Determination of Cd, Cu, Pb and Zn in environmental samples: microwave-assisted total digestion versus aqua regia and nitric acid extraction

We validated the determination of the content of Cd, Cu, Pb and Zn using two digestion protocols: a microwave-assisted total digestion and an aqua regia extraction procedure based on the International Organization for Standardisation (ISO) 11466 method. Our goal in validating these two protocols, along with a nitric acid digestion, is to propose a rapid, cheap and easily automated digestion method for monitoring heavy metal content in environmental samples. We applied the digestion protocols to samples with a wide range of organic matter such as sediments, soils, sludges and plant material.For samples with a low carbonate or organic matter contents, such as sediments and agricultural soils, aqua regia digestion in an aluminium block was revealed to be an optimum estimator for the total metal content. For samples with a high organic matter content, such as organic horizons of forest floor layers, plant material and organic soils, nitric acid digestion could substitute microwave (MW)-hydrofluoric acid (HF) digestion. Except in a few samples with high organic matter or low heavy metal content, the RSD values obtained after the application of the proposed digestion procedures were lower than 5%. Based on the obtained results, a decision flow chart for choosing the fit-for-purpose digestion procedure is suggested.     

Determination of traces of heavy metals (Mn,Cu, Zn,Cd and Pb) in microsamples of teeth material by ETV-ICP-MS

Heavy metal levels in tooth compartments would appear to be a suitable indicator of long-term exposure. A method has been developed to assess the heavy metal levels (Mn, Cu, Zn, Cd and Pb) in tooth compartments like dentin and enamel. For the simultaneous determination of these elements in small dentin sample amounts (in some cases less than 1 mg) inductively coupled plasma mass spectrometry with electrothermal vaporization was the method of choice. Sample preparation, method development and first results of the application of the method for the analysis of tooth compartments have been described. Variation in the elemental concentrations depending on the kind of tooth and the sampling position have been observed. The method is useful for epidemiological studies of the heavy metal exposure of children.     

Determination of traces of heavy metals (Mn, Cu, Zn, Cd and Pb) in microsamples of teeth material by ETV-ICP-MS

Heavy metal levels in tooth compartments would appear to be a suitable indicator of long-term exposure. A method has been developed to assess the heavy metal levels (Mn, Cu, Zn, Cd and Pb) in tooth compartments like dentin and enamel. For the simultaneous determination of these elements in small dentin sample amounts (in some cases less than 1 mg) inductively coupled plasma mass spectrometry with electrothermal vaporization was the method of choice. Sample preparation, method development and first results of the application of the method for the analysis of tooth compartments have been described. Variation in the elemental concentrations depending on the kind of tooth and the sampling position have been observed. The method is useful for epidemiological studies of the heavy metal exposure of children.     

火焰原子吸收光谱法测定蚯蚓中铜、锌、镉和铅

随着工业生产的发展和人们生活水平的不断提高,城市垃圾处理场的重金属含量越来越高。部分重金属通过大气和水进入土壤,由于污染给生物和人类带来危害。大型土壤动物-蚯蚓,是土壤污染中敏感的指示动物,受到国内外学者的重视。因此,通过对蚯蚓的监测来评价土壤的污染程度是常用的方法之一。本法将蚯蚓洗净泥沙,置黑暗处饥饿养殖3天,待其基本排尽粪便,经烘干研磨制成粉,经硝酸-高氯酸消解后,用火焰原子吸收光谱法测定其中的铜锌镉铅含量。方法简便、快速,相对标准偏差为0．5％～3．7％,加标回收率为94．0％～106．0％,获得满意的结果。     

电感耦合等离子体质谱法测定海洋贝类中镉、铬、铜和铅

采用微波消解法处理海洋贝类样品,用电感耦合等离子体质谱法测定样品中镉、铬、铜和铅等4种重金属元素的含量。选择111 Cd、53 Cr、63 Cu和208 Pb等待测元素的同位素克服了质谱干扰。4种元素分别在一定的质量浓度范围内呈线性,检出限(3s)在0.005～0.17μg.L-1之间。镉、铬、铜和铅的回收率分别为94.7%,102.1%,101.9%,105.3%;测定值的相对标准偏差(n=7)分别为4.3%,3.8%,1.5%,6.0%。     

Certification of reference materials for Cd, Cr, Hg and Pb in polypropylene

Two reference materials, at relatively low and high concentrations (GBW08404 and GBW08405), for analysis of the mass fractions of Cd, Cr, Hg and Pb in polypropylene were developed. The reference materials were prepared by doping blank polypropylene base material with Cd, Cr, Hg and Pb in the form of oxides, salts or pigments. Homogeneity and stability studies were performed by inductively coupled plasma mass spectrometry. The certification of the four analytes was carried out by isotope-dilution mass spectrometry (IDMS) with microwave-assisted digestion. Combined uncertainties were calculated from the IDMS uncertainty evaluation budget and the uncertainty of the homogeneity. The mass fractions of Cd, Cr, Hg and Pb of the two certified reference materials (CRMs) were from 8 to 1,000 mg kg⁻¹. The two samples were also used in an interlaboratory comparison scheme in which National Institute of Metrology, China, National Metrological Institute of Japan and Korea Research Institute of Standards and Science participated. The agreement of the comparison results proved that the certification procedure of the CRMs is valid and that the certified values of Cd, Cr, Hg and Pb are accurate and reliable.     

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.

     

ICP-AES法测定环境水样中的微量镉铬铜镍铅锌

应用ＩＣＰ－ＡＥＳ法对环境水样中Ｃｄ、Ｃｒ、Ｃｕ、Ｎｉ、Ｐｂ、Ｚｎ等６种微量元素进行直接测定。考察了环境水样中钙、镁离子对的影响。通过对国标样品及实际样品的测定,加标回收实验,建立了简便、快速、准确、稳定、重现性较好的ＩＣＰ－ＡＥＳ法测定环境水样中６种微量元素的分析方法。     

火焰原子吸收法连续测定茶叶中铅、铜、锌、镉含量

采用火焰原子吸收方法连续测定了茶叶中铜，铜，锌，镉的含量，方法灵敏，准确。测定时无需富集，萃取，操作简便，回收率93．0％－98．1％，相对标准偏差不超过5．3％。     

电感耦合等离子体质谱法测定铅锌矿尾矿渣中铜、铅、锌和镉

采用硝酸-氢氟酸-高氯酸溶解样品,用电感耦合等离子体质谱法测定了铅锌矿尾矿渣中的铜、铅、锌和镉。以铑为内标元素,选择63 Cu,66Zn,208 Pb,114 Cd作为测量同位素。铜、铅、锌的线性范围为200μg·L-1,镉的线性范围为1.0μg·L-1,检出限(3s)分别为0.04,0.10,0.03,0.003μg·g-1。测定值的相对标准偏差(n=11)在0.39%~2.2%之间。用此方法分析标准物质,测定值与认定值相符。     

A study of the direct determination of Cd, Cr, Cu, Pb and Zn in certified reference materials of soils by solid sampling electrothermal atomic absorption spectrometry

A simple and rapid method for the direct determination of Cd, Cr, Cu, Pb and Zn in soil was developed. The method was developed using three certified reference materials of soil: Eutric Cambisol, Orthic Luvisols and Rendzina, which differed in their matrix composition. Chemical modifiers were essential to achieve reproducible and interference-free signals for the analytes studied. The best results were obtained with a Pd/Mg(NO₃)₂ admixture for the determination of Cd, Pb and Zn and NH₄F for Cu. The combination of W (as a permanent modifier) and Mg(NO₃)₂ provided well-defined signal profiles for Cr. The following spectral lines were used: Cd 228.8 nm, Cr 520.6 nm, Cu 218.2 nm, Pb 205.3 nm and Zn 307.6 nm. The limit of detection was 4.2 ng g^− 1 for Cd, 1.1 μg g^− 1 for Cr, 0.5 μg g^− 1 for Cu, 1.3 μg g^− 1 for Pb and 8.6 μg g^− 1 for Zn for the maximum sample mass used. Under optimized conditions, the analyte and matrix were separated effectively in situ, and aqueous standards could be used for calibration.     

Systematic investigations on the heavy metal pollution (Cd, Pb, Cu, Zn, Cr, Ba) of drinking water using atomic absorption spectrometric methods

Summary Systematic investigations were carried out on the heavy metal (Cd, Pb, Cu, Zn, Cr, Ba) pollution of drinking water. The samples were analysed by electrothermal AAS directly and after ATMDTCMIBK chelation extraction preconcentration. Results of both methods were in good agreement. Filterable residue of tap water and sediment of reservoirs in the distribution system were analysed by flame AAS after digestion in acidic medium.Final conclusions as follows: I. At present there is no significant heavy metal pollution originating from surface water. II. Because of the non-aggressive property of the Danube water, no significant dissolution of heavy metals occurs from piping materials, only the zinc content is elevated in some parts of the town. III. Heavy metals are adsorbed on the surface of residue materials and become concentrated in the sediments of the reservoirs. IV. It is desirable from the point of public health that the concentration of filterable residue of tap water is kept under a certain limit.

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Systematische Untersuchung der Verunreinigung durch Schwermetalle (Cd, Pb, Cu, Zn, Cr, Ba) im Trinkwasser mit Hilfe von AAS-Methoden

Zusammenfassung Die Wasserproben wurden mit Hilfe der elektrothermischen AAS direkt sowie nach Anreicherung durch Chelatextraktion (Ammoniumtetramethylen-dithiocarbamat/Methylisobutylketon) bestimmt. Die nach beiden Methoden erhaltenen Werte stimmten gut überein. Filtrierbare Rückstände von Leitungswasser sowie Ausfällungen aus Wasserreservoirs wurden nach saurem Aufschluß mit Hilfe der Flammen-AAS analysiert.Die Ergebnisse führten zu folgenden Feststellungen: I. Zur Zeit gibt es keine von Oberflächenwasser ausgehende signifikante Verunreinigung mit Schwermetallen. II. Wegen der nicht-korrosiven Eigenschaft des Donauwassers werden keine nennenswerten Mengen von Schwermetallen aus den Rohrmaterialien herausgelöst; lediglich der Zn-Gehalt ist in einigen Stadtteilen erhöht. III. Schwermetalle werden an Rückständen adsorbiert und treten konzentriert in den Ablagerungen von Wasserreservoirs auf. IV. Vom gesundheitlichen Standpunkt ist es wünschenswert, daß der Gehalt an filtrierbaren Rückständen in Leitungswasser eine gewisse Grenze nicht überschreitet.

     

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.

     

The utilization of modified BCR three-step sequential extraction procedure for the fractionation of Cd, Cr, Cu, Ni, Pb and Zn in soil reference materials of different origins

A modified three-step sequential extraction procedure for the fractionation of heavy metals, proposed by the Commission of the European Communities Bureau of Reference (BCR) has been applied to the Slovak reference materials of soils (soil orthic luvisols, soil rendzina and soil eutric cambisol), which represent pedologically different types of soils in Slovakia. Analyses were carried out by flame or electrothermal atomic absorption spectrometry (FAAS or ETAAS). The fractions extracted were: exchangeable (extraction step 1), reducible-iron/manganese oxides (extraction step 2), oxidizable-organic matter and sulfides (extraction step 3). The sum of the element contents in the three fractions plus aqua-regia extractable content of the residue was compared to the aqua-regia extractable content of the elements in the origin soils. The accuracy obtained by comparing the determined contents of the elements with certified values, using BCR CRM 701, certified for the extractable contents (mass fractions) of Cd, Cr, Cu, Ni, Pb and Zn in sediment following a modified BCR-three step sequential extraction procedure, was found to be satisfactory.     

Determination of Cr, Ni, Cu, Zn and Cd in niobium by radiochemical proton-activation analysis

A rapid radiochemical proton-activation technique based on the utilization of short-lived indicator radionuclides (t(1/2) = 7-100 min) for the determination of Cr, Ni, Cu, Zn, and Cd in niobium is described. It involves the irradiation of the samples with 13-MeV protons, the post-irradiation decontamination of the sample surface, a rapid sample dissolution, a separation procedure based on anion-exchange from HF medium, and counting the eluate with a high-resolution gamma-spectrometer. In addition, for the determination of Ni, a specific separation procedure is proposed. For a 20-min ir-radiation with a beam intensity of 10 microA and a delay time of 20 min, the limits of detection are 4 ng/g for Cr, 0.5 ng/g for Ni, 60 ng/g for Cu, 0.5 microg/g for Zn and 0.2 microg/g for Cd. For Cr, Ni, and Cu, the results obtained by this technique are compared with data obtained by radiochemical neutron-activation analysis and atomic-absorption spectrometry.     

瓦楞纸板中铅、镉、铬元素的AAS测定

利用AAS分析技术,对试样分解方法、共存元素干扰、仪器分析参数等因素的研究,确定最佳分析条件,建立了连续测定瓦楞纸板中铅、镉、铬有害、有毒元素的分析方法.结果表明,该方法准确、可靠、快速、简单、操作性强.3种元素的回收率在88%～109%之间,相对标准偏差在1.1%～5.4%之间.     

海水中铜、铅、镉、锌国标测定条件优化

对海水中铜、铅、镉、锌国标测定方法进行了条件优化,研究了冲洗溶液、萃取溶剂、络合剂、pH、提取量对实验结果的影响,在优化条件下,铜、铅、镉、锌测定的相对标准偏差在0.0%~2.0%之间,标样测定结果均优于等离子发射光谱法等4种方法。     

Digestion-free determination of heavy metals (Pb, Cd, Cu) in honey using anodic stripping differential pulse voltammetry and potentiometric stripping analysis

Experiments have been carried out to assess the potential of differential pulse voltammetry and potential stripping analysis for determining Pb, Cu and Cd directly in dissolved honey samples using a flow-through cell. With the hanging mercury drop electrode Pb alone can be determined only if the electrode is first modified in-situ with Triton X 100 to increase the separation between the Pb peak and a broad, interfering adsorption peak which overlaps the Cu peak. If the (more sensitive) thin film mercury electrode is used the interference encountered is less so also Cu and Cd can be determined. With potentiometric stripping analysis Cu and Pb can be determined using normal procedures. The determination of Cd, however, can only be carried out if the concentration of the oxidizing agent [Hg(II)] in solution is decreased. A good agreement has been obtained between the values found and those obtained after high pressure digestion of the samples.     

Comparison of digestion procedures for the determination of heavy metals (Cd, Cu, Pb) in blood by anodic stripping voltammetry

Summary The simultaneous determination of cadmium, lead and copper in whole blood by anodic stripping voltammetry is described. Different digestion procedures given in literature were examined. In addition, a sample pretreatment method which did not involve digestion was studied. Based on the experience with these methods two digestion procedures were developed. They utilize digestion with mixtures of nitric, perchloric and sulphuric acids, with and without pressure, respectively. Both methods are suitable for routine analysis of about 20 blood samples per day. Special attention was focussed on the completeness of the digestion, and the magnitude of the blank values. Low blank values and a high sensitivity allowed the determination of cadmium at the sub-ppb level with an electrolysis time of 5 min. The methods, which were controlled by recovery tests, were used to analyze blood samples from unexposed persons, and from workers suspected of exposure to cadmium.

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Vergleich von Aufschlußverfahren für die Bestimmung von Schwermetallen (Cd, Cu, Pb) in Blut durch Anodic Stripping Voltammetrie

Zusammenfassung Verschiedene in der Literatur beschriebene Aufschlußverfahren wurden untersucht und zusätzlich ein Probenvorbereitungsverfahren ohne Aufschluß geprüft. Aufgrund der mit diesen Methoden gewonnenen Erfahrungen wurden zwei Aufschlußverfahren entwickelt, bei denen Mischungen von Salpeter-, Perchlor- und Schwefelsäure mit und ohne Anwendung von Druck eingesetzt werden. Beide Methoden eignen sich für die Routineuntersuchung von etwa 20 Blutproben je Tag. Besondere Aufmerksamkeit wurde der Vollständigkeit des Aufschlusses und der Größe der Blindwerte gewidmet. Niedrige Blindwerte und hohe Empfindlichkeit erlaubten die Bestimmung von Cadmium im sub-ppb-Bereich mit einer Elektrolysezeit von 5 min. Die Methoden wurden durch Wiederauffindungstests geprüft und für die Blutuntersuchung von Personen, die der Einwirkung von Cd ausgesetzt waren, sowie solchen, bei denen dies nicht der Fall war, angewendet.