Biotic and abiotic reductive dechlorination of chloroethenes in aquitards.

Chlorinated solvents occur as dense nonaqueous phase liquid (DNAPL) or as solutes when dissolved in water. They are present in many pollution sites in urban and industrial areas. They are toxic, carcinogenic, and highly recalcitrant in aquifers and aquitards. In the latter case, they migrate by molecular diffusion into the matrix. When aquitards are fractured, chlorinated solvents also penetrate as a free phase through the fractures. The main objective of this study was to analyze the biogeochemical processes occurring inside the matrix surrounding fractures and in the joint-points zones. The broader implications of this objective derive from the fact that, incomplete natural degradation of contaminants in aquitards generates accumulation of daughter products. This causes steep concentration gradients and back-diffusion fluxes between aquitards and high hydraulic conductivity layers. This offers opportunities to develop remediation strategies based, for example, on the coupling of biotic and reactive abiotic processes. The main results showed: 1) Degradation occurred especially in the matrix adjacent to the orthogonal network of fractures and textural heterogeneities, where texture contrasts favored microbial development because these zones constituted ecotones. 2) A dechlorinating bacterium not belonging to the Dehalococcoides genus, namely Propionibacterium acnes, survived under the high concentrations of dissolved perchloroethene (PCE) in contact with the PCE-DNAPL and was able to degrade it to trichloroethene (TCE). Dehalococcoides genus was able to conduct PCE reductive dechlorination at least up to cis-1,2-dichloroethene (cDCE), which shows again the potential of the medium to degrade chloroethenes in aquitards. 3) Degradation of PCE in the matrix resulted from the coupling of reactive abiotic and biotic processes-in the first case, promoted by Fe2+ sorbed to iron oxides, and in the latter case, related to dechlorinating microorganisms. The dechlorination resulting from these coupling processes is slow and limited by the need for an adequate supply of electron donors.

Effect assessment of chelators on bioaccessible and total chromium extraction in soils polluted by chromite processing wastes.

Solid wastes from chromium-processing facilities, when used as fill material, have generated chromium point source contamination of soils and groundwaters, that remains after decades in many urban and peri urban areas all over the world, causing environmental impacts that need to be addressed in a sustainable economic, social and environmental way. Representative surface soil samples, from a polluted area affected by chromite wastes burials, were used to carry on a feasibility study on Phytoextraction applicability, and chelating agents' selection to reduce environmental risks, considering chromium bioaccessible forms reduction as an objective. Tests for natural (only vegetation), and induced phytoextraction (plants + chelating agents) applicability were performed at greenhouse facilities under controlled conditions at two rounds. Natural phytoextraction tests, using first wheat and then corn plants, allowed to observe a low but significant 4,8% reduction in soil chromium. At induced phytoextraction trials, when comparing the action of the different chelating agents versus a blank on final soil chromium concentration, the results were not so conclusive globally (0,5% less soil chromium in trials in which the first crop was wheat followed by corn, and 2% in trials in which the first and the second crop was corn). In each group, the most "effective" chelating agent differed: EDDS for the first set, MGDA for the second one.The addition of chelating compounds in the soil could result in an increasing of the Cr oxidizable fraction mainly composed by Cr species associated to the organ mineral complexes.

Effects on health, performance, and tissue residues of the ionophore antibiotic salinomycin in finishing broilers (21 to 38 d).

A study was conducted to evaluate the effects of feeding salinomycin at the recommended prophylactic level, and at 2 and 3 times this level, to finishing male broilers (d 21 to 38). Four treatment groups were given the experimental diets containing 0, 60, 120, or 180 parts per million (ppm) salinomycin from d 21 to 38. Performance, relative organ weights, selected serum enzymes, and salinomycin residues in liver, muscle, and serum were determined. Salinomycin supplementation had no effect on body weight, feed intake, or feed conversion, and caused no overt signs of toxicity. After a week of being fed the salinomycin diets, the serum activity of aspartate aminotransferase was significantly increased in chickens fed 180 ppm compared with controls. These birds also showed microscopic lesions in breast and thigh muscles, but not in cardiac muscle. Salinomycin residues were not detected by high-performance liquid chromatography coupled to tandem mass spectrometry in liver or muscle samples from the birds fed 0, 60, or 120 ppm salinomycin. However, chickens fed 180 ppm salinomycin had detectable levels in liver and muscle above the maximum residue level of 5 µg/kg established by the European Union. All birds fed salinomycin had salinomycin in their sera with levels ranging from N.D. (not detected) in the controls to 24.4 ± 7.9, 61.4 ± 18.9, and 94.5 ± 9.1 µg/L for salinomycin dietary levels of 60, 120, and 180 ppm, respectively. Serum salinomycin concentration was linearly related with salinomycin content in feed (y = 0.584x - 10, r2 = 0.999). The results showed that even at 3 times the prophylactic level, salinomycin does not induce clinical toxicosis or mortality. No salinomycin residues were found in edible tissues at the recommended dietary level or at 2 times this level. However, salinomycin was detected in serum regardless of the dietary level. A simple method for salinomycin determination in serum is described which can be used as a marker of exposure and/or to predict levels in the diet.

Reductive dechlorination in recalcitrant sources of chloroethenes in the transition zone between aquifers and aquitards.

In the transition zone between aquifers and basal aquitards, the perchloroethene pools at an early time in their evolution are more recalcitrant than those elsewhere in the aquifer. The aim of this study is to demonstrate that the biodegradation of chloroethenes from aged pools (i.e., pools after decades of continuous groundwater flushing and dissolution) of perchloroethene is favored in the transition zone. A field site was selected where an aged pool exists at the bottom of a transition zone. Two boreholes were drilled to obtain sediment and groundwater samples to perform chemical, isotopic, molecular, and clone library analyses and microcosm experiments. The main results were as follows: (i) the transition zone is characterized by a high microbial richness; (ii) reductively dechlorinating microorganisms are present and partial reductive dechlorination coexists with denitrification, Fe and Mn reduction, and sulfate reduction; (iii) reductively dechlorinating microorganisms were also present in the zone of the aged pool; (v) the high concentrations of perchloroethene in this zone resulted in a decrease in microbial richness; (vi) however, the presence of fermenting microorganisms supplying electrons for the reductively dechlorinating microorganisms prevented the reductive dechlorination to be inhibited. These findings suggest that biostimulation and/or bioaugmentation could be applied to promote complete reductive dechlorination and to enhance the dissolution of more nonaqueous phase liquids (DNAPL).

Processes controlling the fate of chloroethenes emanating from DNAPL aged sources in river-aquifer contexts.

This work dealt with the physical and biogeochemical processes that favored the natural attenuation of chloroethene plumes of aged sources located close to influent rivers in the presence of co-contaminants, such as nitrate and sulfate. Two working hypotheses were proposed: i) Reductive dechlorination is increased in areas where the river-aquifer relationship results in the groundwater dilution of electron acceptors, the reduction potential of which exceeds that of specific chloroethenes; ii) zones where silts predominate or where textural changes occur are zones in which biodegradation preferentially takes place. A field site on a Quaternary alluvial aquifer at Torelló, Catalonia (Spain) was selected to validate these hypotheses. This aquifer is adjacent to an influent river, and its redox conditions favor reductive dechlorination. The main findings showed that the low concentrations of nitrate and sulfate due to dilution caused by the input of surface water diminish the competition for electrons between microorganisms that reduce co-contaminants and chloroethenes. Under these conditions, the most bioavailable electron acceptors were PCE and metabolites, which meant that their biodegradation was favored. This led to the possibility of devising remediation strategies based on bioenhancing natural attenuation. The artificial recharge with water that is low in nitrates and sulfates may favor dechlorinating microorganisms if the redox conditions in the mixing water are sufficiently maintained as reducing and if there are nutrients, electron donors and carbon sources necessary for these microorganisms.

Effect of compost and biodegradable chelate addition on phytoextraction of copper by Oenothera picensis grown in Cu-contaminated acid soils.

Oenothera picensis plants (Fragrant Evening Primrose) grow in the acid soils contaminated by Cu smelting in the coastal region of central Chile. We evaluated the effects of compost, at application rate of 5 kg m(-2), and biodegradable chelate MGDA (methylglycinediacetic acid), at application rate of 6 mmol plant(-1), on Cu phytoextraction by O. picensis, in field plots. No significant differences were found between treatments regarding aboveground biomass, shoot Cu concentrations and Cu phytoextraction of O. picensis. This lack of effects of the treatments was provoked by the large variability of soil properties, prior to applying of the treatments. The shoot Cu concentration in O. picensis positively and significantly correlated to exchangeable Cu concentration in the soil. Likewise, the aboveground biomass of O. picensis positively and significantly correlated to soil organic matter content. The Cu phytoextraction by O. picensis, in turn, positively and significantly correlated to both variables, i.e. exchangeable Cu concentration and organic matter content. The average Cu phytoextraction was 1.1 mg plant(-1), which is equivalent to 90 g ha(-1) at planting rate of 8 plants m(-2). In the chelate treatment, Cu phytoextraction was 2.6±2.1 mg plant(-1), which is equivalent to 212±171 g ha(-1) at planting rate of 8 plants m(-2).

Subsoil heterogeneities controlling porewater contaminant mass and microbial diversity at a site with a complex pollution history.

This study seeks to improve our understanding of the conceptual model of pollutant transport and fate in cases of DNAPL contamination at sites with a complex contamination history. The study was carried out in an unconfined aquifer of alluvial fans in the Tarragona Petrochemical Complex (Spain). Two boreholes were drilled and continuous cores were recovered in order to carry out a detailed core description at centimeter scale and a comprehensive sampling of borehole cores. The biogeochemical heterogeneity at these sites is controlled by the conjunction of lithological, hydrochemical and microbiological heterogeneities. Biodegradation processes of contaminant compounds take place not only at the level of the dissolved fraction in the aquifer but also at the level of the fraction retained in the fine, less conductive materials as shown by the biodegradation haloes of parent and metabolite compounds. Sampling the low-conductivity levels also allowed us to identify compounds, e.g. BTEX, that are the remaining traces of the passage of old contaminant plumes whose sources no longer exist. This enabled us to describe past biogeochemical processes and to partially account for the processes occurring today. Transition zones, characterized by numerous textural changes, constitute ecotones whose biostimulation could be effective in promoting the acceleration of the remediation of the multiple pollution at these sites.

Effect of feeding hens trout by-product meal or tuna fish oil on production parameters and yolk fatty acid profile / Efecto de la alimentación de gallinas con ensilaje de vísceras de trucha o aceite de atún en parámetros productivos y perfil de ácidos grasos en yema de huevo / Efeito da alimentação de galinhas com silagem de vísceras de truta ou óleo de atum nos parâmetros produtivos e o perfil de ácidos graxos na gema de ovo

Objective: a study was conducted to evaluate two sources of omega-3 (n-3) fatty acid enrichment, namely a trout by-product meal (TBPM) and tuna fish oil (TFO), as potential sources for egg yolk n-3 enrichment. Methods: Seventy-27 week old commercial layers were assigned to each of seven dietary treatments, as follows. Group 1: control; group 2: 5% TBPM; group 3: 10% TBPM; group 4: 15% TBPM; group 5: 20% TBPM; group 6: 2% TFO; and group 7: 3% TFO. The experimental diets were fed for 28 days. Results: no effect on production parameters was caused by the experimental diets. All diets containing TBPM or TFO significantly (p<0.05) increased n-3 egg yolk fatty acid content. Dietary levels of 5-20% TBPM increased egg yolk n-3 content between 1.97 and 3.54 times compared with control eggs. TFO levels of 2% and 3% increased the n-3 egg yolk content 3.37 and 4.13 times, respectively, compared with control eggs. The n-6/n-3 ratio in egg yolk lipids was significantly (p<0.05) decreased by the experimental diets. The n-6/n-3 ratio in control eggs was 16.79 compared with ratios ranging from 4.34 to 8.11 in enriched eggs. Conclusions: the results showed that both TBPM and TFO are good sources of n-3 fatty acid enrichment in eggs. Further studies are required in order to determine the effects of TBPM and TFO inclusion on the organoleptic quality of eggs.

Objetivo: se realizó un estudio para evaluar dos potenciales fuentes de enriquecimiento de ácidos grasos omega-3 (n-3) en yema de huevo: ensilaje de vísceras de trucha (TBPM) y aceite de atún (TFO). Métodos: un total de 70 gallinas de postura de 27 semanas se asignaron a siete tratamientos dietarios, así: grupo 1: control; grupo 2: 5% TBPM; grupo 3: 10% TBPM; grupo 4: 15% TBPM; grupo 5: 20% TBPM; grupo 6: 2% TFO y grupo 7: 3% TFO. Las dietas experimentales se suministraron durante 28 días. Resultados: no se encontraron efectos sobre los parámetros productivos a causa de las dietas experimentales, pero todas las dietas suplementadas con TBPM o TFO causaron un aumento significativo (p<0.05) en el contenido de n-3 de la yema. La suplementación de 5-20% de TBPM causó un incremento de n-3 de 1.97 a 3.54 veces, comparado con el contenido de n-3 de los huevos control. La suplementación de 2% y 3% de TFO incrementó en contenido de n-3 en 3.37 y 4.13 veces, respectivamente. La relación n-6/n-3 en los lípidos de la yema aumentó significativamente en las dietas experimentales siendo esta relación de 16.79 en los huevos control y de 4.34-8.11 en los huevos de gallinas suplementadas con las fuentes de n-3. Conclusiones: los resultados del presente estudio demuestran que tanto el TBPM como el TFO constituyen fuentes apropiadas de enriquecimiento de huevos con ácidos grasos n-3. Se requieren más estudios para determinar los efectos de estas materias primas en la calidad organoléptica del huevo.

Objetivo: Foi realizado um estudo para avaliar duas fontes potenciais de enriquecimento de ômega-3 (n-3) na gema de ovo: silagem de vísceras de truta (TBPM) e óleo de atum (TFO). Métodos: Um total de 70 galinhas poedeiras de 27 semanas, foram atribuídas a sete tratamentos dietéticos: grupo 1: controle, grupo 2: 5%TBPM, grupo 3: 10% TBPM, grupo 4: 15% TBPM, grupo 5: 20% TBPM, grupo 6: 2% TFO e grupo 7: TFO 3%. As dietas experimentais foram subministradas durante 28 dias. Resultados: Não foram encontradas diferencias nos parâmetros de produção por causa das dietas experimentais, mas todas as dietas suplementadas com TFO ou TBPM causaram um aumento significativo (p<0.05) no conteúdo de n-3 da gema. A suplementação de 5-20% de TBPM causou um aumento de n-3 de 1.97 a 3.54 vezes, em comparação com o conteúdo de n-3 do controle. A suplementação de 2% e 3% de TFO aumentou o conteúdo de n-3 em 3.37 e 4.13 vezes, respectivamente. A relação n-6/n-3 nos lipídios da gema aumentou significativamente nas dietas experimentais, sendo esta relação de 16.79 nos ovos do controle e de 4.43 a 8.11 em ovos de galinha suplementados com fontes de n-3. Conclusões: Os resultados deste estudo demonstram que o TFO e o TBPM são fontes apropriadas de enriquecimento de ovos com n-3 ácidos graxos. Mais estudos são necessários para determinar os efeitos dessas matérias primas na qualidade organoléptica do ovo.

Biodegradable chelate enhances the phytoextraction of copper by Oenothera picensis grown in copper-contaminated acid soils.

Oenothera picensis plants (Fragrant Evening Primrose) grow in the acid soils contaminated by copper smelting in the coastal region of central Chile. We evaluated the effects of the biodegradable chelate MGDA (methylglycinediacetic acid) on copper extraction by O. picensis and on leaching of copper through the soil profile, using an ex situ experiment with soil columns of varying heights. MGDA was applied in four rates: 0 (control), 2, 6 and 10 mmol plant(-1). MGDA application significantly increased biomass production and foliar concentration, permitting an effective increase in copper extraction, from 0.09 mg plant(-1) in the control, to 1.3mg plant(-1) in the 6 and 10 mmol plant(-1) treatments. With 10 mmol plant(-1) rate of MGDA, the copper concentration in the leachate from the 30 cm columns was 20 times higher than in the control. For the 60 cm columns, copper concentration was 2 times higher than the control. It can be concluded that at increased soil depths, copper leaching would be minimal and that MGDA applications at the studied rates would not pose a high risk for leaching into groundwater. It can thus be stated that applications of MGDA are an effective and environmentally safe way to improve copper extraction by O. picensis in these soils.

Analysis of alcohol ethoxylates and alkylamine ethoxylates in agricultural soils using pressurised liquid extraction and liquid chromatography-mass spectrometry.

Nonionic surfactants e.g. alcohol ethoxylates (AEOs) and alkylamine ethoxylates (ANEOs) are commonly utilised as adjuvants in pesticide formulations to enhance their effectiveness. In this study, analytical methods for AEO and ANEO determination in soil samples using pressurised liquid extraction (PLE) were developed and used in connection with LC-MS. The recovery of the method, which was highly dependent on the soil properties, varied in the range 47-106% for AEO and 27-109% for ANEO. Detection limits (LOD) were 7-13 microg kg(-1) for AEO and 24-43 microg kg(-1) for ANEO. The developed method has been applied to determine AEOs and ANEOs in surface soil samples from fields sprayed with glyphosate herbicides. Tallowalkylamine ethoxylates (an ANEO) were detected in the soil before and after pesticide application, with increasing concentrations after treatment. The highest concentration in the soil samples was observed for the ANEO homologues with the longest ethoxy chains; in the clay soil the concentration decreased with the length of the ethoxy chain. ANEOs added to pesticide formulations as a technical mixture will, as demonstrated in this study, behave as individual homologues, which is reflected in their behaviour in the environment.