Sorption of 3,4-dichloroaniline on four contrasting Greek agricultural soils and the effect of liming

Sorption of 3,4-dichloroaniline (3,4-DCA) on four typical Greek agricultural soils, with distinct texture, organic matter content and cation exchange capacities, was compared by using sorption isotherms and the parameters calculated from the fitted Freundlich equations. The sorption process of 3,4-DCA to the soil was completed within 48-72 h. The 3,4-DCA sorption on all soils was well described by the Freundlich equation and all sorption isotherms were of the L-type. The sandy clay loam soil with the highest organic matter content and a slightly acidic pH was the most sorptive, whereas the two other soil types, a high organic matter and neutral pH clay and a low organic matter and acidic loam, had an intermediate sorption capacity. A typical calcareous soil with low organic matter had the lowest sorption capacity which was only slightly higher than that of river sand. The 3,4-DCA sorption correlated best to soil organic matter content and not to clay content or cation exchange capacity, indicating the primary role of organic matter. The distribution coefficient (K(d)) decreased with increasing initial 3,4-DCA concentration and the reduction was most pronounced with the highly sorptive sandy clay loam soil, suggesting that the available sorption sites of the soils are not unlimited. Liming of the two acidic soils (the sandy clay loam and the loam) raised their pH (from 6.2 and 5.3, respectively) to 7.8 and reduced their sorption capacity by about 50 %, indicating that soil pH may be the second in importance factor (after organic matter) determining 3,4-DCA sorption.     

Sorption of chlorpyrifos and fonofos on four soils and turfgrass thatch using membrane filters

Abstract

Chemical transport in soil is a major factor influencing soil and water contamination. Four soils and turfgrass thatch, representing a wide range of organic carbon OC content were studied to determine sorption K_d and K_f parameters for the insecticides chlorpyrifos and fonofos. The batch equilibrium method was used. The concentration of insecticide was measured in the solution as well as in the solid phase to determine the most accurate sorption data. Four soils and thatch were equilibrated for 24 h at 22 ± 1^OC with aqueous insecticide solutions. Four concentrations of the insecticides, each <50% of their respective water solubilities, were selected for the experiments. After extraction with an organic solvent, the concentration of insecticides in the aqueous solution was determined by gas liquid chromatography using electron capture detection for chlorpyrifos, and nitrogen/phosphorus detection for fonofos. Data obtained were fitted to the log and simple linear form of the Freundlich equation. Mass balance Freundlich isotherm exponents n ranged between 0.82 and 0.93 for chlorpyrifos. 0.82 and 1.21 for fonofos, with r² ≥ 0.97. K_oc (percent of organic carbon %OC normalized Sorption coefficient) values were calculated by using experimentally developed K_d and K_f coefficients in relation to OC levels from 0.29 to 34.85%. K_d and K_f coefficients of both insecticides were positively correlated with OC (r² ≥ 0.96). organic matter OM (r² ≥ 0.96), and cation exchange capacity CEC (r² ≥ 0.90).     

Sorption and desorption of sulfentrazone in Brazilian soils

This study was undertaken to obtain information about the behavior of sulfentrazone in soil by evaluating the sorption and desorption of the herbicide in different Brazilian soils. Batch equilibrium method was used and the samples were analyzed by high performance liquid chromatography. Based on the results obtained from the values of Freundlich constants (Kf), we determined the order of sorption (Haplic Planosol < Red-Yellow Latosol < Red Argisol < Humic Cambisol < Regolitic Neosol) and desorption (Regolitic Neosol < Red Argisol < Humic Cambisol < Haplic Planosol < Red-Yellow Latosol) of sulfentrazone in the soils. The process of pesticide sorption in soils was dependent on the levels of organic matter and clay, while desorption was influenced by the organic matter content and soil pH. Thus, the use of sulfentrazone in soils with low clay content and organic matter (low sorption) increases the probability of contaminating future crops.     

Sorption of radiolabelled glyphosate on biochar aged in contrasting soils

Glyphosate mobility from terrestrial to aquatic environments has raised concerns about it. Utilizing soil’s inherent properties along with sorption properties of aged biochar, we hypothesized that selective application of biochar would be more effective in economic terms for glyphosate sorption on contrasting soils. To test this hypothesis, batch experiments and liquid scintillation counting for ¹⁴ Okada, E.; Costa, J. L.; Bedmar, F. Adsorption and mobility of glyphosate in different soils under no-till and conventional tillage. Geoderma 2016, 263, 78–85.[Crossref], [Web of Science ®] , [Google Scholar]C labeled glyphosate were used. The sorption behavior of glyphosate was examined in four contrasting Australian soil types (Oxisol, Vertisol, Entisol, and Inceptisol) amended with aged biochar to determine glyphosate concentrations by measuring ¹⁴ Okada, E.; Costa, J. L.; Bedmar, F. Adsorption and mobility of glyphosate in different soils under no-till and conventional tillage. Geoderma 2016, 263, 78–85.[Crossref], [Web of Science ®] , [Google Scholar]C activity using liquid scintillation counting. Freundlich parameters were calculated for soil-soil/biochar combinations. The pattern of glyphosate sorption was Oxisol?>?Vertisol?>?Entisol?>?Inceptisol. Oxisol adsorbed approximately five times more glyphosate compared with Inceptisol. Oxisol soil system adsorbed maximum amount of glyphosate principally due to the presence of iron-aluminum oxides exhibiting variable charges which got increased due to the presence of aged biochar. Considering all the soil/soil-biochar systems, Inceptisol soil system showed the least adsorption of glyphosate. A significant contribution of char was observed only in the Entisol soil system and the finding is valuable as char can be applied in Entisol soil systems to control glyphosate mobility.     

Evaluation of sorption-desorption processes for metalaxyl in natural and artificial soils

The main process controlling soil-pesticide interaction is the sorption-desorption as influenced by active soil surfaces. The sorption phenomena can influence translocation, volatility, persistence and bioactivity of a pesticide in soil. The present investigation was conducted on natural and artificial soils in order to enumerate the effect of soil components such as montmorillonite and ferrihydrite on the sorption behaviour of the fungicide metalaxyl and if sorption-desorption of the chiral pesticide affects the enantiomeric ratio. The sorption-desorption characteristics of metalaxyl were investigated by batch equilibration technique in a natural soil, two artificial soils, and in pure montmorillonite and ferrihydrite. After extraction, pesticide residues were analyzed by conventional and chiral chromatography using tandem mass spectrometry. A K_dSorp (2.3–6.5) suggests low level sorption of metalaxyl with an appreciable risk of run-off and leaching. Thus, metalaxyl poses a threat to surface and ground water contamination. Furthermore, desorption tests revealed a hysteretic effect (H ≤ 0.8) in natural and artificial soils. Significant amount of metalaxyl was found tightly bound to the adsorbents without desorbing readily after desorption cycle. Desorption of 22–56% of the total amount of the retained metalaxyl was determined. This study reveals that an artificial soil derived from different soil constituents can be used to assess their influence on sorption/desorption processes. The present investigation showed that both montmorillonite and ferrihydrite play a significant role in the sorption of metalaxyl. The sorption doesn't influence the enantiomeric ratio of racemic metalaxyl.     

Sorption and degradation of neonicotinoid insecticides in tropical soils

ABSTRACT

Neonicotinoids are the most widely applied class of insecticides in cocoa farming in Ghana. Despite the intensive application of these insecticides, knowledge of their fate in the Ghanaian and sub-Saharan African environment remains low. This study examined the behavior of neonicotinoids in soils from cocoa plantations in Ghana by estimating their sorption and degradation using established kinetic models and isotherms. Studies of sorption were conducted using the batch equilibrium method on imidacloprid, thiamethoxam, clothianidin, acetamiprid and thiacloprid, while degradation of imidacloprid, thiamethoxam and their respective deuterated counterparts was studied using models proposed by the European forum for coordination of pesticide fate and their use (FOCUS). Analytes were extracted using the quick, easy, cheap, effective, rugged and safe (QuEChERS) procedure and quantified by liquid chromatography-tandem mass spectrometry (LC–MS/MS). Average recoveries were high (≥ 85%) for all analytes. The findings from the study suggest that neonicotinoid insecticides may be persistent in the soils studied based on estimated half-lives > 150 days. The study also revealed generally low-sorption coefficients for neonicotinoids in soils, largely influenced by soil organic carbon.     

Impact of long-term wastewater irrigation on sorption and transport of atrazine in Mexican agricultural soils

In the Mezquital Valley, Mexico, crops have been irrigated with untreated municipal wastewater for more than a century. Atrazine has been applied to maize and alfalfa grown in the area for weed control for 15 years. Our objectives were to analyse (i) how wastewater irrigation affects the filtering of atrazine, and (ii) if the length of irrigation has a significant impact. We compared atrazine sorption to Phaeozems that have been irrigated with raw wastewater for 35 (P35) and 85 (P85) years with sorption to a non-irrigated (P0) Phaeozem soil under rainfed agriculture. The use of bromide as an inert water tracer in column experiments and the subsequent analysis of the tracers’ breakthrough curves allowed the calibration of the hydrodynamic parameters of a two-site non equilibrium convection-dispersion model. The quality of the irrigation water significantly altered the soils’ hydrodynamic properties (hydraulic conductivity, dispersivity and the size of pores that are hydraulically active). The impacts on soil chemical properties (total organic carbon content and pH) were not significant, while the sodium adsorption ratio was significantly increased. Sorption and desorption isotherms, determined in batch and column experiments, showed enhanced atrazine sorption and reduced and slower desorption in wastewater-irrigated soils. These effects increased with the length of irrigation. The intensified sorption-desorption hysteresis in wastewater-irrigated soils indicated that the soil organic matter developed in these soils had fewer high-energy, easily accessible sorption sites available, leading to lower and slower atrazine desorption rates. This study leads to the conclusion that wastewater irrigation decreases atrazine mobility in the Mezquital valley Phaeozems by decreasing the hydraulic conductivity and increasing the soil's sorption capacity.     

Two-Compartment Sorption of Phenanthrene on Eight Soils with Various Organic Carbon Contents

Sorption characteristics of phenanthrene (PHE) were studied on eight soils with organic carbon contents spanning over an order of magnitude using phase distribution relationships (PDRs) at 1 h, 48 h, and 720 h contact times. A new algebraic method was employed to describe the sorption characteristics at different time intervals (between 1 h and 48 h, and 1 h and 720 h). It was found that nonlinearity increased with increasing contact time and sorption that occurred in the subsequent time interval following the initial 1 h exhibited stronger isotherm nonlinearity. Sorption coefficients were positively correlated with the organic carbon contents of the soils. Detailed sorption dynamics were also examined on these soils. A two-compartment, first-order model was used to describe the sorption dynamics. The rate constants of the two compartments differed 18–170 times, suggesting the dissimilar sorption behaviors of the mathematically separated compartments. These two compartments were labeled fast and slow sorption compartment according to the rate constants. Calculation showed that the fast compartment accounted for over 80% of the overall sorption at the initial 1 h, while the slow compartment predominated the total sorption in the following 47 h. By combining the discussion of PDRs and sorption dynamics, the contributions of the two compartments to linear and nonlinear sorption were differentiated. The slow sorption compartment made a major contribution to nonlinear sorption and possibly to sequestration of organic pollutants by these soils.     

农药在土壤上吸着/解吸及其对生物利用率影响的研究进展

正确预测有机污染物在环境中的归宿 ,在很大程度上依赖对它们的吸着 -解吸动力学行为的认识。自 2 0世纪 80年代起 ,吸着 -解吸动力学逐渐受到重视。本文介绍了国内外有关农药在土壤 /沉积物上的吸着 -解吸动力学和吸着 -解吸对土壤有机污染物的生物利用率的影响等方面的近期研究成果 ,着重从实验方法、模型、机理等方面进行了详细的综述     

Degradation and plant uptake of nonylphenol (NP) and nonylphenol-12-ethoxylate (NP12EO) in four contrasting agricultural soils

Nonylphenol polyethoxylates (NPEOs) are surfactants found ubiquitously in the environment due to widespread industrial and domestic use. Biodegradation of NPEOs produces nonylphenol (NP), an endocrine disruptor. Sewage sludge application introduces NPEOs and NP into soils, potentially leading to accumulation in soils and crops. We examined degradation of NP and nonylphenol-12-ethoxylate (NP12EO) in four soils. NP12EO degraded rapidly (initial half time 0.3-5 days). Concentrations became undetectable within 70-90 days, with a small increase in NP concentrations after 30 days. NP initially degraded quickly (mean half time 11.5 days), but in three soils a recalcitrant fraction of 26-35% remained: the non-degrading fraction may consist of branched isomers, resistant to biodegradation. Uptake of NP by bean plants was also examined. Mean bioconcentration factors for shoots and seeds were 0.71 and 0.58, respectively. Removal of NP from the soil by plant uptake was negligible (0.01-0.02% of initial NP). Root concentrations were substantially higher than shoot and seed concentrations.     

The effect of liming agricultural land on the chemistry and biology of the River Esk, north-west England

A land-use study indicated that a reduction in agricultural liming may have been a major factor in the development of acid episodes and consequent fish kills in the River Esk and River Duddon. A field study was carried out to determine whether the reintroduction of catchment liming in the Esk valley could ameliorate acid episodes and thus prevent fish kills. Lime was applied to areas which had been limed in the past, comprising 10% of the Esk catchment. Flow, pH, calcium, aluminium, total humic substances, conductivity and invertebrates were monitored before and after liming. The River Duddon was monitored as a reference. There was a general reduction of the acidity of both the River Esk and the River Duddon during the study period. This appeared to be controlled by rainwater chemistry. There was little evidence for a major effect of liming on water chemistry which suggests that the mortalities of salmonids in the early 1980s were not due to a reduction in agricultural liming.     

Effects of the organic matter from swine wastewater on the adsorption and desorption of alachlor in soil

The application of swine wastewater to the soil for agricultural purposes results in the addition of total and dissolved organic matter to the soil, which may interfere with the dynamics of pesticides in the soil. The objective of this study was to evaluate the effects of the application of total and dissolved organic matter from a biodigester and a treatment lagoon of swine wastewater in the adsorption and desorption of alachlor [2-chloro-2,6-diethyl-N(methoxymethyl acetamide)]. The assay was performed by the batch equilibrium method, and the results were fitted to the Freundlich model. The curve comparison test revealed a greater adsorption of alachlor in the soil treated with swine wastewater from the biodigester. The adsorption and desorption of alachlor increased in the soils where swine wastewater was added, and hysteresis was observed in all of the treatments.     

载钴活性焦对As(V)的吸附性能与去除效果

使用沉淀负载法制备了载钴活性焦,并研究了溶液pH值、反应时间、As(V)初始浓度以及共存阴离子等对载钴活性焦吸附去除水环境中As(V)的影响。结果表明,(1)载钴后活性焦的比表面积和孔容积分别提高了20.87%和43.47%;(2)载钴活性焦对As(V)最佳吸附pH值为4.0,当As(V)的初始浓度为10 mg/L时,As(V)去除率可达97%;(3)吸附过程符合准二级动力学模型(k2=0.66,R2=0.96),吸附等温线为Freundlich型(kF=8.227,1/n=0.396,R2=0.97);(4)稳定性实验验证了载钴活性焦的稳定性,钴不易脱附,最大脱附率仅为0.145%。     

Impact of woodchip biochar amendment on the sorption and dissipation of pesticide acetamiprid in agricultural soils

Pyrolysis of vegetative biomass into biochar and application of the more stable form of carbon to soil have been shown to be effective in reducing the emission of greenhouse gases, improving soil fertility, and sequestering soil contaminants. However, there is still lack of information about the impact of biochar amendment in agricultural soils on the sorption and environmental fate of pesticides. In this study, we investigated the sorption and dissipation of a neonicotinoid insecticide acetamiprid in three typical Chinese agricultural soils, which were amended by a red gum wood (Eucalyptus spp.) derived biochar. Our results showed that the amendment of biochar (0.5% (w/w)) to the soils could significantly increase the sorption of acetamiprid, but the magnitudes of enhancement were varied. Contributions of 0.5% newly-added biochar to the overall sorption of acetamiprid were 52.3%, 27.4% and 11.6% for red soil, paddy soil and black soil, respectively. The dissipation of acetamiprid in soils amended with biochar was retarded compared to that in soils without biochar amendment. Similar to the sorption experiment, in soil with higher content of organic matter, the retardation of biochar on the dissipation of acetamiprid was lower than that with lower content of organic matter. The different effects of biochar in agricultural soils may attribute to the interaction of soil components with biochar, which would block the pore or compete for binding site of biochar. Aging effect of biochar application in agricultural soils and field experiments need to be further investigated.     

Simulation of the effect of remediation on EDB and 1,2-DCA plumes at sites contaminated by leaded gasoline

An analytical model is used to simulate the effects of partial source removal and plume remediation on ethylene dibromide (EDB) and 1,2-dichloroethane (1,2-DCA) plumes at contaminated underground storage tank (UST) sites. The risk posed by EDB, 1,2-DCA, and commingled gasoline hydrocarbons varies throughout the plume over time. Dissolution from the light nonaqueous phase liquid (LNAPL) determines the concentration of each contaminant near the source, but biological decay in the plume has a greater influence as distance downgradient from the source increases. For this reason, compounds that exceed regulatory standards near the source may not in downgradient plume zones. At UST sites, partial removal of a residual LNAPL source mass may serve as a stand alone remedial technique if dissolved concentrations in the source zone are within several orders of magnitude of the applicable government or remedial standards. This may be the case with 1,2-DCA; however, EDB is likely to be found at concentrations that are orders of magnitude higher than its low Maximum Contaminant Level (MCL) of 0.05 μg/L (micrograms per liter). For sites with significant EDB contamination, even when plume remediation is combined with source depletion, significant timeframes may be required to mitigate the impact of this compound. Benzene and MTBE are commonly the focus of remedial efforts at UST sites, but simulations presented here suggest that EDB, and to a lesser extent 1,2-DCA, could be the critical contaminants to consider in the remediation design process at many sites.     

Kresoxim methyl dissipation kinetics and its residue effect on soil extra-cellular and intra-cellular enzymatic activity in four different soils of India

The rate of degradation of kresoxim methyl and its effect on soil extra-cellular (acid phosphatase, alkaline phosphatase and β-glucosidase) and intra-cellular (dehydrogenase) enzymes were explored in four different soils of India. In all the tested soils, the degradation rate was faster at the beginning, which slowed down with time indicating a non-linear pattern of degradation. Rate of degradation in black soil was fastest followed by saline, brown and red soils, respectively and followed 1st or 1st + 1st order kinetics with half-life ranging between 1–6 days for natural soil and 1–19 days for sterile soils. The rate of degradation in natural against sterilized soils suggests that microbial degradation might be the major pathway of residue dissipation. Although small changes in enzyme activities were observed, kresoxim methyl did not have any significant deleterious effect on the enzymatic activity of the various test soils in long run. Simple correlation studies between degradation percentage and individual enzyme activities did not establish any significant relationships. The pattern and change of enzyme activity was primarily due to the effect of the incubation period rather than the effect of kresoxim methyl itself.     

Effect of four experimental insecticides on enzyme activities and levels of adenosine triphosphate in mineral and organic soils

Abstract

A laboratory study was conducted to determine the effect of four experimental insecticides, DOWCO429X, DPX43898, tefluthrin and trimethacarb, on enzyme activities and levels of adenosine 5'‐triphosphate (ATP) in mineral and organic soils. DOWCO429X decreased urease activity in organic soil after 7 days while a stimulatory effect was observed with most treatments after 14 days. No inhibition on acetylene (C₂H₂) reduction by nitrogenase was evident with any of the insecticides in either soil. With the exception of DOWCO429X and tefluthrin at 7 days in organic soil, none of the insecticide treatments inhibited dehydrogenase activity in either soil. Dehydrogenase activity, measured by formazan formation, was greater in many samples in sandy loam than the control throughout the experiment. No inhibitory effect was observed on amylase activity after 2 or 3 days in sandy soil. A stimulatory effect was apparent in many samples after 2 days in organic soil. All insecticide treatments in sandy soil reduced invertase activity at 2 days. However, none of the experimental insecticides inhibited invertase activity after 3 days. A stimulatory effect in invertase activity was apparent in most cases at 2 days in organic soil and no difference was observed after 3 days. Phosphatase activity in insecticide treated samples was equal to or greater than that of control in sandy soil after 2 h. With the exception of DPX43898, the insecticides depressed phosphatase activity in most organic soil samples. The insecticides did not affect ATP levels in either soil. Results indicated that the chemical treatments at the levels tested did not significantly affect activities of enzymes or level of ATP in both soils.     

黑麦草对土壤中残留抗生素的降解及其对微生物活性的影响

为了研究抗生素污染土壤的修复方法,利用黑麦草对土壤中残留抗生素进行降解,并探讨土壤微生物生态活性及根系体表特征的响应。结果表明：黑麦草对土壤中四环素、金霉素、恩诺沙星、洛美沙星、环丙沙星、诺氟沙星的降解速率均显著大于对照（pr=-0.948,p<0.05）。     

不同钝化剂对外源铅在土壤中的钝化效果及粒径分布的影响

通过室内钝化培养实验比较了羊厩肥、石灰和磷酸盐对土壤外源Pb的钝化效果和钝化修复后Pb的粒径分布特征。结果表明：3种钝化剂均能显著降低土壤中DTPA-Pb的含量,且钝化效果与钝化剂添加量成正比;磷酸盐对外源Pb钝化效果最好,P10处理下土壤中DTPA-Pb的含量降幅达80.53%,羊厩肥钝化效果最差,GM1对DTPA-Pb含量的降幅为6.51%;羊厩肥与磷酸盐将弱酸提取态Pb和可还原态Pb转变为活性更低的可氧化态Pb和残渣态Pb,以降低其活性,石灰将可还原态Pb转化为可氧化态Pb,以降低其活性;3种钝化剂添加均会提升土壤Olsen-P的含量。土壤磷淋溶临界值模型显示,当土壤Olsen-P含量>124.25 mg·kg⁻¹时,会发生磷素淋溶现象;Pb在土壤粗砂粒、细沙粒、粉粒和黏粒中的含量差别很大,但赋存形态无明显差异,钝化剂添加会影响外源Pb在各粒级颗粒中的富集及形态分布。相关性分析结果表明,钝化剂主要通过将细沙粒、粉粒和黏粒中的可还原态Pb转化为粉粒和黏粒中的可氧化态Pb来降低土壤Pb的毒害性。研究结果可为3种钝化剂在Pb污染土壤修复中的高效利用及修复后土壤的潜在生态风险管控提供参考。