Modelling of silica diffusion experiments with 32Si in Boom Clay

A mathematical model describing the dissolution of nuclear glass directly disposed in clay combines a first-order dissolution rate law with the diffusion of dissolved silica in clay. According to this model, the main parameters describing the long-term dissolution of the glass are etaR, the product of the diffusion accessible porosity eta and the retardation factor R, and the apparent diffusion coefficient D(app) of dissolved silica in clay. For determining the migration parameters needed for long-term predictions, four Through-Diffusion (T-D) experiments and one percolation test have been performed on undisturbed clay cores. In the Through-Diffusion experiments, the concentration decrease after injection of 32Si (radioactive labelled silica) was measured in the inlet compartment. At the end of the T-D experiments, the clay cores were cut in thin slices and the activity of labelled silica in each slice was determined. The measured activity profiles for these four clay cores are well reproducible. Since no labelled silica could be detected in the outlet compartments, the Through-Diffusion experiments are fitted by two In-Diffusion models: one model assuming linear and reversible sorption equilibrium and a second model taking into account sorption kinetics. Although the kinetic model provides better fits, due to the sufficiently long duration of the experiments, both models give approximately similar values for the fit parameters. The single percolation test leads to an apparent diffusion coefficient value about two to three times lower than those of the Through-Diffusion tests. Therefore, dissolved silica appears to be strongly retarded in Boom Clay. A retardation factor R between 100 and 300 was determined. The corresponding in situ distribution coefficient K(d) is in the range 25-75 cm(3) g(-1). The apparent diffusion coefficient of dissolved silica in Boom Clay is estimated between 2 x 10(-13) and 7 x 10(-13) m(2) s(-1). The pore diffusion coefficient is in the range from 6 x 10(-11) to 1 x 10(-10) m(2) s(-1).     

Effect of MgO and CaO/SiO2 on the immobilization of chromium in synthetic slags

This work investigated the chemical and mineralogical properties of CaO–SiO₂–Cr₂O₃–CaF₂–MgO slags. Synthetic slags were prepared and the effect of the slag basicity (mass ratio CaO/SiO₂) and MgO contents on the stability of the mineralogical species formed was analyzed. The morphology and composition of the slags were analyzed by X-ray powder diffraction (XRD) and scanning electron microscope-energy dispersive spectroscopy (SEM–EDS), whilst their chemical stability was evaluated by leaching with an aqueous acetic acid solution. It was found that in slags with CaO/SiO₂?=?1, the main Cr-compound was MgCr₂O₄ spinel, which forms octahedron crystals. Small amounts of CaCr₂O₄ and CaCrO₄ were also observed. It was found that with increasing the slag basicity from 1 to 2 the compounds MgCr₂O₄ and CaCr₂O₄ were formed together with the Cr(V)-containing compound complex Ca₅(CrO₄)₃F which forms hexagonal crystals. The results showed that the highest Cr concentration levels in the leaching liquors corresponded to slags with CaO/SiO₂?=?2, probably owing to the formation of CaCrO₄ and Ca₅(CrO₄)₃F, whilst the lowest chromium concentration levels corresponded to MgO-based slags owing to the stable binding of chromium in spinel with MgO. Additionally, potential–pH diagrams for the Ca–Cr–H₂O and Mg–Cr–H₂O systems at 25?°C were calculated.     

Application of water quality indices and analysis of the surface water quality monitoring network in semiarid North-Central Chile

Surface water quality has increasing importance worldwide and is particularly relevant in the semiarid North-Central Chile, where agriculture and mining activities are imposing heavy pressure on limited water resources. The current study presents the application of a water quality index in four watersheds of the 29°-33°S realm for the period 1999-2008, based on the Canadian Council of Ministers for the Environment approach and the Chilean regulation for irrigation water quality. In addition, two modifications to the index are tested and a comprehensive characterization of the existing monitoring network is performed through cluster analysis. The basins studied show fairly good water quality in the overall, specially the Limarí basin. On the other hand, the lower index values were obtained for the headwaters of Elqui, associated with the El Indio mining district. The first modification of the indicator (i.e., to consider parameters differentially according to their effect on human health or the environment) did not produce major differences with respect to the original index, given the generally good water quality. The second modification (i.e., to consider as threshold values the more restrictive figures derived from a set of regulations) yielded important differences in the indicator values. Finally, an adequate characterization of the monitoring network was obtained. The results presented spatial coherence and the information can be used as a basis for the optimization of the monitoring network if required.     

Why the Use of Adenoviruses as Water Quality Virologic Marker?

Adenovirus is the virus that contains the highest amount of features favorable to its use as a virologic marker for water quality. Those pathogens are resistant on the environment, abundant, easily detected by molecular methods and are of great importance in public health.     

Monitoring of copper,arsenic and antimony levels in agricultural soils impacted and non-impacted by mining activities,from three regions in Chile

This paper reports a comparative study of the concentration of three important environmental elements that are often found together in mineral deposits and then associated with mining activities; copper, arsenic and antimony. These elements were determined in 26 different agricultural soils from regions I, II and V in Chile, zones where the most important and biggest copper industries of this country are located. As background levels of these elements in soils have not been well established, in this study, both, impacted and non-impacted agricultural soils from different regions were considered. The relationships between the concentrations of these elements in soils were also examined. The concentration ranges for copper, arsenic and antimony were 11-530; 2.7-202 and 0.42-11 mg kg(-1) respectively. The copper concentrations in non-polluted soils from the north and central zone of Chile were similar. However, three sites from the north region have copper concentration as higher as 100 mg kg(-1), values that exceed the critical concentration for copper in soils. The concentration of arsenic and antimony in the north soils were higher than in non-impacted ones and, in the case of arsenic, greatly exceeded the world average concentration reported for this element in soils. The highest arsenic and antimony concentrations were found in Calama and Quillagua soils, two different sites in the Loa valley. The arsenic/antimony concentration ratio was higher in Quillagua soil. The high concentrations of three elements determined in impacted soils from region V (Puchuncaví and Catemu valleys) clearly shows the impact produced in this zone by the industrial and mining activities developed in their proximities. At Puchuncaví valley a clear decrease was observed in copper, arsenic and antimony concentrations in soils on the function of the distance from the industrial complex "Las Ventanas", and all concentrations exceeded the reported critical values for this matrix. Instead at Catemu valley, only the copper concentration was higher than this value. Statistically significant correlation was found for Cu-Sb in all soils; more significant Cu-As, Cu-Sb and Sb-As correlations were evaluated for soils from Puchuncaví and Catemu valleys, corroborating that high concentrations of copper, arsenic and antimony in these soils coming from the same pollution sources, the copper industry and the thermoelectric power plant.     

Multi-year monitoring of estuarine sediments as ultimate sink for DDT, HCH, and other organochlorinated pesticides in Argentina

Forty-nine superficial sediment samples used in this study were collected from eight sites in the Bahia Blanca Estuary, located in the Buenos Aires Province southwest, Argentina, in a period between April 2005 and March 2009, to assess the concentration levels, spatial and seasonal distribution, and putative input sources of 18 selected organochlorine pesticides (OCs), following UNEP-IAEA procedures. Average concentration levels in sediments ranged between 3.54 and 63.79 ng g^???1, d.w. (mean = 15.99 ng g^???1, d.w.), for ??OCs, and from nondetectable to 8.03 ng g^???1, d.w. (mean = 2.16 ng g^???1, d.w.), and from nondetectable to 3.20 ng g^???1 (mean = 0.97 ng g^???1, d.w.) for hexachlorocyclohexanes (HCHs) and dichlorodiphenyltrichloroethanes (DDTs), respectively. Principal component analysis allowed the classification of sampling sites according to the main OCs inputs over the estuary. In comparison to other worldwide locations and to the world coastal sediment concentrations range, sediment DDTs and HCHs levels were in the low range; on the opposite, ??OCs average was in the medium range. OCs seasonal distribution was found to be highly correlated with the precipitations seasonality and sowing seasons in the adjacent agriculture fields. In addition, an ecotoxicological risk assessment pointed industrial and agriculture catchment zones with intermediate probability of adverse effects to biota, while the city sewage outfall was classified with none indication of an immediate threat. Data indicated that the estuary sediments were functioning as a sink for persistent OC pesticides (either in use or banned), however, it was found a declining trend on their environmental burden.     

Natural factors and mining activity bearings on the water quality of the Choapa basin, North Central Chile: insights on the role of mafic volcanic rocks in the buffering of the acid drainage process

This contribution analyzes water chemical data for the Choapa basin, North Central Chile, for the period 1980-2004. The parameters considered are As, Cu Fe, pH, EC, SO??2, Cl?1, and HCO[Formula: see text], from samples taken in nine monitoring stations throughout the basin. Results show rather moderate contents of As, Cu, and Fe, with the exception of the Cuncumén River and the Aucó creek, explained by the influence of the huge porphyry copper deposit of Los Pelambres and by the presence of mining operations, respectively. When compared against results obtained in previous researches at the neighboring Elqui river basin, which host the El Indio Au-Cu-As district, a much reduced grade of pollution is recognized for the Choapa basin. Considering the effect of acid rock drainage (ARD)-related Cu contents on the fine fraction of the sediments of both river basins, the differences recorded are even more striking. Although the Los Pelambres porphyry copper deposit, on the headwaters of the Choapa river basin, is between one and two orders of magnitude bigger than El Indio, stream water and sediments of the former exhibit significantly lower copper contents than those of the latter. A main factor which may explain these results is the smaller degree of H(?+?)-metasomatism on the host rocks of the Los Pelambres deposit, where mafic andesitic volcanic rocks presenting propylitic hydrothermal alteration are dominant. This fact contrast with the highly altered host rocks of El Indio district, where most of them have lost their potential to neutralize ARD.     

A comparative performance evaluation of the AURAMS and CMAQ air-quality modelling systems

A harmonized comparative performance evaluation of A Unified Regional Air-quality Modelling System (AURAMS) v1.3.1b and Community Multiscale Air Quality (CMAQ) v4.6 air-quality modelling systems was conducted on the same North American grid for July 2002 using the same emission inventories, emissions processor, and input meteorology.Comparison of AURAMS- and CMAQ-predicted O₃ concentrations against hourly surface measurement data showed a lower normalized mean bias (NMB) of 20.7% for AURAMS versus 46.4% for CMAQ. However, AURAMS and CMAQ had more similar normalized mean errors (NMEs) of 46.9% and 54.2%, respectively. Both models did similarly well in predicting daily 1-h O₃ maximums; however, AURAMS performed better in calculating daily minimums. CMAQ's poorer performance for O₃ is partly due to its inability to correctly predict nighttime lows.Total PM_2.5 hourly surface concentration was under-predicted by both AURAMS and CMAQ with NMBs of ?10.4% and ?65.2%, respectively. However, as with O₃, both models had similar NMEs of 68.0% and 70.6%, respectively. In general, AURAMS performance was better than CMAQ for all major PM_2.5 species except nitrate and elemental carbon. Both models significantly under-predicted total organic aerosols (TOAs), although the mean AURAMS concentration was over four times larger than CMAQ's. The under-prediction of TOA was partly due to the exclusion of forest-fire emissions. Sea-salt aerosol made up approximately 50.2% of the AURAMS total PM_2.5 surface concentration versus only 6.2% in CMAQ when averaged over all grid cells. When averaged over land cells only, sea-salt still contributed 13.9% to the total PM_2.5 mass in AURAMS versus 2.0% in CMAQ.     

Penguin colonies as secondary sources of contamination with persistent organic pollutants

Although long-range atmospheric transport has been described as the predominant mechanism for exposing polar regions to persistent organic pollutants (POPs), recent studies have suggested that bird activity can also contribute substantially to contaminant levels in some environments. However, because the species so far reported have all been migratory, it has not been demonstrated conclusively whether locally elevated contamination represents transport from lower latitudes by the migrating birds or, alternatively, redistribution and concentration of contaminants that were already present in the high-latitude environments. The present study demonstrates, for the first time, that several POPs are present in elevated concentrations in an environment frequented by a non-migratory species (Adélie penguins) that spends its entire life in the Antarctic. Levels of POPs, such as p,p'-DDE, hexachlorobenzene (HCB), chlordanes (CHLs) and polychlorinated biphenyls (PCBs), were 10 to 100-fold higher in soil samples from penguin colonies than from reference areas. This significant difference is likely related to local penguin activity, such as a higher abundance of guano and the presence of bird carcasses. This hypothesis is also supported by a higher percentage of persistent congeners (PCB 99, 118, 138 and 153) in the soil from the colonies compared to the reference areas. This profile of PCB congeners closely matched profiles seen in penguin eggs or penguin blood.     

Conjunctive Vadose and Saturated Zone Monitoring for Subsurface Contamination

A comprehensive subsurface monitoring program should include contaminant detectors in both the vadose and saturated zones. Vadose zone detectors can provide an early warning of an impending groundwater contamination problem, and also yield information relevant to placing groundwater monitoring wells. Moisture probes, gas monitoring wells, and pore-liquid samplers deployed in the vadose zone complement groundwater detection wells. The objective(s) of a monitoring program, spatial-scales, and hydrogeology are important considerations for designing subsurface monitoring networks. Often, these networks are used to detect potential releases or characterize existing contamination beneath land-based waste storage facilities. A case study in Santa Barbara, California, U.S.A., illustrates the utility of vadose zone monitoring in characterizing a gasoline contamination problem and guiding the placement of groundwater monitoring wells.