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1.
Two alternative extraction methods--a routine ultrasonic bath and a microwave oven--were developed and optimized for their eventual exploitation in the three-stage sequential extraction procedure proposed by the European Standards, Measurements and Testing (S, M & T) Programme, formerly Bureau Communitaire de Reference (BCR), for the operationally defined speciation of Cd, Cr, Cu, Ni and Zn. The conventional BCR three-stage sequential extraction procedure was modified at each stage, applying ultrasonic or microwave devices in order to shorten the required 16 h of shaking in all three steps. The experimental tests and the optimization of the operating parameters were carried out on a highly homogenized estuarine sediment reference material (RM S7) prepared by the Joint Research Centre (JRC) of ISPRA. Extractable metal contents were measured by inductively coupled plasma-mass spectrometry (ICP-MS) and the results obtained in each fraction by all three methods were statistically compared for all the studied elements. The conventional and newly developed alternative extraction methods were finally compared by the analysis of BCR 601, which is certified for the three-step BCR sequential extraction procedure. According to the statistical evaluation of the results, the proposed accelerated sequential extraction methods are valid alternatives to conventional shaking, with much shorter extraction times.  相似文献   

2.
An exploratory study of the area surrounding a historical Pb?CZn mining and smelting area in Zawar, India, detected significant contamination of the terrestrial environment by heavy metals. Soils (n?=?87) were analyzed for pH, EC, total organic matter (TOM), Pb, Zn, Mn, and Cd levels. The statistical analysis indicated that the frequency distribution of the analyzed parameters for these soils was not normal. The median concentrations of metals in surface soils were: Pb 420.21 ?? g/g, Zn 870.25 ?? g/g, Mn 696.70 ?? g/g, and Cd 2.09 ?? g/g. Zn concentrations were significantly correlated with Cd (r?=?0.867), indicating that levels of Cd are dependent on Zn. However, pH, electrical conductivity and total organic matter were not correlated significantly with Cd, Pb, Zn, and Mn. To assess the potential mobility of Cd, Pb, and Zn in soils, single (EDTA) as well as sequential extraction scheme (modified BCR) were applied to representative (n?=?23) soil samples. The amount of Cd, Pb, and Zn extracted by EDTA and their total concentrations showed linear positive correlation, which are statistically significant (r values for Cd, Pb, and Zn being 0.901, 0.971, and 0.795, respectively, and P values being <0.001). The correlation coefficients indicate a strong relation between EDTA-extractable metal and total metal. These results appear to justify the use of ??total?? metal contents as a useful preliminary indicator of areas where the risks of metal excess or deficiency are high. The EDTA extractability was maximum for Cd followed by Pb and Zn in soils from all the locations. As indicated by single extraction, the apparent mobility and potential bioavailability of metals in soils followed the order: Cd ?? Pb >?> Zn. Soil samples were sequentially extracted (modified BCR) so that solid pools of Cd, Zn, and Pb could be partitioned into four operationally defined fractions viz. acid-soluble, reducible, oxidizable, and residual. Cadmium was present appreciably (39.41%) in the acid-soluble fraction and zinc was predominantly associated (32.42%) with residual fraction. Pb (66.86%) and Zn (30.44%) were present mainly in the reducible fraction. Assuming that the mobility and bioavailability are related to solubility of geochemical forms of metals and decrease in the order of extraction, the apparent mobility and potential metal bioavailability for these contaminated soil samples is Cd > Zn > Pb.  相似文献   

3.
The aim of this study was to elucidate the amount of metal released at each step by using different extractants in three sequential extraction schemes for the partitioning of metal contents of car park deposited dust samples. For this purpose, three different sequential extraction procedures (SEP) were employed for the metal fractionation in car park dust samples collected from the campus of Erciyes University, Kayseri, Turkey. While two of the sequential extraction procedures contain five steps the other, namely the BCR sequential extraction scheme, has three steps. The first two methods fractionate metals to be exchangeable, bound to carbonates, bound to Mn oxides, bound to Fe oxides and bound to organic matter, and the BCR protocol fractionates the metals as acid soluble and exchangeable, reducible, and oxidisable. Determination of the metals Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn was performed by flame atomic absorption spectrometry (FAAS). The results obtained by the three methods were compared and showed that the amount of metal released at each step of the leaching procedure depended both on the type of reagents used and the sequence in which they were applied. The most mobile elements were Cd, Pb and Zn which are metals potentially toxic to the environment and are also known to originate from traffic. The calculated enrichment factors for Cd and Pb were substantially high (73.5-187 and 18.4-27.5, respectively) and somewhat lower for Zn (5.1-6.8). These results confirm that they are important metal pollutants for car parks. Detection limits and recoveries were found in the range of 0.01-1.39 microg ml(-1) and 68-126%, respectively, for the metals studied and the three sequential extraction procedures.  相似文献   

4.
This paper provides additional data on a sewage sludge amended soil certified reference material, CRM 483, which was certified in 1997 for its EDTA and acetic acid extractable contents of some trace metals, following standardised extraction procedures. The additional work aimed to test the long-term stability of the material and the applicability of an improved version of the BCR three-step sequential extraction procedure on the sewage sludge amended soil (CRM 483). The paper demonstrates the CRM 483 long-term stability for EDTA and acetic acid extractable contents of Cd, Cr, Cu, Ni, Pb and Zn and gives the results (obtained in the framework of an interlaboratory study) for the extractable contents of the same elements in the CRM 483, following the BCR three-step sequential extraction scheme. The aqua regia extractable contents following the ISO 11466 Standard are also given. The data are given as indicative (not certified) values.  相似文献   

5.
The applicability of the three-step BCR leaching scheme to the continuous-flow fractionation of trace metals (TM) using rotating coiled columns (RCC) has been investigated taking soil and sediment reference samples (SRM-2710, CRM-601, BCR-701) as examples. A particulate sample was retained in the rotating column as the stationary phase under the action of centrifugal forces while different eluents, used according to the original and optimised BCR protocols, were continuously pumped through. The whole procedure required 3-4 h instead of at least 50 h needed for the traditional sequential extraction. It has been shown that in comparison with batch sequential extraction procedures (SEP), the recoveries of Cd, Zn, Cu, and Pb at the first stage (most mobile and potentially dangerous acid soluble forms) are somewhat higher, if a dynamic extraction in RCC is used. Nevertheless, the distribution patterns for TM in the first two leachable fractions (acid soluble and reducible forms) are similar in most cases. Since no heating is used in RCC, the recoveries of TM at the third stage (when hydrogen peroxide is applied to oxidize the organic matter) may be incomplete and matrix-dependent. The effect of eluent volume and flow rate on the recovery of TM in different forms has been investigated. It has been shown that the kinetics of heavy metal leaching vary significantly with samples. Hence, investigating the elution profiles can provide additional important information for risk assessment of TM mobilization.  相似文献   

6.
Fractionation and elemental association of Zn, Cd, and Pb in soils near Zn mining areas were studied using a continuous-flow sequential extraction approach. The recently developed sequential extraction procedure not only gave fractional distribution data for evaluation of the mobility or potential environmental impact of the metals, but also the extraction profiles (extractograms) which were used for study of elemental association. In addition, the elemental atomic ratio plot extractogram can be used to demonstrate the degree of anthropogenic contamination. Seventy-nine soil samples were collected in the vicinity of a Zn mine and were fractionated into 4 phases i.e. exchangeable (F1), acid soluble (F2), reducible (F3) and oxidizable (F4) phases. Most samples were contaminated with Zn, Cd and Pb. The reducible phase is the most abundant fraction for Zn and Pb (>50%) while Cd is concentrated in the first 3 extraction steps. The distribution patterns of Cd were obviously affected by soil pH. 55% of Cd appears predominantly in the F1 fraction for acidic soils while in neutral and alkaline soils, it was mostly (70%) found in the F2 + F3 fractions. The extractograms obtained from the continuous-flow extraction system revealed close association between Zn, Cd, Pb and Fe in the acid soluble phase, Cd-Pb and Zn-Fe in the reducible phase for contaminated soils. A correlation study of the 3 metals using a correlation coefficient was also performed to compare the results with the elemental association revealed by the extractograms. Atomic ratio plot extractograms of Zn/Fe, Cd/Fe and Pb/Fe in the reducible phase, where contaminated metals are predominant, can be used to evaluate the degree of anthropogenic contamination. From the elemental atomic ratio plot, it is obvious that the contaminants Cd and Pb are mostly adsorbed on the surface of Fe oxides. Zn, which is present in an approximately 1 ratio 1 ratio with Fe in contaminated soils, does not show a similar trend to that found for Cd and Pb.  相似文献   

7.
In the determination of the best sequential extraction procedures (SEP) for the speciation of metals in sediment samples from the Lagos lagoon system, three sequential extraction procedures were compared for the fractionation of Cd, Cr, Cu, Pb, and Zn. The SEP compared included a modified Tessier??s procedure carried out in five steps, while the two other procedures were the three-step original Community Bureau of Reference (BCR) and the modified BCR techniques (four steps). Quantification of the metal concentration was achieved with a flame atomic absorption spectrophotometer. The results obtained by the three methods were compared, and the modified BCR and Tessier SEP were found to extract more Cu, Cr, Pb, and Zn in the reducible phase and therefore a decrease in the oxidizable phase than the original BCR SEP. The most mobile elements were found to be Cd, Pb, and Zn. These are of environmental concern, as these potentially toxic metals could be easily released into the aquatic environment with consequent ingestion by aquatic organisms, thereby entering the food chain. The mass balance (percent recovery) was found to be between 85% and 115% in most cases. Prior to the comparison, the analytical performance of the laboratory was tested using a secondary reference material, GLAURM, using the three-step modified BCR procedure. The results showed high reliability of the analytical performance of the laboratory for all the metals considered.  相似文献   

8.
The Standards, Measurements and Testing Programme (formerly BCR) of the European Commission proposed a three-step sequential extraction procedure for sediment analysis, following extensive expert consultations and two interlaboratory studies. This scheme was recently used to certify the extractable trace element contents of a sediment reference material (CRM 601). Although this procedure offers a means to ensure the comparability of data in this field, some difficulties concerning the interlaboratory reproducibility still remain, and a new project is currently being conducted to determine the causes of poor reproducibility in the extraction scheme. The final objective of the project is the certification of new sediment and soil reference materials for their extractable contents of Cd, Cr, Cu, Ni, Pb and Zn. This paper presents the results of a small-scale interlaboratory study, which aimed to test a revised version of the extraction schemes by comparing the original and the modified protocols using the CRM 601 sample. This work offers an improvement to the BCR sequential extraction procedure through intercomparison exercises. This improved procedure will allow the obtaining of CRMs to validate analytical data in the analysis of soils and sediments, and it will also facilitate comparability of data in the European Union.  相似文献   

9.
The increasing demand for environmental pollution control results in the development and use of new procedures for the determination of dangerous chemicals. Simple screening methods, which can be used directly in the field for a preliminary assessment of soil contamination, seem to be extremely advantageous. In our laboratory, we developed and optimized a rapid test for a preliminary evaluation of both the concentration and the mobility of some potentially toxic metals in soils. This screening test consists of a single extraction of the soil sample with a buffer solution, followed by the titration of the extracted solution with dithizone to determine the contents of bi-valent heavy metals (such as Pb, Cu, Zn, and Cd). This screening method was then directly applied in the field during the sampling campaign in the framework of an Italian–Serbian collaborative project, finalized in the study of metal availability in soils. The results obtained in the field with the rapid test were compared with those obtained in the laboratory following the conventional procedure commonly used to evaluate metal bioavailability (diethylenetriaminepentaacetic extraction). Moreover, selected samples were analyzed sequentially in the laboratory using the standardized BCR three-step sequential extraction procedure. The screening test gave results conceptually in good agreement with those obtained via the BCR procedure. These preliminary data show that the proposed screening test is a reliable method for the preliminary rapid evaluation of metal total concentrations and of potential metal mobility in soils, supporting sampling activities directly in the field.  相似文献   

10.
In this study, soil samples were collected from Edirne, Turkey in both summer and winter seasons and subjected to the modified Community Bureau of Reference (BCR) sequential extraction procedure in order to investigate the chemical partitioning of metals in soils and to predict heavy metals uptake by wheat grains which grown at the same soils. The samples were subjected to a three stage extraction procedure proposed by the BCR. The three phases that were separated out in the following order: (1) carbonate, exchangeable, (2) Fe?CMn oxides, and (3) organic matter. Metal concentrations of soil fractions and grain samples were determined by inductively coupled plasma atomic emission spectroscopy. The wheat samples were prepared to analysis using microwave acid digestion procedure. The pseudo-total concentrations of metals were determined after aqua regia digestion. The analytical accuracy of the method was evaluated by using the Standard Reference Materials (BCR 142R Light Sandy Soil, NIST 2711 Montana Soil, and NIST 2704 Buffalo River Sediment). The sum of the metal contents obtained from the modified BCR sequential extraction procedure and pseudo-total metal contents for soil samples were used to calculate recovery values. In order to evaluate the bioavailability of metals, the relationships between the wheat-metal and soil-extractable metal concentrations were compared.  相似文献   

11.
Today there is consensus concerning the road traffic's role as a metal source. However, there are so far only a few studies which focus on the road side immission patterns regarding distance from roads, and especially in combination with the leachability of heavy metals down the soil profile. In this study, the aim was to analyse concentrations of traffic related metals in road side soils, at different depths and distances from roads, both to analyse the immission patterns as well as to explain the importance of the road construction design of the road side terrain. The BCR sequential extraction procedure was performed to be able to address the environmental risk in terms of metal mobility. Approximately 80 soil samples were analysed for seven metals; antimony (Sb), cadmium (Cd), copper (Cu), chromium (Cr), lead (Pb), nickel (Ni) and zinc (Zn). The results showed that, depending on metal, the total metal concentrations in road side soils have increased 3-16 times compared to regional background during the last decades. Each metal had a limited dispersal distance from the roads as well as down in the soil profile and the road construction significantly affected the metal immission distance. Elevated metal concentrations were mostly found for top soils and down to 10 cm in the soil profiles. The labile fractions counted for more than 40% of the total concentrations for Cd, Cu, Ni, Pb and Zn, indicating a potential mobilization of the metals if the road side soils become disturbed. The present soil metal concentration levels are not alarming, but metals with a high accumulation rate might gradually be an upcoming problem if nothing is done to their emission sources.  相似文献   

12.
Accumulation of metals in soil at elevated concentrations causes risks to the environmental quality and human health for more than one hundred million people globally. The rate of metal release and the alteration of metal distribution in soil phases after soil washing with a sulfosuccinamate surfactant solution (Aerosol 22) were evaluated for four contaminated soils. Furthermore, a sequential extraction scheme was carried out using selective extractants (HAcO, NH(2)OH·HCl, H(2)O(2) + NH(4)AcO) to evaluate which metal species are extracted by A22 and the alteration in metal distribution upon surfactant-washing. Efficiency of A22 to remove metals varied among soils. The washing treatment released up to 50% of Cd, 40% of Cu, 20% of Pb and 12% of Zn, mainly from the soluble and reducible soil fractions, therefore, greatly reducing the fraction of metals readily available in soil. Metal speciation analysis for the solutions collected upon soil washing with Aerosol 22 further confirmed these results. Copper and lead in solution were mostly present as soluble complexes, while Cd and Zn were present as free ions. Besides, redistribution of metals in soil was observed upon washing. The ratios of Zn strongly retained in the soil matrix and Cd complexed with organic ligands increased. Lead was mobilized to more weakly retained forms, which indicates a high bioavailability of the remaining Pb in soil after washing. Comprehensive knowledge on chemical forms of metals present in soil allows a feasible assessment of the environmental impact of metals for a given scenario, as well as possible alteration of environmental conditions, and a valuable prediction for potential leaching and groundwater contamination.  相似文献   

13.
In this paper, the main objective was fractionation of Cd, Cu, Ni, Pb, Zn, Ca, Fe, and K in certificate material and sediment samples gathered from and around the Petrochemical Industry using the conventional, microwave and ultrasonic sequential extraction. Microwave oven and ultrasound bath were used as an energy source for achieving faster extraction. Additional heating and boiling of samples were avoided by using lower power and shorter time for microwave and ultrasound extraction. Precision and accuracy of procedure were evaluated by using certificate material (BCR701). Acceptable accuracy of metals (87.0–111.3 %) was achieved for all three-step sequential of conventional extraction protocol. An accuracy of the fourth step has been verified with two certificate materials: BCR143R and 146R. The range of total extracted metal concentrations from sediments was similar for all three extraction techniques. A significant high percentage of Cd, Cu, and Zn were obtained after extraction of the exchangeable and acid soluble sediment fraction. Principal component analysis of values obtained after determination of risk assessment code using conventional and ultrasound sequential extraction show similarity of these values. Accuracy, recovery, and risk assessment code values imply that ultrasound sequential extraction is a more suitable, accelerated sequential extraction procedure (30 min per extraction step) than microwave extraction in applied conditions.  相似文献   

14.
A study was carried out to investigate the fractionation of Cd, Cr, Cu, Fe, Mn, Pb, and Zn in shrimp aquaculture sludge from Selangor, Malaysia, using original (unmodified) and modified four-steps BCR (European Community Bureau of Reference, now known as the Standards Measurements and Testing Program) sequential extraction scheme. Step 2 of the unmodified BCR procedure (subsequently called Method A) involves treatment with 0.1 M hydroxylammonium chloride at pH 2, whereas 0.5 M hydroxylammonium chloride at pH 1.5 was used in the modified BCR procedure (subsequently called Method B). Metal analyses were carried out by flame atomic absorption spectrometry. A pseudo-total aqua-regia digest of BCR CRM 701 has also been undertaken for quality assurance purposes. The recovery of Method A for all metals studied ranges from 96.14% to 105.26%, while the recovery for Method B ranges from 95.94% to 122.40%. Our results reveal that Method A underestimated the proportion of metals bound to the easily reducible fraction except for copper. Therefore, the potential mobility of these elements is higher than others. Thus, to use this sludge as a fertilizer we have to first find a remediation for reduction of heavy metal contamination.  相似文献   

15.
The concentration and speciation of heavy metals (Cr, Ni, Cu, Zn, Cd, Pb) in surface sediments (??≤ 63 μm) of Jinjiang River tidal reach are determined to evaluate the metal behavior. A modified BCR three-step sequential extraction procedure is carried out, and the residual fraction is undertaken by microwave-assisted acid digestion. The index of geo-accumulation indicates that Cd appeared highest among all these heavy metals in surface sediments, Cr, Cu, Zn lower, and Ni, Pb the least. The percentage of Zn, Cd is comparatively higher in the acid soluble fraction, Pb and Cu higher in the reductive fraction, indicating larger potential danger to the environment. So it is essential for developing the future remediation plans and pollution control strategies.  相似文献   

16.
15 road and 14 soil dust samples were collected from an oilfield city, Dongying, from 11/2009-4/2010 and analyzed by inductively coupled plasma-mass spectroscopy (ICP-MS) for V, Cr, Mn, Co, Ni, Cu, Zn, As, Cd and Pb within PM(2.5), PM(10) and PM(100) fractions synchronously. Metal concentrations, sources and human health risk were studied. Results showed that both soil and road dust exhibited higher values for Mn and Zn and lower values for Co and Cd for the three fractions. Mass concentration ratios of PM(2.5)/PM(10) and PM(10)/PM(100) for metals in road and soil dust indicate that most of the heavy metals tend to concentrate in fine particles. Geoaccumulation index and enrichment factors analysis showed that Cu, Zn and Cd exhibited moderate or heavy contamination and significant enrichment, indicating the influence of anthropogenic sources. Vanadium, Cr, Mn and Co were mostly not enriched and were mainly influenced by crustal sources. For Ni, As and Pb, they ranged from not enriched to moderately enriched and were influenced by both crustal materials and anthropogenic sources. The conclusions were confirmed by multivariate analysis methods. Principle component analysis revealed that the major sources were vehicle emission, industrial activities, coal combustion, agricultural activities and crustal materials. The risk assessment results indicated that metal ingestion appeared to be the main exposure route followed by dermal contact. The most likely cause for cancer and other health risks are both the fine particles of soil and road dusts.  相似文献   

17.
This study was aimed to establish background and reference values of total heavy metals in soils from a representative area of Albania (Tirana). Thirty-eight soil samples collected from genetic horizons of major soil types of Tirana were analyzed for important physicochemical properties by standard methods and for total contents of Cd, Cr, Ni, Pb, Zn, and Cu by atomic absorption spectrometer, after extraction with aqua regia. The results showed that the total contents of Cd, Cr, Ni, Pb, Zn, and Cu in surface horizons varied widely with respective mean values of 0.3 (??0.6), 174.2 (??63.7), 305.9 (??133.0), 19.7 (??12.4), 95.5 (??26.3), and 42.7 (??6.8) mg/kg. The highest metal contents were found in two soils developed in limestone. The depth distribution of metals showed a tendency for accumulation of Cd and Pb in the surface horizons of three soils, suggesting that these metals partially come from anthropogenic inputs. Correlation analysis indicated that the metal contents of soils were controlled by soil properties, including pH, CaCO3, clay, organic matter, cation exchange capacity, and Fe oxides. The background values (given as the 90th percentile) were much higher than those reported in the literature, showing that the levels of respective metals were naturally higher. The total metal contents of some soils were above background levels, suggesting metal pollution. The reference values for all the analyzed metals were quite consistent with those of the Dutch system. The proposed background and reference values can be used to evaluate the soil pollution with these elements.  相似文献   

18.
The chemistry of heavy metals in sediments with respect to bio-availability and chemical reactivity is regulated by pH, texture, and organic matter contents of the sediments and specific binding form and coupled reactivity of the metals within. To focus on the metal distribution (Fe, Mn, Pb, Cd, Zn, Co, Cu, and Cr) and behavior in a fresh water aquifer system along with the ecological toxicity parameters, a four-step sequential extraction method was applied on 18 Eastern Ghats’ type sediments from fluorosis-hit Nayagarh district, India. Geo-accumulation index of metals in the sediments indicates that they are practically uncontaminated and/or less contaminated with and Fe, Mn, and Cu; contaminated to moderately contaminated with Pb, Zn, and Cr; and strongly contaminated with Cd. Rather, more than 80 % recovered Cd metal concentration in sediments constitute the labile fractions. Temporal clustering of metal fractions indicates transition metal fraction distribution claiming the sediment pH regulation. Similarly, base metal distribution accounts for organic carbon and soil conductivity due to their greater availability in exchangeable and sulfide fractions. Correlation analysis and factor analysis scores demonstrate lack of inter-relationship between transition group and base metal fractions. High fluoride concentration in ground water is associated with high sodium-bicarbonate-iron affinity with elevated pH values (i.e., >7.0) and high positive factor score with the total iron concentration in ground water.  相似文献   

19.
Previous studies have proposed that Pardosa astrigera L. Koch (Lycosidae) can be used as a biological indicator of heavy metal contamination in soil. In this study, we estimated the bioaccumulation levels and the bioconcentration factors (BCF) of four heavy metals (Cd, Cu, Pb, and Zn) in adult female P. astrigera collected from various field sites according to heavy metal content gradient and broods. The relationship between heavy metal content in the soil and that in spiders was different depending on the heavy metals and the broods. However, heavy metal content in P. astrigera increased with increasing heavy metal content in the soil. While the heavy metal content in the soil was in the order of Zn > Pb > Cu > Cd, its content in P. astrigera was in the order Zn > Cu > Cd > Pb. The BCF for Cd in both of the broods was distinctly higher than those of the other heavy metals evaluated. These results indicate that P. astrigera may be useful as a biological indicator of Cd soil contamination.  相似文献   

20.
赣东北德兴矿区周边女性居民头发中重金属分布特征   总被引:4,自引:0,他引:4  
应用ICP-MS/AFS测定江西德兴矿区(铜矿和铅锌矿)周边地区祝家村和戴村女性居民头发中重金属含量。探讨了河水、土壤、饮用水、人发中的重金属分布,着重分析了人发中重金属含量与年龄间的关系,指出最易受环境污染危害的人群。研究表明,人发中重金属含量与人所处的地质环境密切相关,人发中重金属含量主要受控于地质环境中某个(些)主导因素。不同年龄段人群重金属元素的分布对矿山开发环境的响应不同。人发中一些有害元素(Pb、Cd)在儿童组(15岁以下)普遍表现为高含量。这说明矿山开发释放的污染元素对儿童的危害最大。不同地区不同元素与年龄间的关系不同。人发重金属含量与年龄关系较为复杂,不存在统一的结论,应具体情况具体分析。  相似文献   

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