Prediction of the solubility of zinc, copper, nickel, cadmium, and lead in metal-contaminated soils

Risk assessment of metal-contaminated soil depends on how precisely one can predict the solubility of metals in soils. Responses of plants and soil organisms to metal toxicity are explained by the variation in free metal ion activity in soil pore water. This study was undertaken to predict the free ion activity of Zn, Cu, Ni, Cd, and Pb in metal-contaminated soil as a function of pH, soil organic carbon, and extractable metal content. For this purpose, 21 surface soil samples (0–15 cm) were collected from agricultural lands of various locations receiving sewage sludge and industrial effluents for a long period. One soil sample was also collected from agricultural land which has been under intensive cropping and receiving irrigation through tube well water. Soil samples were varied widely in respect of physicochemical properties including metal content. Total Zn, Cu, Ni, Cd, and Pb in experimental soils were 2,015?±?3,373, 236?±?286, 103?±?192, 29.8?±?6.04, and 141?±?270 mg kg^?1, respectively. Free metal ion activity, viz., pZn²⁺, pCu²⁺, pNi²⁺, pCd²⁺, and pPb²⁺, as estimated by the Baker soil test was 9.37?±?1.89, 13.1?±?1.96, 12.8?±?1.89, 11.9?±?2.00, and 11.6?±?1.52, respectively. Free metal ion activity was predicted by pH-dependent Freundlich equation (solubility model) as a function of pH, organic carbon, and extractable metal. Results indicate that solubility model as a function of pH, Walkley–Black carbon (WBC), and ethylenediaminetetraacetic acid (EDTA)-extractable metals could explain the variation in pZn²⁺, pCu²⁺, pNi²⁺, pCd²⁺, and pPb²⁺ to the extent of 59, 56, 46, 52, and 51 %, respectively. Predictability of the solubility model based on pH, KMnO₄-oxidizable carbon, and diethylenetriaminepentaacetic acid-extractable or CaCl₂-extractable metal was inferior compared to that based on EDTA-extractable metals and WBC.     

Sand as a relevant fraction in geochemical studies in intertidal environments

Soil and sediment samples from several intertidal environment exposed to different types of contamination were studied to investigate the importance of grain size in relation to the capacity of the substrates to retain trace metals. The unfractionated samples (referred to as bulk samples) were separated into the following grain/size fractions: fine–coarse sand (2?0.100 mm), very fine sand (0.100?0.050 mm), silt (0.050?0.002 mm), and clay (0.002 mm). The sample into its fractions was carried out was in a glove box under high-purity N₂ atmosphere in order to minimize any alterations to the samples. The bulk samples were characterized in terms of physicochemical properties such as pH, redox potential, and grain size. The total organic carbon (TOC), total sulfur (S), iron (Fe) pyrite, Fe, and manganese (Mn), and trace metals lead (Pb), mercury (Hg), chromium (Cr), and nickel (Ni) were analyzed in the bulk samples and in each fraction. The sand fractions were also examined by scanning electron microscopy (SEM). Comparisons of the above parameters were made between fractions and between each fraction and the corresponding bulk sample. The fine–coarse sand fraction contained high levels of the primary elements of the geochemical processes that occur in marine sedimentary environments such as TOC, total Fe, Mn, and S. The net concentrations of these four elements were higher in the fine-coarse sand fraction than in the very fine sand fraction and were similar to the net concentrations in the silt and clay fractions. Detailed SEM analysis of the sand coarse fraction revealed the presence of Fe and aluminum oxyhydroxide coatings in the oxic layers, whereas the framboidal pyrites and coatings observed in the anoxic layers were Fe sulfides. The presence of the various coatings explains why the trace metal concentrations in the sand fine–coarse fraction were similar to those in the clay fraction and higher than those in the very fine sand fraction. The present results highlight the importance of the sand fraction, which is generally disregarded in geochemical and environmental studies of sedimentary layers.     

The LUCAS topsoil database and derived information on the regional variability of cropland topsoil properties in the European Union

Approximately 20,000 topsoil samples were collected in 25 European Union (EU) Member States (EU-27 except Bulgaria and Romania) with the aim to produce the first coherent pan-European physical and chemical topsoil database, which can serve as baseline information for an EU wide harmonized soil monitoring. The soil sampling was undertaken within the frame of the Land Use/Land Cover Area Frame Survey (LUCAS), a project to monitor changes in the management and character of the land surface of the EU. Soil samples have been analysed for basic soil properties, including particle size distribution, pH, organic carbon, carbonates, NPK, cation exchange capacity (CEC) and multispectral signatures. Preliminary studies show the outstanding potential of the dataset for enhancing the knowledge base on soils in the EU. The current paper provides an introduction to the LUCAS Topsoil 2009 project and provides an example of data applicability for cropland assessment by highlighting initial results for regional and national comparisons.     

Status and effect of pesticide residues in soils under different land uses of Andaman Islands, India

Pesticides are shown to have a great effect on soil organisms, but the effect varies with pesticide group and concentration, and is modified by soil organic carbon content and soil texture. In the humid tropical islands of Andaman, India, no systematic study was carried out on pesticide residues in soils of different land uses. The present study used the modified QuEChERS method for multiresidue extraction from soils and detection with a gas chromatograph. DDT and its various metabolites, α-endosulfan, β-endosulfan, endosulfan sulfate, aldrin, and fenvalerate, were detected from the study area. Among the different pesticide groups detected, endosulfan and DDT accounted for 41.7 % each followed by aldrin (16.7 %) and synthetic pyrethroid (8.3 %). A significantly higher concentration of pesticide residues was detected in rice–vegetable grown in the valley followed by rice–fallow and vegetable–fallow in the coastal plains. Soil microbial biomass carbon is negatively correlated with the total pesticide residues in soils, and it varied from 181.2 to 350.6 mg?kg^?1. Pesticide residues have adversely affected the soil microbial populations, more significantly the bacterial population. The Azotobacter population has decreased to the extent of 51.8 % while actinomycetes were the least affected though accounted for 32 % when compared to the soils with no residue.     

Ozone facilitated dechlorination of 2-chloroethanol and impact of organic solvents and activated charcoal

The ozone-initiated oxidation of 2-chloroethanol was followed by monitoring the consumption of the halogenated organic substrate. Gas chromatographic analysis of the ozonated products showed an increase in conversion from about 1 % after 3 h of ozone treatment to about 22 % after 12 h. The yields of major ozonated products identified and quantified namely acetaldehyde, acetic acid, and chloride ion increased proportionately as a function of ozone treatment time. The percent conversion of 2-chloroethanol in the presence of acetic acid or ethyl acetate were found to be higher than those under solvent-free conditions with similar products obtained. The use of activated charcoal during the ozonolyis of 2-chloroethanol showed a significant increase in the percent conversion of the substrate compared to solvent free ozonation. Based on the experimental findings, the overall mechanism for the reaction between 2-chloroethanol and ozone is described.     

Arsenic and other trace elements in two catfish species from Paranaguá Estuarine Complex, Paraná, Brazil

Concentrations of arsenic and four additional trace elements (Cu, Cr, Ni, and Zn) were determined by inductively coupled plasma–optical emission spectrometry in the muscular tissue of the yellow catfish (Cathorops spixii) and the urutu catfish (Genidens genidens) from Paranaguá Estuarine Complex, Brazil (PEC). The PEC can be characterized by an environment of high ecological and economic importance in which preserved areas of rainforest and mangroves coexist with urban activities as ports and industries. The average concentrations (in milligram per kilogram dry weight) of elements in the muscle tissue of C. spixii are as follows: Zn (31), As (17), Cu (1.17), Cr (0.62), and Ni (0.28). Similar concentrations could be found in G. genidens with exception of As: Zn (36), As (4.78), Cu (1.14), Cr (0.51), and Ni (0.14). Fish from the geographic northern rural region (Guaraqueçaba–Benito) display higher As concentrations in the muscle tissues than fish found in the south-western (urban) part of the PEC. An international comparison of muscle tissue concentrations of trace elements in fish was made. Except for Ni in C. spixii, a tendency of decrease in element concentration with increasing size (age) of the fish could be observed. According to the National Health Surveillance Agency of Brazil, levels of Cr and As exceeded the permissible limits for seafood. An estimation of the provisional tolerable weekly intake of As was calculated with 109 % for C. spixii and with 29 % for G. genidens.     

Validation of atmospheric aerosols parallel sampling in a multifold device

In this work, particulate matter was collected using an active sampling system consisting of a PM₁₀ (<10 μm) inlet coupled to a multifold device containing six channels, connected to a vacuum pump. Each channel was equipped with a filter holder fitted with adequately chosen filters. The system was fixed on a metallic structure, which was placed on the roof of the laboratory building, at the Faculty of Sciences, in Lisbon. Sampling took place under flow-controlled conditions. Aerosols were extracted from the filters with water, in defined conditions, and the water-soluble fraction was quantified by ion chromatography (IC) for the determination of inorganic anions (Cl^?, NO₃ ^? and SO₄ ^2?). Equivalent sampling through the various channels was validated. Validation was based on the metrological compatibility of the content results for the various filters. Ion masses are metrologically equivalent when their absolute difference is smaller than the respective expanded uncertainty. When this condition is verified, the studied multifold device produces equivalent samples.     

Feasibility study of rainwater harvesting system in Sylhet City

In rural areas in Bangladesh, groundwater is the principal source of water supply. This underground water is available in considerable amount in shallow aquifers. It is free from pathogenic microorganisms and hence water-borne diseases. In plain lands, other than hilly areas, water supply to 97% rural population comes from tube-wells, which is regarded to be a phenomenal achievement in preserving public health. Besides, a dependable water supply system all throughout the country is offset by two factors: (a) high salinity in surface plus groundwater in coastal areas; (b) want of suitable groundwater aquifers in hilly areas and the high cost of setting up tube-wells due to deep underground water table and stony layers. However, presence of arsenic in underground water now poses a serious threat to the success once made in water supply by setting up of manually operated tube-wells in the village areas—the achievement is now on the brink of total collapse. In about 61 districts out of 64, presence of arsenic exceeds a quantity of 0.05 mg/1, a permissible limit as per Bangladeshi water quality standard. Harvesting rainwater can be a pragmatic solution to this problem, which is common in many places in Sylhet especially in the hilly areas on the north eastern part of the city. This can be an alternative source of drinking water because of availability of rainwater from March to October. Heavy rain occurs from end of May till mid September, which is commonly known as the rainy season. This paper focuses on the possibility of harvesting rainwater in rural communities and thickly populated urban areas of Sylhet. It also demonstrates the scopes of harvesting rainwater using simple and low-cost technology. With setting up of a carefully planned rainwater storage tank, a family can have all of its drinking water from rain. Planned use of rainwater through rainwater harvesting in the roof catchments may fulfill the entire annual domestic water demand of a family in the rural areas of Bangladesh.     

Impact of water quality on bacterioplankton assemblage along Cértima River Basin (central western Portugal) assessed by PCR–DGGE and multivariate analysis

The information on bacterial community composition (BCC) in Portuguese water bodies is very scarce. Cértima River (central western Portugal) is known to have high levels of pollution, namely organic. In the present work, the BCC from a set of 16 water samples collected from Cértima River Basin and its main tributaries was characterized using 16S rDNA–denaturing gradient gel electrophoresis, a culture-independent molecular approach. Molecular data were related to environmental parameters through multivariate analysis to investigate potential impact of water pollution along the river. Principal component analysis using environmental data showed a water quality gradient from more pristine waters (at the mountain tributaries) to waters with increasingly eutrophic potential (such as Fermentelos Lake). This gradient was mainly defined by factors such as organic and inorganic nutrient sources, electrical conductivity, hydrogen carbonate concentration, and pH. Molecular results showed variations in BCC along Cértima River Basin but in the main river section, a Bacteroidetes phylotype (Flavobacterium sp.) proved to be dominant throughout the river course. Multivariate analysis suggests that spatial variation of BCC along the Cértima River Basin depended mainly on parameters such as Chl a, total suspended solid (TSS), total organic carbon, electrical conductivity, and HCO _boxclose^-_{3}^{-} levels. Bacteroidetes phylotypes were all related to higher electrical conductivity and HCO₃^-_{3}^{-} levels although some of these were also correlated with high SO₄^2-_{4}^{2-} and others with high soluble reactive phosphorus, nitrate, TN, and Kjeld-N levels. The Gammaproteobacteria occurrence was correlated with high SO₄^2-_{4}^{2-} levels. One of the Betaproteobacteria phylotypes showed to correlate with low redox potential (E_h) and high temperature, pH, TSS, and Chl a levels while another one showed a negative correlation with Chl a values.