Spectroscopic Raman study of sulphate precipitation sequence in Rio Tinto mining district (SW Spain)

Acidic waters and sulphate-rich precipitates are typical by-products of mining activity such as in Rio Tinto (Huelva, SW Spain). This river drains pyrite mines situated in the Iberian Pyrite Belt which have been in operation since the Bronze Age and probably constitutes the oldest continuously operating mining activity over the world. In the present work, we have used Raman spectroscopy to study a wide range of natural mineral samples collected at Rio Tinto which origin is related to evaporation and mineral transformation processes in a wet and extreme acidic environment. In addition, we simulated the phenomenon of mineral precipitation in controlled conditions by using a simulator developed at the laboratory evaporating natural water collected at Rio Tinto. Also, a series of experiments using the same waters as small droplets have been carried out using micro-Raman technique. The droplets were placed on substrates with different chemical composition and reactivity. The results reveal that the precipitation sequence occurred in Rio Tinto mainly comprises copiapite and coquimbite group minerals followed by several other low hydrated iron sulphates. The experiments carried out on droplets allow estimating with higher accuracy the precipitation sequence.     

Passive treatment of acid mine drainage with high metal concentrations using dispersed alkaline substrate

Passive treatment systems based on the dissolution of coarse calcite grains are widely used to remediate acid mine drainage (AMD). Unfortunately, they tolerate only low metal concentrations or acidity loads, because they are prone to passivation (loss of reactivity due to coating) and/or clogging (loss of permeability) by precipitates. To overcome these problems, a dispersed alkaline substrate (DAS) composed of a fine-grained alkaline reagent (calcite sand) mixed with a coarse inert matrix (wood chips) was developed. The small grains provide a large reactive surface and dissolve almost completely before the growing layer of precipitates passivates the substrate, whereas the dispersion of nuclei for precipitation on the inert surfaces retards clogging. Chemical and hydraulic performance of DAS was investigated in two laboratory columns fed at different flow rates with natural AMD of pH 2.3 to 3.5 and inflow net acidity 1350 to 2300 mg/L as CaCO(3). The DAS columns removed 900 to 1600 mg/L net acidity, 3 to 4.5 times more than conventional passive treatment systems. Regardless of the flow rate employed, Al, Fe(III), Cu, and Pb were virtually eliminated. Minor Zn, Ni, and Cd were removed at low flow rates. High acidity removal is possible because these metals accumulate intentionally in DAS, and their precipitation promotes further calcite dissolution. During 15 mo, DAS operated without clogging at 120 g acidity/m(2).d, four times the loading rate recommended for conventional passive systems; DAS may therefore be capable of treating AMD at sites where influent chemistry precludes the use of other passive systems.     

Presence of PAHs in milk of industrial farms from Tizayuca,Hidalgo, Mexico

The objective of this study was to determine the concentrations of polycyclic aromatic hydrocarbons (PAHs) in cow's milk from industrial farms that are located near an industrial park in Hidalgo, Mexico. It was found that the concentrations of PAHs in the raw milk of cattle from industrial farms have increased in recent years. Composite samples were collected between 2008 and 2010 and analysis carried out according to 8100 EPA procedures and analyzed by gas chromatography with FID detection. The results show that combustion PAHs were mostly Ace, Acy, and Fla (0.25, 0.32, and 0.22 µg g^?1, respectively). Diagnostic ratios were used to show that the probable sources were grass and fuel combustion. The sum of concentrations of 16 individual PAHs did not breach permissible levels in milk (25 µg g^?1 according to the United States EPA), indicating a limited health risk to animals and humans in the study area. The industrial park has adequate pollutant emission regulations.     

Time-Consistent Equilibria in Common Access Resource Games with Asymmetric Players Under Partial Cooperation

Given a differential game, if agents have different time preference rates, cooperative (Pareto optimum) solutions obtained by applying Pontryagin’s maximum principle become time inconsistent. We derive a set of dynamic programming equations in continuous time whose solutions are time-consistent equilibria for problems in which agents differ in their utility functions and also in their time preference rates. The solution assumes cooperation between agents at every time. Since coalitions at different times have different time preferences, equilibrium policies are calculated by looking for Markov (subgame perfect) equilibria in a (noncooperative) sequential game. The results are applied to the study of a cake-eating problem describing the management of a common property exhaustible natural resource. The extension of the results to a simple common property renewable natural resource model in infinite horizon is also discussed.     

New trends in the analytical determination of emerging contaminants and their transformation products in environmental waters

Since the so-called emerging contaminants were established as a new group of pollutants of environmental concern, a great effort has been devoted to the knowledge of their distribution, fate and effects in the environment. After more than 20 years of work, a significant improvement in knowledge about these contaminants has been achieved, but there is still a large gap of information on the growing number of new potential contaminants that are appearing and especially of their unpredictable transformation products. Although the environmental problem arising from emerging contaminants must be addressed from an interdisciplinary point of view, it is obvious that analytical chemistry plays an important role as the first step of the study, as it allows establishing the presence of chemicals in the environment, estimate their concentration levels, identify sources and determine their degradation pathways. These tasks involve serious difficulties requiring different analytical solutions adjusted to purpose. Thus, the complexity of the matrices requires highly selective analytical methods; the large number and variety of compounds potentially present in the samples demands the application of wide scope methods; the low concentrations at which these contaminants are present in the samples require a high detection sensitivity, and high demands on the confirmation and high structural information are needed for the characterisation of unknowns. New developments on analytical instrumentation have been applied to solve these difficulties. Furthermore and not less important has been the development of new specific software packages intended for data acquisition and, in particular, for post-run analysis. Thus, the use of sophisticated software tools has allowed successful screening analysis, determining several hundreds of analytes, and assisted in the structural elucidation of unknown compounds in a timely manner.     

Native plant restoration combats environmental change: development of carbon and nitrogen sequestration capacity using small cordgrass in European salt marshes

Restoration of salt marshes is critical in the context of climate change and eutrophication of coastal waters because their vegetation and sediments may act as carbon and nitrogen sinks. Our primary objectives were to quantify carbon (C) and nitrogen (N) stocks and sequestration rates in restored marshes dominated by Spartina maritima to provide support for restoration and management strategies that may offset negative aspects of eutrophication and climate change in estuarine ecosystems. Sediment C content was between ca. 13 mg C g^?1and sediment N content was ca. 1.8 mg N g^?1. The highest C content for S. maritima was recorded in leaves and stems (ca. 420 mg C g^?1) and the lowest in roots (361?±?4 mg C g^?1). S. maritima also concentrated more N in its leaves (31?±?1 mg N g^?1) than in other organs. C stock in the restored marshes was 29.6 t C ha^?1; ca. 16 % was stored in S. maritima tissues. N stock was 3.6 t N ha^?1, with 8.3 % stored in S. maritima. Our results showed that the S. maritima restored marshes, 2.5 years after planting, were sequestering atmospheric C and, therefore, provide some mitigation for global warming. Stands are also capturing nitrogen and reducing eutrophication. The concentrations of C and N contents in sediments, and cordgrass relative cover of 62 %, and low below-ground biomass (BGB) suggest restored marshes can sequester more C and N. S. maritima plantations in low marshes replace bare sediments and invasive populations of exotic Spartina densiflora and increase the C and N sequestration capacity of the marsh by increasing biomass production and accumulation.     

Effects of organic fertilizers on soil physicochemistry and on the yield and botanical composition of forage over 3 years

Organic wastes have been reported to reduce saturation of the exchange complex by Al in Al-rich acid soils. For 3 years, the main soil fertility properties were studied in plots sown with mixed pasture species. These plots were fertilized with cattle slurry, dairy sludge (DS), or granulated broiler litter (BL) in comparison with mineral fertilizer. Al saturation levels were low after the initial inorganic liming treatment (19.00-33.71%) but tended to rise under all treatments (21.09-61.37%) except BL (8.45-30.98%), which was also associated with the highest average soil pH and the highest average levels of exchangeable Ca2+, Mg2+, and K+. Treatment DS performed similarly to mineral fertilizer in most respects, but it led to greater available P levels. Under the dry conditions of the second and third years of the study, BL and DS treatments were associated with significantly greater forage yields than the other treatments. Under DS treatment, available P levels were too low to allow the maintenance of mixed pasture, clover being eliminated by the less P-dependent species.     

Anaerobic Mesophilic Treatment of Cattle Manure in an Upflow Anaerobic Sludge Blanket Reactor with Prior Pasteurization

Abstract

Different autonomous communities located in northern Spain have large populations of dairy cattle. In the case of Asturias, the greatest concentration of dairy farms is found in the areas near the coast, where the elimination of cattle manure by means of its use as a fertilizer may lead to environmental problems. The aim of the present research work was to study the anaerobic treatment of the liquid fraction of cattle manure at mesophilic temperature using an upflow anaerobic sludge blanket (UASB) reactor combined with a settler after a pasteurization process at 70 °C for 2 hr. The manure used in this study came from two different farms, with 40 and 200 cows, respectively. The manure from the smaller farm was pretreated in the laboratory by filtration through a 1-mm mesh, and the manure from the other farm was pretreated on the farm by filtration through a separator screw press (0.5-mm mesh). The pasteurization process removed the pathogenic microorganisms lacking spores, such as Enterococcus, Yersinia, Pseudomonas, and coliforms, but bacterial spores are only reduced by this treatment, not removed. The combination of a UASB reactor and a settler proved to be effective for the treatment of cattle manure. In spite of the variation in the organic loading rate and total solids in the influent during the experiment, the chemical oxygen demand (COD) of the effluent from the settler remained relatively constant, obtaining reductions in the COD of ～85%.     

Human-caused wildfire risk rating for prevention planning in Spain

This paper identifies human factors associated with high forest fire risk in Spain and analyses the spatial distribution of fire occurrence in the country. The spatial units were 6,066 municipalities of the Spanish peninsular territory and Balearic Islands. The study covered a 13-year series of fire occurrence data. One hundred and eight variables were generated and input to a dedicated Geographic Information System (GIS) to model different factors related to fire ignition. After exploratory analysis, 29 were selected to build a predictive model of human fire ignition using logistic regression analysis. The binary model estimated the probability of high or low occurrence of forest fires, as defined by an ignition danger index that is currently used by the Spanish forest service (number of fires divided by forest area in each municipality). Thirteen explanatory variables were identified by the model. They were related to agricultural landscape fragmentation, agricultural abandonment and development processes. The prediction agreement found between the model binary outputs and the historical fire data was 85.3% for the model building dataset (60% of municipalities). A slightly lower predictive power (76.2%) was found for the validation data (the remaining 40%). The probabilistic output of the logistic was significantly related to the raw ignition index (Spearman correlation of 0.710) used by the Spanish Forest Service. Therefore, the model can be considered a good predictor of human-caused fire risk, aiding spatial decisions related to prevention planning in Spanish municipalities.