High efficiencies in the electrochemical oxidation of an anthraquinonic dye with conductive-diamond anodes

Oxidation of anthraquinonic dye Acid Blue 62 by electrolysis with conductive-diamond electrodes is studied in this work. COD, TOC, and color have been selected to monitor the degradation of the molecule as a function of several operating inputs (current density, pH, temperature, and NaCl concentration). Results show that the electrochemical oxidation of this model of large molecules follows a first order kinetics in all the conditions assessed, and it does not depend on the pH and temperature. The occurrence of chloride ions in wastewaters increases the rate of color and COD removal as a consequence of the mediated oxidation promoted by the chlorinated oxidizing species. However, chloride occurrence does not have an influence on the mineralization rate. First-order kinetic-constants for color depletion (attack to chromophores groups), oxidation (COD removal), and mineralization (TOC removal) were found to depend on the current density and to increase significantly with its value. A single model was proposed to explain these changes in terms of the mediated oxidation processes. Rate of mineralization remained very close to that expected for a purely mass transfer-controlled process. This was explained assuming that mediated oxidation does not have a significant influence on the mineralization in spite it has some effect on intermediate oxidation stages. The efficiency of the oxidation was found to depend mainly on the concentration of COD being negligible the effect of the other inputs assessed except for the occurrence of chloride ions. Opposite, the efficiency of mineralization depends on concentration of TOC and current density and it did not depend on the chloride occurrence. This observation was found to have an important influence on the power required to remove a given percentage of the initial TOC or COD. To decrease COD efficiently, the occurrence of chloride in the solution is very important, while to remove TOC efficiently, it is more important to work at low current densities and chloride effect is negligible. Energy consumption could be decreased by folds using the proper conditions.     

Impacts on effluent contaminants from mine sites: risk assessment,fate, and distribution of pollution at basin scale

The environmental implications of mining activities are of worldwide concern. An environmental evaluation at the basin level was conducted because of widespread mining in Cajamarca in Northern Peru. A sediment monitoring program was developed at the Jequetepeque basin, located in Cajamarca. A total of 16 sites were monitored at three different times between June 2009 and July 2010, and a total of 42 samples were collected. All samples were analyzed by microwave digestion and by a sequential extraction scheme following the three-stage European Community Bureau of Reference (three-stage BCR) protocol. Trace element mobilization from the sediments to the water column was assessed by the risk assessment code (RAC). Spatial and temporal distribution of trace elements was evaluated by principal component analysis and hierarchical cluster analysis. Cd, Zn, As, and Pb showed the highest concentrations independent of season. Notably, Cu concentration and mobility increased during the wet season for all samples. Additionally, Hg concentration and mobility increased during the wet season near the mine sites. According to the enrichment factor, the highest enrichments of Cd, Zn, Pb, and As were related to mine runoff. The effect of trace elements near the mine sites at the Jequetepeque basin was considered a significant threat to the environment due to Cd, Zn, Pb, and As, and the concentrations of Cu and Hg were also considered a concern. This work establishes a baseline for the environmental quality status of the Jequetepeque basin that may support water quality management in Peru.     

The combined effects of urea application and simulated acid rain on soil acidification and microbial community structure

Our aim was to test the effects of simulated acid rain (SAR) at different pHs, when applied to fertilized and unfertilized soils, on the leaching of soil cations (K, Ca, Mg, Na) and Al. Their effects on soil pH, exchangeable H⁺ and Al³⁺ and microbial community structure were also determined. A Paleudalfs soil was incubated for 30 days, with and without an initial application of urea (200 mg N kg^?1soil) as nitrogen (N) fertilizer. The soil was held in columns and leached with SAR at three pH levels. Six treatments were tested: SAR of pH 2.5, 4.0 and 5.6 leaching on unfertilized soil (T1, T2 and T3), and on soils fertilized with urea (T4, T5 and T6). Increasing acid inputs proportionally increased cation leaching in both unfertilized and fertilized soils. Urea application increased the initial Ca and Mg leaching, but had no effect on the total concentrations of Ca, Mg and K leached. There was no significant difference for the amount of Na leached between the different treatments. The SAR pH and urea application had significant effects on soil pH, exchangeable H⁺ and Al³⁺. Urea application, SAR treated with various pH, and the interactions between them all had significant impacts on total phospholipid fatty acids (PLFAs). The highest concentration of total PLFAs occurred in fertilized soils with SAR pH5.6 and the lowest in soils leached with the lowest SAR pH. Soils pretreated with urea then leached with SARs of pH 4.0 and 5.6 had larger total PLFA concentrations than soil without urea. Bacterial, fungal, actinomycete, Gram-negative and Gram-positive bacterial PLFAs had generally similar trends to total PLFAs.     

Brain glutathione redox system significance for the control of silica-coated magnetite nanoparticles with or without mercury co-exposures mediated oxidative stress in European eel (Anguilla anguilla L.)

This in vitro study investigates the impact of silica-coated magnetite particles (Fe₃O₄@SiO₂/SiDTC, hereafter called IONP; 2.5 mg L^?1) and its interference with co-exposure to persistent contaminant (mercury, Hg; 50 μg L^?1) during 0, 2, 4, 8, 16, 24, 48, and 72 h on European eel (Anguilla anguilla) brain and evaluates the significance of the glutathione (GSH) redox system in this context. The extent of damage (membrane lipid peroxidation, measured as thiobarbituric acid reactive substances, TBARS; protein oxidation, measured as reactive carbonyls, RCs) decreased with increasing period of exposure to IONP or IONP + Hg which was accompanied with differential responses of glutathione redox system major components (glutathione reductase, GR; glutathione peroxidase, GPX; total GSH, TGSH). The occurrence of antagonism between IONP and Hg impacts was evident at late hour (72 h), where significantly decreased TBARS and RC levels and GR and glutathione sulfo-transferase (GST) activity imply the positive effect of IONP + Hg concomitant exposure against Hg-accrued negative impacts [vs. early (2 h) hour of exposure]. A period of exposure-dependent IONP alone and IONP + Hg joint exposure-accrued impact was perceptible. Additionally, increased susceptibility of the GSH redox system to increased period of exposure to Hg was depicted, where insufficiency of elevated GR for the maintenance of TGSH required for membrane lipid and cellular protein protection was displayed. Overall, a fine-tuning among brain glutathione redox system components was revealed controlling IONP + Hg interactive impacts successfully.     

A Thermodynamic Geography: Night-Time Satellite Imagery as a Proxy Measure of Emergy

Night-time satellite imagery enables the measurement, visualization, and mapping of energy consumption in an area. In this paper, an index of the “sum of lights” as observed by night-time satellite imagery within national boundaries is compared with the emergy of the nations. Emergy is a measure of the solar energy equivalent used, directly or indirectly, to support the processes that characterize the economic activity in a country. Emergy has renewable and non-renewable components. Our results show that the non-renewable component of national emergy use is positively correlated with night-time satellite imagery. This relationship can be used to produce emergy density maps which enable the incorporation of spatially explicit representations of emergy in geographic information systems. The region of Abruzzo (Italy) is used to demonstrate this relationship as a spatially disaggregate case.     

Hypoxia in the Baltic Sea: Biogeochemical Cycles, Benthic Fauna, and Management

Hypoxia has occurred intermittently over the Holocene in the Baltic Sea, but the recent expansion from less than 10 000 km² before 1950 to >60 000 km² since 2000 is mainly caused by enhanced nutrient inputs from land and atmosphere. With worsening hypoxia, the role of sediments changes from nitrogen removal to nitrogen release as ammonium. At present, denitrification in the water column and sediments is equally important. Phosphorus is currently buried in sediments mainly in organic form, with an additional contribution of reduced Fe-phosphate minerals in the deep anoxic basins. Upon the transition to oxic conditions, a significant proportion of the organic phosphorus will be remineralized, with the phosphorus then being bound to iron oxides. This iron-oxide bound phosphorus is readily released to the water column upon the onset of hypoxia again. Important ecosystems services carried out by the benthic fauna, including biogeochemical feedback-loops and biomass production, are also lost with hypoxia. The results provide quantitative knowledge of nutrient release and recycling processes under various environmental conditions in support of decision support tools underlying the Baltic Sea Action Plan.     

Reduction of Baltic Sea Nutrient Inputs and Allocation of Abatement Costs Within the Baltic Sea Catchment

The Baltic Sea Action Plan (BSAP) requires tools to simulate effects and costs of various nutrient abatement strategies. Hierarchically connected databases and models of the entire catchment have been created to allow decision makers to view scenarios via the decision support system NEST. Increased intensity in agriculture in transient countries would result in increased nutrient loads to the Baltic Sea, particularly from Poland, the Baltic States, and Russia. Nutrient retentions are high, which means that the nutrient reduction goals of 135 000 tons N and 15 000 tons P, as formulated in the BSAP from 2007, correspond to a reduction in nutrient loadings to watersheds by 675 000 tons N and 158 000 tons P. A cost-minimization model was used to allocate nutrient reductions to measures and countries where the costs for reducing loads are low. The minimum annual cost to meet BSAP basin targets is estimated to 4.7 billion €.     

Determination of specific gravity of municipal solid waste

This investigation was conducted to evaluate experimental determination of specific gravity (G_s) of municipal solid waste (MSW). Water pycnometry, typically used for testing soils was adapted for testing MSW using a large flask with 2000 mL capacity and specimens with 100–350 g masses. Tests were conducted on manufactured waste samples prepared using US waste constituent components; fresh wastes obtained prior and subsequent to compaction at an MSW landfill; and wastes obtained from various depths at the same landfill. Factors that influence specific gravity were investigated including waste particle size, compaction, and combined decomposition and stress history. The measured average specific gravities were 1.377 and 1.530 for as-prepared/uncompacted and compacted manufactured wastes, respectively; 1.072 and 1.258 for uncompacted and compacted fresh wastes, respectively; and 2.201 for old wastes. The average organic content and degree of decomposition were 77.2% and 0%, respectively for fresh wastes and 22.8% and 88.3%, respectively for old wastes. The G_s increased with decreasing particle size, compaction, and increasing waste age. For fresh wastes, reductions in particle size and compaction caused occluded intraparticle pores to be exposed and waste particles to be deformed resulting in increases in specific gravity. For old wastes, the high G_s resulted from loss of biodegradable components that have low G_s as well as potential access to previously occluded pores and deformation of particles due to both degradation processes and applied mechanical stresses. The G_s was correlated to the degree of decomposition with a linear relationship. Unlike soils, the G_s for MSW was not unique, but varied in a landfill environment due both to physical/mechanical processes and biochemical processes. Specific gravity testing is recommended to be conducted not only using representative waste composition, but also using representative compaction, stress, and degradation states.     

Source apportion of atmospheric particulate matter: a joint Eulerian/Lagrangian approach

PM_2.5 samples were collected during an annual monitoring campaign (January 2012–January 2013) in the urban area of Naples, one of the major cities in Southern Italy. Samples were collected by means of a standard gravimetric sampler (Tecora Echo model) and characterized from a chemical point of view by ion chromatography. As a result, 143 samples together with their ionic composition have been collected. We extend traditional source apportionment techniques, usually based on multivariate factor analysis, interpreting the chemical analysis results within a Lagrangian framework. The Hybrid Single-Particle Lagrangian Integrated Trajectory Model (HYSPLIT) model was used, providing linkages to the source regions in the upwind areas. Results were analyzed in order to quantify the relative weight of different source types/areas. Model results suggested that PM concentrations are strongly affected not only by local emissions but also by transboundary emissions, especially from the Eastern and Northern European countries and African Saharan dust episodes.     

Toward a robust analytical method for separating trace levels of nano-materials in natural waters: cloud point extraction of nano-copper(II) oxide

Cloud point extraction (CPE) factors, namely Triton X-114 (TX-114) concentration, pH, ionic strength, incubation time, and temperature, were optimized for the separation of nano-sized copper(II) oxide (nCuO) in aqueous matrices. The kinetics of phase transfer was studied using UV–visible spectroscopy. From the highest separation rate, the most favorable conditions were observed with 0.2 %?w/v of TX-114, pH?=?9.0, ionic strength of 10 mM NaCl, and incubation at 40 °C for 60 min, yielding an extraction efficiency of 89.2?±?3.9 % and a preconcentration factor of 86. The aggregate size distribution confirmed the formation of very large nCuO–micelle assemblies (11.9 μm) under these conditions. The surface charge of nCuO was also diminished effectively. An extraction efficiency of 91 % was achieved with a mixture of TX-100 and TX-114 containing 30 wt.% of TX-100. Natural organic and particulate matters, represented by humic acid (30 mg/L) and micron-sized silica particles (50 mg/L), respectively, did not significantly reduce the CPE efficiency (<10 %). The recovery of copper(II) ions (20 mg/L) in the presence of humic acid was low (3–10 %). The spiked natural water samples were analyzed either directly or after CPE by inductively coupled plasma mass spectrometry following acid digestion/microwave irradiation. The results indicated the influence of matrix effects and their reduction by CPE. A delay between spiking nCuO and CPE may also influence the recovery of nCuO due to aggregation and dissolution. A detection limit of 0.04 μg Cu/L was achieved for nCuO.