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.     

Laboratory investigation of Waelz slag stabilization

Electric Arc Furnace dusts are considered hazardous waste due to their high heavy metals content (zinc, lead, etc.). The Waelz process is one of the most efficient technologies, in terms of capacity and quality, able to recover nearly the 90% of zinc contained in such EAF dusts. Unfortunately, the resulting slag still has eco-compatibility problems, although its mechanical and chemical properties are suitable for civil engineering applications. Stabilization tests, by quartz addition, were performed on EAF dusts in a laboratory furnace. Temperature, treatment time and cooling rate were varied in order to define the best conditions for regulating the formation of a stable microstructure able to hinder the release of substances. Microstructural characterization was carried-out using SEM and XRD analysis. Leaching tests were performed according to EN 12457-2 standards and water analyses were performed using ICP-OES. The best chemical stability was achieved when dust powders were mixed with 20% of silica and water-cooled.     

Antimony leaching release from brake pads: Effect of pH,temperature and organic acids

Metals from automotive brake pads pollute water, soils and the ambient air. The environmental effect on water of antimony (Sb) contained in brake pads has been largely untested. The content of Sb in one abandoned brake pad reached up to 1.62 × 10⁴ mg/kg. Effects of initial pH, temperature and four organic acids (acetic acid, oxalic acid, citric acid and humic acid) on Sb release from brake pads were studied using batch reactors. Approximately 30% (97 mg/L) of the total Sb contained in the brake pads was released in alkaline aqueous solution and at higher temperature after 30 days of leaching. The organic acids tested restrained Sb release, especially acetic acid and oxalic acid. The pH-dependent concentration change of Sb in aqueous solution was best fitted by a logarithmic function. In addition, Sb contained in topsoil from land where brake pads were discarded (average 9 × 10³ mg/kg) was 3000 times that in uncontaminated soils (2.7 ± 1 mg/kg) in the same areas. Because potentially high amounts of Sb may be released from brake pads, it is important that producers and environmental authorities take precautions.     

Leaching behaviour of different scrap materials at recovery and recycling companies: Full-, pilot- and lab-scale investigation

Scrap material recovery and recycling companies are confronted with waste water that has a highly fluctuating flow rate and composition. Common pollutants, such as COD, nutrients and suspended solids, potentially toxic metals, polyaromatic hydrocarbons and poly chlorinated biphenyls can exceed the discharge limits. An analysis of the leaching behaviour of different scrap materials and scrap yard sweepings was performed at full-scale, pilot-scale and lab-scale in order to find possible preventive solutions for this waste water problem. The results of these leaching tests (with concentrations that frequently exceeded the Flemish discharge limits) showed the importance of regular sweeping campaigns at the company, leak proof or covered storage of specific scrap materials and oil/water separation on particular leachates. The particulate versus dissolved fraction was also studied for the pollutants. For example, up to 98% of the polyaromatic hydrocarbons, poly chlorinated biphenyls and some metals were in the particulate form. This confirms the (potential) applicability of sedimentation and filtration techniques for the treatment of the majority of the leachates, and as such the rainwater run-off as a whole.     

The importance of ammonium mobility in nitrogen-impacted unfertilized grasslands: A critical reassessment

The physico-chemical absorption characteristics of ammonium-N for 10 soils from 5 profiles in York, UK, show its high potential mobility in N deposition-impacted, unfertilized, permanent grassland soils. Substantial proportions of ammonium-N inputs were retained in the solution phase, indicating that ammonium translocation plays an important role in the N cycling in, and losses from, such soils. This conclusion was further supported by measuring the ammonium-N leaching from intact plant/soil microcosms. The ammonium-N absorption characteristics apparently varied with soil pH, depth and soil texture. It was concluded for the most acid soils especially that ammonium-N leached from litter horizons could be seriously limiting the capacity of underlying soils to retain ammonium. Contrary to common opinion, more attention therefore needs to be paid to ammonium leaching and its potential role in biogeochemical N cycling in semi-natural soil systems subject to atmospheric pollution.     

Leaching of copper and zinc from spent antifouling paint particles

Leaching of Cu and Zn from a composite of spent antifouling paint particles, containing about 300 mg g⁻¹ and 110 mg g⁻¹ of the respective metals, was studied in batch experiments. For a given set of simulated environmental conditions, release of Cu was independent of paint particle concentration due to attainment of pseudo-saturation, but Zn was less constrained by solubility effects and release increased with increasing particle concentration. Leaching of Cu increased but Zn decreased with increasing salinity, consistent with mechanisms governing the dissolution of Cu₂O in the presence of chloride and Zn acrylates in the presence of seawater cations. Because of complex reaction kinetics and the presence of calcium carbonate in the paint matrix, metal leaching appeared to be greater at 4 °C than 19 °C under many conditions. These findings have important environmental and biological implications regarding the deliberate or inadvertent disposal of antifouling paint residues.     

The impact of enhanced ammonium sulphate inputs exceeding critical load on calluna vulgaris /peat soil microcosms

Ammonium sulphate at six concentrations in simulated precipitation has been applied weekly over two years to Calluna vulgaris growing in peat soil. The nitrogen deposition treatments were chosen to embrace and exceed critical load. The growth and composition of the Calluna and the changes over time in the chemistry of the peat soil and its soil solution were monitored. In spite of significant increases in foliar nitrogen concentration in new shoots, especially in the first year, growth did not increase significantly in response to nitrogen treatment. Several factors could be contributing to the lack of significant growth response. (1) Increasing ammonium input significantly acidified the soil solution, which could adversely effect growth directly. (2) Foliar calcium concentration was reduced significantly in both years by the ammonium sulphate treatments, and more calcium was undoubtedly lost from the rooting zone at higher nitrogen inputs. (3) Foliar phosphate declined significantly between the first and second year, so lack of growth response might also reflect a phosphorus limitation. There was a distinctly visible darkening of the leaves in response to increasing ammonium applications, especially for the first year's growth, and the chlorophyll a and b concentrations in leaves from new growth at the three highest nitrogen treatments were significantly (at P <0.05) higher than those for the control. The pigment concentrations fell markedly by the end of the second season, and treatment effects were much less consistent. It is suggested that pigment analysis therefore probably has little diagnostic value for assessing damage from pollutant nitrogen effects.     

Sorption Kinetics of Atrazine and Diuron in Soils from Southern Brazil

Abstract

Sorption kinetics of atrazine and diuron was evaluated in soil samples from a typical landscape in Paraná. Samples were collected (0–20 cm) in a no-tillage area from Mamborê, PR, which has been cultivated under a crop rotation for the last six years. Six sampling points of the slope were selected to represent a wide range of soil chemical and physical properties found in this area. Radiolabeled tracers (¹⁴C-atrazine and ¹⁴C-diuron) were used and the radioactivity was detected by liquid scintillation counting (LSC). Sorption was accomplished for increasing equilibration periods (0.5, 1.5, 3, 6, 12, 24, and 48 h). Kinetics data fitted adequately well to Elovich equation, providing evidences that soil reaction occurs in two distinct stages: a fast, initial one followed by a slower one. During the fast phase, 34–42 and 71–79% of total atrazine and diuron applied were sorbed to soil samples. No important differences were found among combinations of soil and herbicide sorption during the slow phase. The unrealistic conditions under batch experiments should be overestimating sorption in the fast phase and underestimating diffusion in the slow phase. Sorption of both herbicides was positively correlated to organic carbon and clay contents of soils, but atrazine was much less sorbed than diuron, showing its higher potential to contaminate groundwater, specially in sandy, low organic carbon soils.     

Leaching of mecoprop and dichlorprop in calcareous soil. Effect of the exogen organic matter addition in this process

Abstract

Leaching studies of mecorprop (R,S)‐2‐(4‐chloro‐2‐methylphenoxy)propanoic acid, and dichlorprop, (R,S)‐2‐(4‐chloro‐2,4‐dichlorophenoxy) propanoic acid, under saturated conditions were conducted in unamended and amended soil columns. The purpose of the study was to investigate the leaching of these herbicides in three type of soils and the exogen organic matter effect on this process. The leaching patterns could be related to variation in the soil texture and diffusion processes of the herbicides into micropores within the walls of conducting pore. The leaching rate in the amended soil columns decreased with the addition of organic matter. The breakthrough curves (BTC) of these herbicides in the leachates of the amended soil columns were wider and more diffused than the BTC obtained for the corresponding unamended soil. The theoretical BTC overestimated the pore volume required for the displacement of these pesticides from the soil column. This may be due to the differences in the adsorption process between the bacth and soil columns methods     

INFLUENCE OF SOIL ORGANIC MATTER ON THE LEACHING OF POLYCYCLIC AROMATIC HYDROCARBONS IN SOIL

Polycyclic aromatic hydrocarbons (PAHs) are one of the main classes of contaminants in the terrestrial environment. Aside from total organic carbon, the ratio among the different organic matter fractions [dissolved organic matter, fulvic acid (FA), humic acid (HA) and humin] can also affect the mobility of these hydrocarbons in soils. In this study the effect of the whole organic carbon pool has been compared with that of HA and FA on the translocation of four PAHs (biphenyl, fluorene, phenanthrene and pyrene) in soil columns. Oxidized and untreated soil columns with and without HA or FA, were prepared, spilled with hydrocarbons and leached with a 0.01 M CaCl₂ solution. The influence of HA and FA on PAH translocation was investigated through determinations of the PAH contents and total organic carbon (TOC) in the layers of the columns. All molecules were moved vertically by the percolating solutions, their concentrations decreasing with depths. The non-oxidized soil tended to retain more PAHs (96%) than the oxidized one (60%), confirming that organic matter plays an important role in controlling PAH leaching. The whole organic matter pool reduced the translocation of pollutants downward the profile. The addition of HA enhanced this behaviour, by increasing the PAH retention in the top layers (7.55 mg and 4.00 mg in the top two layers, respectively) while FA increased their mobility (only 2.30 and 2.90 mg of PAHs were found in the top layers) and favoured leaching. In fact, in the presence of HA alone, the higher amounts of PAHs retained at the surface and the good correlation (r²=0.936) between TOC and hydrocarbon distribution can be attributed to a parallel distribution of PAHs and HA, while in the presence of FA, the higher mobility of PAHs can be attributed to the high mobility of the humic material, as expected by its extensive hydrophilic characteristics.