Exposure to carbonyl compounds in charcoal production plants in Bahia, Brazil

Studies have investigated the exposure levels of carbonyl compounds (CC) in the indoor and outdoor air of homes, vehicles, workplaces, urban and industrial areas, and rural sites. However, an investigation of these emissions and occupational exposure to CC in charcoal production facilities has not been previously conducted. The objective of this study was to measure the atmospheric concentrations of several CC to assess the exposure of workers of two charcoal plants located north of Salvador, Bahia, Brazil. Stationary and personal samples were collected using Sep-Pak® C18 cartridges that were coated with a 0.2 % acidic solution of 2,4-dinitrophenylhydrazine. The quantification of the resulting 2,4-dinitrophenylhydrazone derivatives was conducted using a high-performance liquid chromatography system with UV detection. In the personal samples, the concentrations of formaldehyde, acetaldehyde, propanone, furfural, and C4 isomers (n-butanal-isobutanal-butanone) ranged from 12 to 139, 38 to 165, 136 to 483, 39 to 114, and 63 to 132 μg?m^?3, respectively. In the stationary samples, the concentrations of these CC ranged from 20 to 160, 111 to 284, 328 to 644, 70 to 163, and 100 to 176 μg?m^?3, respectively. When compared to the occupational exposure limits for 8 h, the concentrations of formaldehyde were often greater than the levels recommended by the American National Institute for Occupational Safety and Health, which indicates a health risk for charcoal workers. These results are the first reported concerning the occupational exposure to CC in charcoal plants.     

Glutathione and its dependent enzymes’ modulatory responses to toxic metals and metalloids in fish—a review

Toxic metals and metalloid are being rapidly added from multiple pathways to aquatic ecosystem and causing severe threats to inhabiting fauna including fish. Being common in all the type of aquatic ecosystems such as freshwater, marine and brackish water fish are the first to get prone to toxic metals and metalloids. In addition to a number of physiological/biochemical alterations, toxic metals and metalloids cause enhanced generation of varied reactive oxygen species (ROS) ultimately leading to a situation called oxidative stress. However, as an important component of antioxidant defence system in fish, the tripeptide glutathione (GSH) directly or indirectly regulates the scavenging of ROS and their reaction products. Additionally, several other GSH-associated enzymes such as GSH reductase (GR, EC 1.6.4.2), GSH peroxidase (EC 1.11.1.9), and GSH sulfotransferase (glutathione-S-transferase (GST), EC 2.5.1.18) cumulatively protect fish against ROS and their reaction products accrued anomalies under toxic metals and metalloids stress conditions. The current review highlights recent research findings on the modulation of GSH, its redox couple (reduced glutathione/oxidised glutathione), and other GSH-related enzymes (GR, glutathione peroxidase, GST) involved in the detoxification of harmful ROS and their reaction products in toxic metals and metalloids-exposed fish.     

Effects of glyphosate on the non-target leaf beetle Cerotoma arcuata (Coleoptera: Chrysomelidae) in field and laboratory conditions

This study aimed to assess the glyphosate application effects on the Cerotoma arcuata Oliver (Coleoptera: Chrysomelidae) population in glyphosate-resistant soybean crops. Field studies were conducted with glyphosate and the insecticide endosulfan to observe the effects of these pesticides on C. arcuata, on its damages in the crop and on the populations of natural enemies in glyphosate-resistant soybean crops. Moreover, the lethal and behavioral sublethal response of C. arcuata to glyphosate and endosulfan was conducted in the laboratory. The results of the field and laboratory experiments showed that glyphosate caused moderate toxicity and high irritability in C. arcuata and that endosulfan caused high toxicity and irritability. Therefore, the direct effect of glyphosate on C. arcuata was negative and does not explain the population increases of this pest in glyphosate-resistant soybean. However, the glyphosate also decreased the density of predators. Thus, the negative effect of glyphosate on the predators may be related to population increases of C. arcuata in glyphosate-resistant soybean crops, however, more studies are needed to better evidence this relationship. This study suggests that glyphosate can impact other non-target organisms, such as herbivorous insects and natural enemies and that the use of this herbicide will need to be carefully stewarded to prevent potential disturbances in beneficial insect communities in agricultural systems.     

Assessing dam implementation impact on threatened carnivores: the case of Alqueva in SE Portugal

Large dam construction in water deficient areas is a management decision often controversial. Besides providing water storage, economical benefits, and a source of renewable energy, the construction and flooding caused by large dams cause disruptions in natural systems. We monitored the pre- and post-Alqueva dam impacts on the threatened carnivore species (polecat, otter, wildcat and Iberian lynx) populations in SE Portugal, and assessed which factors mostly contribute to post-dam distribution. Major short term impacts of large dams are: (1) increase in accessibility and human presence; (2) movement of heavy machinery and dam-workers; (3) deforestation with habitat loss and fragmentation; (4) change from lotic to lentic system; (5) lower prey availability and harsher capture; and (6) changes in land use adjacent to the reservoir. Thus, the response to those impacts can be predicted as a decline of polecat, wildcat and lynx distribution ranges, and a recovery of the otter from the severe short term impacts. Our results corroborate this hypothesis for all the species, especially during deforestation/early flooding. Otter's distribution range increased in the phase of greater impact, with a subsequent decrease with flooding. Our results suggest carnivores used "escape" areas with favourable habitat and prey conditions, however, the areas with higher probability of species presence decreased by two fold showing a drastic range reduction. To ensure populations' survival of these charismatic threatened carnivore populations of Mediterranean landscapes of south-east Portugal, we propose continuing the monitoring program and the development of a conservation program for the subsisting areas of optimal and suboptimal habitats.     

Characterization and validation of a Portuguese natural reference soil to be used as substrate for ecotoxicological purposes

This study describes the first attempt to validate a Portuguese natural soil (PTRS1) to be used as reference soil for ecotoxicological purposes, aimed to both: (i) obtain ecotoxicological data for the derivation of Soil Screening Values (SSVs) with regional relevance, acting as a substrate to be spiked with ranges of concentrations of the chemicals under evaluation and (ii) act as control and as substrate for the dilution of contaminated soils in ecotoxicological assays performed to evaluate the ecotoxicity of contaminated soils, in tier 2 of risk assessment frameworks, applied to contaminated lands. The PTRS1 is a cambisol from a granitic area integrated in the Central Iberian Zone. After chemical characterization of the soil in terms of pseudo-total metals, PAHs, PCBs and pesticide contents, it was possible to perceive that some metals (Ba, Be, Co, Cr and V) surpass the Dutch Target Values (Dtvs) corrected for the percentage of organic matter and clay of the PTRS1. Nevertheless, these metals displayed total concentrations below the background total concentrations described for Portuguese soils in general. The same was observed for aldrin, endosulfan I, endosulfan II, heptachlor epoxide, and heptachlor; however the Dtvs corrected become negligible. The performance of invertebrate and plant species, commonly used in standard ecotoxicological assays, was not compromised by both soil properties and soil metal contents. The results obtained suggest that the PTRS1 can be used as a natural reference soil in ecotoxicological assays carried out under the scope of ecological risk assessment.     

Chromium fractionation and speciation in natural waters

It is common for leather industries to dump chromium-contaminated effluent into rivers and other bodies of water. Thus, it is crucial to know the impacts caused by this practice to the environment. A study on chromium partitioning and speciation, with determination at trace levels, was carried out in a potentially contaminated creek. Chromium fractionation and speciation was performed using a flow-injection preconcentration system and detection by flame atomic absorption spectrometry. High levels of this element were found in the particulate material (449-9320 mg kg(-1)), which indicates its compatibility with this fraction. The concentration of Cr(iii) in the water samples collected ranged from 5.2-105.2 μg L(-1). Cr(vi) was always below of the DL (0.3 μg L(-1)). Chromium accumulation observed in the sediment (873-1691 mg kg(-1)) may confirm contamination due to the long term release of contaminated effluents in the creek.     

Development of a robust chromatographic method for the detection of chlorophenols in cork oak forest soils

A major concern for the cork and wine industry is ‘cork taint’ which is associated with chloroanisoles, the microbial degradation metabolites of chlorophenols. The use of chlorophenolic compounds as pesticides within cork forests was prohibited in 1993 in the European Union (EU) following the introduction of industry guidance. However, cork produced outside the EU is still thought to be affected and simple, robust methods for chlorophenol analysis are required for wider environmental assessment by industry and local environmental regulators. Soil samples were collected from three common-use forests in Tunisia and from one privately owned forest in Sardinia, providing examples of varied management practice and degree of human intervention. These provided challenge samples for the optimisation of a HPLC-UV detection method. It produced recoveries consistently >75 % against a soil CRM (ERM-CC008) for pentachlorophenol. The optimised method, with ultraviolet (diode array) detection is able to separate and quantify 16 different chlorophenols at field concentrations greater than the limits of detection ranging from 6.5 to 191.3 μg/kg (dry weight). Application to a range of field samples demonstrated the absence of widespread contamination in forest soils at sites sampled in Sardinia and Tunisia.     

Offshore drilling effects in Brazilian SE marine sediments: a meta-analytical approach

The exploration and production of oil and gas reserves often result to drill cutting accumulations on the seafloor adjacent to drill locations. In this study, the detection of drilling influence on marine sediments was performed by meta-analytical comparison between data from pre- and post-drilling surveys undertaken in offshore Campos Basin, southeast of Brazil. Besides this overall appraisal on the geochemical variables, a multivariate assessment, considering only the post-drilling data, was performed. Among the variables, fines content, carbonates, total organic carbon, barium, chromium, copper, iron, manganese, nickel, lead, vanadium, zinc, and total petroleum hydrocarbons, only barium, copper, and hydrocarbons were related to drilling impacts. In relation to the point of discharge, relative elevated levels in the post-drilling campaigns were observed preferentially up to 500 m in the northeast and southwest directions, associated to the Brazil Current-predominant direction. Other distributed concentrations in the surroundings seem to indicate the dilution and dispersion of drilling waste promoted by meteoceanographic factors.     

Utilization of UV‐A and UV‐C radiation in advanced oxidation processes with the intention of removing color and organic matter from the gross leachate of a stabilized sanitary landfill

The present work investigated color and biochemical oxygen demand (COD) removal from treated landfill leachate via advanced oxidative processes (AOPs) artificially emitted. The AOP H₂O₂/UV, TiO₂/UV, and photolysis were tested in two bench‐scale photoreactors: The first one with UV‐C lamp and the other with UV‐A lamp associated or not with coagulation / flocculation pretreatment. Crude leachate samples with pH ranging from 8 to 3 were used, and time varied in 30, 45, and 60 minutes. Experiments were performed in two stages: step 1 with a 20 mL volume from each sample and step 2 with repetition of the best results from the previous step, adopting the 150 mL volume. In step 1, the AOP applied in the crude leachate sample showed the best results, standing out H₂O₂/UV‐C with 30 minutes and TiO₂/UV‐A with 60 minutes. In step 2, H₂O₂/UV‐C had a 60% color removal and 25% COD reduction, while TiO₂/UV‐A had a 10% color removal and 20% COD reduction. Therefore, the H₂O₂/UV‐C process was the most efficient, because the complex characteristics of the effluent interfered in the TiO₂/UV‐A efficiency, but it is necessary to eliminate the process interferences. The use of artificial radiation is a viable alternative; however, it can be costly, being relevant in the associations between processes with artificial UV and solar UV, as the natural radiation becomes more attractive and allows the process operating costs reduction.     

Evaluation of an approach for the characterization of reactive and available pools of 20 potentially toxic elements in soils: part II--solid-solution partition relationships and ion activity in soil solutions

To assess environmental risks related to contaminants in soil it is essential to predict the available pool of inorganic contaminants at regional scales, accounting for differences between soils from variable geologic and climatic origins. An approach composed of a well-accepted soil extraction procedure (0.01 M CaCl(2)) and empirical Freundlich-type models in combination with mechanistically based models which to date have been used only in temperate regions was applied to 136 soils from a South European area and evaluated for its possible general use in risk assessment. Empirical models based on reactive element pools and soil properties (pH, organic carbon, clay, total Al, Fe and Mn) provided good estimations of available concentrations for a broad range of contaminants including As, Ba, Cd, Co, Cu, Hg, Mo, Ni, Pb, Sb, Se and Zn (r(2): 0.46-0.89). The variation of the pools of total Al in soils expressed the sorptive capacity of aluminosilicates and Al oxides at the surfaces and edges of clay minerals better than the actual variability of clay contents. The approach has led to recommendations for further research with particular emphasis on the impact of clay on the solubility of As and Sb, on the mechanisms controlling Cr and U availability and on differences in binding properties of soil organic matter from different climatic regions. This study showed that such approach may be included with a good degree of certainty for first step risk assessment procedures to identify potential risk areas for leaching and uptake of inorganic contaminants in different environmental settings.