Toxicity of Metal Cations for Daphnia

A statistically significant relationship was established between the median lethal concentrations of metal cations for daphnia and the maximum permissible concentrations of metals for fishery water bodies. A new eco-toxicological approach to the integrated assessment of the surface water contamination by metals, based on the combined risk concept, was developed. This approach can be used for assessment of the metal contamination of water bodies in various climatic zones and for analysis of the inter- and intra-annual trends of water body contamination.     

Uptake,Translocation, and Bioaccumulation of Elements in Forest Nettle (Laportea alatipes)

Elements found in the edible parts of plants are considered to be the main source of nutrients for humans and animals. However, there is insufficient information on the relationship between heavy metal pollution in the growing soil of most edible plants. In this study, the distribution of elements in the edible forest nettle (Laportea alatipes) was evaluated as a function of geographical location. Forest land soils had higher concentrations of minor elements (Cu, Cr, Ni, and Zn) compared to soils from rural and suburban areas. Translocation factors for Cd and Pb showed effective translocation from the roots to the leaves; however, these heavy metals in leaves were still above South African maximum permissible levels for vegetables. Atmospheric depositions may play a significant role in higher Cd and Pb concentrations in the leaves. Bioaccumulation factors showed the plant to accumulate Cu, Mn, and Zn to meet physiological requirement levels. Geoaccumulation indices and enrichment factors showed no soil contamination or minimal enrichment by trace metals. Principal component analysis showed Co, Cr, Cu, Fe, Ni, Pb, and Zn in soil to originate from a common source which may be soil silicates and other minerals.     

Rare-earth elements in soil and pine needle from northern terrestrial ecosystems

The experimental data on heavy metal and rare-earth element concentration in the environmental objects (pine needle and soil) caused by the enterprise for the production of mineral phosphoric fertilisers in Apatity (the industrial region in the Murmansk region, Kola Peninsula) have been obtained. The investigation was performed by neutron activation analysis at the IBR-2 research reactor in the Joint Institute for Nuclear Research. The analysis of nearly 40 element distributions in pine needle and soil from different geographical sites testifies about their contamination by a spectrum of elements, including REEs. Their contamination levels in the soil in the vicinity of the enterprise are significantly high.     

Analysis of Tea for Metals by Flame and Graphite Furnace Atomic Absorption Spectrometry with Multivariate Analysis

The concentrations of iron, zinc, manganese, copper, chromium, nickel, lead, arsenic, and cadmium were determined using flame and graphite furnace atomic absorption spectrometry in nine herbal tea samples. Hawthorn, yarrow, elderflower, and bearberry are herbal teas for which the metal content has been rarely determined. The concentration of cadmium in St John’s wort exceeded the maximum permissible limit of 0.3?mg/kg. The metals were also determined in aqueous extracts following 5, 10, and 20?min of boiling and using different preparations, including acidification with lemon juice. The influence of these factors on metal release was demonstrated using multivariate analyses by redundancy analysis and principal component analysis. The metal release was not considerably affected by the boiling time, while the acidity of the medium was generally positively correlated. For the infusions, arsenic was detected only in acidified mint tea. The extraction efficiencies of metals were determined and classified as highly, moderately, and poorly extractable, with chromium showing largest variations.     

Evaluation of Platanus occidentalis and Pinus sylvestris as bioindicators for lead and cadmium by slurry sampling-electrothermal atomic absorption spectrometry

Two higher plants (Platanus occidentalis and Pinus sylvestris) were used as bioindicators for assessment of contamination by Pb and Cd in an urban and industrialized area. Both toxic metals in plant tissue were determined by transverse-heated electrothermal atomic absorption spectrometry-longitudinal Zeeman background correction combined with automated ultrasonic slurry sampling. Twenty sampling points were established to observe a relationship between metal concentration in plant and traffic density. Screening optimization of variables influencing slurry preparations (sonication time, sonication power, and surfactant concentration) followed a fractional factorial design at 2 levels. No significant effects were observed in the interval of variables studied. Limits of detection of Pb and Cd in the plants were 0.28 and 0.025 microg/g (dry weight), respectively. Metal concentrations in the plants were in the range of 5-51 and 0.05-0.7 microg/g for Pb and Cd, respectively. Factor analysis to data of metal concentration in both plants, extractable metal content in soil, distance to traffic, and traffic density, showed a significant association between features such as concentration of Pb and Cd in leaves of P. occidentalis and traffic density, which accounted for the largest variance. Other features such as extractable metal contents in soil accounted for lesser variance, meaning that soils in the area investigated were less suitable than plants for monitoring metal pollution caused by vehicular traffic.     

Mercury ions complexation with a series of heterocyclic derivatives of 3-hydroxychromone: spectral effects and prospects for ultrasensitive Hg2+ probing

Complexation of three 3-hydroxychromone derivatives bearing a nitrogen-containing heterocyclic moiety in the position 2 of the chromone bicycle - benzimidazole, quinoline, and 2,5-diphenyloxazole, with mercury(II) ions is reported. Formation of chelate complexes with the metal cations coordinated with the cavity formed by 3-OH and 4-C═O groups was shown, as well as the possibility of side moiety heteroatom participation in binding of metal ions. High sensitivity to mercury of 2,5-diphenyloxazole-substituted 3-hydroxychromone was elucidated, allowing to detect Hg(2+) below the maximum permissible concentration for drinking water. This makes the above-mentioned compound a prospective basis for development of sensors for ultralow mercury concentration detection in water. Unusual fluorescence ignition of 2-(quinolin-2-yl)-3-hydroxychromone at low Hg(2+) concentrations, rarely observed for heavy metals ions complexation with organic fluorescent ligands, was discussed.     

Stability and Mobility of Metal-Humic Complexes Isolated from Different Soils

The contamination of potable water aquifers by heavy metals is one of the most severe environmental threats. For the transport of heavy metals from various types of contaminated sites into the ground water and also into surface water aquifers, humic substances (HS) are recognized to be of main importance. Dissolved in natural waters humic substances are readily complexed with a variety of metal ions. Therefore, humic substances are of cardinal importance for the migration and, consequently, the pollution of ground waters with heavy metals. Our paper presents the results of a comprehensive comparison of several isolated humic acids of soils of different origin (different geochemical milieu) and their metal complexes. Two polluted sites in Germany, which differ in their geochemical milieu (pH-value) were selected. The aim of our experiments was to describe the properties of terrestrial humic substances depending on their origin and genesis as well as the effects of the transport of humic substance-bound metals into the water-unsaturated soil zone. After determination of heavy metals in the soils by photon activation analysis the activated soil was used as an inherent tracer in batch experiments with the isolated humic acid. After adsorption of the loaded humic acid on an XAD-8 resin column, the partition of metals mobilized by humic acids could be quantified. There are correlations of the formation of metal-humic complexes with the soil pedogenes, with the pH-value as well as with the humic acid concentration.     

Model for the study of the impact of atmospheric heavy metals on soil microbial biomass

In the Castelporziano (Rome) protected area the inputs of atmospheric heavy metals on the soil-plant system were evaluated by the analysis of stem-flowing water from Quercus ilex L. The heavy metals detected in the soil under the canopies exhibited higher concentrations near to the tree trunks, highlighting the tree's capacity to concentrate such polluting substances. Microbial biomass, its specific respiration and the biomass calculated as a percentage of total soil organic matter, were utilised as indicators of the state of the soil and consequently also its quality with respect to heavy metal contamination.     

Sorption-photometric and test determination of lead in environmental materials

The main analytical characteristics of the reaction of hexaoxacycloazochrom with lead were determined. A method for the sorption preconcentration of lead on the Thiopan 14 sorbent was proposed. Procedures were developed for the photometric determination of lead in natural waters, air, and soil at the level of the maximum permissible concentration. A new melange gel technique for preparing silicic acid xerogels modified with hexaoxacycloazochrom was developed for the test determination of lead in environmental samples at the level of the maximum permissible concentration.     

Study on the feasibility of using transplanted Protousnea magellanica thalli as a bioindicator of atmospheric contamination

An experiment was performed to assess the feasibility of using transplantedProtousnea magellanica (Mont.) Krog thalli as a bioindicator of atmosphericheavy metal contamination. The thalli were collected for pristine areas ofNahuel Huapi National Park and transplanted back in the same site and at differentlocations at Bariloche city. One year later, the thalli were collected andtheir elemental contents were analyzed by instrumental neutron activactionanalysis and atomic absorption spectrometry. The present study shows thatthe use of transplanted thalli as a bioindicator of heavy metals renderedresults which are consistent with a previous study performed native lichenspecies.     

Heavy metals in petroleum-contaminated surface soils in Serbia

Investigation of heavy metal contamination levels as well as their association types with substrates in petroleum-contaminated surface soil was carried out using modified sequential extraction method. In that way, remobilization capacity of metal cations, both in natural conditions and in accidents, has been studied. Moreover, partitioning of heavy metals, originating from spilt oil derivative, among surface soil substrates was estimated. Extreme contamination with lead was discovered, as well as the increased concentrations of zinc and copper. Oil-derived Pb and Zn were found to be distributed between carbonates and amorphous Fe-oxides, whereas Cu was found to be dominantly associated with amorphous Fe-oxides. Appreciable amounts of these metals were also found to be incorporated into more resistant structures. In petroleum-contaminated surface soil, substrates of cadmium are carbonates, whereas nickel has the great affinity toward hydrous Mn-oxides. Cd is proven to be the most mobile metal in oil-contaminated surface soil.     

Gas-Chromatographic Separate Determination of Trace β-Chlorovinylarsonous Dichloroanhydride (Lewisite) and Anhydride (Lewisite Oxide) in Soil and Construction Materials

A method was proposed for the separate gas-chromatographic determination of β-chlorovinylarsonous dichloroanhydride (lewisite) and anhydride (lewisite oxide) in samples of soil and construction materials. Because of the absence of regulations for the maximum permissible concentration (MPC) of lewisite and lewisite oxide in construction materials (concrete, bricks, facing tile, etc.), the MPC level of lewisite in soil (0.1 mg/kg) was taken as the maximum permissible concentration in the development of the method for their determination in the above samples. The method is based on the solid-liquid extraction converting lewisite and lewisite oxide into components that can be separated at the stage of blowing-out the extractant in an inert gas flow and their subsequent conversion into acetylene with a 30% aqueous solution of sodium hydroxide and the chromatography of the vapor phase with flame-ionization detection. The error in the determination is no larger than ±20 rel %. The time of analysis is within 1.5 h.     

Biomonitoring of atmospheric trace element deposition around an industrial town in Ghana

Parmelia sulcata lichen species have been used to study the atmospheric deposition of heavy metals and other toxic elements around an industrial area in Ghana. Natural soil samples were collected at all the sampling points and analysed in order to investigate surface accumulation of the heavy metals. The sampling points used for the study were: Afienya, Doryemu Cemetery and Doryemu River. The surface accumulation of the heavy metals would be used to examine the correlation of the elements in the lichen and soil samples in order to separate contributions from atmospheric deposition and from that of soil minerals. Thermal neutron activation analysis techniques employing a 30 kW tank-in-pool research reactor operating at a thermal neutron flux of 5×10¹¹ s⁻¹ cm⁻² was used to determine Al, Cr, Mn, Fe, Ti, Th and V in both the lichen and soil samples. The level of contamination was quantified using the enrichment factor approach. This approach was adopted in order to ascertain whether these elements are enriched in the soil or in the atmosphere. The sampling points were enriched in the atmosphere with Cr, Mn, Fe, Ti, Th and V in the decreasing order of Afienya, Doryemu Cemetery and Doryemu River.     

Toxic metal species and food regulations--making a healthy choice

As a safeguard for human health, guidelines and regulations stipulating maximum permissible concentrations (MPCs) of metals in foods have been set to limit our dietary exposure to toxic metals. It is now well accepted, however, that the chemical form of the metal must be considered when assessing the possible human health consequences of exposure, and this in turn has led to discussion on the incorporation of speciation data in the setting of MPCs for metals in foods. Some practical aspects and implications of framing food legislation in terms of metal species are presented.     

Some Aspects on Preconcentration for Neutron Activation Analysis

A preconcentration method incorporated with neutron activation analysis was developed for the accurate determination of trace metals in biological and environmental samples. Bismuth diethyldithiocarbamate, thallium diethyldithiocarbarnate, and ammonium pyrrolidinedithiocarbamate were used as the preconcentration agents for three groups of metals. Trace metals were enriched and interfering elements such as Na, Br, P. K. etc. were removed simultaneously during the preconcentration process so that the sensitivity for each metal was greatly improved. Optimal conditions for sample digestion, group preconcentration of trace metals and neutron activation analysis of biological and environmental samples were discussed.     

A rapid fractionation method for heavy metals in soil by continuous-flow sequential extraction assisted by focused microwaves

A microwave-assisted continuous-flow sequential extraction system was developed for rapid fractionation analysis of heavy metals in soil. Insertion of pressure-adjusted air between the extractants provided stable flows of the extractants without mutual mixing and back-pressure influence of a column packed with soil, thereby facilitating reliable continuous-flow extractions. In addition, use of pure water as a pumping solvent removed metal contamination because of direct contact between corrosive extractants and the pump containing metallic materials. Focused microwave irradiation to the soil accelerated the selective extractions of the acid-soluble and reducible fractions of heavy metals in soil in the first and second steps of the sequential extraction conditions, as defined by the Commission of the European Bureau of Reference (BCR). The microwave-assisted continuous-flow extraction provided high correlations in amounts of six heavy metals except Zn in the first step and Cu in the second step extracted from a reference sludge soil, BCR CRM 483, with a conventional batchwise extraction proposed by BCR; continuous-flow extraction assisted by conductive heating provided lower correlations for all the six metals. The proposed method drastically reduced the time required for the sequence extraction to ca. 65 min without losing accuracy and precision of the fractionation analysis of heavy metals in soil, whereas the BCR batchwise method requires ca. 33 h. An erratum to this article can be found at     

Adsorption and desorption of copper and zinc in the surface layer of acid soils

The environmental and health effects of the contamination of soils by heavy metals depend on the ability of the soils to immobilize these contaminants. In this work, the adsorption and desorption of Cu and Zn in the surface layers of 27 acid soils were studied. Adsorption of Cu(II) from 157-3148 mumol L(-1) solutions was much greater than adsorption of Zn(II) from solutions at the same concentration. For both Cu and Zn, the adsorption data were fitted better by the Freundlich equation than by the Langmuir equation. Multiple regression analyses suggest that Cu and Zn adsorption depends to a significant extent on pH and CEC: for both metals these variables accounted for more than 80% of the variance in the Freundlich pre-exponential parameter K(F), and pH also accounted for 57% of the variance in 1/n for Zn and, together with carbon content, for 41% of the variance in 1/n for Cu. The percentage of adsorbed metal susceptible to desorption into 0.01 M NaNO3 was greater for Zn than for Cu, but in both cases depended significantly on pH, decreasing as pH increased. In turn, both pH(H2O) and pH(KCl) are significantly correlated with cation exchange capacity. Desorption of metal adsorbed from solutions at relatively low concentration (787 mumol L(-1)) exhibited power-law dependence on Kd, the quotient expressing distribution between soil and soil solution in the corresponding adsorption experiment, decreasing as increasing Kd reflected increasing affinity of the soil for the metal. The absence of a similarly clear relationship when metal had been adsorbed from solutions at relatively high concentration (2361 mumol L(-1)) is attributed to the scant between-soil variability of Kd at these higher concentrations. In general, adsorption was greater and subsequent desorption less in cultivated soils than in woodland soils.     

土壤重金属污染评价指标的研究进展

土壤重金属污染评价指标主要有：土壤重金属总含量，有效含量，土壤酶活性以及植物中毒临界含量等。由于受重金属污染的土壤中往往伴有多种重金属元素以及元素之间的交互作用，使得临界值的确定更为复杂，目前评价土壤重金属复合污染的方法主要是综合指数法。     

Risk assessment of inhalation exposure for airborne toxic metals using instrumental neutron activation analysis

In order to study the effects of air pollution, about 1,300 samples of airborne particulate matter (APM) were collected at suburban and industrial sites, in Daejeon, Korea from 1998 to 2006. The concentrations of carcinogenic (As and Cr) and non-carcinogenic metals (Al, Mn, and Zn) were determined by using instrumental neutron activation analysis (INAA). These long-term metal concentration data were applied to a risk assessment of inhalation exposure using Monte Carlo analysis (MCA).