Microbial degradation of the benzonitrile herbicides dichlobenil, bromoxynil and ioxynil in soil and subsurface environments--insights into degradation pathways, persistent metabolites and involved degrader organisms

The benzonitriles dichlobenil, bromoxynil and ioxynil are important broad-spectrum or selective herbicides used in agriculture, orchards and public areas worldwide. The dichlobenil metabolite 2,6-dichlorobenzamide is the most frequently encountered groundwater contaminant in Denmark, which suggests that the environmental fate of these three structurally related benzonitrile herbicides should be addressed in detail. This review summarises the current knowledge on microbial degradation of dichlobenil, bromoxynil and ioxynil with particular focus on common features of degradation rates and pathways, accumulation of persistent metabolites and diversity of the involved degrader organisms.     

Traffic and catalytic converter - related atmospheric contamination in the metropolitan region of the city of Rio de Janeiro, Brazil

In this work, 24-h PM10 samples were collected in Rio de Janeiro, Brazil, and analysed for trace elements (Cd, Ce, Cu, La, Mo, Ni, Pb, Pd, Rh, Sb and Sn). The sampling was carried out at five locations (Bonsucesso; Centro, downtown city; Copacabana; Nova Igua?u and Sumaré) with different traffic densities and anthropogenic activities. An analytical method based on the EPA method for the determination of trace elements in airborne particulate matter (PM), using ultrasonic-assisted extraction and inductively coupled plasma mass spectrometry (ICP-MS) was applied. Our results suggest that vehicular traffic is the most important source of environmental pollution at the studied sites. The presence of Mo, Pd and Rh in the analysed filters reflects an additional source of pollution caused by the erosion and deterioration of automotive catalytic converters.     

Biochemical effects of clomazone herbicide on piava (Leporinus obtusidens)

This study aims to verify the effects of the clomazone concentration used in rice fields on acetylcholinesterase (AChE), thiobarbituric acid reactive substances (TBARS), protein carbonyl and catalase activity in tissues of piava (Leporinus obtusidens). LC(50)-96h was 5.0 mg L(-1) and the fish were exposed to 1/10 of LC(50)-96 h: 0.5 mg L(-1) of clomazone for 96 and 192h. The same parameters were also assayed after a recovery period of 192 h in clean water. AChE activity was reduced only in the brain and heart of fish exposed for 96 h. AChE activity was decreased in the brain, muscle and heart tissues after 192 h of exposure. After 192 h of recovery period, AChE activity remained diminished in brain and muscle and showed a decrease in eye. However, after 192 h of recovery, AChE activity in heart was recovered. Fish showed increased TBARS levels in brain at all experimental periods. TBARS levels decreased in liver and muscle tissues after 192 h of exposure. The increase in muscle TBARS persisted in fish transferred to clean water. Protein carbonyl in the liver was increased in all periods studied including the recovery period. Catalase activity was reduced during all periods. The present study demonstrates the occurrence of disorders in AChE, TBARS, protein carbonyl and catalase activity in piava. The results also show changes in fish after exposure to an environmentally relevant concentration of clomazone. Most effects observed persisted after the recovery period. Thus, these parameters may be used to monitor clomazone toxicity in fish.     

Effects of a selenium-enriched diet on antioxidant response in adult crayfish (Procambarus clarkii)

Many diets employed in aquaculture are enriched with selenium to improve the diet quality and its conservation. The aim of the study was to investigate the effects of a diet enriched in selenium (1.21 mg kg(-1)) on the antioxidant response of Procambarus clarkii (Girard, 1852). Crayfish fed a diet with lower selenium content (0.30 mg kg(-1)) were the control. Selenium accumulation, enzymatic activities, and total glutathione were evaluated in hepatopancreas of adults of both sexes fed with both diets for 50 days at two experimental times (T(30), T(50) days). Treated females exhibited the highest selenium bioaccumulation during both experimental times, while treated males displayed the highest selenium concentration after 30 days, compared to control crayfish. A sex-related difference was found for the response of the analyzed enzymes in the selenium diet-treated specimens. In fact, superoxide dismutase, glutathione peroxidase and glyoxalase I activities in males were more sensitive compared with females, showing depleted activities in both experimental times. Catalase activity was induced in females (T(50)), while glutathione S-transferase activity was the highest in treated females and the lowest in treated males, compared with own controls. Only glutathione reductase activity and glutathione content showed the same trend in both sexes, which were both lowered in treated specimens, when compared with control crayfish. This result might be due to the effect of selenium toxicity on this freshwater species. Males and females of P. clarkii showed a different susceptibility to the prooxidant effects in a Se-enriched diet.     

Absorption of nitro-polycyclic aromatic hydrocarbons by biomembrane models: effect of the medium lipophilicity

To demonstrate the relationship between the structure of nitro-polycyclic aromatic hydrocarbons and their effect on biomembranes, we have investigated the influence of three structurally different nitro-polycyclic aromatic hydrocarbons, 2-nitrofluorene, 2,7-dinitrofluorene and 3-nitrofluoranthene, on the thermotropic behavior of dimyristoylphosphatidylcholine multilamellar vesicles, used as biomembrane models, by means of differential scanning calorimetry. The obtained results indicate that the studied nitro-polycyclic aromatic hydrocarbons affected the thermotropic behavior of multilamellar vesicles to various extents, modifying the pretransition and the main phase transition peaks and shifting them to lower temperatures. The effect of the aqueous and lipophilic medium on the absorption process of these compounds by the biomembrane models has been also investigated revealing that the process is hindered by the aqueous medium but strongly allowed by the lipophilic medium.     

The assessment of the coastal vulnerability and exposure degree of Gran Canaria Island (Spain) with a focus on the coastal risk of Las Canteras Beach in Las Palmas de Gran Canaria

The Coastal Vulnerability and Exposure Degree (CVED) of the Gran Canaria Island and the coastal risk of Playa de Las Canteras (Las Palmas de G.C.) have been assessed by means of a GIS analysis. The evaluation of coastal vulnerability (H) has been performed by using two different levels of analysis: the first one regarding the entire Island (Coastal Vulnerability Index method - CVI), the second one regarding specifically Las Canteras Beach, selected for its socio-economic importance (Coastal Vulnerability Assessment method - CVA). The application of the CVI method, based on geologic-geomorphologic and meteomarine data easily available, has allowed the regional scale assessment of coastal vulnerability (H) along the Gran Canaria coastline and, therefore, the individuation of more critical coast stretches deserving further analysis. The application of the CVA method, based on more specific morphologic-sedimentary beach features that allow to consider both the beach retreat due to storm surge and the coastal inundation due to run-up on the beach, has provided a large scale detail on the coastal vulnerability of Las Canteras Beach. Socio-economic and damage indexes have been determined for the 15 coastal municipalities included in the study area and, by means of the resulting matrix product, the degree of exposure (E_x) along the Gran Canaria coast has been assessed. Finally, the combination of coastal vulnerability and exposure levels has allowed to obtain the Coastal Vulnerability and Exposure Degree (CVED) for the entire Island and the risk levels that characterize specifically Las Canteras Beach. Major results in terms of CVED highlight prevailing low vulnerability and exposure levels along the western coast, and overall high vulnerability and exposure levels along the eastern coast, from Las Palmas de G.C. to San Bartolomé de Tirajana. The focus made on Playa de Las Canteras has allowed to identify the areas characterized by medium and high risk levels that represent approximately one third (940 m) of the entire beach and are located in its central part. The used two-level analysis approach has proved its efficiency by highlighting the degree of coastal vulnerability along the study coast and, especially, more critical coast stretches (CVI method) such as the Playa de Las Canteras that can be successfully analysed with the CVA approach allowing for a large-scale assessment of risk aspects, essential for a correct definition of priority management strategies. Results obtained with the present study, along with the awareness of the increasing phenomena of coastal erosion and marine flooding arising on the mid-long term due to the effects of global climate change, highlight the need for the competent public administrations of Gran Canaria to develop a strategic approach to coastal management and sustainable development that considers as a whole socio-economic values and natural resources, coastal vulnerability and exposure degree, and risk aspects.     

Human digit ratios depend on birth order and sex of older siblings and predict maternal fecundity

In men, the length ratio of the second to fourth finger (2D:4D) is smaller, while the length of the fourth finger relative to body height (4D:H) is larger than in women. Inter- and intrasexual variations in 2D:4D and 4D:H may depend on variation in fetal androgen and oestrogen environment. As maternal physiology varies with parity and is differentially affected by gestation of either sex, offspring 2D:4D and 4D:H may change according to sex and number of older siblings and may predict subsequent maternal performance. We analysed 2D:4D and 4D:H in Caucasian university students. 2D:4D was smaller and 4D:H was larger in males than in females, but no sexual dimorphism existed in 2D:H. In males, length ratios did not vary with birth order. 2D:4D became more masculine with increasing proportion of males among older siblings, and 2D:4D and 4D:H became more feminine as the number of older sisters increased. In females, length ratios did not vary with the number of older sisters or brothers. 2D:4D was also not related to birth order, but 4D:H became more masculine with birth order. In females, residual maternal fecundity (number of maternal offspring after the participant) decreased as 4D:H became more masculine. These findings are partly consistent with those from previous studies and suggest that maternal fecundity co-varies with length ratios and thus possibly fetal hormone environment of older offspring. 2D:4D and 4D:H may therefore represent powerful tools to investigate the relationships between fetal environment, offspring phenotype and maternal life history at mechanistic and evolutionary levels.     

Simultaneous determination of parathion and p-nitrophenol in vegetable tissues by derivative spectrophotometry

A first derivative spectrophotometric method has been developedfor the determination of parathion and p-nitrophenol in vegetabletissues. Ethanol was used as solvent for extracting the compoundsfrom the tissues and subsequently the samples were evaluated against a vegetable tissue blank, directly by derivative spectrophotometry. The simultaneous determination of these compounds can be carried out using the zero-crossing approach for parathion at 253.0 nm and for p-nitrophenol at 273.1 nm. In the samples each analyte was determined in the presence of one another in the ranges between 4.9 to 3883.5 g g^-1 forparathion and 4.9 to 3285.3 g g^-1 for p-nitrophenol.The detection limits (3) were found to be 1.5 and 1.4 g g^-1 for parathion and p-nitrophenol, respectively. The relative standard deviations were in all instances less than1.8%. The proposed method was applied to the determination ofthe analytes in spiked leafs of corn. The results show a goodrecovery and they are in agreement with those obtained bypolarography.     

Accumulation of metals in the soil of an overland flow wastewater treatment system

Accumulation of Co, Cu, Cr, Mo, Ni, Pb and Zn was evaluated in a soil profile of an overland flow system used for the post-treatment of urban wastewater. A pilot version of the overland flow system received urban wastewater from five up-flow anaerobic filters filled with bamboo (Bambusa tuldoides) rings. The anaerobic effluent was applied as feed over 18 months at rates varying from 7 to 28 L min(-1), to a vegetated slope length covered with Tifton 85 (Cynodon) sp. grass. Soil and plant samples were collected in triplicate from the top to the bottom of the slope. In addition, the soils were sampled at the depths 0-20 and 20-40 cm. The metal concentrations found in the overall system were compared to those obtained in a control area located at the beginning of the slope onto which nothing was applied. A month of monitoring the urban wastewater of Limeira City (S?o Paulo State, Brazil) showed a drastic change in metals concentration due to the irregular discharge of industrial waste. This irregular discharge introduces Cr, Cu, Ni, Pb and Zn into the system used to treat domestic wastewater. The mass balance indicates the accumulation of metals in the soil and the translocation to the plants; also that they could be evapotranspirated, percolated and discharged.     

Distribution of polycyclic aromatic hydrocarbons in urban stormwater in Queensland, Australia

This paper reports the distribution of Polycyclic Aromatic Hydrocarbons (PAHs) in wash-off in urban stormwater in Gold Coast, Australia. Runoff samples collected from residential, industrial and commercial sites were separated into a dissolved fraction (<0.45 μm), and three particulate fractions (0.45-75 μm, 75-150 μm and >150 μm). Patterns in the distribution of PAHs in the fractions were investigated using Principal Component Analysis. Regardless of the land use and particle size fraction characteristics, the presence of organic carbon plays a dominant role in the distribution of PAHs. The PAHs concentrations were also found to decrease with rainfall duration. Generally, the 1- and 2-year average recurrence interval rainfall events were associated with the majority of the PAHs and the wash-off was a source limiting process. In the context of stormwater quality mitigation, targeting the initial part of the rainfall event is the most effective treatment strategy. The implications of the study results for urban stormwater quality management are also discussed.