Study of processes influencing bioavailability of pesticides in wood-soil systems: Effect of different factors.

Lignocellulosic wastes and by-products containing lignin are now available in large amounts from forestry and industrial activities, and could be promising organic materials for the biosorption of pesticides by soils in order to reduce point-source pollution. Adding these materials to soil requires understanding the process of pesticide sorption-desorption by wood-soils, as sorption capacity could increase, with changes in pesticide bioavailability and final fate. The objective of this work was to study the effect that pine and oak wood added to soils had on the sorption/desorption of the pesticides linuron, alachlor, and metalaxyl. Experiments were conducted with two sandy loam and sandy clay soils each amended with two wood doses (5% and 50%) after different incubation times (0, 5 and 12 months). A low wood dose (5%) had no significant impact on the sorption (Kf) of alachlor, but Kf increased for linuron (up to 5.4-1.7 times) and metalaxyl (up to 4.4 and 8.6 times) in all wood-soil systems. The results were not significantly different after different incubation times. The desorption results indicated that wood decreases the sorption irreversibility of alachlor, and increases that of linuron and metalaxyl, with a varying effect of the wood-soil incubation time. The addition of a high wood dose to soil (50%) was more significant for increasing the sorption of all the pesticides, and the sorbed amounts remaining after desorption (>49% for linuron, >33% for alachlor and >6% for metalaxyl), although there was no apparent discrimination between the two types of woods. The role of the nature of the organic carbón (Koc values) for sorption was evidenced for alachlor and metalaxyl, but not for linuron. These outcomes are of interest for extending wood application to soil as a barrier for avoiding environmental risk by point-source pollution due to the use and management of pesticides in farming systems.

Field versus laboratory experiments to evaluate the fate of azoxystrobin in an amended vineyard soil.

This study reports the effect that adding spent mushroom substrate (SMS) to a representative vineyard soil from La Rioja region (Spain) has on the behaviour of azoxystrobin in two different environmental scenarios. Field dissipation experiments were conducted on experimental plots amended at rates of 50 and 150 t ha(-1), and similar dissipation experiments were simultaneously conducted in the laboratory to identify differences under controlled conditions. Azoxystrobin dissipation followed biphasic kinetics in both scenarios, although the initial dissipation phase was much faster in the field than in the laboratory experiments, and the half-life (DT50) values obtained in the two experiments were 0.34-46.3 days and 89.2-148 days, respectively. Fungicide residues in the soil profile increased in the SMS amended soil and they were much higher in the top two layers (0-20 cm) than in deeper layers. The persistence of fungicide in the soil profile is consistent with changes in azoxystrobin adsorption by unamended and amended soils over time. Changes in the dehydrogenase activity (DHA) of soils under different treatments assayed in the field and in the laboratory indicated that SMS and the fungicide had a stimulatory effect on soil DHA. The results reveal that the laboratory studies usually reported in the literature to explain the fate of pesticides in amended soils are insufficient to explain azoxystrobin behaviour under real conditions. Field studies are necessary to set up efficient applications of SMS and fungicide, with a view to preventing the possible risk of water contamination.

Effect of spent mushroom substrate applied to vineyard soil on the behaviour of copper-based fungicide residues.

The effect of the addition of spent mushroom substrate (SMS) to the soil as an amendment on the distribution and/or fate of copper from a copper-based fungicide applied to a vineyard soil in La Rioja (N. Spain) was studied. The study was carried out on experimental plots amended or not with SMS at rates of 40 and 100 t ha(-1). The variation in total Cu content in the topsoil (0-10 cm) and in the soil profile (0-50 cm), and the distribution of Cu in different fractions of the topsoil were studied as a function of the dose of Cu added (5 and 10 kg ha(-1)) and of the time elapsed since application (0-12 months). In addition, the changes in the chemical properties (solid organic carbon (OC), dissolved organic carbon (DOC) and pH) of the soils were studied. A greater capacity for Cu retention by the amended soils than by the unamended one was observed only when the fungicide was applied at the high dose. No effect of the amendment rate was noted on this retention capacity. The metal content in the topsoil decreased over time in step with the disappearance of the OC in the amended soil due to its oxidation, mineralization and/or leaching. This decrease in total Cu content was possibly due to the formation of soluble Cu complexes with the DOC, which facilitated its transport through the soil. A re-distribution of Cu in the different soil fractions was also observed over time, mainly from the organic to the residual fraction. The results obtained indicate that the increase in OC due to the application of SMS at the rates used does not lead to any significant increase in the persistence of Cu in the soil over time. Of greater interest would be the assessment of the risk for groundwater quality, owing to possible leaching of the fungicide enhanced by the SMS when SMS and Cu-based fungicides are jointly applied to vineyard soils.

Determination of triazines and dealkylated and hydroxylated metabolites in river water using a propazine-imprinted polymer.

A molecularly imprinted polymer (MIP) obtained by precipitation polymerisation using propazine as template has been employed as sorbent for the solid phase extraction of triazines and some of their hydroxylated and dealkylated metabolites from river water. Three configurations were studied: (a) use of the propazine-MIP as a selective sorbent for the extraction of triazines directly from water; (b) use of mixtures of LiChrolut EN (a polymeric sorbent of styrene divinylbenzene) and propazine-MIP as sorbent, and (c) use of propazine-MIP as a clean-up sorbent for organic extracts obtained in a prior SPE procedure with LiChrolut EN. The former two configurations imply that the analytes pass through the propazine-MIP in aqueous medium, whereas in the latter case the analytes percolate through the propazine-MIP in an organic medium coming from the previous SPE step. Different types of water were tested to assess matrix effects. The analytical characteristics of the three configurations were evaluated.

Occupational Mn parkinsonism: magnetic resonance imaging and clinical patterns following CaNa2-EDTA chelation.

We report a case of occupational parkinsonism due to manganese exposure in which professional exposure has been documented both by the high blood and urinary levels of the metal and by its presence in the materials used. A strong relation was evident among chelating treatment, cessation of exposure and clinical improvement. MRI confirmed the evolution of clinical pattern by means of reduction of heavy metal deposition in basal ganglia. These findings also agree with the few experimental and human studies published. This case study points to the need for an accurate occupational history collection and suggests the possibility of useful chelating therapy with CaNa2EDTA.

Electricity generation from wastewaters with starch as carbon source using a mediatorless microbial fuel cell.

Microbial fuel cells represent a new method for producing electricity from the oxidation of organic matter. A mediatorless microbial fuel cell was developed using Escherichia coli as the active bacterial component with synthetic wastewater of potato extract as the energy source. The two-chamber fuel cell, with a relation of volume between anode and cathode chamber of 8:1, was operated in batch mode. The response was similar to that obtained when glucose was used as the carbon source. The performance characteristics of the fuel cell were evaluated with two different anode and cathode shapes, platinised titanium strip or mesh; the highest maximum power density (502mWm(-2)) was achieved in the microbial fuel cell with mesh electrodes. In addition to electricity generation, the MFC exhibited efficient treatment of wastewater so that significant reduction of initial oxygen demand of wastewater by 61% was observed. These results demonstrate that potato starch can be used for power generation in a mediatorless microbial fuel cell with high removal efficiency of chemical oxygen demand.

Use of raw or incubated organic wastes as amendments in reducing pesticide leaching through soil columns.

Soil amendment with organic wastes is becoming a widespread management practice since it can effectively solve the problems of uncontrolled waste accumulation and improve soil quality. However, when simultaneously applied with pesticides, organic wastes can significantly modify the environmental behaviour of these compounds. This study evaluated the effect of sewage sludges (SS), grape marc (GM) and spent mushroom substrates (SMS) on the leaching of linuron, diazinon and myclobutanil in packed columns of a sandy soil with low organic matter (OM) content (<1%). Soil plus amendments had been incubated for one month (1 m) or 12 months (12 m). Data from the experimental breakthrough curves (BTCs) were fitted to the one-dimensional transport model CXTFIT 2.1. All three amendments reduced leaching of linuron and myclobutanil relative to unamended soil. SMS was the most effective in reducing leaching of these two compounds independent of whether soil was incubated for 1 m or 12 m. Soil amendments increased retardation coefficients (Rexp) by factors of 3 to 5 for linuron, 2 to 4 for diazinon and 3 to 5 for myclobutanil relative to unamended soil. Leaching of diazinon was relatively little affected by soil amendment compared to the other two compounds and both SS and SMS amendment with 1m incubation resulted in enhanced leaching of diazinon. The leaching data for linuron and myclobutanil were well described by CXTFIT (mean square error, MSE<4.9·10(-7) and MSE<7.0·10(-7), respectively) whereas those of diazinon were less well fitted (MSE<2.1·10(-6)). The BTCs for pesticides were similar in soils incubated for one month or one year, indicating that the effect of amendment on leaching persists over relatively long periods of time.

Use of a bisphenol-A imprinted polymer as a selective sorbent for the determination of phenols and phenoxyacids in honey by liquid chromatography with diode array and tandem mass spectrometric detection.

An extraction-preconcentration procedure based on the use of a molecularly imprinted polymer (MIP) as selective sorbent has been developed for the determination of several phenolic compounds (bisphenol-A, bisphenol-F and 4-nitrophenol) and phenoxyacid herbicides (2,4-D, 2,4,5-T and 2,4,5-TP) in honey samples. Liquid chromatography with diode array detection (LC-DAD) and electrospray ionisation-ion trap mass spectrometry (LC-IT-MS) were used for the separation, identification and quantification of these analytes. The molecularly imprinted polymer was obtained by precipitation polymerisation with bisphenol-A (BPA) as template and 4-vinylpyridine as the functional monomer. The behaviour of this sorbent was compared with those of other materials frequently used in SPE. The selectivity of the BPA-MIP for the target analytes was tested in samples containing other pesticides in common use. The recoveries achieved for all six compounds were in the 81-96% range. By applying the proposed procedure prior to LC-IT-MS, the limits of detection achieved in commercial honey samples were in the 0.1-3.8 ng g(-1) range, with relative standard deviations of 12-24%.