Anaerobic PAH degradation in soil by a mixed bacterial consortium under denitrifying conditions

Polycyclic aromatic hydrocarbons (PAHs) are one of the main classes of contaminants in the terrestrial environment. Concentrations of biphenyl, fluorene, phenanthrene and pyrene were added to soil samples in order to investigate the anaerobic degradation potential of PAHs under denitrifying conditions. A mixed population of microorganisms obtained from a paddy soil was incubated for 20 days in anaerobic conditions in the presence of soil alone or with nitrate, adding, as electron donors, PAHs and, in some samples, glucose or acetate. At regular time intervals oxidation-reduction potential, PAHs concentration, microbial ATP and nitrate concentration into the solution were measured. Degradation trends for each hydrocarbon are similar under all conditions, indicating that the molecular conformation prevails over other parameters in controlling the degradation. Poor degradation results were obtained when PAHs were the only organic matter available for the inoculum, thus confirming the recalcitrance to degradation of these compounds. Biodegradation was influenced by the addition of other carbon sources. As better degradation results were generally obtained when acetate or glucose were added, the hypothesis of a co-metabolic enhancement of PAH biodegradation seems likely. Thus, anaerobic biodegradation of PAHs studied, biphenyl, fluorene, phenanthrene and pyrene, seems to be possible both through fermentative and respiratory metabolism, provided that low molecular weight co-metabolites and suitable electron acceptors (nitrate) are present.     

Electrochemical degradation of chlorophenoxy and chlorobenzoic herbicides in acidic aqueous medium by the peroxi-coagulation method

The degradation of 4-chlorophenoxyacetic acid (4-CPA), 4-chloro-2-methylphenoxyacetic acid (MCPA), 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) as chlorophenoxy herbicides, as well as of 3,6-dichloro-2-methoxybenzoic acid (dicamba) as chlorobenzoic herbicide, has been studied by peroxi-coagulation. This electrochemical method yields a very effective depollution of all compounds in acidic aqueous medium of pH 3.0 working under pH regulation, since they are oxidized with hydroxyl radicals produced from Fenton's reaction between Fe(2+) and H(2)O(2) generated by the corresponding Fe anode and O(2)-diffusion cathode. Their products can then be removed by mineralization or coagulation with the Fe(OH)(3) precipitate formed. Both degradative paths compete at low currents, but coagulation predominates at high currents. The peroxi-coagulation process of dicamba at I>or=300 mA leads to more than 90% of coagulation, being much more efficient than its comparative electro-Fenton treatment with a Pt anode and 1 mM Fe(2+), where only mineralization takes place. For the chlorophenoxy compounds, electro-Fenton gives a slightly lower depollution than peroxi-coagulation, because more easily oxidable products are produced. Oxidation of chlorinated products during peroxi-coagulation is accompanied by the release of chloride ion to the solution. The efficiency of this method decreases with increasing electrolysis time and current. The decay of all herbicides follows a pseudo-first-order reaction, with a similar constant rate for 4-CPA, MCPA, 2,4-D and 2,4,5-T, and a higher value for dicamba.     

Evaluation of boron removal from water by hydrotalcite-like compounds

Layered double hydroxides (LDHs) or hydrotalcite (HT)-like compounds with different kinds of metal ions (Mg-Al and Mg-Fe) in the brucite-like sheets were prepared and their adsorption properties were studied in the boron removal from aqueous solution under laboratory conditions. The hydrotalcites were synthesized by the coprecipitation method and were characterized by chemical analyses, X-ray diffraction (XRD), Fourier Transform infrared spectroscopy (FTIR) and specific surface area measurements (BET). The affinity of these materials with a mixture of B(OH)(3) and B(OH)(4)(-) was studied as a function of contact time, initial pH of the solutions, HT quantity and B concentration (adsorption isotherms). It was found that 120 min is enough time for the equilibrium state to be reached in boron adsorption. Boron removal was independent of the initial pH of the solutions because of the high buffering capacity of the LDHs. On the other hand, the adsorption capacity increases with increasing the adsorbent quantity. The adsorption isotherms, described by the Langmuir model, are of L-type, suggesting that B(OH)(4)(-) is adsorbed preferentially on HT-like materials. Besides, Mg-Al hydrotalcites showed higher adsorption capacity than Mg-Fe. We proposed that in Mg-Al hydrotalcites, the boron removal occurs by both adsorption on external surface and ion exchange, whereas for Mg-Fe it occurs only by surface adsorption. After treatment of a solution containing 5.2 mgBl(-1) with Mg-Al hydrotalcites the final boron concentration reached the recommended limit by WHO for drinking water (0.5 mgl(-1)).     

In situ assays with tropical cladocerans to evaluate edge-of-field pesticide runoff toxicity

Tropical regions’ economy is usually based on agriculture, which involves an intensive use, and even frequent overuse, of pesticides. Nevertheless, not much research has been done on the impact of pesticides on tropical aquatic ecosystems, which are often contaminated by runoff-related pesticide inputs due to unpredictable and torrential rainfalls. This study aimed to: (i) adapt and evaluate a short-term sublethal in situ assay using post-exposure feeding as an endpoint, to the tropical cladoceran species Diaphanosoma brachyurum (collected at the Pedra do Cavalo dam in the Paraguaçu River basin, Bahia, Brazil), and, (ii) assess the role of the standard species Daphnia magna as an adequate laboratory surrogate. Lethal and sublethal (post-exposure feeding) responses were assessed for the two species. To evaluate these responses under environmentally realistic exposure conditions, a runoff event was simulated in an agricultural area previously contaminated with different deltamethrin concentrations. The resultant runoff water was used to set up microcosms with different dilutions, simulating the entrance of runoff water in an adjacent lentic system. An in situ assay with D. brachyurum was performed inside the microcosms, allowing to discriminate the effects due to deltamethrin from those due to other potential stressors associated with the experimental design (e.g. organism handling, load of suspended particles, microcosm design). Water samples were collected from microcosms to conduct a laboratory assay with D. magna. The in situ methodologies revealed to be suitable to conduct assays with D. brachyurum under tropical conditions, since all exposed organisms were successfully retrieved from the chambers. Furthermore, none of the potential stressors associated with the experimental design influenced the daphnids’ performance. The tropical cladoceran species, exposed under more realistic conditions, revealed to be more sensitive than the laboratory standard species: lethal effects were only observed for D. brachyurum and sublethal effects were noticed at a lower deltamethrin concentration for this species than for D. magna.     

Assessing farming eco-efficiency: a Data Envelopment Analysis approach

This paper assesses farming eco-efficiency using Data Envelopment Analysis (DEA) techniques. Eco-efficiency scores at both farm and environmental pressure-specific levels are computed for a sample of Spanish farmers operating in the rain-fed agricultural system of Campos County. The determinants of eco-efficiency are then studied using truncated regression and bootstrapping techniques. We contribute to previous literature in this field of research by including information on slacks in the assessment of the potential environmental pressure reductions in a DEA framework. Our results reveal that farmers are quite eco-inefficient, with very few differences emerging among specific environmental pressures. Moreover, eco-inefficiency is closely related to technical inefficiencies in the management of inputs. Regarding the determinants of eco-efficiency, farmers benefiting from agri-environmental programs as well as those with university education are found to be more eco-efficient. Concerning the policy implications of these results, public expenditure in agricultural extension and farmer training could be of some help to promote integration between farming and the environment. Furthermore, Common Agricultural Policy agri-environmental programs are an effective policy to improve eco-efficiency, although some doubts arise regarding their cost-benefit balance.     

Waste materials for activated carbon preparation and its use in aqueous-phase treatment: a review

Commercial activated carbon is a preferred adsorbent for the removal of micropollutants from the aqueous phase; however, its widespread use is restricted due to high associated costs. To decrease treatment costs, attempts have been made to find inexpensive alternative activated carbon (AC) precursors, such as waste materials. Some reviews report the use of waste materials for the preparation of AC; however, these studies are restricted to either type of wastes, preparation procedures, or specific aqueous-phase applications. The present work reviews and evaluates literature dedicated both to the preparation of AC by recycling different types of waste materials and also to its application in various aqueous-phase treatments. It is clear that conventional (from agriculture and wood industry) and non-conventional (from municipal and industrial activities) wastes can be used to prepare AC, that can be applied in various aqueous treatment processes, namely to remove organic pollutants, dyes, volatile organic compounds, and heavy metals. Moreover, high surface areas can be obtained using either physical or chemical activation; however, combined treatments might enhance the surface properties of the adsorbent, therefore increasing its adsorption capacity. It is evident from the revision made that AC prepared from both conventional and non-conventional wastes might effectively compete with the commercial ones. This happens mostly when the activation procedures are optimized considering both the raw material used to produce the carbons and the contaminants to be removed.     

An Assessment of Oil Pollution in the Coastal Zone of Patagonia,Argentina

The Patagonian coast is considered a relatively pristine environment. However, studies conducted along coastal Patagonia have showed hydrocarbon pollution mostly concentrated at ports that have fishing, oil loading, general merchant, and/or tourist activities. A high value of total aliphatic hydrocarbons (TAH) was found at the Rawson fishing port (741 μg/g dw). In other ports with and without petroleum-related activities, hydrocarbon values were approximately 100 μg/g dw. The highest values for TAH and total aromatic hydrocarbons (TArH) were found in Faro Aristizábal, north of San Jorge gulf (1304 and 737 μg/g dw, respectively). This is very likely the result of petroleum-related activities at the Comodoro Rivadavia, Caleta Cordova, and Caleta Olivia ports located within this gulf. In other coastal areas away from potential anthropogenic sources, hydrocarbon values were less than 2 and 3 μg/g dw for TAH and TArH, respectively. This review of published and unpublished information suggests that ports are important oil pollution sources in the Patagonian coast. More detailed studies are needed to evaluate the area affected by port activities, to understand the mechanisms of hydrocarbon distribution in surrounding environments, and to assess bioaccumulation in marine organisms. Despite that some regulations exist to control oil pollution derived from port and docked vessel activities, new and stricter management guidelines should be implemented.     

Evaluation of the use of bioaccumulation and biological effects tools in caged mussels,within the European Water Framework Directive

Bioaccumulation and biological effects of pollution were assessed in mussels (Mytilus galloprovincialis) caged for one month at three sites in the Oiartzun estuary (south-eastern Bay of Biscay, Spain) with the aim of evaluating their usefulness within the investigative monitoring defined in the European Union Water Framework Directive (WFD). The highest concentrations of organic contaminants determined in mussels' tissue were detected towards the inner part of the estuary but no gradient pattern was found for metal bioaccumulation. Population fitness responses measured as condition index, stress on stress and gonad index were similar in all caged mussels and did not follow the organic pollution gradient. However, biomarkers determined at tissue, cell and protein level (histopathology, micronuclei frequency, malondialdehyde levels and vitellogenin-like protein levels) revealed a higher stress syndrome at the inner part of the estuary showing signs of genotoxicity, oxidative stress and endocrine disruption. Overall, the integrated chemical–biological approach in connection with mussel caging technique proved to be a useful tool to assess environmental pollution, allowing a better understanding of the cause–effect relationship within the investigative monitoring defined in the WFD.     

Finished leather waste chromium acid extraction and anaerobic biodegradation of the products

Due to the amounts of chromium in the leachate resulting from leather leaching tests, chromium sulfate tanned leather wastes are very often considered hazardous wastes. To overcome this problem, one option could be recovering the chromium and, consequently, lowering its content in the leather scrap. With this objective, chromium leather scrap was leached with sulfuric acid solutions at low temperature also aiming at maximizing chromium removal with minimum attack of the leather matrix. The effects of leather scrap dimension, sulfuric acid and sodium sulfate concentration in the solutions, as well as extraction time and temperature on chromium recovery were studied, and, additionally, organic matrix degradation was evaluated. The best conditions found for chromium recovery were leather scrap conditioning using 25 mL of concentrated H₂SO₄/L solution at 293 or 313 K during 3 or 6 days. Under such conditions, 30–60 ± 5% of chromium was recovered and as low as 3–6 ± 1% of the leather total organic carbon (TOC) was dissolved. Using such treatment, the leather scrap area and volume are reduced and the residue is a more brittle material showing enhanced anaerobic biodegradability. Although good recovery results were achieved, due to the fact that the amount of chromium in eluate exceeded the threshold value this waste was still hazardous. Thus, it needs to be methodically washed in order to remove all the chromium de-linked from collagen.