Organic speciation of atmospheric particles in Alvão Natural Park (Portugal)

PM₁₀ continental rural background aerosols were collected during a summer field campaign (August–September 2006) at Lamas de Ôlo in the upper zone of the Alvão Natural Park, a mountain region of northern Portugal. In addition to the determination of the carbonaceous content by a thermal–optical method, the organic speciation of aerosols was performed by gas chromatography–mass spectrometry in an effort to evaluate photo-oxidation products of biogenic volatile organic compounds and other markers for source characterization. The detailed analysis revealed relatively high concentrations of polyols and short-chain dicarboxylic, tricarboxylic, hydroxycarboxylic, and oxocarboxylic acids, many of which are thought to be indicators of secondary aerosol formation, accounting for about 70% of global chromatographically resolved mass. Major photo-oxidation products of α- and β-pinene have been detected. The tracers for the photo-oxidation of isoprene comprise two diastereoisomeric 2-methyltetrols, C₅-alkene triols, and 2-methylglyceric acid, which have only recently been elucidated. In addition, the occurrence of levoglucosan and other biomass combustion tracers indicates that the site was affected by wildfires. This source contributed to more than 80% of the organic carbon mass during a period of strong forest fire influence.     

Risk of boron and heavy metal pollution from agro-industrial wastes applied for plant nutrition

In this study, the effects of various agro-industrial wastes were investigated when applied to soil alone or in combination with chemical fertilizers, regarding the risks of boron and heavy metal pollution of soils and plants. Nine combinations of production residues from various agro-industries, urban wastes, and mineral fertilizers were applied to potatoes in a field experiment. The content of available boron in the soil differed significantly (p < 0.05) among the applications. Generally, B values were found to be slightly higher when soapstock, prina, and blood were used alone or in combination. Although total Co, Cd, and Pb contents of soils showed no significant differences between the applications, Cr content differed significantly (p < 0.05). No pollution risk was observed in soil in respect to total Co, Cd, Pb, and Cr contents. The amount of boron and heavy metals in leaves showed no significant differences among the applications. Cobalt, Cd, and Pb in leaves were at normal levels whereas Cr was slightly above normal but well under the critical level. Boron was low in tubers and varied significantly between applications such as Co and Cd. The Co content of tubers was high, Cd and Cr contents were below average, and Pb content was between the given values. Some significant correlations were found between soil characteristics and the boron and heavy metal content of soil, leaves, and tubers.     

Modeling 4-Chlorophenol Removal from Aqueous Solutions by Granular Activated Carbon

Since phenols and phenolic compounds in many industrial wastewaters are toxic organic contaminants for humans and aquatic life, to remove these compounds via the most efficient way is very important for environmental remediation treatment. In this context, almost all of the isotherm models (Freundlich, Langmuir, Temkin, Redlich–Peterson, Sips, and Khan) for adsorption in the literature were applied to explain the adsorption mechanism of 4-chlorophenol on activated carbon in this study. Also theoretical modeling data were obtained using model equations; interpolation and analysis of variance were made to compare data by using statistics software. In addition, the thermodynamic and kinetic studies for adsorption mechanism were included in the article. The adsorption of 4-chlorophenol on activated carbon fits well to the pseudo-first-order kinetic model than the pseudo-second-order, intraparticular diffusion and Bangham models. It is also indicated that 4-chlorophenol adsorption by granular activated carbon would be attributed to a type of transition between physical and chemical adsorption rather than a pure physical or chemical adsorption process. As a result, an environmental remediation problem and the adsorption mechanism on activated carbon that can be regarded as a solution to this problem are described and explained using the mathematical models and calculations in this study.     

Assessing the impact of chloroacetanilide herbicides and their metabolites on periphyton in the Leyre River (SW France) via short term growth inhibition tests on autochthonous diatoms

The Leyre River is the main tributary to the Bassin d'Arcachon lagoon. Herbicides belonging to the chloroacetanilide class have been found in the river (S-metolachlor and acetochlor) as well as some of their metabolites at higher concentrations. As the environmental toxicity of these molecules is not well known, ecotoxicological tests have been carried out on river periphyton at different levels of biological diversity: from the clone of one diatom species (Nitzschia nana) to the population of the same species (several clones) up to the multi-specific species community dominated by diatoms. Moreover, tests were performed on diatoms coming from an unpolluted upstream site and from a contaminated downstream site, in order to investigate possible tolerance acquisition to pollutants. The method consisted in measuring diatom growth inhibition at different doses of each substance from the increase of chlorophyll-a concentration after 4 days. It resulted that acetochlor was clearly more toxic than S-metolachlor at all levels of biological diversity. EC(50) values estimated from the tests suggest no effect of contaminants on diatom growth or biomass in the river. The toxicity of the metabolites appeared very low compared to that of their parent compounds. No difference in tolerance to the herbicides was demonstrated between summer diatom communities from the two sites in spite of different specific compositions. However, concerning the populations of N. nana isolated in winter following the highest herbicide concentrations in the river (about 0.5 μg L(-1)), the downstream population showed a higher tolerance to acetochlor but there was no co-tolerance to S-metolachlor. Thus, it appeared that acetochlor represents the highest toxic pressure on periphyton among the other contaminants in the Leyre River.     

Statistical modeling of crystalline silica exposure by trade in the construction industry using a database compiled from the literature

A quantitative determinants-of-exposure analysis of respirable crystalline silica (RCS) levels in the construction industry was performed using a database compiled from an extensive literature review. Statistical models were developed to predict work-shift exposure levels by trade. Monte Carlo simulation was used to recreate exposures derived from summarized measurements which were combined with single measurements for analysis. Modeling was performed using Tobit models within a multimodel inference framework, with year, sampling duration, type of environment, project purpose, project type, sampling strategy and use of exposure controls as potential predictors. 1346 RCS measurements were included in the analysis, of which 318 were non-detects and 228 were simulated from summary statistics. The model containing all the variables explained 22% of total variability. Apart from trade, sampling duration, year and strategy were the most influential predictors of RCS levels. The use of exposure controls was associated with an average decrease of 19% in exposure levels compared to none, and increased concentrations were found for industrial, demolition and renovation projects. Predicted geometric means for year 1999 were the highest for drilling rig operators (0.238 mg m(-3)) and tunnel construction workers (0.224 mg m(-3)), while the estimated exceedance fraction of the ACGIH TLV by trade ranged from 47% to 91%. The predicted geometric means in this study indicated important overexposure compared to the TLV. However, the low proportion of variability explained by the models suggests that the construction trade is only a moderate predictor of work-shift exposure levels. The impact of the different tasks performed during a work shift should also be assessed to provide better management and control of RCS exposure levels on construction sites.     

Soil and vegetation carbon stocks in Brazilian Western Amazonia: relationships and ecological implications for natural landscapes

The relationships between soils attributes, soil carbon stocks and vegetation carbon stocks are poorly know in Amazonia, even at regional scale. In this paper, we used the large and reliable soil database from Western Amazonia obtained from the RADAMBRASIL project and recent estimates of vegetation biomass to investigate some environmental relationships, quantifying C stocks of intact ecosystem in Western Amazonia. The results allowed separating the western Amazonia into 6 sectors, called pedo-zones: Roraima, Rio Negro Basin, Tertiary Plateaux of the Amazon, Javari-Juruá-Purus lowland, Acre Basin and Rondonia uplands. The highest C stock for the whole soil is observed in the Acre and in the Rio Negro sectors. In the former, this is due to the high nutrient status and high clay activity, whereas in the latter, it is attributed to a downward carbon movement attributed to widespread podzolization and arenization, forming spodic horizons. The youthful nature of shallow soils of the Javari-Juruá-Purus lowlands, associated with high Al, results in a high phytomass C/soil C ratio. A similar trend was observed for the shallow soils from the Roraima and Rondonia highlands. A consistent east–west decline in biomass carbon in the Rio Negro Basin sector is associated with increasing rainfall and higher sand amounts. It is related to lesser C protection and greater C loss of sandy soils, subjected to active chemical leaching and widespread podzolization. Also, these soils possess lower cation exchangeable capacity and lower water retention capacity. Zones where deeply weathered Latosols dominate have a overall pattern of high C sequestration, and greater than the shallower soils from the upper Amazon, west of Madeira and Negro rivers. This was attributed to deeper incorporation of carbon in these clayey and highly pedo-bioturbated soils. The results highlight the urgent need for refining soil data at an appropriate scale for C stocks calculations purposes in Amazonia. There is a risk of misinterpreting C stocks in Amazonia when such great pedological variability is not taken into account.     

Heavy metals in water, sediment and tissues of Liza saliens from Esmoriz–Paramos lagoon, Portugal

Esmoriz–Paramos lagoon is an ecosystem of great ecological importance that is located on the northwest coast of Portugal and has been degraded as a result of industrial and anthropogenic activities. Concentrations of heavy metals (Cr, Cu, Pb and Zn) were measured in water, sediment and in tissues (liver and muscle) of Liza saliens, which is the dominant fish from the lagoon. Comparisons between metal concentrations in water and sediments were made with those in tissues of fish caught at the lagoon. Metals in water were quantified predominantly bound to particulate and equalled or exceeded the limit of chronic reference values. Metal concentrations in sediments varied among sampled sites. The relative order of concentrations was “Zn > Cu ∼ Pb > Cr” the same pattern observed for metals in water. Metals in fish tissues showed higher concentrations in liver (262 mg Cu·Kg⁻¹ and 89 mg Zn·Kg⁻¹) than in muscle (<3 mg Cu·Kg⁻¹ and 26 mg Zn·Kg⁻¹), while Pb and Cr were not detected. These results suggest that Cu and Zn are the metals of major concern in the lagoon. Mullet detritivorous feeding habits, bioaccumulation pattern and the high sediment metals concentrations relative to the water suggest that sediments can be the most important source of contamination in this ecosystem. The positive relationship found between Cu in liver and fish length demonstrates that time of exposure is a crucial factor in bioaccumulation. Condition indices (K and HSI) in mullets from the lagoon were higher compared to mullets from sea, suggesting abnormal condition in the lagoon population. We conclude that metals chronic exposure in the lagoon can impose considerable fish stress. The results also show that the lagoon is an area of environmental concern.     

Mixed response in bacterial and biochemical variables to simulated sand mining in placer-rich beach sediments,Ratnagiri, West coast of India

We investigated the influence on bacterial community and biochemical variables through mechanical disturbance of sediment-akin to small-scale mining in Kalbadevi beach, Ratnagiri, a placer-rich beach ecosystem which is a potential mining site. Changes were investigated by comparing three periods, namely phase I before disturbance, phase II just after disturbance, and phase III 24 h after disturbance as the bacterial generation time is ≤7 h. Cores from dune, berm, high-, mid-, and low-tide were examined for changes in distribution of total bacterial abundance, total direct viability (counts under aerobic and anaerobic conditions), culturability and biochemical parameters up to 40 cm depth. Results showed that bacterial abundance decreased by an order from 10⁶ cells g^− 1 sediment, while, viability reduced marginally. Culturability on different-strength nutrient broth increased by 155% during phase II. Changes in sedimentary proteins, carbohydrates, and lipids were marked at berm and dune and masked at other levels by tidal influence. Sedimentary ATP reduced drastically. During phase III, Pearson’s correlation between these variables evolved from non-significant to significant level. Thus, simulated disturbance had a mixed effect on bacterial and biochemical variables of the sediments. It had a negative impact on bacterial abundance, viability and ATP but positive impact on culturability. Viability, culturability, and ATP could act as important indicators reflecting the disturbance in the system at short time intervals. Culturability, which improved by an order, could perhaps be a fraction that contributes to restoration of the system at bacterial level. This baseline information about the potential mining site could help in developing rational approach towards sustainable harnessing of resources with minimum damage to the ecosystem.     

Groundwater contamination evolution in the Guadiamar and Agrio aquifers after the Aznalcóllar spill: assessment and environmental implications

In 1998, the Agrio and Guadiamar rivers underwent an enormous environmental disaster caused by the rupture of the Aznalcóllar tailings dam and the release of 6 hm³ of pyrite sludge and acidic water. Both rivers run over recent alluvial materials which form a small-sized aquifer which is however important because underground water feeds the flow of the rivers. This work analyzes the state of groundwater 10 years after the spill. Before the dam failure, this aquifer was already contaminated in the zone nearest to the mine, to which the impact of the spill was added. Contamination levels in the alluvial aquifer of the Agrio River have decreased remarkably. However, they are still important, with acidic pH values and high concentrations of toxic elements (maximum values of 16 mg/L of Zn and 15 mg/L of Al). There are also important levels of contamination in the Guadiamar alluvial area closest to the mine, as well as in specific zones located further south. The concentration of toxic elements is mainly controlled by pH. The evolution of contaminant levels show a sharp decrease after the first years following the spill, followed by a subsequent stabilization. It is necessary to take measures for the recovery of the aquifer because, otherwise, groundwater will continue contributing contaminants into the Agrio and Guadiamar rivers.