Trace element speciation at cell membranes: aqueous, solid and lipid phase effects

Biological interest in trace element speciation has tended to be polarised in very different ways according to the concerns of the investigators. Much of the ecological interest has centred on the effects of metal ions in the external environment with the "free metal ion model" dominating discussions of potential toxicity. By way of contrast biochemists have been much more concerned with the stereochemical and kinetic aspects of specificity in metal protein interactions in the cytoplasm. Separating these two sets of interests are the membrane biophysicists whose studies have concentrated on the channel concept. All three groups have tended to ignore speciation onto the solid phase. In the overall biological context, trace element speciation in the cell is more concerned with kinetics and the evolution of specificity of interaction between diverse ligands than with the conditions for equilibrium.     

Trace element concentration in groundwater of Pesarlanka Island, Krishna Delta, India

There is a growing concern over the potential accumulation of trace element concentration in groundwater of coastal aquifer owing seawater encroachment in the last several decades. A total of 29 groundwater samples collected from Pesarlanka Island, Krishna delta, Andhra Pradesh, India were analyzed for 13 trace elements (B, V, Mn, Fe, Ni, Co, Cu, Zn, As, Sr, Cd, Ba, and Pb) using inductively coupled plasma mass spectrometry. The results reveal that B, Fe, Ni, As, Sr, and Pb vary from 11.22 to 710.2, 1.25 to 684.6, 0.02 to 37.33, 27.8 to 282.3, 164.1 to 7,009, and 1.97 to 164.4 μg/l, respectively. Ba, Cd, Co, Cu, Ni, V, and Zn are almost within permissible limits for drinking water, but As, Fe, Mn, Pb, B, and Sr are above the permissible limit. The toxic element Pb is 1.64 times more than the maximum permissible limits of drinking water. The minimum value of As is also 2.78 times more, whereas the maximum is 28.2 times the permissible limit. The spatial distributions of alkaline earths (Sr, Ba), transition metals (V, Co, Ni, Fe), metallic elements (Cu, Pb), and (As) were found in considerable variation in the entire Island. Good cross-correlations were found between As, B, Co, and Sr with total dissolved solids and among other trace elements such as B, As, Co, and Sr. The variability observed within the groundwater samples is closely connected to the sea spray input; hence, it is primarily a consequence of geographical and meteorological factors, such as distance from the ocean and time of year. The trace element levels, in particular those of heavy metals, are very low, suggesting an origin from natural sources rather than from anthropogenic contamination. A few trace elements (Sr and B) are found as sensitive parameters responding to changes in fresh to saline groundwater environment. The highly elevated trace elements in this area which may be attributed to marine sediments or death and decay of plants are presented in this paper.     

Trace metal speciation and contamination in an intertidal estuary

An analysis of the geochemical distribution of selected trace metals among various geochemical phases of the sediments in the Tees estuary was carried out using a sequential extraction technique and Differential Stripping Voltammetry. The sediments of the estuary are mainly organic rich clay silts and metal concentrations exceed those in the water column. Speciation results show that contamination of the estuary is mainly from anthropogenic sources. Pb and Zn are associated with the reducible, residual and oxidisable fractions. The speciation pattern of Cd was similar to those of lead and zinc. However there were also some exchangeable and bound to carbonate fractions although these were less significant. Cu is largely associated with the oxidisable and residual fractions, with insignificant bound to carbonate, exchangeable and reducible fractions. The most bioavailable forms of the metals are the free inorganic ions. Total metal concentrations in the estuary display a downward trend since the 1970s.     

Levels and speciation of heavy metals in soils of industrial Southern Nigeria

A knowledge of the total content of trace metals is not enoughto fully assess the environmental impact of polluted soils. Forthis reason, the determination of metal species in solution isimportant to evaluate their behaviour in the environment andtheir mobilization capacity. Sequential extraction procedure wasused to speciate five heavy metals (Cd, Pb, Cu, Ni and Zn) fromfour contaminated soils of Southern Nigeria into sixoperationally defined geochemical species: water soluble,enchangeable, carbonates, Fe-Mn oxide, organic and residual.Metal recoveries were within ± 10% of the independentlydetermined total Cd, Pb, Cu, Ni and Zn concentrations. The highest amount of Cd (avg. 30%) in the nonresidual fractionswas found in the exchangeable fraction, while Cu and Zn weresignificantly associated with the organic fraction. Thecarbonate fraction contained on average 14, 18.6, 12.6, 13 and11% and the residual fraction contained on average 47, 18, 33,50 and 25% of Cd, Pb, Cu, Ni and Zn respectively. Assuming thatmobility and bioavailability of these metals are related to thesolubility of the geochemical form of the metals, and that theydecrease in the order of extraction sequence, the apparentmobility and potential bioavailability for these five metals inthe soil were: Pb > Zn > Cu > Ni > Cd. The mobility indexes ofcopper and nickel correlated positively and significantly withthe total content of metals, while mobility indexes of cadmiumand zinc correlated negatively and significantly with the totalcontent of metals.     

A Framework for Comprehensive,Integrated, Watershed Monitoring in New York City

The International Life SciencesInstitute (ILSI) Risk Science Institute (RSI) convenedan expert panel of scientists to developrecommendations for a comprehensive monitoring programfor the Croton and Catskill/Delaware watersheds, whichprovide drinking water to New York City's residents. This effort was conducted as part of efforts topreserve and enhance the quality of New York City'sreservoir system through a watershed protectionprogram. The panel developed recommendations for astrategic framework on which to construct a monitoringprogram. As part of this activity, the paneldetermined whether existing monitoring activities weredeficient and, where activities were deficient, thepanel developed recommendations for additionalinformation that should be collected.The panel recommended the development and use of anintegrated approach to watershed monitoring, whichdraws on modeling, risk-based planning and analysis,statistical sampling and design, and basic compliancemonitoring. The approach should be designed toprovide an assessment of natural and anthropogenicsources of stress to the system as well as anassessment of water quality trends in response tostresses acting in concert, both over the long termand over the five-year New York City Memorandum ofAgreement (MOA) assessment time frame. It should alsoprovide an assessment of the human health andenvironmental risks posed by a variety of stressors,and the impact of management actions implemented toameliorate stressors.     

Trace metals speciation in coastal particulate matter for marine environmental studies in Antarctica

Solid speciation of some trace metals (Pb, Cd, Fe, Mn, Cu) having environmental relevance was studied in coastal particulate sampled during the Austral Spring 2000/2001. A nearshore station situated in the Gerlache Inlet of Terra Nova Bay (Ross Sea, Antarctica) was sampled from November to February. Samples were collected using the in situ filtration system FIS500, equipped with polycarbonate membrane filters having different pore sizes (10 microm, 2 microm and 0.4 microm) for the size fraction analysis of particles. The total concentration of metals was determined both in dissolved and particulate fractions, while speciation was determined on particulate by applying a sequential extraction procedure. Concerning the surface and sub-surface layers, it has been observed that concentration of elements is mainly affected by the dynamic of the pack ice melting and by phytoplankton activity.The solid speciation in November and December is similar for all the studied elements, while some differences can be noted in February, when the pack has completely melted and phytoplankton bloom occurs. With the exception of iron, during this sampling period the quantity of metal associated to the labile fraction increases.     

Distribution, speciation, and risk assessment of selected metals in the gold and iron mine soils of the catchment area of Miyun Reservoir, Beijing, China

In order to investigate the metal distribution, speciation, correlation and origin, risk assessment, 86 surface soil samples from the catchment area around the Miyun Reservoir, Beijing, including samples from gold and iron mine areas, were monitored for fractions of heavy metal and total contents. Most of the metal concentrations in the gold and iron mine soil samples exceeded the metal background levels in Beijing. The contents of most elements in the gold mine tailings were noticeably higher than those in the iron mine tailings. Geochemical speciation data of the metals showed that the residual fraction dominated most of the heavy metals in both mines. In both mine areas, Mn had the greatest the acid-soluble fraction (F1) per portion. The high secondary-phase fraction portion of Cd in gold mine samples indicated that there was a direct potential hazard to organisms in the tested areas. Multivariate analysis coupled with the contents of selected metals, showed that Hg, Pb, Cr, and Ni in gold mine areas represented anthropogenic sources; Cd, Pb, and Cr in iron mine areas represented industrial sources. There was moderate to high contamination of a few metals in the gold and iron soil samples, the contamination levels were relatively higher in gold mine than in iron mine soils.     

Survey of carbon monoxide concentrations in selected urban microenvironments

Carbon monoxide concentrations were measured in six shops situated in narrow busy streets of the city centre for ten days in winter and ten days in summer and correlated with the measurements simultaneaously performed at an outdoor background reference point. The correlation was significant for four out of six shops in winter, but not in summer. Day-to-day variations seemed to be influenced by gross contamination due to changing weather conditions whereas differences in concentration levels from site to site were strongly influenced by the proximity and density of traffic. The exposure of a pedestrian in winter was in good correlation with background outdoor levels and it was considerably lower than that of a car driver driving though the city.     

Indoor concentrations of carbon monoxide in selected urban microenvironments

CO concentrations were measured in five kindergartens, one children's hospital and two homes for aged, practically without indoor sources, all situated in the city centre, for ten random days in winter and ten in summer. The indoor CO concentrations were the result of the distance from and the traffic density in the nearest street, of general pollution level, seasonal differences, day-to-day variations and daily cycle of air pollution, the vicinity of traffic having a dominant influence. Therefore location of institutions for sensitive population groups in old city centres within a block of houses seems to be a suitable solution as far as exposure to CO is concerned.Revised version of a paper presented as poster at the VIth World Congress on Air Quality, Paris 1983.     

Soil phosphorus forms and their variations in selected paddy soils of Iran

Fractionation of soil phosphorus (P) can provide useful information for assessing the risk of soil P as the potential sources of eutrophication in aquatic systems. Little information exists on P forms in paddy soils of Isfahan Province in central Iran, where P fertilizers have been continuously applied for at least 45 years. The objectives of this study were to investigate concentrations and proportions of P forms in paddy soils and correlate the content of P forms with basic soil properties. Soil samples from three paddy sites were obtained, and soil P forms were determined by a modified Hedley fraction method. Results show that the total P concentrations ranged from 288 to 850 mg kg^?1 and were enriched in site 1. In all sites, the rank order of P fractions was HCl-P (CARB-P)?>?residual-P (RES-P)?>?NaOH-P (Fe-Al-P)?>?KCl-P (EXCH-P), indicating that Ca compounds are the main soil components contributing to P retention in these calcareous paddy soils. The EXCH-P represented on average?<?1 % of the total P, while the Fe-Al-P ranged 3.3–18 %. The CARB-P showed considerable contribution (63.6–85.6 %) to the total P. The Pearson correlation matrix indicated that Fe-Al-P only was positively correlated with total P, but did not show any significant correlations with other soil geochemical properties. Calcium-bound P fraction was significantly correlated with the clay, silt, cation exchange capacity, and total P.     

Microbial activities and trace element contents in an urban soil

Soil biological properties are influenced by trace metals. The main sources of these pollutants in the urban areas are industrial plants, power stations, domestic heating systems and motor vehicles. The aim of this work was to evaluate, in relation to distance from urban roads, soil trace metal concentrations (Pb, Cu, Cr, Cd and V) and their influence on C-microbial biomass as well as on soil respiration and enzyme activities (phosphatase glucosidase, galactosidase, xylanase, cellulase, trealase, protease and invertase). The samplings were carried out at four sites, along a route that goes from Giannone Street to Passionisti Street, two heavily travelled roads at two different times of the year (spring and autumn). Heavy metal contents and microbial activities were highest at the sites near the roads. The highest values of microbial activities were found in the inner site; here, on the contrary, the lowest concentrations of heavy metals were measured. Significant and negative correlations were found between microbial activity and heavy metal contents.     

Monitoring of total and bioavailable heavy metals concentration in agricultural soils

The aim of this paper is to evaluate total and bioavailable concentration of heavy metals in agricultural soils in order to estimate their distribution, to identify the possible correlations among toxic elements and the pollution sources, to distinguish the samples in relation to sampling site or to sampling depth, and to evaluate the available fraction providing information about the risky for plants. In particular, we reinvestigated total concentrations of As, Be, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, V, and Zn and available concentrations of As, Be, Cd, Cr, Cu, Hg, Ni, Pb, Sb, and Zn in soil from Apulia (Southern Italy). Analytical results showed that total concentrations, for all soils, are in the range permitted by regulations in force in Italy, but some soils evidence slight enrichment of Cd, Cr, Cu, Pb, and Zn. All the heavy metals in the available fraction were below the detection limits of the analytical techniques used except Cu, Ni, Pb, and Zn.     

Trace metal concentration in scalp hair of occupationally exposed autodrivers

The concentrations of Cr, Pb, Zn, Cu, Ni and Cd wereanalyzed by Atomic Absorption Spectrophotometer in thescalp hair of professional male autodrivers who areoccupationally exposed to the vehicular/industrialpollutants in the industrial city of Coimbatore, TamilNadu. The unwashed hair samples when compared with thewashed hair showed a significantly higher levels of Cr,Zn and Pb. The correlation coefficient showed a strongmutual dependence on the scalp hair of the exposedindividuals and no correlation was found among the tracemetals except for Ni–Pb and Ni–Cd. The results ingeneral showed a positive exogenous contribution of allthe analyzed industrial trace metals. The drivers who are occupationally exposed to vehicular/industrial pollution are at risk.     

Trace element content in tea brewed in traditional metallic and stainless steel teapots

The migration of metals in tea brewed in metallic teapots was investigated. The teapots were obtained from North Africa stores in Brussels in 2005–2006 and in 2011. Chinese gunpowder green tea, the most commonly used tea in the Moroccan community, was used to prepare the tea. Tea brewed in metallic teapots was compared to tea brewed in a glass vessel in order to evaluate the contribution of the tea and the teapots to the metal concentrations in the brewed tea. Tea samples were also collected in Moroccan households and in tearooms in Brussels. The elements As, Cd, Pb, Sn, Mn, Fe, Cr, Co, Ni, Cr, Cu, Zn, and Al were analyzed by high-resolution sector field inductively coupled mass spectrometry. The relationship between the metal composition of the alloy of the teapot and the metal concentration in tea was also investigated. Migration of Pb and to a lesser amount Ni, Cu, and Zn was observed in brass teapots and migration of Cd from a number of stainless steel teapots was observed. The soldering connecting the sprout to the teapot was shown to be an important source of Pb to the tea. High levels of Mn and Al were also observed in the brewed tea and these elements where shown to originate from the tea itself. Metal exposure from tea drinking was calculated for different tea consumption levels and different metal concentration levels and compared to toxicological reference values.     

Potentially toxic elements in urban soils: source apportionment and contamination assessment

Soils play a vital role in the quality of the urban environment and the health of its residents. City soils and street dusts accumulate various contaminants and particularly potentially toxic elements (PTEs) from a variety of human activities. This study investigates the current condition of elemental concentration in the urban soils of Hamedan, the largest and the fastest-growing city in western Iran. Thirty-four composite soil samples were collected from 0 to 10 cm topsoil of various land uses in Hamedan city and were analyzed for total concentration of 63 elements by ICP-MS. The possible sources of elemental loadings were verified using multivariate statistical methods (principal component analysis and cluster analysis) and geochemical indices. The spatial variability of the main PTEs was mapped using geographic information system (GIS) technique. The results revealed a concentration for As, Co, Cr, Mn, Mo, Ni, and V in the soil samples comparable to the background values as well as a range of associations among these elements in a single component suggesting geogenic sources related to geological and pedogenic processes, while the soils mostly presented a moderate to considerable enrichment/contamination of Cd, Zn, Pb, and Sb and moderate enrichment/contamination of Cu, Zn, and Mo. It was found that anthropogenic factors, vehicular traffic in particular, control the concentration of a spectrum of elements that are typical of human activities, i.e., Cd, Cu, Hg, Pb, Sb, and Zn. Lead and Sb were both the most enriched elements in soils with no correlation with land use highlighting general urban emissions over time and the impact of transport networks directly on soil quality. The highest concentrations of As were recorded in the southern part of the city reflecting the influence of metamorphic rocks. The effect of the geological substrate on the Co and Ni contents was confirmed by their maximum concentrations in the city’s marginal areas. However, high spatial variability of urban elements’ contents displayed the contribution of various human activities. In particular, the increased concentration of Cd, Sb, and Pb was found to be consistent with the areas where vehicular traffic is heaviest.     

Trace element biomonitoring using mosses in urban areas affected by mud volcanoes around Mt. Etna. The case of the Salinelle, Italy

Trace element impact was assessed using mosses in a densely inhabited area affected by mud volcanoes. Such volcanoes, locally called Salinelle, are phenomena that occur around Mt. Etna (Sicily, Italy) and are interpreted as the surface outflow of a hydrothermal system located below Mt. Etna, releasing sedimentary fluids (hydrocarbons and NaCl brines) along with magmatic gases (mainly CO(2) and He). To date, scarce data are available about the presence of trace elements, and no biomonitoring campaigns are reported about the cumulative effects of such emissions. In this study, concentrations of Al, As, Cd, Cr, Cu, Hg, Mn, Ni, Pb, V, and Zn were detected in the moss Bryum argenteum, in soil and water. Results showed that the trace element contribution of the Salinelle to the general pollution was significant for Al, Mn, Ni, and Zn. The comparison of trace concentrations in mosses from Salinelle and Etna showed that the mud volcanoes release a greater amount of Al and Mn, whereas similar values of Ni were found. Natural emissions of trace elements could be hazardous in human settlements, in particular, the Salinelle seem to play an important role in environmental pollution.     

Total concentrations and speciation of heavy metals in soils of the Shenyang Zhangshi Irrigation Area, China

The Shenyang Zhangshi Irrigation Area (SZIA) was used for the spreading of municipal and industrial waste water, which is an economic way of irrigating crops, recycling nutrients and water treatment. Long-term irrigation resulted in a severe metal contamination of soils. To identify the soil phases implicated in retaining the metals, sequential extractions were performed. The most predominant metal was cadmium which was mainly associated with mobile, easily soluble and easily reducible fractions. Copper was mainly associated with the residual, EDTA extractable and moderately reducible fractions. Lead was bound to organic matter and poorly crystalline Fe-oxides. Nickel and zinc were mainly associated with the residual and strongly reducible fractions. Although copper, lead, nickel and zinc concentrations were of minor importance mobile metal concentrations of these metals as well as of cadmium exceeded German trigger values for plant production and plant growth.     

Heavy metal contamination of urban soils and dusts in Guangzhou, South China

The heavy metal concentrations of soil and dust samples from roadside, residential areas, parks, campus sport grounds, and commercial sites were studied in Guangzhou, South China. Heavy metals in samples were determined by inductively coupled plasma atomic emission spectrophotometer following acidic digestion with HClO₄ + HF + HNO₃. High concentrations, especially of Cd, Pb, and Zn, were found with mean concentrations of Cd, Cr, Cu, Ni, Pb, and Zn in the urban dusts being 4.22?±?1.21, 62.2?±?27.1, 116?±?30, 31.9?±?12.6, 72.6?±?17.9, and 504?±?191 mg/kg dry weight, respectively. The respective levels in urban soils (0.23?±?0.19, 22.4?±?13.8, 41.6?±?29.4, 11.1?±?5.3, 65.4?±?40.2, and 277?±?214 mg/kg dry weight, respectively), were significantly lower. The integrated pollution index of six metals varied from 0.25 to 3.4 and from 2.5 to 8.4 in urban soils and dusts, respectively, with 61 % of urban soil samples being classified as moderately to highly polluted and all dust samples being classified as highly polluted. The statistical analysis results for the urban dust showed good agreement between principal component analysis and cluster analysis, but distinctly different elemental associations and clustering patterns were observed among heavy metals in the urban soils. The results of multivariate statistic analysis indicated that Cr and Ni concentrations were mainly of natural origin, while Cd, Cu, Pb, and Zn were derived from anthropogenic activities.