Electrochemical oxidation of benzene on boron-doped diamond electrodes

This work presents an electrochemical investigation of the benzene oxidation process in aqueous solution on boron-doped diamond (BDD) electrodes. Additionally, in order to determine the main products generated during the oxidation process, electrolysis and high performance liquid chromatography experiments were carried out. The complete degradation of this compound was performed aiming to a further application in waste water treatment. The cyclic voltammetry studies indicate that benzene is irreversibly oxidized in acid medium (H₂SO₄ 0.5 M) on the BDD electrode surface at 2.0 V versus Ag/AgCl in a diffusion controlled process. During the cycling, other products are generated, and a pair of peaks was observed that can be associated with the oxi-reduction of anyone of the following species: hydroquinone, benzoquinone, resorcinol or catechol. The electrolysis experiments were carried out at 2.4 and 2.5 V on the BDD electrode surface in a solution containing 1 × 10⁻² M of benzene (below the saturation concentration in aqueous solution), for 3 and 5 h, respectively. The main products measured were: hydroquinone, resorcinol, p-benzoquinone, catechol and phenol. The complete electrochemical benzene degradation was performed in the electrolysis experiments using a rotating BDD disc electrode (2.5 V for 5 h) and the main products detected were all measured at concentrations lower than 10⁻⁵ M in this condition. The boron-doped diamond electrode had proved to be a valuable tool for the electrochemical degradation of the benzene, a very stable chemical compound.     

Influence of ozone pre-treatment on sludge anaerobic digestion: removal of pharmaceutical and personal care products

The effect of an oxidative pre-treatment with ozone on the removal of Pharmaceutical and Personal Care Products (PPCPs) during the anaerobic digestion of sewage sludge has been investigated. Besides, the digested sludge characteristics in terms of pathogens content, dewatering properties, heavy metals content and linear alkylbenzene sulfonates (LAS) were determined. During ozonation (20mg O(3)/g TSS), about 8% of volatile solids (VS) and 60% of the chemical oxygen demand (COD) were solubilized. However, no mineralization was observed. The elimination of VS and total COD during anaerobic digestion were not affected by ozone treatment with efficiencies ranging from 60% to 65%. All PPCPs considered were removed during anaerobic treatment of sludge, with efficiencies ranging from 20% to 99%. No significant influence of ozone pre-treatment was observed on PPCPs elimination except for carbamazepine. Pathogens, heavy metals and LAS contents after conventional and pre-ozonation treatment of sewage sludge were below the legal requirements. However, the dewatering properties of sludge were deteriorated when the ozone pre-treatment was applied.     

Eutrophication and Sedimentation Patterns in Complete Exploitation of Water Resources Scenarios: An Example from Northwestern Semi-arid Mexico

Water requirements to supply human needs lead water stakeholders to store more water during surplus periods to fulfil the demand during – not only – scarcity periods. At the reservoirs, mostly those in semi-arid regions, water level then fluctuates extremely between rises and downward during one single year. Besides of water management implications, changes on physical, chemical and biological dynamics of these drawdown and refilling are little known yet. This paper shows the results, throughout a year, on solids, nutrients (N and P), chlorophyll-a, and sedimentation changes on the dynamics, when the former policy was applied in a reservoir from the semi-arid Northwestern Mexico. Water level sinusoidal trend impinged changes on thermal stratification and mixing, modifying nutrient cycling and primary producer responses. According to nitrogen and phosphorus concentration as well as chlorophyll-a, reservoir was mesotrophic, becoming hypertrophic during drawdown. Nutrient concentrations were high (1.22 ± 0.70 and 0.14 ± 0.12 mg P l⁻¹), increasing phosphorus and lowering N:P significantly throughout the study period, although no intensive agricultural, no urban development, neither industrial activities take place in the watershed. This suggests nutrient recycling complex mechanisms, including nutrient release from the sediment–water interface as the main nutrient pathway when shallowness, at the same time as mineralization, increases. Outflows controlled nitrogen and phosphorus availability on the ecosystem while organic matter depended on river inflows. As on other subtropical aquatic ecosystems, nitrogen limited primary productivity (Spearman correlation R = 0.75) but chlorophyll-a seasonal pattern showed an irregular trend, prompting other no-nutrient related limitants. Shallowness induced a homogeneous temporal pattern on water quality. This observed temporal variability was mainly explained statistically by changes on solids (mineral and organic), chlorophyll-a and flows (62.3%). Annual sedimentation rates of total solids ranged from 11.73 to 16.29 kg m⁻² year⁻¹ with organic matter comprising around 30%. N:P ratio on sedimentation rates were as high as could be expected in a resuspension dominated ecosystem, and spatially inverse related with N:P ratio on bottom sediments. Distance from river inlet into the reservoir reveals a marked spatial heterogeneity on solid and nitrogen sedimentation, showing the system dependence on river inflows and supporting resuspension as the main phosphorus pathway. Accretion rates (2.19 ± 0.40 cm year⁻¹) were not related to hydrological variability but decreased with the distance to the river input. Total sediment accumulation (9,895 tons km⁻² year⁻¹) denotes siltation as other serious environmental problem in reservoirs but possibly not related with operational procedures.     

Derivation of motor vehicle tailpipe particle emission factors suitable for modelling urban fleet emissions and air quality assessments

Background, aim and scope  

Urban motor vehicle fleets are a major source of particulate matter pollution, especially of ultrafine particles (diameters < 0.1 μm), and exposure to particulate matter has known serious health effects. A considerable body of literature is available on vehicle particle emission factors derived using a wide range of different measurement methods for different particle sizes, conducted in different parts of the world. Therefore, the choice as to which are the most suitable particle emission factors to use in transport modelling and health impact assessments presented as a very difficult task. The aim of this study was to derive a comprehensive set of tailpipe particle emission factors for different vehicle and road type combinations, covering the full size range of particles emitted, which are suitable for modelling urban fleet emissions.     

Analysis of atmospheric aerosol (PM2.5) in Recife city,Brazil

Several studies indicate that mortality and morbidity can be well correlated to atmospheric aerosol concentrations with aerodynamic diameter less than 2.5 µm (PM_2.5). In this work the PM_2.5 at Recife city was analyzed as part of a main research project (INAIRA) to evaluate the air pollution impact on human health in six Brazilian metropolitan areas. The average concentration, for 309 samples (24-hr), from June 2007 to July 2008, was 7.3 µg/m³, with an average of 1.1 µg/m³ of black carbon. The elemental concentrations of samples were obtained by x-ray fluorescence. The concentrations were then used for characterizing the aerosol, and also were employed for receptor modelling to identify the major local sources of PM_2.5. Positive matrix factorization analysis indicated six main factors, with four being associated to soil dust, vehicles and sea spray, metallurgical activities, and biomass burning, while for a chlorine factor, and others related to S, Ca, Br, and Na, we could make no specific source association. Principal component analysis also indicated six dominant factors, with some specific characteristics. Four factors were associated to soil dust, vehicles, biomass burning, and sea spray, while for the two others, a chlorine- and copper-related factor and a nickel-related factor, it was not possible to do a specific source association. The association of the factors to the likely sources was possible thanks to meteorological analysis and sources information. Each model, although giving similar results, showed factors’ peculiarities, especially for source apportionment. The observed PM_2.5 concentration levels were acceptable, notwithstanding the high urbanization of the metropolitan area, probably due to favorable conditions for air pollution dispersion. More than a valuable historical register, these results should be very important for the next analysis, which will correlate health data, PM_2.5 levels, and sources contributions in the context of the six studied Brazilian metropolises.

Implications: The analysis of fine particulate matter (PM_2.5) in Recife city, Brazil, gave a significant picture of the local concentration and composition of this pollutant, which exhibits robust associations to adverse human health effects. Data from 1 year of sampling evaluated the seasonal variability and its connections with weather patterns. Source apportionment in this metropolitan area was obtained based in a combination of receptor models: principal component analysis (PCA)/chemical mass balance (CMB) and positive matrix factorization (PMF). These results give guidelines for local air pollution control actions, providing significant information for a health study in the context of establishing a new national air pollution protocol based on Brazilian cities data.     

Land-Use Planning in the Chaco Plain (Burruyacú, Argentina): Part 2: Generating a Consensus Plan to Mitigate Land-Use Conflicts and Minimize Land Degradation

The Burruyacú district (Tucumán province, Northwest Argentina) has been traditionally an area with rural activities based on the exploitation of the Chaco forest for timber and livestock browsing. Since the 1960s, local institutions started promoting soybean due to favorable land conditions and good market prices. Soybean extension, as from the 1970s, has resulted in important reduction of the Chaco forest and also caused physical soil degradation, especially soil compaction and erosion. A land-use-planning exercise was carried out using the Land-Use Planning and Information System (LUPIS) as a spatial decision support system. LUPIS facilitates the generation of alternative land-use plans by adjusting the relative importance attributed by multiple stakeholders to preference and avoidance policies. The system leads to the allocation of competing land uses to land map units in accordance with their preferred resource requirements, conditional upon the resource base of the area and the stakeholders' demands. After generating a land use plan for each stakeholder category identified in the study area, including commercial farmers, conservative/conventional farmers, and conservationists, a consensus plan was established to address the land-use conflicts between mechanized agriculture, traditional agriculture and forest conservation, and to mitigate soil degradation caused by extensive dry-farming. Although the planning exercise did not directly involve the stakeholders, the results are sufficiently practical and realistic to suggest that the approach could be extended to the entire Chaco plain region.     

A method for measuring the anoxic biodegradability under denitrifying conditions

A test for assessing the anoxic biodegradability of organic compounds under denitrifying conditions is proposed. The method is based on the recovery and quantification of the CO2 produced, which is evidence of complete biodegradation of the test compound (added as the sole carbon source). The tests were carried out in a mineral medium, with nitrate as electron acceptor. Whole lake sediments, sediment extracts and a commercial inoculum were assayed as a possible inoculum source by means of glucose biodegradability tests. It was found that the sediment extracts constitute a suitable and environmentally-relevant inoculum source, since they add non-significant amounts of carbon to the tests. Two xenobiotic compounds, namely, aniline and phenol, were tested in the aforementioned conditions as well as in a standard aerobic biodegradability test. Both aniline and phenol attained a biodegradation level higher than 60% in a short time period (<28 days) and thus can be considered as readily biodegradable in denitrifying environments. Nevertheless, the kinetics obtained in the anoxic test were slower than in aerobic conditions, and even suggested the accumulation of intermediate metabolites in the case of phenol. The results of this study indicate that the fate of xenobiotic compounds under anoxic conditions differs from that observed in an oxic environment, and therefore it should be considered by standard biodegradability testing procedures.     

Influence of solid waste and topography on urban floods: The case of Mexico City

Floods in cities are increasingly common as a consequence of multifactor watershed dynamics, including geomorphology, land-use changes and land subsidence. However, urban managers have focused on infrastructure to address floods by reducing blocked sewage infrastructure, without significant success. Using Mexico City as a case study, we generated a spatial flood risk model with geomorphology and anthropogenic variables. The results helped contrast the implications of different public policies in land use and waste disposal, and correlating them with flood hazards. Waste disposal was only related to small floods. 58% of the city has a high risk of experiencing small floods, and 24% of the city has a risk for large floods. Half of the population with the lowest income is located in the high-risk areas for large floods. These models are easy to build, generate fast results and are able to help to flood policies, by understanding flood interactions in urban areas within the watershed.     

Biogas upgrading by cryogenic techniques

Environmental Chemistry Letters - The scarcity of fossil fuels and the worldwide pollution have led the scientific community to seek renewable energy alternatives. In particular, biogas has become...     

Polychlorinated Biphenyls (PCBs) in Mussels along the Chilean Coast

- DOI: http://dx.doi.org/10.1065/espr2006.01.011 Goal, Scope and Background Chile signed the Stockholm Convention, which establishes measures to reduce or eliminate Persistent Organic Pollutants (POPs) release into the environment, including the prohibition of their use and reduction of secondary products release, as well as management related with waste treatment. Among POPs, PCBs are a family of 209 compounds that differ in chlorine level and position. These substances present a wide variability in their physicochemical properties such as vapor pressure, water solubility and partition coefficients that determine their behavior and mobility within the different environmental compartments. In Chile, as in other countries, the use of these compounds were and continue to occur in diverse industrial applications such as dielectric fluid in transformers and condensers, with a use in Chile of approximately 550,000 L. A sampling of bivalves was performed during the years 2000-2002 in order to obtain information on the spatial distribution of the PCB levels for the length of the long Chilean coast (180–540 South latitude, 4,200 km), contributing in this way to a better understanding of the PCB trend and eventual fractionation along latitudinal gradients in Chile, using as the bivalve Perumytilus purpuratus ('Chorito Maico') bioindicator. Methods The marine bivalves Perumytilus purpuratus were collected in 16 localities in northern and southern Chile. All samples were lyophilized, and PCBs (51 congeners) were extracted in a Soxhlet system (24 h) with n-hexane. Samples were cleaned in florisil and analyzed by GC-ECD. Blanks, certified reference materials and standards were processed along with the samples. Results and Discussion The results obtained for P. purpuratus indicate a congeneric distribution profile associated to a latitudinal gradient, and the statistical analysis of the congeneric composition of the PCBs indicated five groups in relation to the molecular weight (number of chlorines), where the lighter congeners were observed in areas corresponding to high latitudes with total PCB values of 298 ng/g dry weight. Conclusion P. purpuratus turns out to be a good bioindicator of PCB levels in the coastal areas of Chile due to its wide distribution. The highest concentrations and the more volatile congeners were found in southern Chile, which could be the result of processes of long-range transport or illegal discharge occurring in such remote areas. These results confirm previous data from the International Mussel Watch project ten years ago. Recommendation and Outlook Future studies are needed to confirm our findings utilizing another environmental matrix such as soil/sediments and air samples.