Geochemical and environmental controls on the genesis of soluble efflorescent salts in Coastal Mine Tailings Deposits: A discussion based on reactive transport modeling

Water-soluble efflorescent salts often form on tailings in hyperarid climates. Their high solubility together with the high risk of human exposure to heavy metals such as Cu, Ni, Zn, etc., makes this occurrence a serious environmental problem.Understanding their formation (genesis) is therefore key to designing prevention and remediation strategies.A significant amount of these efflorescences has been described on the coastal area of Chañaral (Chile). There, highly soluble salts such as halite (NaCl) and eriochalcite (CuCl₂·2H₂O) form on 4 km² of marine shore tailings. Natural occurrence of eriochalcite is rare: its formation requires extreme environmental and geochemical conditions such as high evaporation rate and low relative air humidity, and continuous Cl and Cu supply from groundwater, etc. Its formation was examined by means of reactive transport modeling.A scenario is proposed involving sea water and subsequently a mixture of sea water/freshwater in the groundwater composition in the formation of these efflorescences. The strong competition from other halides (i.e. halite and silvite (KCl)) for the Cl may inhibit the precipitation of eriochalcite. Therefore, the Cl/Na ratio trend > 1 is a key parameter in its formation. Cation-exchange between Na⁺ and other major ions such as K⁺, Ca²⁺, Mg²⁺ and Cu²⁺ in the clay fraction of tailings is proposed to account for realistic Cl/Na ratios.With regard to preventing the formation of eriochalcite, a capillary barrier on the tailings surface is proposed as a suitable alternative. Its efficiency as a barrier is also tested by means of reactive transport models.     

Chemical composition and mass closure of ambient PM10 at urban sites

The chemical composition of PM10 was studied during summer and winter sampling campaigns conducted at two different urban sites in the city of Thessaloniki, Greece (urban-traffic, UT and urban-industrial, UI). PM10 samples were chemically analysed for minerals (Si, Al, Ca, Mg, Fe, Ti, K), trace elements (Cd, Cr, Cu, Mn, Pb, V, Zn, Te, Co, Ni, Se, Sr, As, and Sb), water-soluble ions (Cl^?, NO₃^?, SO₄^2?, Na⁺, K⁺, NH₄⁺, Ca²⁺, Mg²⁺) and carbonaceous compounds (OC, EC). Spatial variations of atmospheric concentrations showed significantly higher levels of minerals, some trace metals and TC at the UI site, while at the UT site significantly higher levels of elements like Cd, Ba, Sn, Sb and Te were observed. Crustal elements, excepting Ca at the UI site, did not exhibit significant seasonal variations at any site pointing to constant emissions throughout the year. In order to reconstruct the particle mass, the determined components were classified into six classes as follows: mineral matter (MIN), trace elements (TE), organic matter (OM), elemental carbon (EC), sea salt (SS) and secondary inorganic aerosol (SIA). Good correlations with slopes close to 1 were found between chemically determined and gravimetrically measured PM10 masses for both sites. According to the chemical mass closure obtained, the major components of PM10 at both sites were MIN (soil-derived compounds), followed by OM and SIA. The fraction unaccounted for by chemical analysis comprised on average 8% during winter and 15% during summer at the urban-industrial site, while at the urban-traffic site the percentages were 21.5% in winter and 4.8% in summer.     

Wet precipitation chemistry at a high-altitude site (3,326 m a.s.l.) in the southeastern Tibetan Plateau

This paper presents the results of wet precipitation chemistry from September 2009 to August 2010 at a high-altitude forest site in the southeastern Tibetan Plateau (TP). The alkaline wet precipitation, with pH ranging from 6.25 to 9.27, was attributed to the neutralization of dust in the atmosphere. Wet deposition levels of major ions and trace elements were generally comparable with other alpine and remote sites around the world. However, the apparently greater contents/fluxes of trace elements (V, Co, Ni, Cu, Zn, and Cd), compared to those in central and southern TP and pristine sites of the world, reflected potential anthropogenic disturbances. The almost equal mole concentrations and perfect linear relationships of Na⁺ and Cl^? suggested significant sea-salts sources, and was confirmed by calculating diverse sources. Crust mineral dust was responsible for a minor fraction of the chemical components (less than 15 %) except Al and Fe, while most species (without Na⁺, Cl^?, Mg²⁺, Al, and Fe) arose mainly from anthropogenic activities. High values of as-K⁺ (anthropogenic sources potassium), as-SO₄ ^2?, and as-NO₃ ^? observed in winter and spring demonstrated the great effects of biomass burning and fossil fuel combustion in these seasons, which coincided with haze layer outburst in South Asia. Atmospheric circulation exerted significant influences on the chemical components in wet deposition. Marine air masses mainly originating from the Bay of Bengal provided a large number of sea salts to the chemical composition, while trace elements during summer monsoon seasons were greatly affected by industrial emissions from South Asia. The flux of wet deposition was 1.12 kg?N?ha^?1?year^?1 for NH₄ ⁺–N and 0.29 kg?N?ha^?1?year^?1 for NO₃ ^?–N. The total atmospheric deposition of N was estimated to be 6.41 kg?N?ha^?1?year^?1, implying potential impacts on the alpine ecosystem in this region.     

Hydrochemical characteristics of mine waters from abandoned mining sites in Serbia and their impact on surface water quality

Upon completion of exploration and extraction of mineral resources, many mining sites have been abandoned without previously putting environmental protection measures in place. As a consequence, mine waters originating from such sites are discharged freely into surface water. Regional scale analyses were conducted to determine the hydrochemical characteristics of mine waters from abandoned sites featuring metal (Cu, Pb–Zn, Au, Fe, Sb, Mo, Bi, Hg) deposits, non-metallic minerals (coal, Mg, F, B) and uranium. The study included 80 mine water samples from 59 abandoned mining sites. Their cation composition was dominated by Ca²⁺, while the most common anions were found to be SO₄ ^2? and HCO₃ ^?. Strong correlations were established between the pH level and metal (Fe, Mn, Zn, Cu) concentrations in the mine waters. Hierarchical cluster analysis was applied to parameters generally indicative of pollution, such as pH, TDS, SO₄ ^2?, Fe total, and As total. Following this approach, mine water samples were grouped into three main clusters and six subclusters, depending on their potential environmental impact. Principal component analysis was used to group together variables that share the same variance. The extracted principal components indicated that sulfide oxidation and weathering of silicate and carbonate rocks were the primary processes, while pH buffering, adsorption and ion exchange were secondary drivers of the chemical composition of the analyzed mine waters. Surface waters, which received the mine waters, were examined. Analysis showed increases of sulfate and metal concentrations and general degradation of surface water quality.     

Ionic composition of TSP and PM2.5 during dust storms and air pollution episodes at Xi'an,China

TSP and PM_2.5 samples were collected at Xi'an, China during dust storms (DSs) and several types of pollution events, including haze, biomass burning, and firework displays. Aerosol mass concentrations were up to 2 times higher during the particulate matter (PM) events than on normal days (NDs), and all types of PM led to decreased visibility. Water-soluble ions (Na⁺, NH₄⁺, K⁺, Mg²⁺, Ca²⁺, F^?, Cl^?, NO₃^?, and SO₄^2?). were major aerosol components during the pollution episodes, but their concentrations were lower during DSs. NH₄⁺, K⁺, F^?, Cl^?, NO₃^?, and SO₄^2? were more abundant in PM_2.5 than TSP but the opposite was true for Mg²⁺ and Ca²⁺. PM collected on hazy days was enriched with secondary species (NH₄⁺, NO₃^?, and SO₄²) while PM from straw combustion showed high K⁺ and Cl^?. Firework displays caused increases in K⁺ and also enrichments of NO₃^? relative to SO₄^2?. During DSs, the concentrations of secondary aerosol components were low, but Ca²⁺ was abundant. Ion balance calculations indicate that PM from haze and straw combustion was acidic while the DSs samples were alkaline and the fireworks' PM was close to neutral. Ion ratios (SO₄^2?/K⁺, NO₃^?/SO₄^2?, and Cl^?/K⁺) proved effective as indicators for different pollution episodes.     

Quantitative chemical composition and characteristics of aerosols over western India: One-year record of temporal variability

One-year quantitative chemical data set consisting of water-soluble constituents (NH₄⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Cl^?, NO₃^?, SO₄^2? and HCO₃^?), crustal and trace elements (Al, Fe, Ca, Mg, K, Mn, Zn, Pb) and carbonaceous species (OC, EC) in ambient aerosols, collected over an urban site located in a high-dust semi-arid region of western India, reveals excellent linear relationship (r² = 0.92; slope = 0.96 ± 0.05) between gravimetrically assessed TSP (total suspended particulates) and chemically analyzed aerosol mass. The TSP abundance ranging from 60 to 250 μg m^?3, over a period of 12 months (January–December), is dominated by mineral dust (～70%); whereas contribution from sea-salts, anthropogenic and carbonaceous species exhibits significant temporal variability depending upon the wind regimes. The mineral dust is enriched in Ca, Mg and Fe with respect to upper continental crust (UCC); whereas Zn and Pb exhibit a characteristic anthropogenic source and high enrichment factors. The carbonaceous species show significant seasonality; with dominance of OC (range: 4.6–28 μg m^?3; average: 12.8 μg m^?3; SD: 6.8) and minor contribution from EC (range: 0.3–4.4 μg m^?3; average: 2.4 μg m^?3; SD: 1.4). The observed concentrations are significantly lower than those reported for the metro cities in South Asia but the OC/EC ratios (range: 4.3–35; average: 8.3; SD: 5.7) are significantly higher than the characteristic ratio (～2–4) reported for the urban atmosphere. Such quantitative chemical characterization of aerosols is essential in assessing their role in atmospheric chemistry and climate change. This study could also be useful in understanding the physical and optical aerosol properties documented from the same site and thus, in validating regional climate models.     

Characterization of major pollution events (dust, haze, and two festival events) at Agra, India

Total suspended particulate (TSP) samples were collected during dust, haze, and two festival events (Holi and Diwali) from February 2009 to June 2010. Pollutant gases (NO₂, SO₂, and O₃) along with the meteorological parameters were also measured during the four pollution events at Agra. The concentration of pollutant gases decreases during dust events (DEs), but the levels of the gases increase during other pollution events indicating the impact of anthropogenic emissions. The mass concentrations were about two times higher during pollution events than normal days (NDs). High TSP concentrations during Holi and Diwali events may be attributed to anthropogenic activities while increased combustion sources in addition to stagnant meteorological conditions contributed to high TSP mass during haze events. On the other hand, long-range transport of atmospheric particles plays a major role during DEs. In the dust samples, Ca²⁺, Cl^?, NO₃ ^?, and SO₄ ^2? were the most abundant ions and Ca²⁺ alone accounted for 22 % of the total ionic mass, while during haze event, the concentrations of secondary aerosols species, viz., NO₃ ^?, SO₄ ^2?, and NH₄ ⁺, were 3.6, 3.3, and 5.1 times higher than the normal days. During Diwali, SO₄ ^2? concentration (17.8 μg?m^?3) was highest followed by NO₃ ^?, K⁺, and Cl^? while the Holi samples were strongly enriched with Cl^? and K⁺ which together made up 32.7 % of the total water-soluble ions. The ion balances indicate that the haze samples were acidic. On the other hand, Holi, Diwali, and DE samples were enriched with cations. The carbonaceous aerosol shows strong variation with the highest concentration during Holi followed by haze, Diwali, DEs, and NDs. However, the secondary organic carbon concentration follows the order haze > DEs > Diwali > Holi > NDs. The scanning electron microscope/EDX results indicate that KCl and carbon-rich particles were more dominant during Holi and haze events while DE samples were enriched with particles of crustal origin.     

Major ionic compositions of fine particulate matter in an animal feeding operation facility and its vicinity

Animal feeding operations (AFOs) produce particulate matter (PM) and gaseous pollutants. Investigation of the chemical composition of PM_2.5 inside and in the local vicinity of AFOs can help to understand the impact of the AFO emissions on ambient secondary PM formation. This study was conducted on a commercial egg production farm in North Carolina. Samples of PM_2.5 were collected from five stations, with one located in an egg production house and the other four located in the vicinity of the farm along four wind directions. The major ions of NH₄⁺, Na⁺, K⁺, SO₄^2?, Cl^?, and NO₃^? were analyzed using ion chromatography (IC). In the house, the mostly abundant ions were SO₄^2?, Cl^?, and K⁺. At ambient stations, SO₄^2?, and NH₄⁺ were the two most abundant ions. In the house, NH₄⁺, SO₄^2?, and NO₃^? accounted for only 10% of the PM_2.5 mass; at ambient locations, NH₄⁺, SO₄^2?, and NO₃^? accounted for 36–41% of the PM_2.5 mass. In the house, NH₄⁺ had small seasonal variations indicating that gas-phase NH₃ was not the only major force driving its gas–particle partitioning. At the ambient stations, NH₄⁺ had the highest concentrations in summer. In the house, K⁺, Na⁺, and Cl^? were highly correlated with each other. In ambient locations, SO₄^2? and NH₄⁺ had a strong correlation, whereas in the house, SO₄^2? and NH₄⁺ had a very weak correlation. Ambient temperature and solar radiation were positively correlated with NH₄⁺ and SO₄^2?. This study suggests that secondary PM formation inside the animal house was not an important source of PM_2.5. In the vicinity, NH₃ emissions had greater impact on PM_2.5 formation.

ImplicationsThe chemical composition of PM_2.5 inside and in the local vicinity of AFOs showed the impact of the AFO emissions on ambient secondary PM_2.5 formation, and the fate and transport of air pollutants associated with AFOs. The results may help to manage in-house animal facility air quality, and to develop regional air quality control strategies and policies, especially in animal agriculture-concentrated areas.     

Quality of roof runoff waters from an urban region (Gda sk, Poland)

The paper presents the results of testing of roof runoff waters from buildings in the city of Gda sk (Poland), carried out as a part of a broader research project aimed at the determination of pollutant levels in precipitation. The analytes determined included volatile organohalogen compounds, petroleum hydrocarbons, Na⁺, K⁺, NH₄⁺, Mg²⁺, Ca²⁺, F⁻, Cl⁻, NO₂⁻, NO₃⁻, PO₄³⁻, SO₄²⁻ ions, as well as organonitrogen, organophosphorus and organochlorine pesticides. In addition, the toxicity and pH of the samples were examined. The samples were collected over a period of six months, during or immediately following precipitation events. More than half of the samples (25) were found to be toxic, with inhibition exceeding 20%. The toxicity was weakly correlated to the levels of organonitrogen and organophosphorus pesticides in runoff waters. It was established that at least in some cases the roofing material affected the levels of the pollutants found in the samples.     

Mine water geochemistry and metal flux in a major historic Pb-Zn-F orefield, the Yorkshire Pennines, UK

Recent studies have shown up to 6 % of rivers in England and Wales to be impacted by discharges from abandoned metal mines. Despite the large extent of impacts, there are still many areas where mine water impact assessments are limited by data availability. This study provides an overview of water quality, trace element composition and flux arising from one such area; the Yorkshire Pennine Orefield in the UK. Mine drainage waters across the orefield are characterised by Ca–HCO₃–SO₄-type waters, with moderate mineralization (specific electrical conductance: 160–525 μS cm^?1) and enrichment of dissolved Zn (≤2003 μg?L^?1), Ba (≤971 μg?L^?1), Pb (≤183 μg?L^?1) and Cd (≤12 μg?L^?1). The major ion composition of the waters reflects the Carboniferous gritstone and limestone-dominated country rock, the latter of which is heavily karstified in parts of the orefield, while sulphate and trace element enrichment is a product of the oxidation of galena, sphalerite and barite mineralization. Contaminant flux measurements at discharge sites highlight the disproportionate importance of large drainage levels across the region, which generally discharge into first-order headwater streams. Synoptic metal loading surveys undertaken in the Hebden Beck sub-catchment of the river Wharfe highlight the importance of major drainage levels to instream baseflow contamination, with diffuse sources from identifiable expanses of waste rock becoming increasingly prominent as river flows increase.     

Ion chromatographic determination of anions in rainwater

High acidity rainwater has recently become an issue in environmental pollution because of its great influence on ecological systems with special reference to the human environment. To solve this problem, the chemical behaviors of various pollutants in the air, particularly in the wet atmosphere must be studied. Ion chromatography was used for rapid analysis of trace amounts of anions.As a result, it was found that a combination of 2mM Na₂CO₃ and 5mM NaOH as an eluent was suitable for the separation of various anions. The reproducibility of determination of anions in standard solutions was found to be satisfactory with a coefficient of variation (CV) of 2–4% for F^?, Br^?, NO^?₃, SO^2?₃, SO^2?₄, and PO^3?₄, but not for NO^?₂. The determination of NO^?₂ was accomplished by preparing an eluent having almost the same composition and cencentration as that of the standard and sample solutions. The precision of the method with rainwater samples was less than 10%, and was considered to be usable for data analysis.In addition, a considerable number of ions in rainwater samples could be determined by using 1–3 ml of the sample without pretreatment. It was found that ion chromatography was one of the best means to obtain information on the chemical behaviors of trace amounts of anions in rainwater.     

Trends and variations of pH and hardness in a typical semi-arid river in a monsoon climate region during 1985–2009

The rapid growth of urbanization and industrialization, along with dramatic climate change, has strongly influenced hydrochemical characteristics in recent decades in China and thus could cause the variation of pH and general total hardness of a river. To explore such variations and their potential influencing factors in a river of the monsoon climate region, we analyzed a long-term monitoring dataset of pH, SO₄ ^2?, NO_x, general total hardness (GH), Mg²⁺, Ca²⁺, and Cl^? in surface water and groundwater in the Luan River basin from 1985 to 2009. The nonparametric Seasonal Kendall trend test was used to test the long-term trends of pH and GH. Relationship between the affecting factors, pH and GH were discussed. Results showed that pH showed a decreasing trend and that GH had an increasing trend in the long-term. Seasonal variation of pH and GH was mainly due to the typical monsoon climate. Results of correlation analysis showed that the unit area usage amounts of chemical fertilizer, NO₃ ^?, and SO₄ ^2? were negatively correlated with pH in groundwater. In addition, mining activity affected GH spatial variation. Acid deposition, drought, and increasing the use of chemical fertilizers would contribute to the acidification trend, and mining activities would affect the spatial variation of GH. Variations of precipitation and runoff in semi-arid monsoon climate areas had significant influences on the pH and GH. Our findings implied that human activities played a critical role in river acidification in the semi-arid monsoon climate region of northern China.     

Wet-deposition fluxes of soluble chemical species and the elements in insoluble materials

From March to June 1996, eight rain events were collected by sequential sampling on time and volume basis in Kyoto University, Uji, Japan. Soluble chemical species Cl⁻, NO₃⁻, SO₄²⁻, Na⁺, NH₄⁺, K⁺, Ca²⁺ and Mg²⁺ were measured by Ion Chromatography (IC); and the elements Si, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Br and Pb in insoluble materials were measured by proton-induced X-ray emission (PIXE) technique. The wet-deposition flux of a soluble chemical species (or an element in insoluble materials) was calculated by the product of the chemical species (or the element) concentration and the corresponding rain intensity. The characteristics of sequential cumulative wet-deposition flux of the soluble chemical species and the elements in insoluble materials were examined. The factor controlling wet-deposition flux was discussed.     

Ammonium,Nitrate and Nitrite Nitrogen and Nitrate Reductase Enzyme Activity in Groundnut (Arachis hypogaea L.) Fields After Diazinon,Imidacloprid and Lindane Treatments

Impacts of diazinon (O,O-diethyl O-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate), imidacloprid [1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine] and lindane (1,2,3,4,5.6-hexachlorocyclohexane) treatments on ammonium, nitrate, and nitrite nitrogen and nitrate reductase enzyme activities were determined in groundnut (Arachis hypogaea L.) field for three consecutive years (1997 to 1999). Diazinon was applied for both seed- and soil-treatments but imidacloprid and lindane were used for seed treatments only at recommended rates. Diazinon residues persisted for 60 days in both the cases. Average half-lives (t_1/2) of diazinon were found 29.3 and 34.8 days respectively in seed and soil treatments. In diazinon seed treatment, NH₄ ⁺, NO₃ ^?, and NO₂ ^? nitrogen and nitrate reductase activity were not affected. Whereas, diazinon soil treatment indicated significant increase in NH₄ ⁺-N in a 1-day sample, which continued until 90 days. Some declines in NO₃ ^?N were found from 15 to 60 days. Along with this decline, significant increases in NO₂ ^?N and nitrate reductase activity were found between 1 and 30 days. Imidacloprid and lindane persisted for 90 and 120 days with average half-lives (t_1/2) of 40.9 and 53.3 days, respectively. Within 90 days, imidacloprid residues lost by 73.17% to 82.49% while such losses for lindane residues were found 78.19% to 79.86 % within 120 days. In imidacloprid seed-treated field, stimulation of NO₃ ^?N and the decline in NH₄ ⁺NO₂ ^?-N and nitrate reductase enzyme activity were observed between 15 to 90 days. However, lindane seed treatment indicated significant increases in NH₄ ⁺-N, NO₂ ^?-N and nitrate reductase activity and some adverse effects on NO₃ ^?N between 15 and 90 days.     

Water soluble ions of atmospheric aerosols in three New Zealand cities: seasonal changes and sources

The results of one year's measurements (typically a two week sampling campaign in each season) of the concentrations of eight major water soluble ions, namely Na⁺, NH₄⁺, K⁺, Mg²⁺, Ca²⁺, Cl⁻, NO₃⁻ and SO₄²⁻, in atmospheric aerosols collected in three New Zealand cities (Auckland, Christchurch and Hamilton) are presented. The data has provided important information on particulate soluble ion profiles in New Zealand urban areas and revealed some useful trends.A significant correlation has been found between the average meteorological conditions in a sampling campaign and the average particulate concentrations of some of these soluble ions in the campaign. For example, average particulate NO₃⁻ concentration in a campaign was found to correlate well with the average calm or weak wind duration percentage in the campaign, and the average concentrations of Na⁺, Mg²⁺ and Cl⁻ related closely to the average wind pattern and rainfall in the campaign.Significant site and seasonal variations have been observed with Hamilton having the lowest overall concentrations of all the soluble ions in the particles sampled. On average all sites had the highest particulate concentrations of Na⁺, Mg²⁺ and Cl⁻ in the summer but the highest particulate concentrations of NH₄⁺ and non-sea-salt Ca²⁺ (nss-Ca²⁺) in the winter. The possible sources of PM₁₀ mass have been deduced and in particular the relative contribution of sea salts to PM₁₀ mass in the cities are reported.     

Size partitioning of particulate inorganic nitrogen species between the fine and coarse mode ranges and its implication to their deposition on the surface ocean

In order to discuss the dry deposition fluxes of atmospheric fixed nitrogen species, observations of aerosol chemistry including nitrate (NO₃^?) and ammonium (NH₄⁺) were conducted at two islands, Rishiri Island and Sado Island, over the Sea of Japan. Although the atmospheric concentrations of particulate NH₄⁺–N showed higher values than those of particulate NO₃^?–N at both sites, the dry deposition fluxes of the particulate NO₃^?–N were estimated to be higher than those of the particulate NH₄⁺–N. This was caused by the difference of particle sizes between the particulate NO₃^? and NH₄⁺; NH₄⁺ was almost totally contained in fine particles (d < 2.5 μm) with smaller deposition velocity, whereas NO₃^? was mainly contained in coarse particles (d > 2.5 μm) with greater deposition velocity. Fine mode NO₃^? was strongly associated with fine mode sea-salt and mineral particles, of which higher concentrations shifted the size of particulate NO₃^? toward the fine mode range. This size shift would decrease the dry deposition flux of the fixed nitrogen species on coastal waters and accelerate atmospheric transport of them to the remote oceanic areas.     

Impacts of simulated acid rain on recalcitrance of two different soils

Laboratory experiments were conducted to estimate the impacts of simulated acid rain (SAR) on recalcitrance in a Plinthudult and a Paleudalfs soil in south China, which were a variable and a permanent charge soil, respectively. Simulated acid rains were prepared at pH 2.0, 3.5, 5.0, and 6.0, by additions of different volumes of H₂SO₄ plus HNO₃ at a ratio of 6 to 1. The leaching period was designed to represent 5 years of local annual rainfall (1,200 mm) with a 33 % surface runoff loss. Both soils underwent both acidification stages of (1) cation exchange and (2) mineral weathering at SAR pH?2.0, whereas only cation exchange occurred above SAR pH?3.5, i.e., weathering did not commence. The cation exchange stage was more easily changed into that of mineral weathering in the Plinthudult than in the Paleudalfs soil, and there were some K⁺ and Mg²⁺ ions released on the stages of mineral weathering in the Paleudalfs soil. During the leaching, the release of exchangeable base cations followed the order Ca²⁺?>?K⁺?>?Mg²⁺?>?Na⁺ for the Plinthudult and Ca²⁺?>?Mg²⁺?>?Na⁺?>?K⁺ for the Paleudalfs soil. The SARs above pH?3.5 did not decrease soil pH or pH buffering capacity, while the SAR at pH?2.0 decreased soil pH and the buffering capacity significantly. We conclude that acid rain, which always has a pH from 3.5 to 5.6, only makes a small contribution to the acidification of agricultural soils of south China in the short term of 5 years. Also, Paleudalfs soils are more resistant to acid rain than Plinthudult soils. The different abilities to prevent leaching by acid rain depend upon the parent materials, types of clay minerals, and soil development degrees.     

Sources of submicron aerosol during fog-dominated wintertime at Kanpur

The main objective of this atmospheric study was to determine the major sources of PM₁ (particles having aerodynamic diameter <1.0 μm) within and near the city of Kanpur, in the Indo-Gangetic Plain. Day and night, 10 h long each, filter-based aerosol samples were collected for 4 months (November 2009 to February 2010) throughout the winter season. These samples were subjected to gravimetric and quantitative chemical analyses for determining water-soluble ions (NH₄ ⁺, F^?, Cl^?, NO₃ ^?, and SO₄ ^2?) using an ion chromatograph and trace elements using an inductively coupled plasma–optical emission spectrometer. The mean PM₁ mass concentrations were recorded as 114?±?71 μg/m³ (day) and 143?±?86 μg/m³ (night), respectively. A significantly higher diurnal contribution of ions (NH₄ ⁺, F^?, Cl^?, NO₃ ^?, and SO₄ ^2?) in PM₁ mass was observed during the fog-affected days and nights throughout the winter season, for which the average values were recorded as 38.09?±?13.39 % (day) and 34.98?±?12.59 % (night), respectively, of the total PM₁ mass. This chemical dataset was then used in a source-receptor model, UNMIX, and the model results are described in detail. UNMIX provided a maximum number of five source factors, including crustal material, composite vehicle, secondary aerosol, coal combustion, and iron/steel production and metallurgical industries, as the dominant air pollution sources for this study.     

An alkaline phosphatase from Bacillus amyloliquefaciens YP6 of new application in biodegradation of five broad-spectrum organophosphorus pesticides

In recent decades, biodegradation has been considered a promising and eco-friendly way to eliminate organophosphorus pesticides (OPs) from the environment. To enrich current biodegrading-enzyme resources, an alkaline phosphatase (AP3) from Bacillus amyloliquefaciens YP6 was characterized and utilized to test the potential for new applications in the biodegradation of five broad-spectrum OPs. Characterization of AP3 demonstrated that activity was optimal at 40?°C and pH 10.3. The activity of AP3 was enhanced by Mg²⁺, Ca²⁺, and Cu²⁺, and strongly inhibited by Mn²⁺, EDTA, and L-Cys. Compared to disodium phenyl phosphate, p-nitrophenyl phosphate (pNPP) was more suitable to AP3, and the V_m, K_m, k_cat, k_cat/K_m values of AP3 for pNPP were 4,033?U mg^?1, 12.2?mmol L^?1, 3.3?×?10⁶ s^?1, and 2.7?×?10⁸ s^?1mol^?1L, respectively. Degradation of the five OPs, which included chlorpyrifos, dichlorvos, dipterex, phoxim, and triazophos, was 18.7%, 53.0%, 5.5%, 68.3%, and 96.3%, respectively, after treatment with AP3 for 1?h. After treatment of the OP for 8?h, AP3 activities remained more than 80%, with the exception of phoxim. It can be postulated that AP3 may have a broad OP-degradation ability and could possibly provide excellent potential for biodegradation and bioremediation in polluted ecosystems.     

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.