Mercury in European Blushers,Amanita rubescens,mushrooms and topsoils: Bioconcentration potential and intake assessment

Total mercury content has been determined in fruiting bodies of European Blushers and topsoils collected from 11 sites across Poland in 2006-2008. Mercury analysis was carried out using a validated analytical method and cold-vapour atomic absorption (CV-AAS). The European Blusher effectively accumulated mercury in fruiting bodies. The mean values of total mercury in caps of European Blushers from background (uncontaminated) areas were from 0.22 to 1.0 (0.067-3.2) and in stipes from 0.16 to 0.65 (0.071-2.7) μg/g dry weight. In topsoil beneath to fruiting bodies, the median Hg concentration at 10 sites in Northern Poland varied between 0.030 and 0.072 (0.0096–0.19) μg/g dw, and in one site in Southern Poland was 0.20 (0.079–0.34) μg/g dw. Data on Hg in European Blushers from different countries were reviewed. The mean concentrations of total Hg in caps of European Blushers from two “pristine” sites in northern part of Poland were ～1.0 μg/g dw. A meal made with 300–500 g of fresh caps of European Blushers collected at such sites (assuming 90% water content in caps) can result in Hg intake of 0.0003–0.0005 mg Hg/kg bm (assuming a 60 kg bm), which is a dose equipotent to a new provisional tolerable weekly intake (PTWI) value set for inorganic Hg.     

Reduced downward mobility of metribuzin in fly ash-amended soils

Metribuzin, a triazine herbicide, is poorly sorbed in the soils, therefore leaches to lower soil profile. Fly ash amendment, which enhanced metribuzin sorption in soils, may play a significant role in reducing the downward mobility of herbicide. Therefore, the present study reports the effect of Inderprastha fly ash amendment on metribuzin leaching in three soil types. Fly ash was amended at 1, 2 and 5% levels in the upper 15 cm of 30 cm long packed soil columns. Results suggested a significant reduction in the leaching losses of metribuzin in fly ash-amended columns of all the three soil types and effect increased with increase in the level of fly ash. Even after percolating water equivalent to 362 mm rainfall no metribuzin was recovered in the leachate of 5% fly ash-amended columns. Fly ash application affected both metribuzin breakthrough time and its maximum concentration in the leachate. Further, it resulted in greater retention of metribuzin in the application zone and better effect was observed in the organic carbon poor soils.     

A correlation between the fate and non-extractable residue formation of 14C-metalaxyl and enzymatic activities in soil

Extracellular, oxidative soil enzymes like monophenol oxidases and peroxidases play an important role in transformation of xenobiotics and the formation of organic matter in soil. Additionally, these enzymes may be involved in the formation of non-extractable residues (NERs) of xenobiotics during humification processes. To examine this correlation, the fate of the fungicide ¹⁴C metalaxyl in soil samples from Ultuna (Sweden) was studied. Using different soil sterilization techniques, it was possible to differentiate between free, immobilized, and abiotic (“pseudoenzyme”-like) oxidative activities. A correlation between the formation of metalaxyl NER and soil organic matter content, biotic activities, as well as extracellular phenoloxidase and peroxidase activities in the bulk soil and its particle size fractions was determined. Extracellular soil-bound enzymes were involved in NER formation (up to 8% of applied radioactivity after 92 days) of the fungicide independently from the presence of living microbes and different distributions of the NER in the soil humic subfractions.     

Metabolic fate of the 14C-labeled herbicide clodinafop-propargyl in soil

The metabolic fate of ¹⁴C-phenyl-labeled herbicide clodinafop-propargyl (CfP) was studied for 28 days in lab assays using a soil from Germany (A_p horizon, silt loam, and cambisol). Mineralization amounted to 12.40% of applied ¹⁴C after 28 days showing a distinct lag phase until day 7 of incubation. Portions of radioactivity extractable by means of 0.01 M CaCl₂ solution (bioavailable fraction) decreased rapidly and were 4.41% after 28 days. Even immediately after application, only 57.31% were extracted with the aqueous solvent. Subsequent extraction using accelerated solvent extraction (ASE; acetonitrile/water 4:1, v/v) released 39.91% of applied ¹⁴C with day 0 and 26.16% with day 28 of incubation from the samples. Non-extractable portions of radioactivity thus, increased with time amounting to 11.99% (day 0) and 65.00% (day 28). A remarkable increase was observed between 14 and 28 days correlating with the distinct increase of mineralization. No correlation was found throughout incubation with general microbial activity as determined by DMSO reduction. Analysis of the CaCl₂ and ASE extracts by radio-TLC, radio-HPLC and GC/MS revealed that CfP was rapidly cleaved to free acid clodinafop (Cf), which was further (bio-) transformed; DT₅₀ values (based on radio-TLC detection of the parent compound) were far below 1 day (CfP) and about 7 days (Cf). TLC analysis pointed to 2-(4-hydroxyphenoxy)-propionic acid as further metabolite. Due to fractionation of non-extractable residues, most of the ¹⁴C was associated with fulvic and humic acids, portions in humin fractions and non-humics were moderate and low, respectively. Using a special strategy, which included pre-incubation of the soil with CfP and then mineralization of ¹⁴C-CfP as criterion, a microorganism was isolated from the soil examined. The microorganism grew using CfP as sole carbon source with concomitant evolution of ¹⁴CO₂. The bacterium was characterized by growth on commonly used carbon sources and by 16S rDNA sequence analysis. The sequence exhibited high similarity with that of Rhodococcus wratislaviensis (99.56%; DSM 44107, NCIMB 13082).     

Changes in TcpA gene frequency explain 2,4,6-trichlorophenol degradation in mesocosms

Soils are often polluted by chlorophenols in timber production areas in the northern hemisphere. The tcpA gene encodes the first step of 2,4,6-trichlorophenol (246-TCP) degradation. We tested tcpA gene frequency in three natural pristine soils with different 246-TCP degradation capacity. Gene tcpA frequency increased more in spiked than non-spiked 10-L pails containing coniferous humus soil with high degradation capacity, in contrast to soils where degradation was slower. As the soil in each mesocosm originated from a spatially separate field plot, changes in tcpA gene frequency affected 246-TCP degradation over a range of soil origins. This indicates that the abundance of and changes in tcpA gene frequency could be utilized in estimating the efficacy of natural attenuation and biostimulation treatments in controlled conditions.     

Leaching,mobility and persistence of tebufenozide in columns packed with forest litter and soil

Abstract

Leaching, downward mobility and persistence of tebufenozide was investigated under laboratory conditions in columns packed with forest litter and soil, after fortification with the analytical grade material (purity > 99.6%) and with two commercial formulations, RH‐5992 2F (aqueous flowable) and RH‐5992 ES (emulsion suspension). Two types of litter and soil were used: one type with relatively high amounts of sand and the other with high amounts of clay.

The concentrations eluted in the leachates were lower when the analytical material (dissolved in acetone) was used for fortification, than when the two formulations (diluted with water) were used. The amount leached was higher for RH‐5992 2F than for RH‐5992 ES. The type of substrate, i.e., sandy or clay type, had only marginal influence on the amounts eluted in the leachates. Downward movement of tebufenozide from the top 2‐cm layer to the untreated middle and bottom layers (3‐cm segments) was consistently lower when the analytical material was used for fortification, than when the two formulations were used. Downward movement was higher for RH‐5992 2F than for RH‐5992 ES. Persistence of tebufenozide in substrates, maintained under submerged conditions for 70 days after leaching, indicated an initial 2‐week lag period prior to the onset of degradation. Formulation‐related differences were observed in the half‐life (DT₅₀) values. When the analytical material was used for fortification, the DT₅₀ ranged from ca 54 to 59 d. However, when the formulations were used for fortification, the DT₅₀ showed a higher range, i.e., from ca 62 to 67 d for RH‐5992 2F and ca 70 to 80 d for RH‐5992 ES. Formulation ingredients appear to have caused enhanced adsorption of tebufenozide onto the substrates, thus delaying degradation.     

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     

Volatilization of 1,2‐dibromo‐3‐chloropropane (DBCP) from soils

Abstract

The volatilization of DBCP from soils, as affected by the soil characteristics and application techniques, was studied in a laboratory experiment. The volatilization rate of DBCP applied in water was higher from sandy and silty loam soils than from clay soil. Water added after DBCP application acted as a soil cover, decreasing the volatilization rate. The results obtained with DBCP application in hexane to air‐dry soils, indicate that adsorption could be an important factor in reducing the volatilization losses.

Diffusion coefficients were calculated from the volatilization parameters, by using a simplified relationship between volatilization losses and diffusion through soil.     

Persistence and biodegradation of carbaryl in soils

Abstract

The persistence of the methylcarbamate pesticide carbaryl was studied in four soils under flooded conditions. A substantial portion of the pesticide was recovered from all soils even after 15 days of its application, with the recovery ranging from 37% in an alluvial soil to 73% in an acid sulfate soil. The degradation of carbaryl was more rapid under flooded conditions than under nonflooded conditions. A bacterium, Pseudomonas cepacia, isolated from a flooded soil amended with a related methylcarbamate pesticide carbofuran, degraded carbaryl in a mineral medium supplemented with yeast extract.     

Observations on the influence of water and soil pH on the persistence of insecticides

Abstract

The pH‐disappearance rate profiles were determined at ca. 25°C for 24 insecticides at 4 or 5 pH values over the range 4.5 to 8.0 in sterile phosphate buffers prepared in water‐ethanol (99: 1 v/v). Half‐lives measured at pH 8 were generally smaller than at lower pH values. Changes in half lives between pH 8.0 and 4.5 were largest (>1000x) for the aryl carbamates, carbofuran and carbaryl, the oxime carbamate, oxamyl, and the organophosphorus insecticide, trichlorfon. In contrast, half lives of phorate, terbufos, heptachlor, fensulfothion and aldicarb were affected only slightly by pH changes. Under the experimental conditions described half lives at pH8 varied from 1–2 days for trichlorfon and oxamyl to >1 year for fensulfothion and cyper‐methrin. Insecticide persistence on alumina (acid, neutral and basic), mineral soils amended with aluminum sulfate or calcium hydroxide to different pH values and four natural soils of different pH was examined. No correlation was observed between the measured pH of these solids and the rate of disappearance of selected insecticides applied to them. These observations demonstrate the difficulty of extrapolating the pH dependent disappearance behaviour observed in homogeneous solution to partially solid heterogeneous systems such as soil.