Degradation and leaching of the herbicides metolachlor and diuron: a case study in an area of Northern Italy

In this work the degradation of the herbicides metolachlor, diuron, monuron and of the metabolites 2-ethyl-6-methylaniline (EMA), and 3,4-dichloroaniline (DCA) was assessed in laboratory experiments on microbiologically active and sterilized soils. Their leaching potentials were calculated, using Gustafson's equation, by determining their mobility (as Koc) and persistence (expressed as DT50). Lysimeter experiments were also conducted to assess the actual leaching of the studied herbicides in a cereal crop tillage area vulnerable to groundwater contamination. The data obtained from the field were compared to the laboratory results. Moreover, some compounds of particular concern were searched for in the groundwater located near the experimental area in order to evaluate actual contamination and to test the reliability of the leaching potential. The GUS index, computed on data from microbiologically active soil, shows monuron as a leacher compound, EMA and DCA as non-leachers, metolachlor and diuron as transient ones. The presence of metolachlor in the groundwater monitored, even at concentrations up to 0.1 mug/l, confirms the possibility that transient compounds can be leached if microbial activity has not completely occurred in active surface soil.     

Practical considerations for addressing uncertainties in monitoring bulk deposition

The assessment of the deposition of both wet (rain and cloud) and dry sedimenting particles is a prerequisite for estimating element fluxes in ecosystem research. Many nations and institutions operate deposition networks using different types of sampler. However, these samplers have rarely been characterized with respect to their sink properties. Major errors in assessing bulk deposition can result from poor sampling properties and defective sampling strategies. Relevant properties are: sampler geometry and material, in particular the shape of the rim; sink properties for gases and aerosols; and microbial transformations of the collected samples. An adequate number of replicates allows the identification of samples which are contaminated, in particular by bird droppings. The paper discusses physical and chemical properties of the samplers themselves. The dependence of measurement accuracy on the number of replicates and the sampling area exposed is discussed. Recommendations are given for sampling strategies, and for making corrections and substitution of missing data.     

Influence of acidification of CCB (Cu/Cr/B) impregnated wood on fungal copper tolerance

Copper tolerant fungi are known for more than 60 years but the complete mechanisms of copper tolerance by these fungi are still not fully understood. Copper tolerance has previously been linked to oxalic acid excretion by copper tolerant brown rot fungi. The oxalic acid then reacts with copper in the wood to form an insoluble and therefore less toxic copper oxalate. It has been suggested that copper tolerance could be due to lowering of the pH of the medium rather than the low solubility of copper oxalate. In order to elucidate this presumption, copper/chromium/boron (CCB) treated wood specimens were acidified with organic (oxalic, acetic, lactic, formic) and inorganic (sulphuric) acids and exposed to copper tolerant (Antrodia vaillantii, Leucogyrophana pinastri) and copper sensitive (Poria monticola, Gloeophyllum trabeum) brown rot fungal strains according to the mini block procedure. After eight weeks of exposure, the wood specimens were isolated and their mass losses determined. Additionally, electron paramagnetic resonance (EPR) measurements on the exposed specimens were performed. The EPR spectra of the specimens decayed by A. vaillantii were very similar to the EPR spectra of the specimens acidified with oxalic acid. Additionally, acidification of the CCB impregnated specimens made them significantly more susceptible to decay by both the copper tolerant and copper sensitive brown rot fungi.     

Effects of hand weeding strip and nitrogen fertilizer on corn plants

The objective of the present research was to evaluate effects of different strip weed control associated with nitrogen fertilizer on corn applied after planting. The experiment was set and conducted in Botucatu, S?o Paulo State, Brazil, and the hybrid planted was Dekalb 333-B. A completely randomized block design with four replications was used. Experimental plots were disposed as a factorial scheme 2 x 2 x 4, constituted by two types of weeding on row (with or without manual hoeing), two types of weeding on inter-row (with or without manual hoeing), and four nitrogen levels applied after planting (00, 60, 90, and 120 kg ha(-1)). Plots were composed by six rows with 5 m length. Nitrogen fertilizer was applied at 35 days after emergence (d.a.e). For weed community it was evaluated: weed density, dominancy, frequency, and relative importance. The main weed species were: Brachiaria plantiginea, Amaranthus retroflexus, Bidens pilosa, Cyperus rotunds, Brachiaria decumbens, Euphorbia heterofila, Oxalis latifolia, Acanthospermum hispidum, Commelina benghalensis. It was evaluated corn height at 40 and 100 d.a.e., first ear insertion height at 100 d.a.e., and final grain yield at harvesting. Plants and first ear insertion height were affected when nitrogen fertilizer was not applied. Treatments without weed control showed that weed interfered negatively with plants height. There were no correlation between weeds and nitrogen fertilizer for all parameters evaluated. Parcels without weed showed the highest ear weights and final grain production. Treatments that received nitrogen fertilizer, independently of studied arrangement, provided higher yields.     

Adsorption of phenolic compounds by activated carbon--a critical review

Adsorption of phenol and its derivatives on activated carbons is considered based on numerous papers related to this issue. Special attention is paid to the effects of carbon surface functionalities, pH of solution and heterogeneity effects that accompany adsorption of phenolic compounds. Moreover, in this paper the most important aspects are overviewed referring to irreversible adsorption of phenols and impact of different substituents of phenolic compounds on their uptake by activated carbons is considered. Finally, some remarks pertaining to applications of novel adsorbents for phenol adsorption are discussed and illustrated by means of a few examples.     

Accumulation of trinitrotoluene (TNT) in aquatic organisms: part 2--Bioconcentration in aquatic invertebrates and potential for trophic transfer to channel catfish (Ictalurus punctatus)

The potential of TNT to accumulate in aquatic organisms was assessed by determining bioconcentration factors for TNT and TNT biotransformation products using two benthic invertebrates (Chironomus tentans and Lumbriculus variegatus), and by determining the bioaccumulation factor of TNT and TNT biotransformation products due to TNT exposure via feeding for channel catfish (Ictalurus punctatus). In all three species, TNT was rapidly biotransformed resulting in minimal accumulation. The bioconcentration factors for parent TNT ranged from 3 to 4 ml g(-1) for the invertebrates studied, while the TNT bioaccumulation factor for catfish via oral exposure of food pellets was 2.4x10(-5) g g(-1) based on the concentration of TNT in the food pellet. As indicated by this small bioaccumulation factor, TNT accumulation in channel catfish through trophic transfer would be negligible compared to aqueous exposure (previously reported BCF of 0.79 ml g(-1)). TNT extractable biotransformation products accumulated to a greater degree than parent TNT for all three species. In addition, a large fraction of the radioactivity within all three species resisted solvent extraction. The highest bioconcentration factors occurred in L. variegatus with extractable radioactivity measuring 76 ml g(-1) and total radioactivity measuring 216 ml g(-1). Because the bioaccumulation of TNT is very low compared to the bioaccumulation of its biotransformation products, further research including identifying and determining the relative toxicities of these biotransformation products is necessary to fully evaluate the environmental risk posed by exposure to TNT.     

Detection of organic pollutants in sandy soils via TDR and eigendecomposition

In this study, organic pollutants in sandy soils are detected using a time domain relectrometry (TDR) probe system and eigendecomposition technique. As a demonstration, four types of organic fluids (motor oil, diesel oil, methanol and ethanol) were examined. Samples were prepared with different combinations of deionized water and organic fluid contents. For each experiment, reflected signals were captured by an oscilloscope, and their characteristics were identified using eigendecomposition technique. Autoregressive modeling and singular value decomposition methods were utilized for calculating the eigenvalues. The most significant eigenvalues were then identified based on their relative magnitude. Experimental results indicated that the presented system is sensitive to both water and pore fluid organic contents. For saturated conditions, signature curves were determined for identification of organic and/or water contents in soil pore fluids.     

Physical versus chemical effects on bacterial and bromide transport as determined from on site sediment column pulse experiments

Twenty-eight bacterial and Br transport experiments were performed in the field to determine the effects of physical and chemical heterogeneity of the aquifer sediment. The experiments were performed using groundwater from two field locations to examine the effects of groundwater chemistry on transport. Groundwater was extracted from multilevel samplers and pumped through 7-cm-long columns of intact sediment or repacked sieved and coated or uncoated sediment from the underlying aquifer. Two bacterial strains, Comamonas sp. DA001 and Paenibacillus polymyxa FER-02, were injected along with Br into the influent end of columns to examine the effect of cell morphology and cell surface properties on bacterial transport. The effects of column sediment grain size and mineral coatings coupled with groundwater geochemistry were also investigated. Significant irreversible attachment of DA001 was observed in the Fe oxyhydroxide-coated columns, but only in the suboxic groundwater where the concentrations of dissolved organic carbon (DOC) were ca. 1 ppm. In the oxic groundwater where DOC was ca. 8 ppm, little attachment of DA001 to the Fe oxyhydroxide-coated columns was observed. This indicates that DOC can significantly reduce bacterial attachment due electrostatic interactions. The larger and more negatively charged FER-02 displayed increasing attachment with decreasing grain size regardless of DOC concentration, and modeling of FER-02 attachment revealed that the presence of Fe and Al coatings on the sediment also promoted attachment. Finally, the presence of Al coatings and Al containing minerals appeared to significantly retard the Br tracer regardless of the concentration of DOC. These findings suggest that DOC in shallow oxic groundwater aquifers can significantly enhance the transport of bacteria by reducing attachment to Fe, Mn and Al oxyhydroxides. This effect appears to be profound for weakly and strongly charged hydrophilic bacteria and may contribute to differences in observations between laboratory experiments versus field-scale investigations particularly if the groundwater pH remains subneutral and Fe oxyhydroxide phases exist. These observation validate the novel approach taken in the experiments outlined here of performing laboratory-scale experiments on site to facilitate the use of fresh groundwater and thus be more representative of in situ groundwater conditions.     

Influence of solid dairy manure and compost with and without alum on survival of indicator bacteria in soil and on potato

We measured Escherichia coli, Enterococcus spp. and fecal coliform numbers in soil and on fresh potato skins after addition of solid dairy manure and dairy compost with and without alum (Al(2)(SO(4))(3)) treatment 1, 7, 14, 28, 179 and 297 days after application. The addition of dairy compost or solid dairy manure at rates to meet crop phosphorus uptake did not consistently increase E. coli and Enterococcus spp. and fecal coliform bacteria in the soil. We did not detect E. coli in any soil sample after the first sampling day. Seven, 14, 28, 179 and 297 days after solid dairy waste and compost and alum were applied to soil, alum did not consistently affect Enterococcus spp. and fecal coliform bacteria in the soil. We did not detect E. coli in any soil, fresh potato skin or potato wash-water at 214 days after dairy manure or compost application regardless of alum treatment. Dairy compost or solid dairy manure application to soil at rates to meet crop phosphorus uptake did not consistently increase Enterococcus spp. and fecal coliform numbers in bulk soil. Solid dairy manure application to soil at rates to meet crop phosphorus uptake, increased Enterococcus spp. and fecal coliform numbers in potato rhizosphere soil. However, fresh potato skins had higher Enterococcus spp. and fecal coliform numbers when solid dairy manure was added to soil compared to compost, N and P inorganic fertilizer and N fertilizer treatments. We did not find any E. coli, Enterococcus or total coliform bacteria on the exterior of the tuber, within the peel or within a whole baked potato after microwave cooking for 5 min.     

The influence of organic ligands on the retention of lead in soil

Organic acids are commonly produced and exuded by plant roots and soil microorganisms. Some of these organic compounds are effective chelating agents and have the potential to enhance metal mobility. The effect of citrate and salicylate on the leaching of lead in soil was investigated in a laboratory experiment. In short-term batch experiments, adsorption of lead to soil was slightly enhanced with increasing salicylate concentration (500-5000 microM) but decreased significantly in the presence of citrate. These observations suggested that citrate may enhance Pb leaching, but this was not observed in the column study. Soluble Pb in the presence and absence citrate or salicylate (up to 5000 microM) was added to soil columns at a moderate flow rate, but no Pb was observed to emerge from the soil in any of the soil columns. Rapid biodegradation of citrate in soil eliminated potential complexing ability. Breakthrough of Pb from soil was noted only when using small columns at high flow rates (>20 pore volumes per day). Under these conditions of physical and chemical non-equilibrium, citrate was not degraded and significantly enhanced Pb mobility. As in the batch adsorption experiments, the presence of salicylate reduced Pb leaching. Considering the extreme conditions required to induce Pb leaching, it is likely that Pb will remain relatively immobile in soil even in the presence of a strong complexing agent such as citrate.