Certification of the contents of some heavy metals (Cd, Cu, Hg, Ni, Pb and Zn) in three types of soils

Summary The element contents of Cd, Cu, Hg, Ni, Pb and Zn of three types of soil were certified. The preparation, homogeneity and stability are reported. The certified contents as well as values for Co, Cr, Mn and Se and for the aqua regia soluble contents Cd, Cr, Cu, Mn, Ni, Pb and Zn are given.

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Zertifizierung von Schwermetallspuren (Cd, Cu, Hg, Ni, Pb und Zn) in drei Bodenproben

Zusammenfassung In drei verschiedenen Bodenproben wurden die Elementgehalte an Cd, Cu, Hg, Ni, Pb und Zn zertifiziert. Es wird berichtet über die Bereitung, Homogenität und Stabilität. Die zertifizierten Gehalte sowie der Gehalt an Cr, Co, Mn und Se und der Gehalt an königswasserlöslichem Cd, Cr, Cu, Mn, Ni, Pb und Zn werden angegeben.

     

Certification of the contents of some heavy metals (Cd, Co, Cu, Mn, Hg, Ni, Pb and Zn) in three types of sewage sludge

Summary The element contents of Cd, Co, Cu, Mn, Hg, Ni, Pb and Zn of three different types of sewage sludge were certified. The preparation, the homogeneity and the stability are reported. The certified contents as well as values for Cr and Se and for the aqua regia soluble contents of Cd, Cr, Co, Cu, Mn, Ni, Pb and Zn are given.

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Zertifizierung von Schwermetallspuren (Cd, Co, Cu, Mn, Hg, Ni, Pb und Zn) in drei Klärschlammproben

Zusammenfassung In drei verschiedenen Klärschlammproben wurden die Elementgehalte an Cd, Co, Cu, Mn, Hg, Ni, Pb und Zn zertifiziert. Es wird berichtet über die Herstellung, Homogenität und Stabilität. Die zertifizierten Gehalte sowie der Gehalt von Cr, Se und der Gehalt an königswasserlöslichem Cd, Cr, Co, Cu, Mn, Ni, Pb und Zn werden angegeben.

     

Mineral constituents of edible parasol mushroom Macrolepiota procera (Scop. ex Fr.) Sing and soils beneath its fruiting bodies collected from a rural forest area

Concentrations and interrelationships of twenty elements were studied in parasol mushroom and in the top layer of soil (0–10 cm) from the area of Kiwity (Poland). K, P, Mg, Ca, and Zn were found to be the most abundant elements in the mushroom. Higher concentrations of Fe, Mn, Na, Ni occurred in stipes then in caps, while Cd, Cr, Cu, Hg, Rb dominated in caps. Ag, Al, and Ba concentrations in caps and stipes were similar. Parasol mushroom is efficient in up-take and separation of Ag, Cd, Cu, Hg, K (in caps, the bioconcentration factor is BCF ≥ 100), Na, P, Rb (50 < BCF < 100), and Mg, Zn (BCF > 10) in its fruiting bodies, while Al, Ba, Ca, Co, Cr, Fe, Mn, Sr, and Pb are eliminated (BCF < 1). Parasol mushroom from rural forest area in the north-eastern region of Poland is of hygienic concern for human health because of toxic mercury and cadmium content in the edible caps, which are also rich in essential Cu, Fe, and their K, Mn, and Zn content is also high.     

Availability of essential trace elements in medicinal herbs used for diabetes mellitus and their possible correlations

Four plant parts (leaves, roots, fruits and seeds) of twenty samples of sixteen antidiabetic herbs including three commercially marketed capsules have been analyzed for 6 minor (Na, K, Ca, Cl, Mg, and P) and 21 trace (As, Ba, Br, Ce, Co, Cr, Cs, Cu, Eu, Fe, Hg, La, Mn, Rb, Sb, Sc, Se, Sm, Th, V and Zn) elements by instrumental neutron activation analysis (INAA). Further, Ni, Cd and Pb contents were determined by AAS. Elemental data were validated by simultaneously analyzing reference material (RM), MPH-2 Mixed Polish Herbs. Several elements such as Cr and V (1–2 μg/g), Rb (10–40 μg/g), Cs (80–300 ng/g), Se (∼100 ng/g) and Zn (25–60 μg/g) play an important role in diabetes mellitus. Interelemental linear correlations have been observed for Cu vs. Zn (r = 0.89) and Rb vs. Cs (r = 0.87). K/P ratio varies in a narrow range with a mean value of 6.2 ± 1.4. Toxic elements As and Hg were found in <1 μg/g whereas Cd and Pb were in ∼5 μg/g and <10 μg/g, respectively.     

Determination of heavy metals in air conditioner dust using FAAS and INAA

The elements Cd, Cr, Cu, Mn, Ni, Pb and Zn were determined in dust samples collected from air conditioner (AC) filters from 15 commercial sites of Lahore using flame atomic absorption spectroscopy (FAAS). The elements Cr, Mn and Zn were also determined using instrumental neutron activation analysis (INAA). The results obtained showed that higher amounts of these metals were measured in these dust samples than normally found in soil. This was especially true for Cd, Cu, Pb and Zn. Generally the amounts of Cd, Cr and Mn did not vary throughout the city of Lahore but the amounts of the traffic related Cu, Pb and Zn elements had the more variable ranges of 30–140, 30–230 and 74–2810 mg/kg respectively. The concentrations obtained for Cr, Mn and Zn by INAA were found to be higher than those obtained using FAAS. Analysis of the data obtained showed the digestion procedure employed to be the possible cause for this occurrence. It was also found that Mn was being over-estimated by INAA due to the interference from the Mg peak.     

Use of enzymatic hydrolysis for the multi-element determination in mussel soft tissue by inductively coupled plasma-atomic emission spectrometry

A systematic evaluation of different variables affecting the enzymatic hydrolysis of mussel soft tissue by five enzymes, three proteases (pepsin, pancreatin and trypsin), lipase and amylase, has been carried out for the determination of trace elements (As, Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn) by inductively coupled plasma-atomic emission spectrometry (ICP-AES). Enzymatic hydrolysis methods offers advantages such as a less species alteration, safer laboratory conditions and a less contaminant wastes. The enzymatic hydrolysis was performed in an incubation camera Boxcult with orbital and horizontal shaker. Variables affecting the enzymatic hydrolysis process were simultaneously studied by applying a Plackett-Burman design (PBD). For a confidence interval of 95%, the significant factors for all enzymes and for most of the elements were the pH, the incubation temperature and the ionic strength. These significant factors were optimized later by using a central composite design (CCD), which gave optimum conditions at pH of 1, incubation temperature of 37 °C and ionic strength fixed by sodium chloride at 0.2 M when using pepsin. For pancreatin, trypsin, lipase and amylase there were found two different optimum condition sets. The first one involves the use of a 0.5 M phosphate buffer (ionic strength), at a pH of 6 and at an incubation temperature of 37 °C, which allows the quantitative extraction of Al, Cr, Mn, Pb and Zn. The second conditions set employees a 0.1 M phosphate buffer (ionic strength), a pH of 9 and an incubation temperature at 37 °C, and it results adequate to extract As, Cd, Cu, Fe and Ni. Analytical performances, repeatability of the over-all procedure and accuracy, by analyzing DORM-1, DORM-2 and TORT-1 certified reference materials, were finally assessed for each enzyme. Good agreement with certified values has been assessed for most of the elements (As, Cd, Cr, Cu, Mn, Ni, Pb and Zn) when using trypsin, pepsin and/or pancreatin, except for Cd and Pb in DORM-1 and DORM-2 because of the certified contents in such certified reference materials are lower than the limit of detection (0.10 and 0.16 μg g⁻¹ for Cd and Pb, respectively, for the use of trypsin).     

Establishment of SI-traceable reference values for the content of various elements in the IMEP-14 sediment sample

For the first time in the International Measurement Evaluation Programme (IMEP)-14, a sediment sample was offered to analytical laboratories to perform measurements of As, Cd, Cr, Cu, Fe, Pb, Hg, Ni, U and Zn. In line with IMEP policy, the results were presented according to the certified / assigned reference values established by several reference laboratories around the world. The certification campaign is described in detail. Isotope dilution mass spectrometry was applied as a primary method of measurement, whenever possible, to achieve SI-traceable results. For reference measurements of As, Fe, Hg and Zn, k₀-neutron activation analysis and Zeeman atomic absorption spectrometry were applied. The reference values (ranges) were characterised as ”certified” (for Cd, Cr, Pb, Ni and U) or ”assigned” (for As, Cu, Fe, Hg and Zn) according to IMEP policy. The measurement uncertainty of the certified / assured reference values was calculated according to the ISO/BIPM Guide. Received: 7 June 2001-10-27 Accepted: 19 August 2001     

Co-precipitative pre-concentration with sodium diethyldithiocarbamate and ICP-AES determination of Se, Cu, Pb, Zn, Fe, Co, Ni, Mn, Cr and Cd in water

Sodium diethyldithiocarbamate in the presence of a weak oxidizing agent is used as a co-precipitative agent for the pre-concentration of Se, Cu, Pb, Zn, Fe, Co, Ni, Mn, Cr and Cd. A procedure was developed for ICP-AES determination of these elements after pre-concentration in river and waste water (an enrichment factor of 40). The recovery of all the elements tested for was more than 98%. The limits of determination (mg l⁻¹) (10 S.D. blank) are 0.001 (Cu, Co, Cr, Mn), 0.0007 (Zn, Cd), 0.003 (Se), 0.004 (Fe), 0.007 (Ni), and 0.01 (Pb).     

Assessment of trace metals contamination in estuarine sediments using a sequential extraction technique and principal component analysis

Fractionation of the metals Cd, Cr, Cu, Ni, Pb and Zn in sediments was performed for samples collected from eight locations in the Poxim river estuary of Sergipe State, northeast Brazil, using the 3-stage sequential extraction procedure proposed by the European Community Bureau of Reference (BCR). The extraction method was found to be satisfactory for analysis of certified reference material BCR-701, with recovery values ranging from 85% (Cu) to 117% (Cr). The detection limits obtained were 0.001 to 0.305 µg g^− 1. Zn exhibited greatest mobility and bioavailability, indicative of anthropogenic sources, while Cr was mainly found in the residual fraction and could be used as an indicator for the contribution from natural sources. Cd, Cu, Ni and Pb were associated with the oxidizable fraction, and Pb, Cr and Ni with the reducible fraction. Principal component analysis (PCA) clearly separated the metals into three groups: I (Zn); II (Pb); III (Cd, Cu, Cr and Ni). These groupings were mainly due to different distributions of the metals in the various fractions, in sediments from the different locations. Risk assessment code (RAC) analysis indicated that although the metals presented a moderate overall risk to the aquatic environment, nickel showed a low risk (RAC < 10%) at three sites, while zinc presented a high risk (RAC > 30%) at four other sites.     

Certification of trace element contents (As, Cd, Co, Cu, Fe, Mn, Hg, Na, Pb and Zn) in a fly ash obtained from the combustion of pulverised coal

Summary The element contents of As, Cd, Co, Cu, Fe, Mn, Hg, Na, Pb und Zn of a fly ash from pulverised coal are certified. The procedures and their results for the homogenisation, the contamination and homogeneity checks and the analytical campaign are reported. The certified mass fractions and indicative values for Cr, Ni, Th, V and water soluble sulphate are given. The work was carried out within the framework of the activities of the Community Bureau of Reference (BCR) of the Commission of the European Communities.

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Zertifizierung von Spurengehalten (As, Cd, Co, Cu, Fe, Mn, Hg, Na, Pb und Zn) in einer Flugasche aus Pulverkohle

Zusammenfassung In einer Flugasche aus Pulverkohle wurden die Elementgehalte an As, Cd, Co, Cu, Fe, Mn, Hg, Na, Pb und Zn zertifiziert. Über die Homogenisierung, die Kontrolle der Kontaminierung und Homogenität und die analytischen Ringversuche wird berichtet. Die zertifizierten Gehalte sowie der Gehalt von Cr, Ni, Th, V und wasserlöslichem Sulfat werden gegeben. Die Arbeit wurde ausgeführt im Rahmen des Programms des Referenzbüros der Kommission der Europäischen Gemeinschaften (BCR).

     

Concentrations of major and trace elements in polished rice and paddy soils collected in Aomori,Japan

Rice grain samples and surface paddy soil samples were collected from 20 sites throughout Aomori Prefecture, Japan, and the concentrations of 25 elements in the polished rice and 33 elements in the soils were determined by neutron activation analysis, inductively coupled plasma-mass spectrometer or atomic adsorption spectrometer. The range of essential element concentrations in the polished rice was within one order of magnitude, however, the range for most of the trace elements was more than one order of magnitude. The range of element concentrations, except for I, in the paddy soils was within one order of magnitude. The ±95% confidence intervals of the soil-to-polished rice transfer factors for all elements, except for Pb, were within two orders of magnitude, and the geometric mean values were as follows: Cl, Mo and Zn (0.1–1); K, Cu, Cd, Rb, Mg, Mn, and Ag (0.01–0.1); Ni, As, Ca, Se and I (0.001–0.01); Na, Cs, Sr, Co, Cr, V, Ba, Pb, Fe and Al (<0.001).     

Ultrasound-Assisted Extraction for the Evaluation of Element Mobility in Bottom Sediment Collected at Mining and Smelting Pb–Zn Ores Area in Poland

The current BCR procedure for metal fractionation recommended by the Standard Measurement and Testing Programme requires rather time-consuming sample pretreatment. Ultrasonic energy seems to be an attractive alternative for leaching metal from solid samples into a liquid extractant phase. This study aims at optimizing ultrasonic extraction in order to replace the BCR method of leaching using acetic acid and to apply the procedure of assessing element mobility in bottom sediment rich in moderately soluble carbonate minerals. The application of ICP-MS allowed the determination of As, Cd, Cr, Cu, Pb, Ni, Tl and Zn in extracts, in a wide range of concentration without any special treatment. Finally, 40’min extraction in an ultrasonic bath was proposed for evaluation of the mobile fraction of As, Cd, Cr, Cu, Pb and Zn as an assessment of environmental risk. The recovery of the ultrasound-assisted extraction in comparison to the shake-filter method, as applied in the common BCR procedure, was slightly higher than 100% for As, Cr and Pb, reasonably high (about 70%) for Cd, Zn and Cd, but did not exceed 21% for Tl. Also, the mobility and extractability (relative mobility) of the studied elements from sediment collected over one year were compares. According to the results obtained after 40’min of ultrasound-assisted extraction it can be concluded that mobility did not change over one year for Cr, Cu, As, Cd, Ni and Tl, but noticeable differences for Zn and Pb were observed. The total content of all studied elements was almost the same in samples taken in the years 2003 and 2004, respectively.     

Assessment of the health of a river ecosystem due to the impact of pollution from industrial discharge using instrumental neutron activation analysis and inductively coupled plasma-mass spectrometry

Inductively coupled plasma-mass spectrometry (ICP-MS) and neutron activation analysis (NAA) were employed in the determination of heavy metal concentrations in water, plant and sediment samples to assess the extent of heavy metal pollution in a river system which is located within an industrial zone. Elemental concentrations of As, Pb, Hg, Cr, Cu, Cd, Ni and Zn were measured in the samples. Statistical analysis was performed on the data obtained to look for trends in the pollution pattern of these elements on the river system. The trend in concentrations of heavy metals pollution in water samples is in the order of Zn > Cu > Ni > Cr > As > Pb > Hg > Cd, whereas in plants the order is Zn > Cr > Cu > Pb > Ni > As > Hg > Cd and in sediments Zn > Cu > Pb > Ni > As > Hg.     

Trace metal accumulation in tissues of sole (Solea senegalensis) and the relationships with the abiotic environment

The distribution patterns and the organ-specific accumulation trends of 10 trace metals (iron, manganese, zinc, copper, chromium, nickel, cobalt, lead, cadmium and silver) and 4 major elements (sodium, potassium, calcium and magnesium) in 10 different tissues (heart, muscle, kidney, stomach, intestine, liver, gill, gonads, white skin and dark skin) of a benthic fish species (Solea senegalensis) from a densely populated coastal area affected by anthropogenic activities, the Bay of Cadiz (SW Spain), have been investigated. High variability of metal concentrations among tissues were found for Ca, Fe, Zn, Cu, Pb and Ag. Factor analysis was applied to study this variability. Five principal components were found explaining the 92.95% of the total variance and similarities in behavioural patterns of bioaccumulation were described. They associated Mg, Cr, Ni and Mn to intestine and stomach tissues (PC1), Ag, Cu and Cd to liver (PC2), Zn, K and Co to gonads (PC3), Na, Fe and Pb to gill, heart and kidney tissues (PC4) and Ca, Pb and Mn to gill and dark skin (PC5). The metallic concentration in the sediment and water was also studied. The pollution in this area was found moderate with outstanding values of Zn, Cu and Pb (average values of 139, 50.4 and 75.6?mg?kg^?1, respectively) in sediment and dissolved Cu (average value of 2.5?µg?L^?1). Metal bioconcentration trends followed the order Zn?>?Cu?>?Cd?>?Pb for dissolved metals in seawater, Cu?>?Zn?>?Cd?>?Pb?≈?Mn?>?Fe?≈?Ni?≈?Co for metals associated to particulate matter and Zn?≈?Cu?>?Cd?>?Mn?>?Co?≈?Fe?>?Ni?≈?Pb?>?Cr for metals in the sediment. Higher values were found for copper in liver, zinc in gonads and lead in gill, showing the relationship between biotic and abiotic environment. In addition, Cd bioconcentration factors were found high in liver and gill showing the sensitivity of sole to this metal even at low concentrations.     

Semiquantitative Analysis of Biological Materials by Inductively Coupled Plasma–Mass Spectrometry

Semiquantitative analysis with accuracy of ±30 to 50% is a valuable tool for rapid screening of samples prior to quantitative determination of trace metals. In this study semiquantitative analysis software available with commercial inductively coupled plasma–mass spectrometry (ICP-MS) instrumentation is applied for rapid multielemental analysis, and the accuracy and precision of this semiquantitative analysis approach is evaluated with biological certified reference materials. Samples were prepared by high-pressure, high-temperature nitric acid vapor-phase digestion. For most elements the measured semiquantitative results are in the range of the certified values. With appropriate analyte solution dilution, the measured concentrations of the major elements (e.g., Ca) also agree with certified values. The accuracy is within ±10% for 28 element determinations that include 16 individual elements (Ag, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Rb, Sb, Sr, Tl, and Zn) and ±20% for 54 element determinations that include three more elements (Mg, V, and U) in eight certified reference materials including water. The method precision is 11 ± 11% (relative standard deviation,n= 65).     

Grundlagen zur halbquantitativen Bestimmung von zwanzig Elementen in der Lasermikrospektralanalyse

Zusammenfassung Für die folgenden 20 Elemente wurden die Grundlagen für eine halbquantitative Konzentrationsbestimmung mit Hilfe des Laser-Mikrospektralanalysators ermittelt, und zwar differenziert für Untersuchungen an oxidischen und an metallischen Materialien: Mg, Al, Si, Cr, Mn, Co, Ni, Cu, Zn, Ga, Ge, Pd, Ag, Cd, In, Sn, Sb, Pb, Bi, Fe bzw. Au.

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Principles of semi-quantitative determination of 20 elements by laser-microspectroscopy

The principles for the determination of the following 20 elements by Laser-microspectroscopy have been investigated separately for oxidic and metallic materials: Mg, Al, Si, Cr, Mn, Co, Ni, Cu, Zn, Ga, Ge, Pd, Ag, Cd, In, Sn, Sb, Pb, Bi, Fe resp. Au.

     

Epsilon5高能偏振能量色散X-射线荧光光谱仪测定垃圾焚烧灰渣中有害元素

使用粉末样品压片制样,用Epsilon5高能偏振能量色散X射线荧光(EDXRF)光谱仪测定垃圾焚烧灰渣中S、Cl、Ba、Cr、Cu、Na、Mn、Pb、Zn、Cd、As、Mo等多种有害元素,采用土壤、水系沉积物、海底沉积物、矿物等国家标准物质和人工合成标样作为校准。     

Trace metals in mussel shells and corresponding soft tissue samples: a validation experiment for the use of <Emphasis Type="Italic">Perna perna</Emphasis> shells in pollution monitoring

The uptake of Cr, Mn, Ni, Cu, Zn, Cd and Pb in soft tissue of Perna perna mussels and their shells has been studied in aquarium experiments in which mussels were exposed for 30 or 60 days to seawater spiked with different concentrations of these contaminants (125 and 500 μg L⁻¹). Tissue samples were analyzed after acid digestion by conventional solution nebulization ICP–MS. Laser ablation ICP–MS was used for the quantitative determination of trace elements in different areas of the corresponding shells. With the exception of Mn and Zn, all other elements studied showed a significant concentration enhancements in soft tissue, with the magnitude of this enhancement following the order: Cr > Ni > Cd > Cu > Pb. A corresponding increase in most contaminants, although less pronounced, was also observed in the newly formed growth rings of mussel shells, contributing to the validation of Perna perna mussel shell as a bioindicator of toxic elements.     

Determination of bioavailable fractions of Zn, Cu, Ni, Pb and Cd in soils and sludges by atomic absorption spectrometry

The single extraction procedures validated by the standards, measurement and testing programme (formerly BCR), extraction with 0.05 mol l⁻¹ EDTA and 0.43 mol l⁻¹ acetic acid, have been applied to reference materials of soils and sludges with certified total values of elements, in order to determine bioavailable contents of Cd, Cu, Ni, Pb and Zn. These soils, which represent uncontaminated pedologically different types of soils from Slovakia and sludges from city water treatment are characterized for the bioavailable fraction of the metals using the procedures followed by SM&T Programme. Concentrations of the elements under the study in the extracts were determined by flame (FAAS) using calibration curves in appropriate extractants and by electrothermal (ETAAS) atomic absorption spectrometry, using technique of standard additions for the evaluation of the results. The accuracy of the extraction procedures and determinations of the elements in the extracts was controlled using CRM 483 certified for EDTA- and acetic acid-extractable contents of Cd, Cu, Ni, Pb and Zn in sewage sludge amended soil.     

Trace elements in Variegated Bolete (Suillus variegatus) fungi

Metallic elements such as Ag, Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Rb, Sr, and Zn were determined using ICP-OES in a representative set of fifteen fruiting bodies of the edible fungus Suillus variegatus. Fruiting bodies were collected from unpolluted areas near the village of Lubichowo of the Bory Tucholskie forest complex in northern Poland in 2007?C2008. The caps were richer in Ag, Al, Cd, Cr, Cu, Fe, K,Mg, Ni, Rb, and Zn, and the stipes in Ba, Ca, Mn, Na, Pb, and Sr. Cobalt concentration in the caps and stipes was similar. In the caps, the content of the elements decreased in the order (mg per kg of dry weight): K 29000 ± 3700, Fe 1600 ± 80, Mg 990 ± 110, Rb 320 ± 86, Zn 90 ± 19, Ca 75 ± 34, Al 68 ± 32, Na 40 ± 18, Cu 19 ± 7, Mn 13 ± 7, Cd 1.0 ± 0.5, Ni 0.64 ± 0.32, Ag 0.40 ± 0.20, Cr 0.33 ± 0.06, Pb 0.20 ± 0.17, Ba 0.19 ± 0.11, Sr 0.15 ± 0.09, and Co 0.070 ± 0.050. Apparently, S. variegatus collected from background areas are relatively low in Pb and Cd and so are suitable for human consumption.