Determination of Cu, Pb, Zn, Ni, Co, Cd, and Mn in road dusts of Samsun City

The dust samples from 52 different locations in central roads of Samsun City were collected in a study area of 40 km long for the purpose of determining total metal concentrations of dust samples by flame atomic absorption spectrometry. The concentrations of Cu, Pb, Co, Zn, Ni, Mn, and Cd were found in the ranges of 11.92–352.43, 5.47–223.57, 4.52–41.69, 40.85–173.10, 18.71–131.29, 133.19–179.13, and 0.02–6.16 mg/kg, respectively. The results showed that metal levels were higher around the industrial area than other locations. Principal component analysis was also carried out to ascertain the possible contributing factors towards the metal concentrations. Validation of the analytical results was tested by analysis of the BCR 032 Moroccan phosphate rock certified reference material.     

Competitive sorption of Cd, Cu, Mn, Ni, Pb and Zn in polluted and unpolluted calcareous soils

The objectives of this study were to investigate competitive sorption behaviour of heavy metals (Cd, Cu, Mn, Ni, Pb and Zn) under different management practices and identify soil characteristics that can be correlated with the retention and mobility of heavy metals using 65 calcareous soil samples. The lowest sorption was found for Mn and Ni in competition with the other metals, indicating the high mobility of these two cations. The Freundlich equation adequately described heavy metals adsorption. On the basis of Freundlich distribution coefficient, the selectivity sequence of the metal adsorption was Cu?>?Pb?>?Cd?>?Zn?>?Ni?>?Mn. The mean value of the joint distribution coefficient (K _dΣsp) was 182.1, 364.1, 414.7, 250.1, 277.7, 459.9 and 344.8 l kg^?1 for garden, garlic, pasture, potato, vegetables, wheat and polluted soils, respectively. The lowest observed K _dΣsp in garden soil samples was due to the lower cation exchange capacity and lower carbonate content. The results of the geochemical modelling under low and high metal addition indicated that Cd, Ni, Mn and Zn were mainly retained via adsorption, while Pb and Cu were retained via adsorption and precipitation. Stepwise forward regression analysis showed that clay, organic matter and CaCO₃ were the most important soil properties influencing competitive adsorption of Cd, Mn, Ni and Zn. The results in this study point to a relatively easy way to estimate distribution coefficient values.     

Accumulation of Cu, Cd, Cr, Mn and Pb from artificially contaminated soil by Bacopa Monnieri

The metal accumulation potential of Bacopa monnieri L. was assessed under simulated laboratory conditions. This study was carried out in mixed metals (Cu, Cd, Pb, Cr, Mn) condition and repeated exposures in artificial contaminated soil. The growing shoots were planted in garden subsoil containing 3, 16, 32, 64, 160 M each of the above metals. After 8 weeks, plants were refeeded to three times higher concentrations of each metal than initially used to assess the maximum accumulating potential of the metals. The accumulation of the metals by the root and shoot was concentration and duration dependent. The metal accumulation was considerably higher in the fine root than in the shoot and showed the following order : Mn > Cr > Cu > Cd > Pb. The plants showed high tolerance to the metals as no visible phytotoxic symptom was produced after 8 weeks. However, as a result of combined metal toxicity, chlorophyll content was reduced by 62% after 12 weeks. The highest metal concentration was lethal to the plant at 16 weeks. In view of their high tolerance, the plants of B. monnieri may be considered for the amelioration of industrially-polluted wetlands experiencing regular flushing of wastewaters.     

Assessment of the effects of Cr, Cu, Ni and Pb soil contamination by ecotoxicological tests

This study aimed to assess soil quality by chemical and ecotoxicological investigations and to check the correspondence between soil metal concentrations and ecotoxicity. For these purposes, surface soils collected at four adjacent roadside urban parks and at a former industrial area were characterized for C/N, organic matter content, texture, and pH. Cr, Cu, Ni and Pb, chosen among the most representative soil metal contaminants, were measured as total content and as available and water soluble fractions. In addition, the total concentrations of the investigated metals were used to calculate two chemical indices: the contamination and the potential ecological risk factors. The toxicity of the investigated soils was evaluated by an ecotoxicity test battery carried out on both soil samples (Vibrio fischeri, Heterocypris incongruens and Sinapis alba) and elutriates (Vibrio fischeri, Daphnia magna and Selenastrum capricornutum). The findings, both by the chemical and ecotoxicological approaches, would suggest that the soils with high metal contamination pose ecological risks. On the other hand, moderately metal contaminated soils did not exclude soil ecotoxicity. In fact, toxic effects were also highlighted in soils with low metal content, toxicity being affected by metal availability and soil characteristics. Moreover, the results suggest the importance of using a battery of tests to assess soil ecotoxicity.     

Trace Level Determination of U, Zn, Cd, Pb and Cu in Drinking Water Samples

The concentration of uranium has been assessed in drinking water samples collected from different locations in Bathinda district, Punjab, India. The water samples are taken from hand pumps and tube wells. Uranium is determined using fission track technique. Uranium concentration in the water samples varies from 2.23± 0.05 to 87.05± 0.29 μg/L. These values are compared with safe limit values recommended for drinking water. The uranium concentration in almost all drinking water samples is found to be more than the safe limit. Analysis of some heavy metals viz. Zn, Cd, Pb and Cu in water is made. The concentration of sodium, potassium, calcium, magnesium, chlorine and total hardness along with the pH value and conductivity of the water samples are measured. Some of the samples show stunningly high values of these parameters.     

Environmentally safe sewage sludge disposal: the impact of liming on the behaviour of Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn

Dewatered sewage sludge containing relatively high total concentrations of Cr (945 micrograms ml-1), Cu (523 micrograms ml-1), Ni (1186 micrograms ml-1) and Zn (2950 micrograms ml-1) was treated with quicklime and sawdust for sludge disinfection and post-stabilisation. The mobility of the heavy metals in the sludge samples was assessed by applying a modified five-step Tessier sequential extraction procedure. Water was added as a first step for estimation of the proportion of the easily soluble metal fractions. To check the precision of the analytical work the concentrations of heavy metals in steps 1-6 of the extraction procedure were summed and compared to the total metal concentrations. The mass balance agreed within +/- 3% for Cd, Cu, Cr, and Zn and within +/- 5% for Ni, Pb, Fe and Mn. Data from the partitioning study indicate that in the lime-treated sludge at a pH of 12 the mobility of Cu and Ni notably increased with the solubilisation of these metals from their organic and/or carbonate and Fe and Mn oxide and hydroxide fractions, respectively. Liming slightly decreased the proportion of other heavy metals in the easily soluble fractions while its impact on the partitioning between other sludge phases was almost insignificant. Due to the increased solubility of Ni and Cu as well as potential Cr oxidation at high pH, liming cannot be recommended for sludge disinfection. Addition of sawdust did not change the heavy metal partitioning.     

Pollution, fractionation, and mobility of Pb, Cd, Cu, and Zn in garden and paddy soils from a Pb/Zn mining area

This study was conducted to investigate the pollution load index, fraction distributions, and mobility of Pb, Cd, Cu, and Zn in garden and paddy soils collected from a Pb/Zn mine in Chenzhou City, China. The samples were analyzed using Leleyter and Probst’s sequential extraction procedures. Total metal concentrations including Pb, Cd, Cu, and Zn exceeded the maximum permissible limits for soils set by the Ministry of Environmental Protection of China, and the order of the pollution index was Cd > Zn > Pb > Cu, indicating that the soils from both sites seriously suffered from heavy metal pollution, especially Cd. The sums of metal fractions were in agreement with the total contents of heavy metals. However, there were significant differences in fraction distributions of heavy metals in garden and paddy soils. The residual fractions of heavy metals were the predominant form with 43.0% for Pb, 32.3% for Cd, 33.5% for Cu, and 44.2% for Zn in garden soil, while 51.6% for Pb, 40.4% for Cd, 40.3% for Cu, and 40.9% for Zn in paddy soil. Furthermore, the proportions of water-soluble and exchangeable fractions extracted by the selected analytical methods were the lowest among all fractions. On the basis of the speciation of heavy metals, the mobility factor values of heavy metals have the following order: Cd (25.2–19.8%) > Cu (22.6–6.3%) > Zn (9.6–6.0%) > Pb (6.7–2.5%) in both contaminated soils.     

Solid phase extraction of Cd,Pb, Ni,Cu, and Zn in environmental samples on multiwalled carbon nanotubes

A simple and sensitive solid phase extraction (SPE) method on multiwalled carbon nanotubes (MWCNTs) is presented for the determination of cadmium, lead, nickel, copper, and zinc at trace levels combined with flame atomic absorption spectrometry. The effects of parameters like pH, sample volume, sample and eluent flow rates, eluent concentration, and volume and type of eluent on the recovery of trace elements was examined. The metals retained on the nanotube at pH 6.5 as α-benzoin oxime complexes were eluted by 10 mL 2 M HNO₃ in acetone. The influence of matrix ions on the developed method was also evaluated. The preconcentration factor of the method was found to be 50. The detection limits for Cd(II), Pb(II), Ni(II), Cu(II), and Zn(II) were found as 1.7, 5.5, 6.0, 2.3, and 2.4 μg L^?1, respectively. To test the accuracy of the method, the method was applied to TMDA-70 fortified lake water and Spinach 1570A standard reference materials. Addition recovery studies were applied to tap water and cracked wheat samples, and determination of the analyte elements was carried out in some food samples with good results.     

M3法测定土壤有效态Cd、Cr、Pb和Ni

通过M3法对耕地土壤重金属的联合测定,为土壤重金属污染监测应用提供快速联合测定的方法。用M3法测定北方耕地土壤的有效Cd、Cr、Pb和Ni,通过对M3法与其他方法进行有效重金属测定值差异性及其相关性比较,与全量的浸出率分析等探讨M3法对耕地土壤有效重金属测定的特征。结果表明,M3法在《土壤环境质量标准》(GB 15618—1995)的土壤重金属含量范围内可以测定土壤有效态重金属Cd、Cr、Pb和Ni,且呈线性极显著相关。M3法与其他方法有效Cd、Cr、Pb和Ni有较好的相关性,与DTPA法呈极显著相关;与NaNO₃法除有效Pb外,呈极显著和显著相关;与HCl法除褐土和潮土的有效Pb外,也呈极显著和显著相关。M3法的有效态Cd、Cr、Pb和Ni的测定值均为最大。M3法对4种耕地土壤有效Cd、Cr、Pb和Ni的浸出率,因土壤类型不同,有效重金属含量所占比率不同,但利用M3法测定的有效态Cd、Cr、Pb和Ni的浸出率最大。     

Evaluation of Pb, Cu, Zn, Cd, Ni and Fe levels in Rosmarinus officinalis labaiatae (Rosemary) medicinal plant and soils in selected zones in Jordan

The concentration of heavy metals including Pb, Cu, Zn, Cd, Ni and Fe in different parts of Rosmarinus officinalis medicinal plant grown in Jordan were evaluated. Medicinal plant samples and soil samples were collected from three different zones in Jordan (Irbid, Al-Mafraq and Ma’an). Samples were analyzed by atomic absorption spectrometry (AAS) after chemical treatments using acid digestion procedures. Heavy metal levels in washed and unwashed in each part of R. officinalis were analyzed and compared statistically. Results show that concentrations of investigated heavy metals were varied from plant part to another part of R. officinalis. For example, Pb, Zn, Cu and Cd in most parts of R. officinalis in the three zones were concentrated in the following order: flowers, leaves, stems, whereas Pb, Ni and Fe were concentrated in order as follows: leaves, flowers and stems. Heavy metal concentrations in soil samples was evaluated and correlated with their levels in R. officinalis. Two standard reference materials of plant (SRM 1790a; spinach leaves and CRM 281; rye grass) and one standard reference materials of soil (GBW 07406) were examined to validate the method used. Results show that high recoveries were obtained.     

Assessment of potential health risk for inhabitants living near a former lead smelter. Part 2: site-specific human health risk assessment of Cd and Pb contamination in kitchen gardens

Metal contamination of urban soils and homegrown products has caused major concern. In Part 1, we investigated the long-term effects of a former smelter on the degree of kitchen garden-soil contamination and the quality of the homegrown vegetables from these gardens. The results showed that the soils retained a high level of contamination and that a large proportion of the vegetables produced did not comply with the legislation on the levels of metals allowed for human consumption. The present study aims to assess the associated potential health risk to local inhabitants through consumption of homegrown vegetables and ingestion of soil particles using a land use-based approach. For lead (Pb), the standard hazard quotient (HQ)-based risk assessment method was used to determine the HQ. For cadmium (Cd), the approach consisted of calculating the HQs and then deriving site-specific assessment criteria (SSAC) using the SNIFFER method. The results suggested that the exposure pathways considered should not engender any form of deleterious health effects for adults. For children, Pb was the main concern and induced a relatively high health risk through soil particle ingestion, and most total soil Cd concentrations exceeded the derived SSAC, in particular, through consumption of vegetables. The metal bioaccessibility in soils was incorporated into the methods to establish more realistic risk assessment measures. This study proposes an approach to integrate different human health risk assessment methods. Further investigations should complete the assessment to improve risk determination, e.g., the determination of metal bioaccessibility in vegetables.     

Determination of heavy metals (Cd, Cr, Cu, Fe, Ni, Pb, Zn) by ICP-OES and their speciation in Algerian Mediterranean Sea sediments after a five-stage sequential extraction procedure

Surface sediment samples (n = 18) were collected from the Algerian Mediterranean coasts and analyzed for seven metals using inductively coupled plasma-optical emission spectrometry in order to asses the distribution and bioavailability of metals and to study the anthropogenic factors affecting their concentrations. Sediment samples were size-fractionated into three sizes: 1,080–500 (coarse), 500–250 (medium), and <250 mm (fine). Bulk sediments were subjected to both sequential extraction and total digestion to evaluate the reliability of the sequential extraction procedure (SEP), while the fractions have been only sequentially extracted for metals speciation. The metals were sequentially extracted into five phases namely exchangeable (P1), carbonates (P2), Fe–Mn oxides (P3), organic (P4) and residual (P5). Metal recoveries in sequential extractions were ±20% of the independently measured total metal concentrations; the high recovery rates indicate the good reliability of the SEP used in this study. Correlation coefficients indicated that the grain size has an effect on the distribution of metals in the investigated samples. The order of metal levels in the fractions was medium > fine > coarse for all the metals. The average total extractable metal concentrations for Cd, Cr, Cu, Fe, Ni, Pb, and Zn were 1.1, 8.8, 4.7, 1,291.3, 13.9, 5.7 and 20.4 μg/g, respectively. The northeastern shelf had the lowest metal levels while the highest were in northwestern part mainly due to the significant tourism activities in the northwestern part. Comparison of our results to Earth’s crust values and to previous studies points out that our samples were relatively unpolluted with respect to the heavy metals investigated; most of the metals are not from anthropogenic sources. Enrichment factors as the criteria for examining the impact of the anthropogenic sources of heavy metals were calculated, and it was observed that the investigated samples were not contaminated with Cr, Cu, and Fe, moderately contaminated with Ni, Pb, and Cd, and contaminated with Cd in some sites. The P5 phase had the highest percents of Cr, Cu, Fe, Ni, and Zn. Cadmium and lead were predominant in the P4 phase, while Cu, Fe and Zn were distributed in the order P5 > P3 > P4 > P2 > P1. The following order of bioavailability was found with the heavy metals Pb > Cr > Cd > Ni > Zn > Cu > Fe.     

Characterization of soil contamination by lead around a former battery factory by applying an analytical hybrid method

Former battery factories have created environmental and health problems for years and the exposure to lead in surface soils has been underestimated. Nonetheless, the identification of lead contamination and its spatial distribution is crucial. The determination of heavy metals in soils can be performed using inductively coupled plasma mass spectrometry (ICP-MS). However, alternative techniques such as X-ray fluorescence (XRF) have been used lately in environmental studies since measurements can be taken in the field in a prompt manner, despite its lower accuracy. In this study, a former battery factory site in Monterrey, Mexico, has been studied in order to detect lead contamination. Soil samples were assessed for contamination by using an analytical hybrid method that comprises both analytical techniques, namely, ICP-MS and XRF. Samples were taken in 215 locations and, after a simple homogenization process, they were analyzed by using a portable XRF device. Within those 215 sampling points, 25 samples were analyzed concurrently by using ICP-MS according to international sampling guidelines. Results obtained were adjusted in order to define an analytical hybrid method, which encompasses the advantages of each technique. An improved characterization was achieved by using the proposed analytical hybrid method since maps of lead distribution and calculated areas of concern showed better predictability. The combination of spectroscopic techniques is of great applicability for environmental agencies and decision makers.     

Evaluation of diffusive gradients in thin films technique (DGT) for measuring Al, Cd, Co, Cu, Mn, Ni, and Zn in Amazonian rivers

Studies concerning the lability and bioavailability of trace metals have played a prominent role in the search for contamination of water resources. This work describes the first application yet of the diffusive gradients in thin films technique (DGT) to the determination of the fraction of free plus labile metals in waters from the Amazon Basin. Due to the complexity of the use of DGT for samples with low ionic strength and high organic matter content (characteristic of Amazonian rivers), a new analytical procedure was developed. The method is based on the determinations of apparent diffusion coefficients (D_ap) in the laboratory, by performing deployments in samples collected in the corresponding sites of study. The D_ap thereby determined is then used for in situ measurements. The suitability of the proposed approach for determination of labile Al, Cd, Co, Cu, Mn, Ni, and Zn in the Amazon River and Rio Negro (English: Black River) was evaluated. Except for Co, Mn (in a deployment at Rio Negro), Ni and Zn (in a deployment at Amazon River), labile in situ measurements were lower or similar to dissolved concentrations, indicating suitability of the proposed approach.     

SI-traceable certification of Cu, Cr, Cd and Pb in sediment and fly ash candidate reference materials

Many fields in environmental analytical chemistry deal with very low limits and thresholds as set by governmental legislations or transnational regulations. The need for the accuracy, comparability and traceability of analytical measurements in environmental analytical chemistry has significantly increased and total uncertainties are even asked for by accreditation bodies of environmental laboratories. This paper addresses achieving these goals to guarantee accuracy, quality control, quality assurance or validation of a method by means of certified reference materials. The assessment of analytical results in certified reference materials must be as accurate as possible and every single step has to be fully evaluated. This paper presents the SI-traceable certification of Cu, Cr, Cd and Pb contents in geological and environmentally relevant matrices (three sediments and one fly ash sample). Certification was achieved using isotope dilution (ID) ICPMS as a primary method of measurement. In order to reduce significantly the number of analytical steps and intermediate samples a multiple spiking approach was developed. The full methodology is documented and total uncertainty budgets are calculated for all certified values. A non-element specific sample digestion process was optimised. All wet chemical digestion methods examined resulted in a more or less pronounced amount of precipitate. It is demonstrated that these precipitates originate mainly from secondary formation of fluorides (essentially CaF2) and that their formation takes place after isotopic equilibration. The contribution to the total uncertainty of the final values resulting from the formation of such precipitates was in general < 0.1% for all investigated elements. Other sources of uncertainty scrutinised included the moisture content determination, procedural blank determination, cross-contamination from the different spike materials, correction for spectral interferences, instrumental background and deadtime effects, as well as the use of either certified values or IUPAC data in the IDMS equation. The average elemental content in the sediment samples was 30-130 micrograms g-1 for Pb, 0.5-3 micrograms g-1 for Cd and 50-70 micrograms g-1 for Cu. Cr was measured in one sample and was about 60 micrograms g-1. The concentrations in the fly ash sample were up to 2 orders of magnitude higher. Expanded uncertainty for the investigated elements was about 3% (coverae factor k = 2) except for Cr, (measured by high resolution ICPMS), for which the expanded uncertainty was about 7% (k = 2).     

Chemical speciation and partitioning of trace metals (Cd, Co, Cu, Ni, Pb) in the lower Athabasca river and its tributaries (Alberta, Canada)

Concentrations of Cd, Co, Cu, Ni and Pb were measured in particulate and dissolved phases at 11 sites located upstream and near Athabasca oil sands development. The in situ discrimination between non-labile and labile dissolved metals was done using diffusive gradients in thin-films (DGT) devices. The DGT-labile fraction of Co and Ni was 30% lower near development sites whereas Cu, Cd and Pb showed minor changes spatially. It was found that an 8-fold increase in dissolved organic matter (DOM) near development induced a rapid decrease in DGT-labile metals. Dissolved metal concentrations were used along with DOM, major ions, nutrients, pH and conductivity to calculate the distribution of dissolved metal species using the speciation model WHAM. Labile-DGT metal concentrations agreed well with WHAM-predicted concentrations. It was also found that a significant amount of metals were associated with the non-DGT labile fraction (i.e. colloidal DOM) and colloid abundance was more important than suspended particulate matter abundance in influencing metal mobility near Athabasca oil soils development. Since changes in colloidal DOM levels are likely to be the result of surface mining activities, this confirms the serious effects of oil sands activities on metal biogeochemical cycles in the lower Athabasca River.     

Certification of the extractable contents of Cd, Cr, Cu, Ni, Pb and Zn in a freshwater sediment following a collaboratively tested and optimised three-step sequential extraction procedure

Sequential extraction procedures have been used during the last decades to study and determine trace element mobility in aquatic sediments. However, the results obtained are operationally defined and, therefore, the significance of the analytical results is related to the extraction scheme used. So, there is a need for suitable reference materials for this type of study to enable the validation of the methodologies and to control the quality of the measurements. This paper describes the preparation of a sediment reference material, BCR-701, the homogeneity and stability studies and the analytical work performed for the certification of the extractable contents of some trace elements, following a collaboratively tested and optimised sequential (three-step) extraction procedure. The paper contains all the results and gives the methods used to certify the extractable contents (mass fractions expressed as mg kg-1 on a dry matter basis) of Cd, Cr, Cu, Ni, Pb and Zn in all steps. Moreover, indicative values are given for the aqua regia extractable contents of the six elements in the sediment and the residue obtained after sequential extraction.     

Diurnal concentrations variations,size distributions for ambient air particles and metallic pollutants (Cr,Mn, Ni,Cd, Pb) during summer season at a traffic area

This study characterized and discussed particulate ambient air particulate concentrations and seasonal variations for PM₁₈, PM₁₀, PM_2.5, and PM₁ during June 2013–July 2013 at this traffic sampling site. In addition, this study also characterized the ambient air particulates size distributions by using MOUDI-100S4 sampler to collect 1-day the ambient suspended particles (PM₁₈, PM₁₀, PM_2.5, and PM₁) at this sampling site. In addition, the study also showed that the main pollutants contributions were from traffic and residual areas. As for the pollutants seasonal concentrations variations, the results indicated that the average particle concentrations orders were all displayed as daytime?>?nighttime for PM₁₈, PM₁₀, PM_2.5 and PM₁ at this characteristic sampling site. The results further indicated that the mean highest of metal concentrations in this study indicated that the average metal concentration were all displayed as Mn?>?Cr?>?Ni?>?Pb?>?Cd for PM₁₈, PM₁₀, PM_2.5 and PM₁ on daytime and nighttime at this characteristic sampling site.