Adsorption studies of the herbicide simazine in agricultural soils of the Aconcagua valley, central Chile

Simazine is a s-triazine herbicide that has been applied worldwide for agriculture. This herbicide is the second most commonly detected pesticide in surface and groundwater in the United States, Europe and Australia. In this study, simazine adsorption behaviour was studied in two agricultural soils of the Aconcagua valley, central Chile. The two studied soils were soil A (loam, 8.5% organic matter content) and soil B (clay-loam, 3.5% organic matter content). Three times higher simazine adsorption capacity was observed in soil A (68.03 mg kg⁻¹) compared to soil B (22.03 mg kg⁻¹). The simazine adsorption distribution coefficients (K_d) were 9.32 L kg⁻¹ for soil A and 7.74 L kg⁻¹ for soil B. The simazine adsorption enthalpy in soil A was −21.0 kJ mol⁻¹ while in soil B the adsorption enthalpy value was −11.5 kJ mol⁻¹. These results indicate that simazine adsorption process in these soils is exothermic, governing H bonds the adsorption process of simazine in both the loam and clay-loam soils. These results and the potentiometric profiles of both soils, suggest that simazine adsorption in soil A is mainly governed by simazine–organic matter interactions and in soil B by simazine–clay interactions. The understanding of simazine sorption–desorption processes is essential to determine the pesticide fate and availability in soil for pest control, biodegradation, runoff and leaching.     

Sorption of polar and nonpolar organic contaminants by oil-contaminated soil

Sorption of nonpolar (phenanthrene and butylate) and polar (atrazine and diuron) organic chemicals to oil-contaminated soil was examined to investigate oil effects on sorption of organic chemicals and to derive oil–water distribution coefficients (K_oil). The resulting oil-contaminated soil–water distribution coefficients (K_d) for phenanthrene demonstrated sorption-enhancing effects at both lower and higher oil concentrations (C_oil) but sorption-reducing (competitive) effects at intermediate C_oil (approximately 1 g kg⁻¹). Rationalization of the different dominant effects was attempted in terms of the relative aliphatic carbon content which determines the accessibility of the aromatic cores to phenanthrene. Little or no competitive effect occurred for butylate because its sorption was dominated by partitioning. For atrazine and diuron, the changes in K_d at C_oil above approximately 1 g kg⁻¹ were negligible, indicating that the presently investigated oil has little or no effect on the two tested compounds even though the polarity of the oil is much less than soil organic matter (SOM). Therefore, specific interactions with the active groups (aromatic and polar domains) are dominantly responsible for the sorption of polar sorbates, and thus their sorption is controlled by available sorption sites. This study showed that the oil has the potential to be a dominant sorptive phase for nonpolar pollutants when compared to SOM, but hardly so for polar compounds. The results may aid in a better understanding of the role of the aliphatic and aromatic domains in sorption of nonpolar and polar organic pollutants.     

Sorption of atrazine and metolachlor by earthworm surface castings and soil

Abstract

Atrazine and metolachlor were more strongly retained on earthworm (Lumbricus terrestris L.) castings than on soil, suggesting that earthworm castings at the surface or at depth can reduce herbicide movement in soil. Herbicide sorption by castings was related to the food source available to the earthworms. Both atrazine and metolachlor sorption increased with increasing organic carbon (C) content in castings, and Freundlich constants (K_f values) generally decreased in the order: soybean‐fed > corn‐fed > not‐fed‐earthworm‐castings. The amount of atrazine or metolachlor sorbed per unit organic carbon (K_oc values) was significantly greater for corn‐castings compared with other castings, or soil, suggesting that the composition of organic matter in castings is also an important factor in determining the retention of herbicides in soils. Herbicide desorption was dependent on both the initial herbicide concentration, and the type of absorbent. At small equilibrium herbicide concentrations, atrazine desorption was significantly greater from soil than from any of the three casting treatments. At large equilibrium herbicide concentrations, however, the greater organic C content in castings had no significant effect on atrazine desorption, relative to soil. For metolachlor, regardless of the equilibrium herbicide concentration, desorption from soybean‐ and corn‐castings treatments was always less than desorption from soil and not‐fed earthworm castings treatments. The results of this study indicate that, under field conditions, the extent of herbicide retention on earthworm castings will tend to be related to crop and crop residue management practices.     

Differences in herbicide adsorption on soil using several soil ph modification techniques

Abstract

Effects of soil pH on weak acid and weak base herbicide adsorption by soil are often determined by modifying soil pH in the laboratory. Modification of soil pH with acidic or basic amendments such as HCl or NaOH can cause changes in the soil‐solution system that may affect pesticide adsorption. The partition coefficients (K_d) for atrazine and dicamba by Waukegan, Piano, and Walla Walla silt loam soils stabilized in the field at different pH levels were compared to the K_d obtained when the soil pH was adjusted with acidic or basic amendments before herbicide addition. NaOH addition to raise soil pH generally increased the soluble soil organic carbon (SSOC) concentration in solution compared to field soils at the same pH and to soil treated with Ca(OH)₂. NaOH decreased the soil solution ionic strength slightly. Acidifying soils increased the soil solution ionic strength, when compared to field soils at the same pH and had no effect on SSOC concentration. Dicamba adsorption to soil was minimal (K_d < 0.22) and not influenced by soil pH in the range of 4.1 to 6.0; adsorption by laboratory amended soils in some cases underestimated adsorption compared to nonamended soils. Atrazine adsorption increased with decreased pH in all soils, and was overestimated slightly by several laboratory treatments to reduce pH compared to adsorption by field soils. Treatments to raise the pH did not affect atrazine adsorption. Overall, herbicide adsorption differences due to pH modification were small (<30%), and were not affected by soil solution ionic strength, saturating cation, or SSOC concentration in solution.     

Adsorption and desorption variability of four herbicides used in paddy rice production

This investigation was performed to determine the effect of physicochemical soil properties on penoxsulam, molinate, bentazon, and MCPA adsorption–desorption processes. Four soils from Melozal (35° 43′ S; 71° 41′ W), Parral (36° 08′ S; 71° 52′ W), San Carlos (36° 24′ S; 71° 57′ W), and Panimavida (35° 44′ S; 71° 24′ W) were utilized. Herbicide adsorption reached equilibrium after 4 h in all soils. The Freundlich L-type isotherm described the adsorption process, which showed a high affinity between herbicides and sorption sites mainly because of hydrophobic and H-bonds interaction. Penoxsulam showed the highest adsorption coefficients (4.23 ± 0.72 to 10.69 ± 1.58 mL g^?1) and were related to soil pH. Molinate showed K_d values between 1.72 ± 0.01 and 2.3 ± 0.01 mL g^?1and were related to soil pH and organic matter, specifically to the amount of humic substances. Bentazon had a high relationship with pH and humic substances and its K_d values were the lowest, ranging from 0.11 ± 0.01 to 0.42 ± 0.01 mL g^?1. MCPA K_d ranged from 0.14 ± 0.02 to 2.72 ± 0.01 mL g^?1, however its adsorption was related to humic acids and clay content. According to these results, the soil factors that could explain the sorption process of the studied herbicides under paddy rice soil conditions, were principally humic substances and soil pH. Considering the sorption variability observed in this study and the potential risk for groundwater contamination, it is necessary to develop weed rice management strategies that limit use of herbicides that exhibit low soil adsorption in areas with predisposing conditions to soil leaching.     

Water pressure head and temperature impact on isoxaflutole degradation in crop residues and loamy surface soil under conventional and conservation tillage management

Laboratory incubations were performed in order to evaluate the dissipation of the proherbicide isoxaflutole in seedbed layer soil samples from conventional and conservation tillage systems and in maize and oat residues left at the soil surface under conservation tillage. The effects of temperature and water pressure head on radiolabelled isoxaflutole degradation were studied for each sample for 21 d. Mineralisation of isoxaflutole was low for all samples and ranged from 0.0% to 0.9% of applied ¹⁴C in soil samples and from 0.0% to 2.4% of applied ¹⁴C in residue samples. In soil samples, degradation half-life of isoxaflutole ranged from 9 to 26 h, with significantly higher values under conservation tillage. In residue samples, degradation half-life ranged from 3 to 31 h, with significantly higher values in maize residues, despite a higher mineralisation and bound residue formation than in oat residues. Whatever the sample, most of the applied ¹⁴C remained extractable during the experiment and, after 21 d, less than 15% of applied ¹⁴C were unextractable. This extractable fraction was composed of diketonitrile, benzoic acid derivative and several unidentified metabolites, with one of them accounting for more than 17% of applied ¹⁴C. This study showed that tillage system design, including crop residues management, could help reducing the environmental impacts of isoxaflutole.     

Adsorption-desorption and leaching of pyraclostrobin in Indian soils

Pyraclostrobin is a new broad-spectrum foliar applied and seed protectant fungicide of the strobilurin group. In this paper, adsorption-desorption of pyraclostrobin has been investigated in three different soils viz. Inceptisol (sandy loam, Delhi), Vertisol (sandy clay, Hyderabad) and Ultisol (sandy clay loam, Thrissur). Effect of organic matter and clay content on sorption was also studied in Inceptisol of Delhi. Leaching potential of pyraclostrobin as influenced by rainfall was studied in intact soil columns to confirm the results of adsorption-desorption studies. The adsorption studies were carried out at initial concentrations of 0.05, 0.1, 0.5, 1 and 1.5 μg mL^?1. The distribution coefficient (K_d) values in three test soils ranged from 4.91 to 18.26 indicating moderate to high adsorption. Among the three test soils, adsorption was the highest in Ultisol (K_d 18.26), followed by Vertisol (K_d 9.87) and Inceptisol (K_d 4.91). K_F value was also highest for Ultisol soil (66.21), followed by Vertisol (40.88) and Inceptisol (8.59). S-type adsorption isotherms were observed in all the three test soils. K_d values in organic carbon-removed soil and clay-removed soil were 3.57 and 2.83 respectively, indicating lower adsorption than normal Inceptisol. Desorption studies were carried out at initial concentrations of 0.5, 1 and 1.5 μg mL^?1. Desorption was the greatest in Inceptisol, followed by Vertisol and Ultisol. Amounts of pyraclostrobin desorbed in three desorption cycles for different concentrations were 23.1–25.3%, 9.4–20.7% and 8.1–13.6% in Inceptisol, Vertisol and Ultisol respectively. Desorption was higher in clay fraction-removed and organic carbonremoved soils than normal Inceptisol. Desorption was slower than adsorption in all the test soils, indicating hysteresis effect (with hysteresis coefficient values varying from 0.05 to 0.20). Low values of hysteresis coefficient suggest high hysteresis effect indicating easy and strong adsorption, and slow desorption, of pyraclostrobin in soils. Higher hysteresis coefficient values in organic carbon removed soil (0.25–0.30) and clay fraction removed soil (0.28–0.36) as compared to normal Inceptisol soil suggest relatively weak adsorption and easy desorption of pyraclostrobin. Results of regression analysis suggest that the organic matter and pH of the soil play a major role in adsorption of pyraclostrobin. Leaching studies were carried out in intact soil columns in Inceptisol. The columns were leached with different amounts of water simulating different amounts of rainfall. The results suggest that most of the pyraclostrobin residues will remain present in the top soil layers even under high rainfall conditions and chances of pyraclostrobin moving to lower soil depth are almost negligible.     

Sorption of polar and nonpolar organic contaminants by oil-contaminated soil

Sorption of nonpolar (phenanthrene and butylate) and polar (atrazine and diuron) organic chemicals to oil-contaminated soil was examined to investigate oil effects on sorption of organic chemicals and to derive oil–water distribution coefficients (K_oil). The resulting oil-contaminated soil–water distribution coefficients (K_d) for phenanthrene demonstrated sorption-enhancing effects at both lower and higher oil concentrations (C_oil) but sorption-reducing (competitive) effects at intermediate C_oil (approximately 1 g kg⁻¹). Rationalization of the different dominant effects was attempted in terms of the relative aliphatic carbon content which determines the accessibility of the aromatic cores to phenanthrene. Little or no competitive effect occurred for butylate because its sorption was dominated by partitioning. For atrazine and diuron, the changes in K_d at C_oil above approximately 1 g kg⁻¹ were negligible, indicating that the presently investigated oil has little or no effect on the two tested compounds even though the polarity of the oil is much less than soil organic matter (SOM). Therefore, specific interactions with the active groups (aromatic and polar domains) are dominantly responsible for the sorption of polar sorbates, and thus their sorption is controlled by available sorption sites. This study showed that the oil has the potential to be a dominant sorptive phase for nonpolar pollutants when compared to SOM, but hardly so for polar compounds. The results may aid in a better understanding of the role of the aliphatic and aromatic domains in sorption of nonpolar and polar organic pollutants.     

Sorption of Isoxaflutole Diketonitrile Degradate (DKN) and Dicamba in Unsaturated Soil

When analyzing the sorption characteristics of weakly sorbing or labile pesticides, batch methods tend to yield a high margin of error attributable to errors in concentration measurement and to degradation, respectively. This study employs a recently developed unsaturated transient flow method to determine the sorption of isoxaflutole's herbicidally active diketonitrile degradate (DKN) and dicamba. A 20-cm acrylic column was packed with soils with varied texture that had been uniformly treated with ¹⁴C-labeled chemical.

The antecedent solution herbicide in equilibrium with sorbed phase herbicide was displaced by herbicide-free water, which was infiltrated into the column. Sorption coefficients, K_d, were obtained from a plot of total herbicide concentration in the soil versus water content in the region where the antecedent solution accumulated. DKN K_d values were ～2–3 times (average K_d = 0.71 L kg^?1) greater using the unsaturated transient flow method as compared to the batch equilibration method in clay loam (K_d = 0.33 L kg^?1), but similar for the two methods in sand (0.12 vs 0.09 L kg^?1) soils. Dicamba K_d values were 3 times greater using the unsaturated transient flow method as compared to the batch equilibration method in the clay loam soil (0.38 vs 0.13 L kg^?1), however, the K_d values were the same for the two methods in the sand (～0.06 L kg^?1). This demonstrates that to determine sorption coefficients for labile hydrophilic pesticides, an unsaturated transient flow method may be a suitable alternative to the batch method. In fact, it may be better in cases where transport models have overpredicted herbicide leaching when batch sorption coefficients have been used.     

Potential of conservation agriculture modules for energy conservation and sustainability of rice-based production systems of Indo-Gangetic Plain region

Rice-based cropping systems are the most energy-intensive production systems in South Asia. Sustainability of the rice-based cropping systems is nowadays questioned with declining natural resource base, soil degradation, environmental pollution, and declining factor productivity. As a consequence, the search for energy and resource conservation agro-techniques is increasing for sustainable and cleaner production. Conservation agriculture (CA) practices have been recommended for resource conservation, soil health restoration and sustaining crop productivity. The present study aimed to assess the different CA modules in rice-based cropping systems for energy conservation, energy productivity, and to define energy-economic relations. A field experiment consisted of four different tillage-based crop establishment practices (puddled-transplanted rice followed by (fb) conventional-till maize/wheat (CTTPR-CT), non-puddled transplanted rice fb zero-till maize/wheat (NPTPR-ZT), zero-till transplanted rice fb zero-till maize/wheat (ZTTPR-ZT), zero-till direct-seeded rice fb zero-till maize/wheat (ZTDSR-ZT)), with two residue management treatments (residue removal, residue retention) in rice–wheat and rice–maize rotations were evaluated for energy budgeting and energy-economic relations. Conservation-tillage treatments (NPTPR-ZT, ZTTPR-ZT, and ZTDSR-ZT) reduced the energy requirements over conventional tillage treatments, with the greater reduction in ZTTPR-ZT and ZTDSR-ZT treatments. Savings of energy in conservation-tillage treatments were attributed to reduced energy use in land preparation (69–100%) and irrigation (23–27%), which consumed a large amount of fuel energy. Conservation-tillage treatments increased grain and straw/stover yields of crops, eventually increased the output energy (6–16%), net energy (14–26%), energy ratio (25–33%), and energy productivity (23–34%) as compared with CTTPR-CT. For these energy parameters, the treatment order was ZTDSR-ZT ≥ ZTTPR-ZT > NPTPR-ZT > CTTPR-CT (p < 0.05). Crop residue retention reduced net energy, energy ratio, and energy productivity when compared with residue removal. Our results of energy-economic relations favored the “conservative hypothesis,” which envisages that energy and monetary investments are not essentially the determinants of crop productivity. Thus, zero tillage-based crop establishments (ZTTPR-ZT, ZTDSR-ZT) in rice-based production systems could be the sustainable alternative to conventional tillage-based agriculture (CTTPR-CT) as they conserved non-renewable energy sources, reduced water requirement, and increased crop productivity.

     

Phytoremediation potential of the novel atrazine tolerant Lolium multiflorum and studies on the mechanisms involved

Atrazine impact on human health and the environment have been extensively studied. Phytoremediation emerged as a low cost, environmental friendly biotechnological solution for atrazine pollution in soil and water. In vitro atrazine tolerance assays were performed and Lolium multiflorum was found as a novel tolerant species, able to germinate and grow in the presence of 1 mg kg⁻¹ of the herbicide. L. multiflorum presented 20% higher atrazine removal capacity than the natural attenuation, with high initial degradation rate in microcosms. The mechanisms involved in atrazine tolerance such as mutation in psbA gene, enzymatic detoxification via P₄₅₀ or chemical hydrolysis through benzoxazinones were evaluated. It was demonstrated that atrazine tolerance is conferred by enhanced enzymatic detoxification via P₄₅₀. Due to its atrazine degradation capacity in soil and its agronomical properties, L. multiflorum is a candidate for designing phytoremediation strategies for atrazine contaminated agricultural soils, especially those involving run-off avoiding.     

Sorption of chlorinated solvents and degradation products on natural clayey tills

The sorption of chlorinated solvents and degradation products on seven natural clayey till samples from three contaminated sites was investigated by laboratory batch experiments in order to obtain reliable sorption coefficients (K_d values). The sorption isotherms for all compounds were nearly linear, but fitted by Freundlich isotherms slightly better over the entire concentration range. For chloroethylenes, tetrachloroethylene (PCE) was most strongly sorbed to the clayey till samples (K_d = 0.84-2.45 L kg⁻¹), followed by trichloroethylene (TCE, K_d = 0.62-0.96 L kg⁻¹), cis-dichloroethylene (cis-DCE, K_d = 0.17-0.82 L kg⁻¹) and vinyl chloride (VC, K_d = 0.12-0.36 L kg⁻¹). For chloroethanes, 1,1,1-trichloroethane (1,1,1-TCA) was most strongly sorbed (K_d = 0.2-0.45 L kg⁻¹), followed by 1,1-dichloroethane (1,1-DCA, K_d = 0.16-0.24 L kg⁻¹) and chloroethane (CA, K_d = 0.12-0.18 L kg⁻¹). This is consistent with the order of hydrophobicity of the compounds. The octanol-water coefficient (log K_ow) correlated slightly better with log K_d values than log K_oc values indicating that the K_d values may be independent of the actual organic carbon content (f_oc). The estimated log K_oc or log K_d for chlorinated solvents and degradation products determined by regression of data in this study were significantly higher than values determined by previously published empirical relationships. The site specific K_d values as well as the new empirical relationship compared well with calculations on water and soil core concentration for cis-DCE and VC from the Rugårdsvej site. In conclusion, this study with a wide range of chlorinated ethenes and ethanes - in line with previous studies on PCE and TCE - suggest that sorption in clayey tills could be higher than typically expected.     

Sugarcane straw management and soil attributes on alachlor and diuron sorption in highly weathered tropical soils

This research evaluated the effects of the new sugarcane harvesting system (without straw burning) and soil attributes on the organic carbon (OC) accumulation and sorption of alachlor (2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)acetamide) and diuron (3-(3,4-dichlorophenyl)-1,1-dimethylurea) in highly weathered Brazilian soils. Alachlor was more likely to leach (K _d,app = 1.0–7.0 L kg^?1 and mean K _oc,app = 174 L kg^?1) than diuron (K _d,app = 6.2–116.3 L kg^?1 and mean K _oc,app = 1789 L kg^?1). The sorption coefficient (K _d,app) values correlated better with soil OC contents, but the Fe-oxides also played an important role in these highly weathered soils. Sorption was enhanced in the areas without straw burning mostly due to OC accumulation that was higher in the clayey soils, but it was not enough to change their mobility classification.     

Dissipation and sorption of six commonly used pesticides in two contrasting soils of New Zealand

We investigated dissipation and sorption of atrazine, terbuthylazine, bromacil, diazinon, hexazinone and procymidone in two contrasting New Zealand soils (0–10 cm and 40–50 cm) under controlled laboratory conditions. The six pesticides showed marked differences in their degradation rates in both top- and subsoils, and the estimated DT₅₀ values for the compounds were: 19–120 (atrazine), 10–36 (terbuthylazine), 12–46 (bromacil), 7–25 (diazinon), 8–92 (hexazinone) and 13–60 days for procymidone. Diazinon had the lowest range for DT₅₀ values, while bromacil and hexazinone gave the highest DT₅₀ values under any given condition on any soil type. Batch derived effective distribution coefficient (K _d ^eff) values for the pesticides varied markedly with bromacil and hexazinone exhibiting low sorption affinity for the soils at either depth, while diazinon gave high sorption values. Comparison of pesticide degradation in sterile and non-sterile soils suggests that microbial degradation was the major dissipation pathway for all six compounds, although little influence of abiotic degradation was noticeable for diazinon and procymidone.     

Surfactant solubilization of hydrophobic compounds in soil and water

The soil/water partition coefficient (K_d) of hexachlorobenzene (HCB) ranged from 220 1/kg to 1800 1/kg for eight soils having a wide range of physico-chemical properties. K_d normalised to soil organic carbon (K_oc) was found to be 28000 ± 4800 1/kg. Anionic surfactant dodecylsulphate (DS) present at concentrations above the critical micellar concentration (CMC) caused reductions in the apparent soil/water partition coefficient (K_d ^*) in the range of 3–26 times for most soils and up to 36–91 times for sandy soils. Below CMC, at environmentally relevant surfactant concentrations, K_d ^* was reduced by a factor of 1–13. For clay and calcareous soils significant adsorption/complexation/precipitation of DS occurred. At the lowest DS concentration this produced a two-fold increase in K_d ^*. At increasing DS concentrations this effect was shielded by the solubihzing effect from DS. Monomer (K_mn) and micellar (K_mc) surfactant/water partition coefficients for HCB were determined to be, 980 ± 190 1/kg and 21000 ± 1600 1/kg, respectively.     

Adsorption of lambda-cyhalothrin and cypermethrin on two typical Chinese soils as affected by copper

Background, aim, and scope  Pesticides and heavy metals pollution in soil environment has become a serious problem in many countries including China. Repeated applications of bordeaux mixture (a blend of copper sulfate and calcium hydroxide) and pyrethroid (Pys) insecticides have led to elevated copper (Cu) and Pys concentrations in vineyard surface soils. However, few studies focused on the interaction of Pys and heavy metals in the soil environment. Our previous studies had indicated the combined effect of cypermethrin (CPM) and Cu on soil catalase activity. Also, we had suggested that the addition of Cu could catalyze photo-degradation of CPM and lambda-cyhalothrin (λ-CHT) in aqueous solution and restrain their degradation in soil. To better understand the potential influence of Cu on the fate of Pys in the soil environment, the aim of the present work was to examine the effect of Cu on the adsorption of λ-CHT and CPM on two typical Chinese soils with different soil characteristics, which was one of the key processes controlling the fate of Pys, and to provide more information about the potential ecological risk of chemicals on the soil ecosystem. Fourier transform infrared and point charges analysis using the MOPAC program of the Gaussian system were also used to reveal the probable adsorption mechanism of λ-CHT and CPM on soils. Materials and methods  Two vineyard soils with different properties were chosen as experimental samples. They were sampled from 0 to 10 cm, dried, and sieved to 2 mm. Each soil was spiked with copper sulfate solution to obtain the following total soil Cu concentrations: 100, 200, 400, 800, and 1,600 mg·kg⁻¹. The treated soils were incubated for 2 weeks and then dried at 20°C. For each soil sample and at each soil Cu concentration, the adsorption of λ-CHT and CPM was measured using a batch equilibrium method. The concentration of λ-CHT was determined by HPLC, and the amount of λ-CHT and CPM adsorbed by the soil sample at equilibrium was determined by the difference between the initial and equilibrium concentrations in solution corrected by the blank adsorption measurement. Results  Without the addition of Cu, the adsorption of λ-CHT and CPM on Black soil is greater than that on Red soil, while the adsorption of λ-CHT on both soils is significantly stronger than that of CPM. As the soil Cu concentration increased from 19 (or 18; background) to 1,600 mg·kg⁻¹, the adsorption coefficient (K _d) of λ-CHT decreased from 12.2 to 5.9 L·kg⁻¹ for Red soil, and from 26.1 to 16.8 L·kg⁻¹ for Black soil, whereas the CPM adsorption coefficient in both soils decreased nearly by 100% (K _d decreased from 9.4 to 0.2 L·kg⁻¹ for Red soil and from 16.2 to 0.5 L·kg⁻¹ for Black soil). Discussion  Pys adsorption is a surface phenomenon which depends on the surface area and the organic matter content. Thus, the Black soil, having higher organic matter and greater surface area than that of the Red soil, show greater adsorption affinity to λ-CHT and CPM. In our study, the different adsorption affinity of the two Pys was obtained, which was probably attributed to differences with respect to their physical–chemical properties. Further comparison upon the two Pys was conducted. The point charges of halogen atoms in the λ-CHT and CPM were calculated, the differences of which probably lead to the fact that λ-CHT has a stronger binding capacity to soils than CPM. Also, FTIR spectra show that competitive adsorption occurs between CPM and Cu for the same adsorption sites, which is responsible for the obtained suppression of CPM adsorption affected by Cu. Conclusions  Lambda-cyhalothrin shows a significantly stronger adsorption than cypermethrin on both soils. This phenomenon may be due to several reasons: (1) λ-CHT has lower solubility and a higher octanol–water partition coefficient value than CPM; (2) λ-CHT consists of specific isomers, whereas CPM is mixtures of eight different isomers; (3) the chlorine and fluorine atoms in the λ-CHT have a negative point charge, whereas the chlorine atoms in the CPM have a positive point charge. As the soil Cu concentrations increased from 19 (or 18) mg·kg⁻¹ to 1,600 mg·kg⁻¹, the adsorption coefficient of λ-CHT and CPM decreased on both soils. This is mainly due to a competition between Cu and Pys for occupying the adsorption sites on soils. The information from this study have important implications for vineyard and orchard soils, which often contain elevated levels of Cu and Pys. These results are also useful in assessing the environmental fate and health effect of λ-CHT and CPM. Recommendations and perspectives  It is important for environmental scientists and engineers to get a better understanding of soil–metal–organic contaminant interactions. However, pesticide adsorption involves complex processes, and shortcomings in understanding them still restrict the ability to predict the fate and behavior of pesticide. Therefore, considerable research should be carried out to understand the mechanism of interaction between Pys and heavy metal on soils clearly.     

Phenylurea herbicide sorption to biochars and agricultural soil

Biochar is increasingly been used as a soil amendment to improve water-holding capacity, reduce nutrient leaching, increase soil pH, and also as a means to reduce contamination through sorption of heavy metals or organic pollutants. The sorption behavior of three phenylurea herbicides (monuron, diuron and linuron) on five biochars (Enhanced Biochar, Hog Waste, Turkey Litter, Walnut Shell and Wood Feedstock) and an agricultural soil (Yolo silt loam) was investigated using a batch equilibration method. Sorption isotherms of herbicides to biochars were well described by the Freundlich model (R² = 0.93–0.97). The adsorption K_F values ranged from 6.94 to 1306.95 mg kg^?1 and indicated the sorption of herbicides in the biochars and Yolo soil was in the sequence of linuron > diuron > monuron and walnut shell biochar > wood feedstock biochar > turkey litter biochar > enhanced biochar > hog waste biochar > Yolo soil. These data show that sorption of herbicides to biochar can have both positive (reduced off-site transport) and negative (reduced herbicide efficacy) implications and specific biochar properties, such as H/C ratio and surface area, should be considered together with soil type, agriculture chemical and climate condition in biochar application to agricultural soil to optimize the system for both agricultural and environmental benefits.     

Assessment of the ecological security of immobilized enzyme remediation process with biological indicators of soil health

This study used the enzymes extracted from an atrazine-degrading strain, Arthrobacter sp. DNS10, which had been immobilized by sodium alginate to rehabilitate atrazine-polluted soil. Meanwhile, a range of biological indices were selected to assess the ecological health of contaminated soils and the ecological security of this bioremediation method. The results showed that there was no atrazine detected in soil samples after 28 days in EN?+?AT (the soil containing atrazine and immobilized enzyme) treatment. However, the residual atrazine concentration of the sample in AT (the soil containing atrazine only) treatment was about 5.02?±?0.93 mg?kg^?1. These results suggest that the immobilized enzyme exhibits an excellent ability in atrazine degradation. Furthermore, the immobilized enzyme could relieve soil microbial biomass carbon and soil microbial respiration intensity to 772.33?±?34.93 mg?C?kg^?1 and 5.01?±?0.17 mg?CO₂?g^?1?soil?h^?1, respectively. The results of the polymerase chain reaction–degeneration gradient gel electrophoresis experiment indicated that the immobilized enzyme also could make the Shannon–Wiener index and evenness index of the soil sample increase from 1.02 and 0.74 to 1.51 and 0.84, respectively. These results indicated that the immobilized enzymes not only could relieve the impact from atrazine on the soil, but also revealed that the immobilized enzymes did no significant harm on the soil ecological health.