Factor analysis and linear regression model (LRM) of metal speciation and physico-chemical characters of groundwater samples

An approach is described for viewing the interrelationship between different variables and also tracing the sources of pollution of groundwater of north Chennai (India). The data set of 43 variables which include major ions, minor ions and trace metal speciation (Cu, Pb, Cd and Zn) collected during the pre-monsoon and post-monsoon seasons of the year 2000–2001, was subjected to R-mode factor analysis to comprehend the distribution pattern of the said variables. It was found that first factor measures salinity and hardness which explained 19.12% of the total variance (comprised of variables EC, TDS, Na⁺, K⁺, Ca²⁺, Mg²⁺, total hardness, Cl⁻ and SO₄ ²⁻) during pre-monsoon, while it was 25.08% during post-monsoon. The second and third factors were attributed to speciation of zinc and copper ions during both pre-monsoon and post-monsoon. Although there were two more factors, loaded with speciation parameters of lead and cadmium, the variance of them were less than 10%. From this study it is seen that sea water intrusion, municipal solid waste disposal are the identified sources of component of pollution. The importance of metal ions is taking a secondary role and the anthropogenic origin-industrial activity, is the reason in the evaluation of pollution status as they come in the second, third, fourth and fifth factors. As the trace metal speciation was grouped in separate factors, linear regression model (LRM) with correlation analysis was applied to check its validity for prediction of speciation and to apply LRM for rapid monitoring of water pollution.     

The influence of diet on intra and inter-individual variability of urinary excretion of arsenic species in Italian healthy individuals

To study the effect of eating foods with a high arsenic (As) content on the intra and inter-individual variability of urinary concentrations of the As species, daily urine samples were collected for 10 consecutive days from 12 healthy male subjects. A daily food diary was kept throughout the study period. Personal exposure to airborne As was measured once during the study. As³, As⁵, monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) and arsenobetaine were determined in all urine samples by inductive coupled plasma mass spectrometry, and the sum of As³ + As⁵ + MMA + DMA (iAs) by hydride generation-atomic absorption spectrophotometry. Exposure to airborne As was below the limit of detection in all samplings. As³ was found in only 19.2% and As⁵ in only 3.3% of the urine samples, whereas high urinary concentrations of arsenobetaine were observed. With the exception of arsenobetaine, expressed as a percentage, a significant inter-individual variability was observed for all species of As, for iAs and for the MMA/DMA ratio (p < 0.001). Instead, the intra-individual variability was significant only for the MMA/DMA ratio (p < 0.001). Among foods with a high As content, only a heavy consumption of seafood was shown to influence inter-individual variability of DMA%, arsenobetaine expressed as μg g⁻¹ creatinine and iAs. In conclusion, even in populations with a high intake of organic As through foods, the finding of a significant inter-individual but no significant intra-individual variability of urinary species confirms the usefulness of urinary As speciation for biological monitoring of exposure to As.     

植物-微生物联合修复石油-重金属复合污染土壤的研究

植物及微生物联合修复石油-重金属复合污染土壤具有很大的潜力。但重金属以不同形态存在关系到石油-重金属复合污染土壤生物修复过程中,植物、微生物的修复效率以及是否需要增加辅助工程解决重金属污染等问题,因此石油-重金属复合污染土壤修复过程中就必须考虑重金属有效态及形态的变化特征。     

玉米秸秆添加比例对污泥堆肥中Cu和Zn形态的影响

采用BCR连续提取法研究了玉米秸秆添加比例对污泥堆肥中Cu和Zn形态的影响.结果表明:重金属不同形态分配比例的变化能够准确反映重金属形态之间的转化规律;堆肥处理重金属总量不会变化,只是不稳定形态之间相互转化,Cu和Zn被大幅"浓缩",玉米秸秆比例越大,"浓缩效应"越明显;玉米秸秆比例增加有助于酸溶态Cu向可氧化态转化,...     

Determination of zinc speciation in basic oxygen furnace flying dust by chemical extractions and X-ray spectroscopy

There is a growing concern regarding the environmental and public health risks associated with airborne particulate matter (PM). The basic oxygen furnace is one of the most important atmospheric dust sources of the steel manufacturing process. It emits dust enriched in heavy metal such as Zn, which is assumed to contribute to the toxic potential of atmospheric PM. Dust collected before and after the filtration system was analyzed to determine Zn speciation. To this end, a variety of analytical tools were used and a sequential extraction protocol has been specifically developed for iron and steel dust. The Zn speciation results obtained by EXAFS and sequential extraction were in excellent agreement. Before filtration, the speciation of Zn in BOF was 43% ZnFe₂O₄, 23% ZnCO₃ and 16% ZnO. The same species were detected after filtration with different proportions. BOF dust after filtration contains more soluble Zn phases which may play a role in the toxic effects of the emissions.     

One-dimensional model for biogeochemical interactions and permeability reduction in soils during leachate permeation

This paper uses the findings from a column study to develop a reactive model for exploring the interactions occurring in leachate-contaminated soils. The changes occurring in the concentrations of acetic acid, sulphate, suspended and attached biomass, Fe(II), Mn(II), calcium, carbonate ions, and pH in the column are assessed. The mathematical model considers geochemical equilibrium, kinetic biodegradation, precipitation-dissolution reactions, bacterial and substrate transport, and permeability reduction arising from bacterial growth and gas production. A two-step sequential operator splitting method is used to solve the coupled transport and biogeochemical reaction equations. The model gives satisfactory fits to experimental data and the simulations show that the transport of metals in soil is controlled by multiple competing biotic and abiotic reactions. These findings suggest that bioaccumulation and gas formation, compared to chemical precipitation, have a larger influence on hydraulic conductivity reduction.     

Arsenic accumulation by the aquatic fern Azolla: comparison of arsenate uptake, speciation and efflux by A. caroliniana and A. filiculoides

This study investigates As accumulation and tolerance of the aquatic fern Azolla. Fifty strains of Azolla showed a large variation in As accumulation. The highest- and lowest-accumulating ferns among the 50 strains were chosen for further investigations. Azolla caroliniana accumulated two times more As than Azolla filiculoides owing to a higher influx velocity for arsenate. A. filiculoides was more resistant to external arsenate due to a lower uptake. Both strains showed a similar degree of tolerance to internal As. Arsenate and arsenite were the dominant As species in both Azolla strains, with methlyated As species accounting for <5% of the total As. A. filiculoides had a higher proportion of arsenite than A. caroliniana. Both strains effluxed more arsenate than arsenite, and the amount of As efflux was proportional to the amount of As accumulation. The potential of growing Azolla in paddy fields to reduce As transfer from soil and water to rice should be further evaluated.     

Accumulation, speciation and cellular localization of copper in Sesbania drummondii

Growth, accumulation and intracellular speciation and distribution of copper (Cu) in Sesbania drummondii was studied using scanning-electron microscopy (SEM), X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). The growth of seedlings was assessed in terms of biomass accumulation. The growth of the seedling was enhanced by 73.5% at a low Cu concentration (50 mg l⁻¹) compared to the control treatment. Additionally, seedling growth was inhibited by 18% at 300 mg l⁻¹ Cu with respect to the control. Copper concentration in roots and shoots was increased with increasing Cu concentration in the growth solution. The accumulation of Cu was found to be higher in roots than in the shoots. At a concentration of 300 mg l⁻¹ Cu, the roots accumulated 27,440 mg Cu kg⁻¹ dry weight (dw) while shoots accumulated 1282 mg Cu kg⁻¹ dw. Seedlings were assessed for photosynthetic activity by measuring chlorophyll a fluorescence parameters: F_v/F_m and F_v/F₀ values. Photosynthetic integrity was not affected by any of the Cu treatments. The X-ray absorption spectroscopic (XAS) studies showed that Cu was predominantly present as Cu(II) in Sesbania tissue. In addition, from the XAS studies it was shown that the Cu exists in a mixture of different coordination states consisting of Cu bound to sugars and small organic acids with some possible precipitated copper oxide. From the EXAFS studies, the coordination of Cu was determined to have four equatorial oxygen(nitrogen) ligands at 1.96 Å and two axial oxygen ligands at 2.31 Å. Scanning-electron microscopy studies revealed the distribution of Cu within the seedlings tissues, predominantly accumulated in the cortical and vascular (xylem) regions of root tissues. In the stem, most of the Cu was found within the xylem tissue. However, the deposition of Cu within the leaf tissues was in the parenchyma. The present study demonstrates the mechanisms employed by S. drummondii for Cu uptake and its biotransformation.     

Speciation of Solutes in Drainage and Pore Waters of Two Former Lignite Mines (Germany)

An experimental speciation scheme consisting of ultra-filtration(1 kD), cation and anion exchange has been developed. Parallel calculations of the ion balances are performed using the computerroutine MINTEQA2. The experimental and computed ion balances suffer from non-equilibrium conditions, incalculability of metal-binding colloids or sub-colloids, inaccurate Eh measurements and analytical errors. In most samples colloidal or sub-colloidal structures of Fe oxy-hydroxides and/or gypsum influence the behavior of many trace elements. The comparison of theory and experiment has to be restricted to acid waters (pH < 5) where colloids (1–450 nm) and non-filterable colloids or sub-colloids (<1 nm) play a minor role. Yet, only a few transition metals such as Mn, Fe, Co, Ni, Cu, Zn, or Cd remain more or less free of colloidal influence in low pH waters. The effect of DOC on Al may be estimated by model substances like citrate.     

Urban geochemistry: research strategies to assist risk assessment and remediation of brownfield sites in urban areas

Urban geochemical maps of Wolverhampton and Nottingham, based on multielement analysis of surface soils, have shown distribution patterns of “total” metals concentrations relating to past and present industrial and domestic land use and transport systems. Several methods have been used to estimate the solubility and potential bioavailability of metals, their mineral forms and potential risks to urban population groups. These include sequential chemical extraction, soil pore water extraction and analysis, mineralogical analysis by scanning electron microscopy, source apportionment by lead isotope analysis and the development of models to predict metal uptake by homegrown vegetables to provide an estimate of risk from metal consumption and exposure. The results from these research strategies have been integrated with a geographical information system (GIS) to provide data for future land-use planning.