Levels of some toxic elements and frequency of bacterial heavy metal resistance in sediment and sea water

The Golden Horn Estuary located in the Istanbul region of Turkey has been thought to be a heavily polluted area since the 1950s: the concentration of the elements, which include heavy metals such as Cu2+, Mn2+, Ni2+, Zn2+, Pb2+, Cd2+, and Fe2+, was therefore investigated in sediment and water samples of the area. The resistance of Enterobacteriaceae members to some heavy metal salts was investigated to determine levels of metal-resistant bacteria in the Golden Horn Estuary after the environmental restoration project in 1998. The sediment samples were collected with an Ekman-Grab in the period from November 2002 to February 2004 from depths of 4-15 m and analyzed by means of an atomic absorption spectrophotometer. Analyses of average heavy metals of sediment samples yielded the following results: 131.5 ppm Cu, 405.5 ppm Mn, 46.5 ppm Ni, 191.2 ppm Zn, 81.5 ppm Pb and 27668 ppm Fe. As with water, Ni concentrations in sediment were found lower than that in limit values. Frequency of heavy metals resistance to Cu, Zn, Fe, Ni, Mn, Pb and Cd was detected as an average of 65.0%, 64.4%, 62.5%, 38.4%, 37.3%, 36.2% and 28.4%, respectively in a total of 192 strains isolated from sediment samples. It was observed that there was no statistically significant difference among the results of analyses with respect to sampling dates. Despite the environmental restoration project in 1998, our study results showed that heavy metal levels were still high in the sediment and this situation induced the tolerance of bacteria to some heavy metals.     

Element content of propolis collected from different areas of South Spain

The aim of this work is to determine the content of essential and toxic elements in 25 raw propolis samples, when considering pollution agents and geographical and botanical factors. The microwave-assisted digestion was the most reliable and accurate method for determination of inorganic elements in propolis samples. The results were obtained using certified reference materials in a good agreement with certified values. Inductively coupled plasma atomic emission spectroscopy was used for the determination of 23 macro- and microelements (Ag, Al, As, B, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, S, Sb, Se, Si, Sn, and Zn). A Mercury analyzer was also utilized for the detection of the total Hg. Among the analyzed metals, Ca, K, Mg, Zn, Si, S, Fe, Al, P, and Na were found to be the most predominant. Heavy metals (As, Cd, Hg, and Pb) were determined in minimal concentration, and Pb was the highest mean contained toxic (<3.80 mg/kg), without influence on provisional tolerable weekly intake values. The method can be applied for routine analysis and quality and environmental pollution controls of toxic elements in propolis samples. The results obtained indicate no pollution of the collection areas and naturally high concentration of Al (460?±?62.2 mg/kg).     

Major and trace element contents in apples from a cultivated area of central Greece

Forty-two soil and apple samples from central Greece were collected and analyzed with regards to the content in major (Ca, Fe, K, Mg, Na, P, and S) and trace elements (As, B, Ba, Cd, Co, Cr, Cu, Hg, Mn, Mo, Ni, Pb, Sb, Sc, Se, Sr, Ti, and Zn). Soil samples were analyzed by inductively coupled plasma atomic emission spectrometry, while for the apples inductively coupled plasma mass spectrometry was implemented. Several elements such as As, B, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Se, Ti, and Zn, represent high concentrations in apples from the study area. These relatively high concentrations may be a consequence of the local geology, along with the excessive application of agricultural products such as fertilizers and agrochemicals.     

Homogeneity and stability study of the candidate reference material Adamussium colbecki for trace elements

The preparation of a new candidate certified reference material (CRM) for trace elements based on the antarctic bivalve Adamussium colbecki(IRMM 813) was carried out by the Istituto Superiore di Sanità(ISS, Rome, Italy) in cooperation with the Institute for Reference Materials and Measurements, Joint Research Centre of the European Commission (EC-JRC-IRMM), in the frame of the Italian National Programme of Research in Antarctica (Programma Nazionale di Ricerca in Antartide, PNRA). Samples were collected at Terra Nova Bay (Ross Sea) during the 2000-2001 expedition in Antarctica. The preparation of a material suitable for certification was performed by the EC-JRC-IRMM. Measurements for homogeneity and short-term stability tests were carried out by ISS. The elements selected for the certification project were As, Cd, Cu, Cr, Fe, Mn, Ni and Zn. For the above-mentioned tests, the determination of the elements of interest was performed on samples mineralised by microwave-assisted acid digestion. The analytical techniques employed to this end were inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma dynamic reaction cell quadrupole mass spectrometry (ICP-DRC-Q-MS). The candidate material was shown to be fit for purpose with regard to homogeneity and short-term stability, thus allowing the following phases of the certification project to be undertaken, in the first place the selection of expert laboratories for the accomplishment of the certification campaign.     

Monitoring of trace elements in honey from the Republic of Macedonia by atomic absorption spectrometry

Contents of Zn, Cu, Fe, Mn, Cd, Na, K, Ca and Mg in 123 honey samples from different regions of the Republic of Macedonia were determined by atomic absorption spectrometry. A microwave digestion system was applied for digestion of the samples. The mean content for the elements determined was found to be: 2.252, 0.696, 1.885, 1.752, 0.004, 29.52, 984.8, 40.11, 18.24 mg kg(-1) for Zn, Cu, Fe, Mn, Cd, Na, K, Ca and Mg, respectively. Based on a comparison of statistical parameters, the spatial distribution of particular elements in Macedonian honey and the results of factor analysis, two natural and one anthropogenic geochemical associations were identified. The natural geochemical associations (Mg, Mn, Ca, K and Fe, Zn, Ca, -K, -Na) are influenced mainly by lithology. The anthropogenic associations (Cd and -Cu) are mostly a result of metallurgical activities, namely lead production in the town of Veles.     

Distribution of Iron, Manganese, Zinc and Atrazine in Groundwater in Parts of Palar and Cheyyar River Basins, South India

A study was carried out in a part of Palar and Cheyyar river basin to evaluate the current status of iron, manganese, zinc and atrazine concentrations, their origin and distribution in groundwater. Groundwater samples were collected during post-monsoon (March 1998 and February 1999) and pre-monsoon (June 1999) periods from 41 sampling wells distributed throughout the study area. The groundwater samples were analyzed for trace metals using AAS and atrazine using HPLC. The concentration of the trace elements in groundwater is predominant during pre-monsoon period. Distribution pattern indicates that the concentration of these elements increases from west to northeast and towards Palar river. Lower concentrations in the central part may be due to recharge of fresh water from the lakes located here. During most of the months, as there is no flow in Palar river, the concentrations of trace elements in groundwater are high. Drinking water standards indicate that Mn and Zn cross the permissible limit recommended by EPA during the pre-monsoon period. A comparison of groundwater data with trace element chemistry of rock samples shows the abundance of trace elements both in the rock and water in the order of Fe > Mn > Zn and Fe > Zn > Mn. This indicates that iron in groundwater is derived from lithogenic origin. Further, Fe, Mn and Zn have good correlation in rock samples, while it is reverse in the case of water samples, indicating the non-lithogenic origin of Mn and Zn. Atrazine (a herbicide) was not detected in any of the groundwater samples in the study area, perhaps due to low-application rate and adsorption in the soil materials.     

Fractionation of eleven elements by chemical bonding from airborne particulate matter collected in an industrial city in Argentina

A four-step chemical sequential extraction procedure was used to evaluate the distribution of Al, As, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V and Zn in airborne particulate matter collected on glass fibre filters using a high-volume sampler. Two sets of samples were collected in 2001 (winter and summer campaigns) in representative zones of an industrial city of Argentina. The leaching scheme was applied to PM-10 particles and consisted in extracting the elements in four fractions, namely soluble and exchangeable elements; carbonates, oxides and reducible elements; bound to organic matter and sulfidic metals; and residual elements. Metals and metalloids at microg g(-1) level were determined in each fraction by inductively coupled plasma optical emission spectrometry (ICP OES). Analyte concentration varied from 14 microg g(-1) (equivalent to 1.0 ng m(-3)) for As to 11.8 mg g(-1) (equivalent to 2,089 ng m(-3)) for Al. Seven elements, namely Al, Cr, Fe, Mn, Pb, Ti and Zn showed similar distributions in both seasons while As was distributed in a significantly different manner in each season. The results exhibited low As contents in the first and second fractions that could be associated with routine coal combustion and a high content in the third and fourth fractions of the summer samples that could be linked to the use of pesticides. Aluminium, As, Cu, Mn, Ni, Ti, V and Zn were found in different percentages in the more bioavailable aqueous fraction with As, Mn, V and Zn exhibiting solubilities greater than 1% while Cr and Pb being insoluble. The content of Al, Cr, Cu, Fe, Ni, Pb, and Zn in the residual fraction was, in average, higher than 50%. A comparative assessment of the use of the underlying information available from fractionation studies compared to that obtained from total element content was done for Fe and Mn. It showed that the results obtained using chemical sequential extraction procedures allowed further discrimination of the potential air pollution sources.     

上海浦东新区环境空气重金属污染特征及来源解析

于2012年3月—2013年2月在浦东新区城区点和郊区点采集TSP样品,利用双酸消解原子荧光法、ICP法分析了样品中的13种元素。结果表明,除As略超标外其他元素均达标,城区点和郊区点环境空气重金属年均值排在前3位的元素是:Fe、Sn、Zn,占样品金属总量的83%~87%;排在末4位的元素是:Ni、Cr、As、Cd,占金属总量的1%~2%。通过EPA PMF 5.0模型运算结果,在城区中6个因子贡献比最高的31.5%为Sn+Fe+Mn,贡献比最低的2.1%为Hg;在郊区中6个因子贡献比最高的36.4%为Pb+Cu,贡献比最低的9.2%为Fe+Sn+Mn。浦东新区富集因子E≤10的元素有Cr、V、Ba、Mn、Ni、Fe、Hg城、Cu郊、As;富集因子E10的元素有Hg郊、Cu城、Zn、Pb、Cd、Sn。     

Heavy metal concentration and distribution in a dated sediment core of Nainital Lake in the Himalayan region

The concentrations and distribution of the elements, including heavy metals such as As, Ba, Br, Co, Cr, Cs, Fe, Ga, K, Mn, Na, Rb, Sc, Sr, Th and Zn, were investigated in dated sediment cores of Nainital Lake located in the Himalayan region, in Uttar Pradesh state of India, which is considered as a remote background area. The concentrations of the elements were measured by instrumental neutron activation analysis using the k0 method. The International Atomic Energy Agency certified reference material SL-3 was used to evaluate the accuracy of the method. The normalized data for a series of elements were used to understand the source of loading. Elements like Br, Co, Cr, Fe, K, Mn and Zn show a negative correlation with increasing depth whereas elements like As, Ba, Cs, Na and Rb show a positive correlation with increasing depth. By considering the concentration for the bottom segments of the core as close to the baseline concentration, recent flux values for different elements were calculated. An increase in the flux value was observed for Br, Cr, Fe, K, Mn and Zn, which can be attributed to anthropogenic contribution in recent years.     

Heavy Metal Pollution of Surface Soil in the Thrace Region, Turkey

Abstact Samples of surface soil were collected at 73 sites in the Thrace region, northwest part of Turkey. Two complementary analytical techniques, epithermal neutron activation analysis (ENAA) and atomic absorption spectrometry (AAS) with flame and graphite furnace atomization were used to determine 35 elements in the soil samples. Concentrations of As, Cd, Co, Cu, Mn, Ni, Pb and Zn were determined using AAS and GF AAS, and ENAA was used for the remaining 27 elements. Results for As, Ba, Br, Ca, Cd, Ce, Co, Cr, Cs, Cu Eu, Fe, Hf, I, In, K, La, Mn, Mo, Na, Nd, Ni, Pb, Rb, Sb, Sc, Sm, Sr, Ta, Tb, Th, Ti, U, V and Zn are reported for the first time for soils from this region. The results show that concentrations of most elements were little affected by the industrial and other anthropogenic activities performed in region. Except for distinctly higher levels of Pb, Cu, Cd and Zn in Istanbul district than the median values for the Thrace region, the observed distributions seem to be mainly associated with lithogenic variations. Spatial distributions of As, Cd, Cr, Cu, Ni, Pb and Zn were plotted in relation to the concentration values in soil using Geographic Information System (GIS) technology     

Distribution and Fractionation of Heavy Metals in Solid Waste from Selected Sites in the Industrial Belt of Delhi, India

Solid waste samples were collected from five small-scale industrial sites in the National Capital Territory (NCT) of Delhi. These industrial sites represent the regional spread of the industrial belt in the NCT of Delhi. Solid waste samples were digested using aqua-regia and HF in air tight teflon bombs for the quantitative analysis of heavy metals (Hg, Pb, Cd, Mn, Fe, Ni, Cu and Zn) by GBC model 902 atomic absorption spectrophotometer. Hg was analysed using hydrid generator attachment. Beside this sequential extraction was used to fractionate five heavy metals (Pb, Ni, Cd, Cu and Zn) into six operationally defined phases, viz. water soluble, exchangeable, carbonate-bound, Fe-Mn oxides, organic-bound and residual fractions to ascertain the relative mobility of these metals. The result obtained showed metal concentration to be in the range of Hg 0.42-2.3; Pb 23-530; Cd 014-224; Mn 494-19 964; Fe 35 684-233 119; Ni 192-1534; Cu 3065-10 144 and Zn 116-23 321 (all units in mg kg(-1)) in all the industrial areas studied. The fractionated toxic metals like Pb, Ni and Cd were observed to be in the range of 25-35, 15-50 and 40-50%, respectively, in mobile or bio-available fractions of solid waste. As this waste is often disposed-off by the roadsides, low lying areas, abandoned quarries or in landfill sites which are often not properly planned, thus posing potential risk to ground and surface water quality to millions of people living downstream.     

Geochemical fractionation of trace elements in sediments of Hugli River (Ganges) and Sundarban wetland (West Bengal, India)

A sequential extraction procedure was carried out to determinate the concentrations of 11 elements (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Zn) in different geochemical phases of sediments collected along the Hugli (Ganges) River Estuary and in the Sundarban mangrove wetland, eastern coastal part of India. The chemical speciation of elements was determined using the three-step sequential extraction procedure described by the European Community Bureau of Reference. Total metal concentration was determined using a microwave-assisted acid digestion procedure. Metal concentrations were near the background level except for As for which a moderate pollution can be hypothesized. The mobility order of the metals was: Cd?>?Mn?>?Cu?>?Zn?>?As?>?Co?>?Pb?>?Ni?>?Fe?>?Cr?>?Al. The highest percentage of Cd (>60%) was found in the most labile phase. Residual fraction was prevailing for Fe, Cr and Al, while Pb was mainly associated with the reducible fraction. Data were compared with Sediment Quality Guidelines to estimate the relationship between element concentrations and adverse biological effects on benthic community, finding the possibility of some toxic effects due to the presence of As in the entire studied area and Cd, only in Calcutta.     

Determination of selected heavy metals in air samples from the northern part of Jordan

In this work, the atmospheric concentrations of selected heavy metals including lead (Pb), iron (Fe), cadmium (Cd), copper (Cu), nickel (Ni), manganese (Mn), and zinc (Zn) were measured for two different sampling sites (urban and rural) in the northern part of Jordan (Irbid city). Samples were collected according to a certain schedule for 1 year. High volume air samplers and glass fiber filters were used to collect the samples. Collected samples were digested using a mixture of analytical grade nitric acid and analytical grade hydrochloric acid, and analyzed to evaluate the levels of heavy metals by atomic absorption spectrophotometry. Six heavy metals (Pb, Fe, Cu, Ni, Mn, and Zn) were measured in all samples; the concentrations of Cd and Co were not detected in Irbid atmosphere by atomic absorption spectroscopy. The results were used to determine the levels of heavy metal pollutants in air, possible sources, and to compare the levels of selected heavy metals in the two studied sites. Aerosols from the rural site have lower concentrations for all the metals compared to those from the urban site. The daily and monthly variations of the elements were investigated. All heavy metals in urban and rural sites reached maximum concentrations in June, July, and August. This is consistent with the increased activities leading to particulate matter emission during the summer period. The enrichment factors with respect to earth crust and correlation coefficients of heavy metals were investigated to predict the possible sources of heavy metals in air.     

Distribution of heavy metals in water and sediments of selected sites of Yamuna river (India)

The concentration of Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn metals in water and sediments of Yamuna river were determined by atomic absorption spectrophotometry in the year 1981. The data showed that there was considerable variation in the concentration of elements from one sampling station to the other which may be due to the variation in the quality of industrial and sewage wasters being added to the river at different sampling stations. The sediment samples collected from different sampling stations were also analysed for calcium carbonate, organic matter, potassium, and phosphorus.     

Dissolved and particulate metals in water from Sonora Coast: a pristine zone of Gulf of California

The purpose of this study was to investigate the distribution of metals (Cd, Pb, Hg, Cu, Fe, Mn, and Zn) in dissolved and particulate fractions in seawater from Bacochibampo Bay, Northern part of Mexico. Water samples were collected from November 2004 to October 2005. Metal analysis was done by graphite furnace atomic absorption spectroscopy. Results indicated highest concentrations of dissolved Cd and Zn in the sites localized at the mouth and center of the bay. During summer and spring, the highest levels of Cd, Mn, and Fe were detected, Zn in fall, and Pb and Cu in winter and spring. Mercury was the only metal that was not found in this fraction. In particulate fraction, Fe, Hg, and Mn were the most abundant elements in all the sampling sites, followed by Zn, Cu, Pb, and Cd. The highest levels of the majority of the metals were observed in the coastline, suggesting a continental and/or urban source for these chemicals. The highest level of Cd was detected during the summer and the rest of the metals in the fall. Statistically significant correlations were observed between dissolved and particulate forms of Pb:Mn, Cu:Fe, and Cu:Mn. The mean partition coefficient values were as follows: Fe>Mn>Cu>Pb>Cd>Zn. All dissolved metal concentrations found, except Pb, were lower than EPA-recommended water quality values. The levels of dissolved metals in this study reveal low bioavailability and toxic potential. However, further toxicological and sediment chemistry studies in this area are needed for a full risk assessment.     

抚顺市PM10中元素分布特征及来源分析

为了确定抚顺市PM10中元素的浓度特征及其来源,于2006—2007年的采暖季、风沙季和非采暖季在抚顺市的6个采样点采集PM10样品,并用等离子体原子发射光谱法(ICP-AES)测定样品中Ti、Al、Mn、Mg、Ca、Na、K、Cu、Zn、As、Pb、Cr、Ni、Co、Cd、Fe、V等17种元素的含量。结果表明,Al、Mg、Ca、Na、K、Mn、Fe等地壳元素在17种元素中占有较大比重,全年平均达到97.0%。富集因子分析结果表明,Cu、Zn、Pb、Cr、Co、Cd等元素在各季和各采样点明显受到人为活动影响,是典型的污染元素。主因子分析结果显示,土壤风沙尘、建筑尘、燃煤尘、道路扬尘、机动车尾气排放、金属冶炼、锰、铜、钛工业源是抚顺市PM10中元素的主要来源。     

Chemical speciation in natural and brine sea waters

A combined approach consisting of monitoring and thermodynamic modeling was used in order to calculate the concentration of trace element species in water samples of a broad salinity range and to explain their chemical behaviour. The study was performed on water samples (fresh, marine, hyper-saline) taken from the area of Burgas Bay, Bulgaria. The ion association model based on Debye-Hückel theory using the sst2008.dat database and the ion interaction model based on Pitzer theory using a new pit2010.dat database were compared and combined for the purposes of this study. The new pit2010.dat database combines the sst2008.dat database and the pitzer.dat database of the PHREEQCI computer program as well as the thermodynamic data for the elements Fe, Mn, Cu, Zn, Cd and Pb and their Pitzer ion interaction parameters. The results showed that: (1) the predominant species in fresh waters were free ions of Mn(2+) (73.6%), Zn(2+) (58.0%) and Cd(2+) ions (78.3%) as well as carbonate species CuCO?? (81.8%), PbCO?? (77.2%) and hydroxy species Fe(OH) ??(55.2%) and Fe(OH)+?(35.6%); (2) an increase in chloride species MeCl2(n)-(n)(n = 1-4, Me = Mn, Zn, Cu, Pb and Cd) and of the hydroxy species Fe(OH)?? for Fe was calculated for sea and hyper-saline water.     

Study of leachability and fractional alteration of arsenic and co-existing elements in stabilized contaminated sludge using a flow-through extraction system

This study investigates the stabilization of As in the contaminated sludge after treatment with MnO(2) or Ca(OH)(2), and the influence of the stabilizing materials on the leachability of the co-existing elements Pb and Zn. By exploiting a continuous-flow assembly facilitating a modified Wenzel's sequential extraction scheme (designed for the fractionation of arsenic), it is possible to ascertain the leachability, mobility and fractional alteration of these elements under stimulated natural (flow-through) leaching conditions. The fractionation data show that more than 80% of As, Pb and Zn in the untreated sludge are bound in the amorphous Fe oxides fraction and residual fraction. The addition of MnO(2) has only an insignificant effect on As fractional transformation, while Ca(OH)(2) caused an increase in As mobility. For Pb, the decrease in leachability was clearly visible. The extractable Pb was reduced by 18% and 40% in stabilized MnO(2) and Ca(OH)(2) sludge samples, respectively. Unlike that of Pb, the mobility of Zn was not affected by the additives used. Their fractional distribution patterns before and after the stabilization process remained the same. The ability to produce detailed leaching profiles for As and other elements (Pb, Zn, Ca, Mn and Fe) meant that elemental associations in individual fractions could be examined. From the MnO(2)-treated sludge, the coincidence of the As, Pb, Zn, Fe, and Mn peaks seems to indicate a close association of these elements in the Fe-oxides-bound fraction. Furthermore, the leaching profiles may be used as evidence of a strong affinity between these elements and added MnO(2).     

Essential and toxic elements in infant foods from Spain, UK, China and USA

Spanish gluten-free rice, cereals with gluten, and pureed baby foods were analysed for essential macro-elements (Ca and Na), essential trace elements (Fe, Cu, Zn, Mn, Se, Cr, Co and Ni) and non-essential trace elements (As, Pb, Cd and Hg) using ICP-MS and AAS. Baby cereals were an excellent source of most of the essential elements (Ca, Fe, Cu, Mn and Zn). Sodium content was high in pureed foods to improve their flavour; fish products were also rich in Se. USA pure baby rice samples had the highest contents of all studied essential elements, showing a different nutrient pattern compared to those of other countries. Mineral fortification was not always properly stated in the labelling of infant foods. Complementary infant foods may also contain significant amounts of contaminants. The contents of Hg and Cd were low enough to guarantee the safety of these infant foods. However, it will be necessary to identify the source and reduce the levels of Pb, Cr and As in Spanish foods. Pure baby rice samples contained too much: Pb in Spain; As in UK; As, Cr and Ni in USA; and Cr and Cd in China.     

Heavy metals in Yeniçağa Lake and its potential sources: soil,water, sediment,and plankton

The distribution and accumulation of heavy metals (Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Mo, Cd, Sn, Ba, Pb) in the water, sediments, plankton of Yeniça?a Lake, and its potential sources (creeks, sewage, artesian well, soil) were investigated during 1-year study period as monthly or seasonally. Element analyses were performed by ICP–MS. Results showed that the trace and toxic elements (Al, As, Mn, Pb, Fe) concentration in lake water and/or its feeding sources were above the recommended water standards (WHO, EC, EPA, TS-266). It was found that the maximum accumulation of the heavy metals iron, aluminum, manganese, zinc, and barium in the sediment of Yeniça?a Lake. The accumulation order of trace metals were Fe > Al > Mn > Zn > Ba > Ni > Cr > As > Cu > Pb > Co > Mo > Sn > Cd in the lake, creeks sediment, and soil samples. The similar results suggest that the accumulation of heavy metals in the sediment is a natural process. Metals accumulated in the lake are naturally mixed from the soil. However, the presence of heavy metals in the analysis of artesian well water and sewage reveals that the transportation occurs also from the groundwater to the lake. The results obtained in plankton in Yeniça?a Lake showed that aluminum, iron, manganese, zinc, and barium were most accumulated elements in the plankton. The lower averages of lead prevalent in the water and sediment during some months were seen to have a significant mean accumulation in the plankton.