Easy and fast extraction methods to determine organochlorine pesticides in sewage sludge,soil, and water samples based at low temperature

Organochlorine pesticides present in sewage sludge can contaminate soil and water when they are used as either fertilizer or agricultural soil conditioner. In this study, the technique solid–liquid extraction with low temperature purification was optimized and validated for determination of ten organochlorine pesticides in sewage sludge and soil samples. Liquid–liquid extraction with low temperature purification was also validated for the same compounds in water. Analyses were performed by gas chromatography-mass spectrometry operating in the selective ion monitoring mode. After optimization, the methods showed recoveries between 70% and 115% with relative standard deviation lower than 13% for all target analytes in the three matrices. The linearity was demonstrated in the range of 20 to 70 µg L^?1, 0.5 to 60 µg L^?1, and 3 to 13 µg L^?1, for sludge, soil, and acetonitrile, respectively. The limit of quantification ranged between 2 and 40 µg kg^?1, 1 and 6 µg kg^?1, and 0.5 µg L^?1 for sludge, soil, and water, respectively. The methods were used in the study of pesticide lixiviation carried out in a poly vinyl chlorine column filled with soil, which had its surface layer mixed with sludge. The results showed that pesticides are not leached into soil, part of them is adsorbed by the sewage sludge (4–40%), and most pesticides are lost by volatilization.     

Predictability by Box-Behnken model for carbaryl adsorption by soils of Indian origin

This study was undertaken to investigate the adsorption capacity of carbaryl on four Indian soils with different physiochemical properties. A batch adsorption study was carried out in order to evaluate the maximum adsorption capacity of carbaryl using a Response Surface Methodology (RSM). The effects of operating parameter such as initial carbaryl concentration (1–20 mgL^?1), adsorbent dosage (0.5–6 g) and contact time (10–180 min) were examined. The proposed quadratic model for Box-Behnken design fits very well to the experimental data because it may be used to navigate design space according to ANOVA results. The regression co-efficient (R²) of the models developed and the results of validation experiments conducted at optimal conditions strongly suggests that the predicted values are in good agreement with experimental results. Contour and response surface plots are used to determine the interactions effects of main factors and optimal conditions of the process. The experiment can be utilized as a guideline for better understanding of carbaryl adsorption onto soil under different operating conditions. The results show that the forest soil is most efficient in binding carbaryl (Sevin) than the other types of soil tested.     

Concentration and dissipation of chlorantraniliprole and thiamethoxam residues in maize straw,maize, and soil

To study the dissipation rates and final residual levels of chlorantraniliprole and thiamethoxam in maize straw, maize, and soil, two independent field trials were conducted during the 2014 cropping season in Beijing and Anhui Provinces of China. A 40% wettable powder (20% chlorantraniliprole?+?20% thiamethoxam) was sprayed onto maize straw and soil at an application rate of 118 g of active ingredient per hectare (g a.i.ha^?1). The residual concentrations were determined by ultra-high-performance liquid chromatography–tandem mass spectrometry. The chlorantraniliprole half-lives in maize straw and soil were 9.0–10.8 and 9.5–21.7 days, respectively. The thiamethoxam half-lives in maize straw and soil were 8.4–9.8 and 4.3–11.7 days, respectively. The final residues of chlorantraniliprole and thiamethoxam in maize straw, maize, and soil were measured after the pesticides had been sprayed two and three times with an interval of 7 days using 1 and 1.5 times the recommended rate (72 g a.i. ha^?1 and 108 g a.i. ha^?1, respectively). Representative maize straw, maize, and soil samples were collected after the last treatment at pre-harvest intervals of 7, 14, and 28 days. The chlorantraniliprole residue was below 0.01 mg kg^?1 in maize, between 0.01 and 0.31 mg kg^?1 in maize straw, and between 0.03 and 1.91 mg kg^?1 in soil. The thiamethoxam residue concentrations in maize, maize straw, and soil were <0.01, <0.01, and 0.01–0.03 mg kg^?1, respectively. The final pesticide residues on maize were lower than the maximum residue limit (MRL) of 0.02 mg kg^?1 after a 14-day pre-harvest interval. Therefore, a dosage of 72 g a.i. ha^?1 was recommended, as it can be considered safe to human beings and animals.     

How to assess the feeding activity in ecotoxicological laboratory tests using enchytraeids?

The risk assessment of pesticides on soil fauna is an issue to protect agroecosystem sustainability. Enchytraeids are recognized as relevant soil bioindicators of chemical stress in agroecosystems. In laboratory, the reproduction test was found to be sensitive to reveal chemical impacts on enchytraeids. However, it does not allow to assess the impacts on ecological functions in which enchytraeids are involved. The objectives of this study were (i) to explore the feasibility of the bait-lamina test with enchytraeids under laboratory conditions and (ii) to compare its sensitivity with the Enchytraeid Reproduction Test. We exposed individuals of Enchytraeus albidus to two commercial formulations of fungicides widely used in Europe. The EC50 reproduction for the Swing^® Gold (50 g L^?1 epoxiconazole and 133 g L^?1 dimoxystrobin) and the Cuprafor micro^® (50% copper oxychloride) were respectively estimated at 1.66?±?0.93 times the recommended dose and >?496 mg kg^?1 of copper. However, no impact was found on the feeding activity of enchytraeids. The bait-lamina test thus appeared less sensitive than the Enchytraeid Reproduction Test to the tested fungicides. Despite that, this test which is achievable under laboratory conditions and allows assessing indirect effects of pesticides is quick, cheap, and easy to perform. It would deserve to be used to explore longer-exposure effects through the repeated addition of bait-lamina sticks.     

Development,validation, and application of a method for the GC-MS analysis of fipronil and three of its degradation products in samples of water,soil, and sediment

A method for the identification and quantification of pesticide residues in water, soil, and sediment samples has been developed, validated, and applied for the analysis of real samples. The specificity was determined by the retention time and the confirmation and quantification of analyte ions. Linearity was demonstrated over the concentration range of 20 to 120 µg L^?1, and the correlation coefficients varied between 0.979 and 0.996, depending on the analytes. The recovery rates for all analytes in the studied matrix were between 86% and 112%. The intermediate precision and repeatability were determined at three concentration levels (40, 80, and 120 µg L^?1), with the relative standard deviation for the intermediate precision between 1% and 5.3% and the repeatability varying between 2% and 13.4% for individual analytes. The limits of detection and quantification for fipronil, fipronil sulfide, fipronil-sulfone, and fipronil-desulfinyl were 6.2, 3.0, 6.6, and 4.0 ng L^?1 and 20.4, 9.0, 21.6, and 13.0 ng L^?1, respectively. The method developed was used in water, soil, and sediment samples containing 2.1 mg L^?1 and 1.2% and 5.3% of carbon, respectively. The recovery of pesticides in the environmental matrices varied from 88.26 to 109.63% for the lowest fortification level (40 and 100 µg kg^?1), from 91.17 to 110.18% for the intermediate level (80 and 200 µg kg^?1), and from 89.09 to 109.82% for the highest fortification level (120 and 300 µg kg^?1). The relative standard deviation for the recovery of pesticides was under 15%.     

Residues levels of organochlorine pesticide in cow's milk from industrial farms in Hidalgo,Mexico

A survey was carried out from 2008 to 2010 to determine the concentrations of 16 organochlorine pesticide residues (OPRs) from Tizayuca, Hidalgo, Mexico. Organochlorine residue determinations were made from milk fat, using chromatographic cleanup and analysis by gas chromatography with an electron capture detector. The OPR concentrations found were from below the detection limit (DL) to 0.91 ng g^?1 in 2008, DL to 0.38 ng g^?1 in 2009 and DL to 0.59 ng g^?1 in 2010. In general concentrations of organochlorine pesticides were higher in the wet season (3.37 ng g^?1 and 4.79 ng g^?1) than the dry season (1.92 ng g^?1 and 2.71 ng g^?1) for 2009 and 2010, due to control of pests in the pasture and sheds. According to Codex Alimentarius regulations, individual pesticides did not exceed the permissible limits, which for example were 10 μg kg^?1 for alpha hexachlorocyclohexane (HCH) and endosulfan I, 20 μg kg^?1 for p,p’-DDT, and 6 μg kg^?1 for dieldrin, endrin and heptachlor. A reduction of organochlorine pesticide concentrations in cow's milk was noted, indicating that the Mexican government has achieved reduction or elimination of some organochlorine pesticides in response to global agreements on persistent organic pollutants.     

Controlled release systems to prevent the agro-environmental pollution derived from pesticide use

Different controlled release formulations (CRFs) of isoproturon, imidacloprid and cyromazine have been studied to contribute to diminish, somehow, the problems related to the application of conventional formulations. The alginate-based CRFs were based on sodium alginate (1.90%), Technical grade (TG) isoproturon or imidacloprid (1.20%), natural bentonite (3.30%), and water (93.6%), and the lignin-based CRF was based on kraft lignin (50.0%) and TG cyromazine (50.0%). The mobility of non-formulated TG pesticides and CRFs were compared by using soil columns. The use of CRFs retard release and reduce the presence of pesticides in the leachate and, moreover, the pesticides stay in the soil longer. Sorption capacity of the soil for pesticides was measured using batch experiments. The results obtained (11.67 mg kg^{? 1} for isoproturon, 3.17 mg kg^{? 1} for imidacloprid and 0.63 mg kg^?1 for cyromazine) were in agreement with those obtained under dynamic conditions.     

Novel pipette-tip graphene/poly (vinyl alcohol) cryogel composite extractor for the analysis of carbofuran and carbaryl in water

A novel pipette-tip extractor of a graphene/poly (vinyl alcohol) cryogel (graphene/PVA) composite sorbent was prepared to preconcentrate carbamate pesticides in environmental water samples before analysis with a gas chromatograph-flame ionization detector (GC-FID). This novel pipette-tip extractor with the graphene/PVA sorbent exhibited a high porosity when observed through a scanning electron micrograph (SEM). Under optimal conditions, using only 1.0 mL of sample and 0.75 mL of eluting solvent, the developed method provided a wide linear range of 10–700 ng mL^?1 and 10–500 ng mL^?1 with limit of detection (LOD) of 6.40 ± 0.18 and 9.17 ± 0.34 ng mL^?1 for carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate) and carbaryl (1-naphthyl methylcarbamate), respectively. The pipette-tip extractor provided high extraction efficiency with high accuracy indicated, by good recoveries in the range of 74.5 ± 4.8% to 119.7 ± 1.6% and 76 ± 15% to 114 ± 19% for carbofuran and carbaryl, respectively. In addition, the fabrication procedure showed a good pipette-tip extractor-to-pipette-tip extractor reproducibility with a relative standard deviation of 1.3–9.8% (n = 5). When the developed pipette-tip extractor was applied for the extraction of carbofuran and carbaryl in surface water samples near vegetable plantation areas, 25.9 ± 8.2 ng mL^?1 of carbofuran was found, and carbaryl was also detected in concentrations that ranged from 45.0 ± 4.0 to 191 ± 13 ng mL^?1.     

Dissipation of spiromesifen and spiromesifen-enol on tomato fruit,tomato leaf,and soil under field and controlled environmental conditions

Dissipation of spiromesifen and its metabolite, spiromesifen-enol, on tomato fruit, tomato leaf, and soil was studied in the open field and controlled environmental conditions. Sample preparation was carried out by QuEChERS method and analysis using LC-MS/MS. Method validation for analysis of the compounds was carried out as per “single laboratory method validation guidelines.” Method validation studies gave satisfactory recoveries for spiromesifen and spiromesifen-enol (71.59–105.3%) with relative standard deviation (RSD) < 20%. LOD and LOQ of the method were 0.0015 μg mL^?1 and 0.005 mg kg^?1, respectively. Spiromesifen residues on tomato fruits were 0.855 and 1.545 mg kg^?1 in open field and 0.976 and 1.670 mg kg^?1 under polyhouse condition, from treatments at the standard and double doses of 125 and 250 g a.i. ha^?1, respectively. On tomato leaves, the residues were 5.64 and 8.226 mg kg^?1 in open field and 6.874 and 10.187 mg kg^?1 in the polyhouse. In soil, the residues were 0.532 and 1.032 mg kg^?1 and 0.486 and 0.925 mg kg^?1 under open field and polyhouse conditions, respectively. The half-life of degradation of spiromesifen on tomato fruit was 6–6.5 days in the open field and 8.1–9.3 days in the polyhouse. On tomato leaves, it was 7–7.6 and 17.6–18.4 days and in soil 5.6–7.4 and 8.4–9.5 days, respectively. Metabolite, spiromesifen-enol, was not detected in any of the sample throughout the study period. Photodegradation could be the major route for dissipation of spiromesifen in the tomato leaves, whereas in the fruits, it may be the combination of photodegradation and dilution due to fruit growth. The results of the study can be utilized for application of spiromesifen in plant protection of tomato crop under protected environmental conditions.     

Responses of earthworm to aluminum toxicity in latosol

Excess aluminum (Al) in soils due to acid rain leaching is toxic to water resources and harmful to soil organisms and plants. This study investigated adverse impacts of Al levels upon earthworms (Eisenia fetida) from the latosol (acidic red soil). Laboratory experiments were performed to examine the survival and avoidance of earthworms from high Al concentrations and investigate the response of earthworms upon Al toxicity at seven different Al concentrations that ranged from 0 to 300 mg kg^?1 over a 28-day period. Our study showed that the rate of the earthworm survival was 100 % within the first 7 days and decreased as time elapsed, especially for the Al concentrations at 200 and 300 mg kg^?1. A very good linear correlation existed between the earthworm avoidance and the soil Al concentration. There was no Al toxicity to earthworms with the Al concentration ≤50 mg kg^?1, and the toxicity started with the Al concentration ≥100 mg kg^?1. Low Al concentration (i.e., <50 mg kg^?1) enhanced the growth of the earthworms, while high Al concentration (>100 mg kg^?1) retarded the growth of the earthworms. The weight of earthworms and the uptake of Al by earthworms increased with the Al concentrations from 0 to 50 mg kg^?1 and decreased with the Al concentrations from 50 to 300 mg kg^?1. The protein content in the earthworms decreased with the Al concentrations from 0 to 100 mg kg^?1 and increased from 100 to 300 mg kg^?1. In contrast, the catalase (CAT) and superoxide dismutase (SOD) activities in the earthworms increased with the Al concentrations from 0 to 100 mg kg^?1 and decreased from 100 to 300 mg kg^?1. The highest CAT and SOD activities and lowest protein content were found at the Al concentration of 100 mg kg^?1. Results suggest that a high level of Al content in latosol was harmful to earthworms.     

Mobility and efficacy of 2,4-D herbicide from slow-release delivery systems based on organo-zeolite and organo-bentonite complexes

This research aimed to develop slow-release formulations (SRFs) of 2,4-dichlorophenoxyacetic acid (2,4-D) using zeolite and bentonite minerals modified with cetyltrimethylammonium (CTMA) surfactant. Adsorption–desorption, greenhouse bioassay and column experiments were carried out to assess the potential of the SRFs to control weeds while reducing the herbicide leaching losses to deep layers of soil. The results showed that only 6.5 mmol 2,4-D kg^?1 was retained by Na-bent, and the herbicide was not adsorbed by Na-zeol at all. The surface modification with CTMA surfactant, however, improved the 2,4-D adsorption capacity of the zeolite and bentonite up to 207.5 and 415.8 mmol kg^?1, respectively. The synthesized organo-minerals slowly released the retained 2,4-D discharging 22 to 64% of the adsorbed 2,4-D to the solution phase within 7 days. The SRFs significantly (P = 0.05) reduced the herbicide mobility within the soil columns keeping a great portion of the herbicide active ingredient in the upper 5 cm soil layer. The SRFs were significantly (P = 0.05) as effective as the free technical herbicide in weed control without harming the ryegrass as the main plant. Therefore, the synthesized SRFs could be considered as useful tools for weed control in sustainable agriculture.     

Mercury in the Grisette,Amanita vaginata Fr. and soil below the fruiting bodies

This study examined the mercury concentration in the Grisette Amanita vaginata Fr. and soil below the fruiting bodies collected between 2000 and 2008 from the wild at seven distant sites across Poland. The Hg content in samples was determined by cold atomic absorption method (CV-AAS) at a wavelength of 253.7 nm. Mean Hg contents varied from 0.096 ± 0.052 to 0.48 ± 0.13 mg kg^?1 dry matter (dm) in caps (range, 0.043–0.73 mg kg^?1), from 0.047 ± 0.02 to 0.23 ± 0.07 mg kg^?1 dm (range, 0.028–0.47 mg kg^?1) in stipes, and in underlying soil were from 0.035 ± 0.018 to 0.096 ± 0.036 mg kg^?1 dm (range, 0.017 to 0.16 mg kg^?1). The median Qc/s values ranged from 1.2 to 2.2 (mean 1.2 ± 0.4 to 2.1 ± 0.5) indicating that Hg content in stipes was generally lower than in caps. This mushroom species has some potential to bioconcentrate Hg in the fruiting bodies, as the values of the bioconcentration factor (BCF) varied for the sites between 1.2 ± 0.6 to 11 ± 5 for caps and 0.61 ± 0.26 to 7.4 ± 3.9 for stipes. Also available literature data on Hg in A. vaginata are reviewed and discussed.     

Distribution of potentially toxic elements (PTEs) in tailings,soils, and plants around Gol-E-Gohar iron mine,a case study in Iran

This study investigated the concentration of potentially toxic elements (PTEs) including Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Sb, V, and Zn in 102 soils (in the Near and Far areas of the mine), 7 tailings, and 60 plant samples (shoots and roots of Artemisia sieberi and Zygophylum species) collected at the Gol-E-Gohar iron ore mine in Iran. The elemental concentrations in tailings and soil samples (in Near and Far areas) varied between 7.4 and 35.8 mg kg^?1 for As (with a mean of 25.39 mg kg^?1 for tailings), 7.9 and 261.5 mg kg^?1 (mean 189.83 mg kg^?1 for tailings) for Co, 17.7 and 885.03 mg kg^?1 (mean 472.77 mg kg^?1 for tailings) for Cu, 12,500 and 400,000 mg kg^?1 (mean 120,642.86 mg kg^?1 for tailings) for Fe, and 28.1 and 278.1 mg kg^?1 (mean 150.29 mg kg^?1 for tailings) for Ni. A number of physicochemical parameters and pollution index for soils were determined around the mine. Sequential extractions of tailings and soil samples indicated that Fe, Cr, and Co were the least mobile and that Mn, Zn, Cu, and As were potentially available for plants uptake. Similar to soil, the concentration of Al, As, Co, Cr, Cu, Fe, Mn, Mo, Ni, and Zn in plant samples decreased with the distance from the mining/processing areas. Data on plants showed that metal concentrations in shoots usually exceeded those in roots and varied significantly between the two investigated species (Artemisia sieberi > Zygophylum). All the reported results suggest that the soil and plants near the iron ore mine are contaminated with PTEs and that they can be potentially dispersed in the environment via aerosol transport and deposition.     

Insights into the mercury(II) adsorption and binding mechanism onto several typical soils in China

To better understand the Hg(II) adsorption by some typical soils and explore the insights about the binding between Hg(II) and soils, a batch of adsorption and characteristic experiments was conducted. Results showed that Hg(II) adsorption was well fitted by the Langmuir and Freundlich. The maximum adsorption amount of cinnamon soil (2094.73 mg kg^?1) was nearly tenfold as much as that of saline soil (229.49 mg kg^?1). The specific adsorption of Hg(II) on four soil surface was confirmed by X-ray photoelectron spectroscopy (XPS) owing to the change of elemental bonding energy after adsorption. However, the specific adsorption is mainly derived from some substances in the soil. Fourier transform infrared spectroscopy (FTIR) demonstrated that multiple oxygen-containing functional groups (O–H, C=O, and C–O) were involved in the Hg(II) adsorption, and the content of oxygen functional groups determined the adsorption capacity of the soil. Meanwhile, scanning electron microscopy combined with X-ray energy dispersive spectrometer (SEM–EDS) more intuitive revealed the binding of mercury to organic matter, metal oxides, and clay minerals in the soil and fundamentally confirmed the results of XPS and FTIR to further elucidate adsorptive phenomena. The complexation with oxygen-containing functional groups and the precipitation with minerals were likely the primary mechanisms for Hg(II) adsorption on several typical soils. This study is critical in understanding the transportation of Hg(II) in different soils and discovering potential preventative measures.     

Antibiotic uptake by plants from manure-amended soils

Antibiotics are extensively given to livestock to promote growth and reduce diseases. Therefore, animal manure often contains antibiotics. Once manure is applied to agricultural land to improve soil productivity, crops would be exposed to antibiotics which may persist in soils from a few to several hundred days. The objective of this study was to evaluate the uptake of gentamicin and streptomycin by carrot (Daucus carota), lettuce (Lactuca sativa) and radish (Rhaphanus sativus) from manure-amended soil. The treatments were 0, 0.5 and 1 mg of antibiotic kg^?1 of soil. Two pot experiments were carried out in the greenhouse. The first was conducted on the three crops and the second exclusively on radish. In radish, the increase in the concentrations of gentamicin was significant between the 0 and both of 0.5 and 1.0 mg kg^?1 treatments, but not significant between the 0.5 and 1.0 mg kg^?1. The average values were 35.5, 60.0 and 57.4 μg kg^?1 for the 0, 0.5 and 1 mg kg^?1 rates, respectively. However, the increase in streptomycin concentration in radish was not significant between the three treatments, and the average values were, 12.1, 15.2 and 17.4 μg kg^?1 for the 0, 0.5 and 1 mg kg^?1 rates, respectively. In carrot roots and lettuce leaves no significant increase in the concentrations of gentamicin or streptomycin was observed between the treatments. The three crops absorbed relatively higher amounts of gentamicin (small molecule) than streptomycin (large molecule). Generally the levels of antibiotics in plant tissue increased with increasing the antibiotic concentration in the manure (1 mg kg^?1 > 0.5 mg kg^?1).     

Sorption of selected pesticides on soils,sediment and straw from a constructed agricultural drainage ditch or pond

Buffer zones such as ponds and ditches are used to reduce field-scale losses of pesticides from subsurface drainage waters to surface waters. The objective of this study was to assess the efficiency of these buffer zones, in particular constructed wetlands, focusing specifically on sorption processes. We modelled the sorption processes of three herbicides [2-methyl-4-chlorophenoxyacetic acid (2,4-MCPA), isoproturon and napropamide] and three fungicides (boscalid, prochloraz and tebuconazole) on four substrates (two soils, sediment and straw) commonly found in a pond and ditch in Lorraine (France). A wide range of Freundlich coefficient (K _fads) values was obtained, from 0.74 to 442.63 mg^1???n ?L ⁿ ?kg^?1, and the corresponding K _foc values ranged from 56 to 3,725 mg^1???n ?L ⁿ ?kg^?1. Based on potential retention, the substrates may be classified as straw >> sediments > soils. These results show the importance of organic carbon content and nature in the process of sorption. Similarly, the studied pesticides could be classified according to their adsorption capacity as follows: prochloraz >> tebuconazole–boscalid > napropamide >> MCPA–isoproturon. This classification is strongly influenced by the physico-chemical properties of pesticides, especially solubility and K _oc. Straw exhibited the largest quantity of non-desorbable pesticide residues, from 12.1 to 224.2 mg/L for all pesticides. The presence of plants could increase soil–sediment sorption capacity. Thus, establishment and maintenance of plants and straw filters should be promoted to optimise sorption processes and the efficiency of ponds and ditches in reducing surface water pollution.     

Leaching of S-metolachlor,terbuthylazine, desethyl-terbuthylazine,mesotrione, flufenacet,isoxaflutole, and diketonitrile in field lysimeters as affected by the time elapsed between spraying and first leaching event

The effect of elapsed time between spraying and first leaching event on the leaching behavior of five herbicides (terbuthylazine, S-metolachlor, mesotrione, flufenacet, and isoxaflutole) and two metabolites (desethyl-terbuthylazine and diketonitrile) was evaluated in a 2011–2012 study in northwest Italy. A battery of 12 lysimeters (8.4 m² long with a depth of 1.8 m) were used in the study, each filled with silty-loam soil and treated during pre-emergence with the selected herbicides by applying a mixture of commercial products Lumax (4 L ha^?1) and Merlin Gold (1 L ha^?1). During treatment periods, no gravity water was present in lysimeters. Irrigation events capable of producing leaching (40 mm) were conducted on independent groups of three lysimeters on 1 day after treatment (1 DAT), 7 DAT, 14 DAT, and 28 DAT. The series was then repeated 14 days later. Leachate samples were collected a few days after irrigation; compounds were extracted by solid phase extraction and analyzed by high-performance liquid chromatography and gas chromatography–mass spectrometry. Under study conditions, terbuthylazine and S-metolachlor showed the highest leaching potentials. Specifically, S-metolachlor concentrations were always found above 0.25 µg L^?1. Desethyl-terbuthylazine was often detected in leached waters, in most cases at concentrations above 0.1 µg L^?1. Flufenacet leached only when irrigation occurred close to the time of herbicide spraying. Isoxaflutole and mesotrione were not measured (<0.1 µg L^?1), while diketonitrile was detected in concentrations above 0.1 µg L^?1 on 1 DAT in 2011 only.     

Soil pH and Anion Abundance Affects on Copper Adsorption

Abstract

Copper (Cu) input to agricultural soils results from Cu containing pesticides and/or that in soil amendments, such as manure or sewage sludge. Soil and soil solution properties influence the adsorption and desorption of Cu by the soil, which in turn determines its plant availability and/or phytotoxicities. Effects of different anion enrichment in the equilibrium solution on Cu adsorption by different soils (pH range of 6.2–9.9) were investigated in this study over a range of Cu concentrations. With Cu concentrations in the range of 0–100 mg L^?1 in the equilibration solution, 95–99% of applied Cu was adsorbed by all three soils. The adsorption of Cu was similar regardless of using either 0.01 M CaCl₂ or Ca(NO₃)₂ as the equilibration solution. When the Cu concentration in the equilibration solution was further increased in the range of 500–2000 mg L^?1, the adsorption of Cu decreased from 60 to 24% of applied Cu in two soils with pH 6.2–7.9. In a high pH soil (pH = 9.9), the Cu adsorption decreased from 77 to 34%. Addition of incinerated sewage sludge (ISS) to a Palouse silt loam soil (pH = 6.2) increased the Cu adsorption as compared to that by unamended soil. This was, in part, due to an increase in the soil suspension pH with ISS amendment.     

Adsorption/Desorption of Copper by a Sandy Soil Amended with Various Rates of Manure,Sewage Sludge,and Incinerated Sewage Sludge

Organic amendments are sometimes applied to agricultural soils to improve the physical, chemical, and microbiological properties of the soils. The organic fractions in these soil amendments also influence metal reaction, particularly the adsorption and desorption of metals, which, in turn, determine the bioavailability of the metals and hence their phytotoxicities. In this study, a Quincy fine sandy (mixed, mesic, Xeric Torripsamments) soil was treated with 0 to 160 g kg^?1 rates of either manure, sewage sludge (SS), or incinerated sewage sludge (ISS) and equilibrated in a greenhouse at near field capacity moisture content for 100 days. Following the incubation period, the soil was dried and adsorption of copper (Cu) was evaluated in a batch equilibration study at either 0, 100, 200, or 400 mg L^?1 Cu concentrations in a 0.01M CaCl₂ solution. The desorption of adsorbed Cu was evaluated by three successive elutions in 0.01M CaCl₂. Copper adsorption increased with an increase in manure rates. At the highest rate of manure addition (160 g kg^?1 soil), Cu adsorption was two-fold greater than that by the unamended soil at all rates of Cu additions. With increasing rates of Cu additions, the adsorption of Cu decreased from 99.4 to 77.6% of Cu applied to the 160 g kg^?1 manure amended soil. The desorption of Cu decreased with an increase in rate of manure amendment. Effects of sewage sludge amendments on Cu adsorption were somewhat similar to those as described for manure additions. Likewise, the desorption of Cu was the least at the high rate of SS addition (160 g kg^?1), although at the lower rates there was not a clear indication of the rate effects. In contrast to the above two amendments, the ISS amendment had the least effect on Cu adsorption. At the highest rate of ISS amendment, the Cu adsorption was roughly 50% of that at the similar rate of either manure or SS amendments, across all Cu rates.     

Mineral constituents in Leccinum scabrum from lowland locations in the central Europe and their relation to concentration in forest topsoil

Leccinum scabrum is an edible mushroom common in European regions in the northern hemisphere. Macro and trace mineral constituents such as Ag, Al, Ba, Ca, Cd, Co, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, P, Rb, Sr and Zn were studied in L. scabrum and in the top soil collected from the same location underneath soil substratum. The “pseudo-total” and labile (extractable fraction of minerals) were measured to get insight into the levels, distribution between the morphological parts of fruiting bodies, potential for their bioconcentration by mushroom and evaluated for human exposure via consumption of the mushroom. The sampling sites include the Dar?lubska Wilderness, Trójmiejski Landscape Park, Sobieszewo Island, Wdzydze Landscape Park and outskirts of the K?trzyn town in Mazury from the norther part of Poland. Median values of K, Rb and P concentrations in dehydrated L. scabrum were for caps in range 27,000–44,000 mg kg^?1, 90–320 mg kg^?1 and 6,200–9,100 mg kg^?1, and followed by Mg at 880–1,000 mg kg^?1, Ca at 48–210 mg kg^?1 and Al at 15–120 mg kg^?1. The median concentrations of Cu, Fe, Mn and Zn in caps were in range 15–27 mg kg^?1 db 38–140 mg kg^?1, 5.3–27 mg kg^?1 and 130–270 mg kg^?1. For Ba and Sr, concentrations on the average were at ～1 mg kg^?1, and almost equally distributed between the caps and stipes of the fruiting bodies. L. scabrum mushrooms were low in toxic Ag, Cd, Hg and Pb, for which the median values in dried caps from five locations were, respectively, in range 0.48–0.98 mg kg^?1 (cap to stipe index, Q_C/S, was 2.5–4.1), 1.0–5.8 mg kg^?1 (Q_C/S 2.9–3.8), 0.36–0.59 mg kg^?1 (Q_C/S 1.6–2.7) and 0.20–0.91 mg kg^?1 (Q_C/S 1.2–1.9). Substantial variations in the concentrations of the “pseudo-total” fraction (extracted by aqua regia) or labile fraction (extracted by 20% solution of nitric acid) of the elements determined in forest topsoils were noted between some of the locations examined. The elements K, P, Cd, Cu, Hg, Mn, Na, Rb and Zn can be considered as those which were bioconcentrated by L. scabrum in fruiting bodies, while the rates of accumulation varied with the sampling location.