the percolation modes of these pesticides in the soil matrix, thus contributing to the sustainable use of resources.     

Sorption kinetic characteristics of polybrominated diphenyl ethers on natural soils

Sorption kinetic characteristics of BDE-28 and BDE-47 on five natural soils with different organic carbon fractions were investigated, and could be satisfactorily described by a two (fast and slow)-compartment first-order model with the ratio of rate constants ranged from 9 to 94 times. The fast compartment made a dominant contribution (71% ∼ 94%) to the total sorption amount in the whole process, and accounted for over 90% of the increase in the total sorption amount at initial 5 h. The influence of the slow compartment on the increase in the total sorption amount became principal (above 90%) in the subsequent stage approximately from 9 h or 25 h to the apparent equilibrium at 265 h. The results proposed the different sorption behaviors of the mathematically classified compartments for BDE-28 and BDE-47, which may correspond to the different soil components, such as soil organic fractions with amorphous and condensed structures, respectively.     

土壤-植物系统中磷和砷相互作用关系的研究进展

砷元素导致的环境污染问题日益突出,施磷已成为植物修复砷污染土壤过程中必要强化措施之一。土壤-植物系统中磷和砷的相互作用关系是非常复杂的,研究表明：磷和砷在土壤中往往是共生的,但又存在竞争吸附关系;磷和砷在不同植物中的相互作用关系主要有拮抗效应和协同效应;有必要通过分子生物学手段对磷和砷表达基理进行深入研究,获得对砷具有超积累能力的植株。     

Part V—sorption of pharmaceuticals and personal care products

Background, aim, and scope  Pharmaceuticals and personal care products (PPCPs) including antibiotics, endocrine-disrupting chemicals, and veterinary pharmaceuticals are emerging pollutants, and their environmental risk was not emphasized until a decade ago. These compounds have been reported to cause adverse impacts on wildlife and human. However, compared to the studies on hydrophobic organic contaminants (HOCs) whose sorption characteristics is reviewed in Part IV of this review series, information on PPCPs is very limited. Thus, a summary of recent research progress on PPCP sorption in soils or sediments is necessary to clarify research requirements and directions. Main features  We reviewed the research progress on PPCP sorption in soils or sediments highlighting PPCP sorption different from that of HOCs. Special function of humic substances (HSs) on PPCP behavior is summarized according to several features of PPCP–soil or sediment interaction. In addition, we discussed the behavior of xenobiotic chemicals in a three-phase system (dissolved organic matter (DOM)–mineral–water). The complexity of three-phase systems was also discussed. Results  Nonideal sorption of PPCPs in soils or sediments is generally reported, and PPCP sorption behavior is relatively a more complicated process compared to HOC sorption, such as the contribution of inorganic fractions, fast degradation and metabolite sorption, and species-specific sorption mechanism. Thus, mechanistic studies are urgently needed for a better understanding of their environmental risk and for pollution control. Discussion  Recent research progress on nonideal sorption has not been incorporated into fate modeling of xenobiotic chemicals. A major reason is the complexity of the three-phase system. First of all, lack of knowledge in describing DOM fractionation after adsorption by mineral particles is one of the major restrictions for an accurate prediction of xenobiotic chemical behavior in the presence of DOM. Secondly, no explicit mathematical relationship between HS chemical–physical properties, and their sorption characteristics has been proposed. Last but not least, nonlinear interactions could exponentially increase the complexity and uncertainties of environmental fate models for xenobiotics. Discussion on proper simplification of fate modeling in the framework of nonlinear interactions is still unavailable. Conclusions  Although the methodologies and concepts for studying HOC environmental fate could be adopted for PPCP study, their differences should be highly understood. Prediction of PPCP environmental behavior needs to combine contributions from various fractions of soils or sediments and the sorption of their metabolites and different species. Recommendations and perspectives  More detailed studies on PPCP sorption in separated soil or sediment fractions are needed in order to propose a model predicting PPCP sorption in soils or sediments based on soil or sediment properties. The information on sorption of PPCP metabolites and species and the competition between them is still not enough to be incorporated into any predictive models.     

Influence of fertilizing on the Cs soil–plant transfer in a spruce forest of Southern Germany

Fertilization with 2.5 t/ha limestone: (83% CaCO₃, 8% MgO, 6% K₂O, 3% P₂O₅) reduces the ¹³⁷Cs transfer from spruce forest soil into plants like fern (Dryopteris carthusiana) and blackberry (Rubus fruticosus) by a factor of 2–5 during at least 11 years as measured by the aggregated transfer factor T_ag. In 1997 and 2006 these results were confirmed by additional measurements of the ¹³⁷Cs transfer factor TF, related to the root zone (O_h horizon), which were explained by the selective sorption of ¹³⁷Cs in the root zone by measurements of the Radiocaesium Interception Potential (RIP) in fertilized (RIP > 179 meq/kg) and non-fertilized soils (RIP < 74 meq/kg).     

Sorption and Desorption Behavior of Chloroanilines and Chlorophenols on Montmorillonite and Kaolinite

The bioavailability of pollutants, pesticides and/or their degradation products in soil depends on the strength of their sorption by the different soil components, particularly by the clay minerals. This study reports the sorption-desorption behavior of the environmentally hazardous industrial pollutants and certain pesticides degradation products, 3-chloroaniline, 3,4-dichloroaniline, 2,4,6-trichloroaniline, 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol on the reference clays kaolinite KGa-1 and Na-montmorillonite SWy-l. In batch studies, 2.0 g of clay were equilibrated with 100.0 mL solutions of each chemical at concentrations ranging from 10.0 to 200.0 mg/L. The uptake of the compounds was deduced from the results of HPLC-UV-Vis analysis. The lipophilic species were best retained by both clay materials. The most lipophilic chemical used in the study, 2,4,6-trichloroaniline, was also the most strongly retained, with sorption of up to 8 mg/g. In desorption experiments, which also relied on HPLC-UV-Vis technique, 2,4,6-trichloroaniline was the least desorbed from montmorillonite. However, on kaolinite all of the compounds under study were irreversibly retained. The experimental data have been modelled according to the Langmuir and Freundlich isotherms. A hypothesis is proposed concerning the sorption mechanism and potential applications of the findings in remediation strategies have been suggested.     

2,4-D mineralization in unsaturated and near-saturated surface soils of an undulating,cultivated Canadian prairie landscape

The herbicide 2,4-D [2,4-(dichlorophenoxy) acetic acid] is one of the most widely used pesticides in the Canadian prairies and is frequently detected as a ground and surface water contaminant. The objective of this paper was to determine the magnitude and extent of variation of 2,4-D mineralization in a cultivated undulating prairie landscape. Microcosm incubation experiments, using a 4 × 3 × 2 factorial experimental design (soil moisture, 4 levels: 60, 85, 110, 135% of field capacity; slope position, 3 levels: upper-, mid- and lower-slopes; soil depth, 2 levels: 0–5 and 5–15 cm), were used to assess 2,4-D mineralization. The first-order mineralization rate constant (k₁) varied from 0.03 to 0.22 day^{? 1}, while total 2,4-D mineralization varied from 31 to 52%. At near-saturated conditions (110 and 135% of field capacity), the onset of 2,4-D degradation was delayed in soil obtained from the upper- and mid-slopes but not in soils obtained from the lower-slope position. The k₁ and total 2,4-D mineralizationwas significantly influenced by all three factors and their interactions. The Freundlich sorption coefficient of 2,4-D ranged from 0.83 to 2.46 ug ^1–1/ng^{? 1} mL^1/n and was significantly influenced by variations in soil organic carbon content across slope positions. The infield variability of 2,4-D sorption and mineralization observed across slope positions in this undulating field was comparable in magnitude and extent to the regional variability of 2,4-D sorption and mineralization observed in surface soils across Manitoba. The large variability of 2,4-D mineralization and sorption at different slope positions in this cultivated undulating field suggests that landform segmentation models, which are used to delineate slope positions, are important considerations in pesticide fate studies.     

2,4-D Mineralization in soil profiles of a cultivated hummocky landscape in Manitoba,Canada

The objective of this study was to quantify 2,4-D (2,4-dichlorophenoxyacetic acid) mineralization in soil profiles characteristic of hummocky, calcareous-soil landscapes in western Canada. Twenty-five soil cores (8 cm inner diameter, 50 to 125 cm length) were collected along a 360 m transect running west to east in an agricultural field and then segmented by soil-landscape position (upper slopes, mid slopes, lower slopes and depressions) and soil horizon (A, B, and C horizons). In the A horizon, 2,4-D mineralization commenced instantaneously and the mineralization rate followed first-order kinetics. In both the B and C horizons, 2,4-D mineralization only commenced after a lag period of typically 5 to 7 days and the mineralization rate was biphasic. In the A horizon, 2,4-D mineralization parameters including the first-order mineralization rate constant (k ₁), the growth-linked mineralization rate constant (k ₂) and total 2,4-D mineralization at the end of the experiment at 56 days, were most strongly correlated to parameters describing 2,4-D sorption by soil, but were also adequately correlated to soil organic carbon content, soil pH, and carbonate content. In both B and C horizons, there was no significant correlation between 2,4-D mineralization and 2,4-D sorption parameters, and the correlation between soil properties and 2,4-D mineralization parameters was very poor. The k ₁ significantly decreased in sequence of A horizon (0.113% day^?1) > B horizon (0.024% day^?1) = C horizon (0.026% day^?1) and in each soil horizon was greater than k ₂. Total 2,4-D mineralization at 56 days also significantly decreased in sequence of A horizon (42%) > B horizon (31%) = C horizon (27%). In the A horizon, slope position had little influence on k ₁ or k ₂, except that k ₁ was significantly greater in upper slopes (0.170% day^?1) than in lower slopes (0.080% day^?1). Neither k ₁ nor k ₂ was significantly influenced by slope position in the B or C horizons. Total 2,4-D mineralization at 56 days was not influenced by slope positions in any horizon. Our results suggest that, when predicting 2,4-D transport at the field scale, pesticide fate models should consider the strong differences in 2,4-D mineralization between surface and subsurface horizons. This suggests that 2,4-D mineralization is best predicted using a model that has the ability to describe a range of non-linear mineralization curves. We also conclude that the horizontal variations in 2,4-D mineralization at the field scale will be difficult to consider in predictions of 2,4-D transport at the field scale because, within each horizon, 2,4-D mineralization was highly variable across the twenty-five soil cores, and this variability was poorly correlated to soil properties or soil-landscape position.     

Development of IC-ELISA for detection of organophosphorus pesticides in water

Diethyl (carboxymethyl) phosphonate (DECP) was used as the hapten to develop an indirect competitive enzyme-linked immunosorbent assay (IC-ELISA) for detecting organophosphorus pesticides (OPs). Conjugator of DECP with bovin serum albumin (BSA) was used as the immunogen for producing the polyclonal antibodies (PcAbs). Three antisera were obtained after the immune procedure. Characterization studies of the PcAbs indicated that the titer of antiserum-1 was highest in 3 antisera, and antiserum-1 had high affinity and specificity to the parathion, dichlorvos and pirimiphos. The IC-ELISA showed an IC₅₀ of 0.428 μ g/mL with a detection limit of 0.0125 μ g/mL to parathion. The assay also indicated that the IC₅₀ values of pirimiphos and dichlorvos were 0.331 μ g/mL and 1.25 μ g/mL respectively, and the detection limits of pirimiphos and dichlorvos were 0.0116 μ g/mL and 0.048 μ g/mL respectively. Recoveries of parathion, pirimiphos and dichlorvos spiked into water samples ranged from 90% to 160%. The results indicated that the ELISA could be a convenient and supplemental analytical tool for monitoring OPs residues in environmental water samples.