Immobilization of 8-hydroxyquinoline onto silicone tubing for the determination of trace elements in seawater using flow injection ICP-MS

A rapid and simple on-line method is described for the preconcentration of Mn, Co, Ni, Cu, Zn, Cd and Pb from sea water using 8-hydroxyquinoline immobilized onto silicone tubing (Sil-8-HQ) via the Mannich reaction. Recoveries between 35 and 95% and limits of detection in the ppt range were obtained using a 2 m long Sil-8-HQ tube with a sample flow rate of 1.0 ml min(-1). A tube could be subjected to sample loading and elution cycles over 200 times. The capacity was 1.5 and 1.3 mug cm(-2) for Cu and Mn, respectively. Cu, Cd, Co, Pb, Mn, Zn and Ni were determined in coastal and open ocean seawater using flow injection inductively coupled plasma mass spectrometry (FI-ICP-MS). Good agreement with certified values for the certified reference materials NASS-4 and CASS-3 was demonstrated when quantitation was undertaken by the method of additions.     

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).     

Preconcentration and determination of trace elements with 2,6-diacetylpyridine functionalized Amberlite XAD-4 by flow injection and atomic spectroscopy

An on-line flow injection method for the direct determination of trace elements in environmental samples is described. A mini-column packed with 2,6-diacetylpyridine functionalized Amberlite XAD-4 was used to preconcentrate and separate 8 trace metals (Cd, Co, Cu, Mn, Ni, Pb, U and Zn) from water and extracts from solid samples. The metals were eluted with 0.1 M HNO(3) directly to the detection system (either inductively coupled plasma-mass spectrometry (ICP-MS) or flame atomic absorption spectrometry (FAAS)). As well as demonstrating that the resin could be used to preconcentrate ultra-trace analytes from natural waters, it was also shown to work well at a pH of 5.5. Therefore, after treatment of sample digests with sodium fluoride, samples that contain extremely large concentrations of iron may be analysed for trace analytes without the excess iron overloading the capacity of the resin. To this end, the analytes Cd, Co, Cu and Ni were preconcentrated from acid extracts of certified soil/sediment samples and then eluted with nitric acid to be determined on-line. Limits of detection (3sigma) of Cd = 0.33 microg l(-1), Co = 0.094 microg l(-1), Cu = 0.34 microg l(-1), Mn = 0.32 microg l(-1), Ni = 0.30 microg l(-1), Pb = 0.43 microg l(-1), U = 0.067 microg l(-1) and Zn = 0.20 microg l(-1) for the FI-ICP-MS system and Cd = 22 microg l(-1), Co = 60 microg l(-1), Cu = 10 microg l(-1) and Ni = 4.8 microg l(-1) for the FI-FAAS system were obtained. Analysis of certified reference materials showed good agreement with the certified values using the two methods.     

Heavy metals content in rain water collected in three different locations in Italy during 1999

Rain water samples collected at three different locations in Italy during 1999 were analysed for heavy metals determination. Results for V, Cr, Mn, Co, Cu, Cd, Sb, Pb, Al and Ni are reported in this paper. For most of the elements higher concentration values have been measured in the samples from Alpe Gera (rural site): only for Cd and V were the concentrations higher at Pisa. The total annual deposition (microg m(-2) y(-1)) shows a similar behaviour, with Alpe Gera being the location with highest total annual input for Cr, Mn, Co, and in particular for Cu, Sb, Pb and Al. The reason of the higher deposition at a rural site in comparison to a urban one (Milan) is not known: further experimental work and investigations are needed. Generally, no evident seasonal trends have been observed for the measured concentrations, while few correlations have been found among elements within the same station. Crustal contribution to total concentration varies from about 20% for V to less than 1% for Cu, Cd, Sb, Pb and Ni.     

Senio river ecosystem: characterization and distribution of inorganic species in water and sediments

Analytical results are reported for the determination of inorganic species in water and sediments sampled in the Senio river ecosystem. The species determined are Cu, Pb, Cd, Zn, Co, Cr, Ni, Fe, Mn, Hg, F-, Cl-, Br, NO3-, SO4-, Na+, K+, Ca++, Mg++, NH4+ in integrated water, and Cu, Pb, Cd, Zn, Co, Cr, Ni, Fe, Mn, Hg in sediments. For all the elements, in addition to detection limits, precision and accuracy are given: the former, expressed as relative standard deviation (sr), and the latter, expressed as relative error (e), were good, being in all cases lower than 6%. Limitedly to Cu, Pb, Cd and Zn a critical comparison with voltammetric measurements is also discussed.     

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.

     

Inorganic species in water and sediments of the Lamone and Marzeno rivers ecosystem

Analytical results are reported for the determination of inorganic species in water and sediments sampled in the Lamone and Marzeno rivers ecosystem. The species determined are Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Zn, Hg, F-, Cl- Br-, NO3-, SO4--, Na+, K+, Mg++, Ca++, NH4+ in superficial water, and Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Zn, Hg in sediments. For all the elements, in addition to detection limits, precision and accuracy are given: the former, expressed as relative standard deviation (s(r)), and the latter, expressed as relative error (e), were good, being in all cases lower than 6%.     

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.

     

Sorption of trace metals on human hair and application for cadmium and lead pre-concentration with flame atomic absorption determination

Human hair shavings were characterized as a sorbent for trace metals. At pH 7.0 metal sorption follows the order Pb(II)>Cd(II)>Cr(VI)>Fe(III)>Cu(II)>Ni(II)>Mn(VI). Metal recovery is quantitative for Pb and Cd after 30 min of equilibration. Recovery of other metals is less quantitative and varies with pH. For example, while Cu is best recovered at pH 5, Ni and Mn are sorbed optimally in the basic pH region. Sorbed metals can be washed off the sorbent with 0.5 mol L(-1) strong mineral acids or more completely with 0.1 mol L(-1) ethylenediaminetetraacetic acid (EDTA). Typical sorption isotherms were obtained for Cd and Pb with sorption capacities of 39 and 26 micromol g(-1), respectively.Hair sorbent was used for 40-fold pre-concentration of Cd and Pb from treated wastewater samples followed by flame atomic absorption spectroscopic (FAAS) determination. Comparison of the data obtained for lead and cadmium by the proposed pre-concentration method with that by graphite furnace atomic absorption spectroscopy (GFAAS) showed 79 to 86% recovery and comparable analytical precision. Common cations and anions at the levels normally present in natural water do not interfere in the proposed pre-concentration-FAAS method.     

Solid phase extraction and diffusive gradients in thin films techniques for determination of total and labile concentrations of Cd(II), Cu(II), Ni(II) and Pb(II) in Black Sea water

Total dissolved and labile concentrations of Cd(II), Cu(II), Ni(II) and Pb(II) were determined at six locations of the Bourgas Gulf of the Bulgarian Black Sea coast. Solid phase extraction procedure based on monodisperse, submicrometer silica spheres modified with 3-aminopropyltrimethoxysilane followed by the electrothermal atomic absorption spectrometry (ETAAS) was developed and applied to quantify the total dissolved metal concentrations in sea water. Quantitative sorption of Cd, Cu, Ni and Pb was achieved in the pH range 7.5–8, for 30?min, adsorbed elements were easily eluted with 2?mL 2?mol?L^?1 HNO₃. Since the optimal pH for quantitative sorption coincides with typical pH of Black Sea water (7.9–8.2), on-site pre-concentration of the analytes without any additional treatment was possible. Detection limits achieved for total dissolved metal quantification were: Cd 0.002?µg?L^?1, Cu 0.005?µg?L^?1, Ni 0.03?µg?L^?1, Pb 0.02?µg?L^?1 and relative standard deviations varied from 5–13% for all studied elements (for typical Cd, Cu, Ni and Pb concentrations in Black Sea water). Open pore diffusive gradients in thin films (DGT) technique was employed for in-situ sampling and pre-concentration of the sea water and in combination with ETAAS was used to determine the proportion of dynamic (mobile and kinetically labile) species of Cd(II), Cu(II), Ni(II) and Pb(II) in the sea water. Obtained results showed strong complexation for Cu and Pb with sea water dissolved organic matter. The ratios between DGT-labile and total dissolved concentrations found for Cu(II) and Pb(II) were in the range 0.2–0.4. For Cd and Ni, these ratios varied from 0.6 to 0.8, suggesting higher degree of free and kinetically labile species of these metals in sea water.     

煤中痕量元素在循环流化床锅炉中的迁移行为与富集特性

对天津市某电厂循环流化床(CFB)锅炉燃用的原煤及燃烧产物底灰、飞灰、细飞灰(≤50 μm)进行痕量元素含量的测定,分析了Be、Zn、Hg、V、Cr、Mn、Co、Ni、Cu、As、Se、Cd、Pb 13种痕量元素在燃烧过程中的迁移行为,揭示了痕量元素在CFB锅炉中的分配、富集特性。结果表明,CFB锅炉中,较低的炉温对于痕量元素的迁移富集产生了较大的影响。由相对富集系数得知,Be、V、Co、Se在底灰中耗散,在飞灰中富集,Zn、Mn倾向于在底灰中富集,元素Cd、Pb、Ni、Cu挥发性较强,在底灰和飞灰中均是耗散。As受钙氧化物影响,挥发性表现并不明显。Hg在底灰和飞灰中相对富集系数均很低,表明Hg在整个燃烧过程中以气态形式排放;Hg、As、Se、V、Cr、Mn、Co、Ni、Cu、Zn、Pb均有向小颗粒物中富集的趋势。根据相对富集系数以及研究的13种元素在低温CFB锅炉中的迁移行为,将这些元素分为三类:A类(E_R<0.1),主要是以气态形式排放元素Hg;B类(0.1R≤0.85),较易挥发元素As、Be、Ni、Cu、Se、Cd、Pb、Co、V;C类(E_R>0.85),主要残留在固体产物中元素Zn、Mn、Cr。     

Mg(OH)_2共沉淀和直接稀释联用ICP-MS法准确测定海水中的多种常量-微量元素

对海水中多种常量/微量元素分别用Mg(OH)_2共沉淀和直接稀释ICP-MS法进行方法比较研究,分别确定了这些元素适宜的准确分析方法,为海水中常量/微量元素的ICP-MS测定提供了实用的检测手段。结果表明,Mg(OH)_2共沉淀法能够实现对V,Cr,Mn,Co,Cd及稀土元素(La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu)等19种微量元素的分离富集和准确测定;10倍直接稀释法能够同时准确测定海水中B,Sr,Li,Rb,I,V,Cr,As,Cd,U,Mo,Cu,Mn 13种微量元素,但不适合Zn,Ni,Co和Pb,以及稀土元素等在海水中浓度过低元素的测定;两种方法对适宜测定的元素均操作简便快速,具有较高的准确度和精密度。这两种方法联用,就可用约50 mL的海水实现大洋和近海海水中Co,La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu(这15个元素采用Mg(OH)_2共沉淀法)及B,Sr,Li,Rb,I,V,Cr,As,Cd,U,Mo,Cu,Mn(这13个元素采用10倍直接稀释法)等28种元素的准确测定。     

CID-ICP-AES法同时测定煤矸石中13种微量元素

讨论了煤矸石的采样、样品分解方法,以及用全谱直读ICP-CID光谱仪测定煤矸石中As、Ba、Cd、Co、Cr、Cu、Mn、Ni、Pb、Se、Sr、V和Zn等13种微量元素的方法.除As和Ni的RSD较大外,其余11种微量元素的RSD均在5%内;除Zn的回收率为107.1%外,其余12种微量元素的回收率均在95%～105%之间;人工合成样品分析结果令人满意.     

A new chelating resin for preconcentration and determination of Mn(II), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(II) by flame atomic absorption spectrometry

A new polychelatogen, AXAD-16-1,2-diphenylethanolamine, was developed by chemically modifying Amberlite XAD-16 with 1,2-diphenylethanolamine to produce an effective metal-chelating functionality for the preconcentration of Mn(II), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(II) and their determination by flame atomic absorption spectrometry. Various physiochemical parameters that influence the quantitative preconcentration and recovery of metal were optimized by both static and dynamic techniques. The resin showed superior extraction efficiency with high-metal loading capacity values of 0.73, 0.80, 0.77, 0.87, 0.74, and 0.81 mmol/g for Mn(II), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(II), respectively. The system also showed rapid metal-ion extraction and stripping, with complete saturation in the sorbent phase within 15 min for all the metal ions. The optimum condition for effective metal-ion extraction was found to be a neutral pH, which is a great advantage in the preconcentration of trace metal ions from natural water samples without any chemical pretreatment of the sample. The resin also demonstrated exclusive ion selectivity toward targeted metal ions by showing greater resistivity to various complexing species and more common metal ions during analyte concentration, which ultimately led to high preconcentration factors of 700 for Cu(II); 600 for Mn(II), Ni(II), and Zn(II); and 500 for Cd(II) and Pb(II), arising from a larger sample breakthrough volume. The lower limits of metal-ion detection were 7 ng/mL for Mn(II) and Ni(II); 5 ng/mL for Cu(II), Zn(II), and Cd(II), and 10 ng/mL for Pb(II). The developed resin was successful in preconcentrating metal ions from synthetic and real water samples, multivitamin-multimineral tablets, and curry leaves (Murraya koenigii) with relative standard deviations of < or = 3.0% for all analytical measurements, which demonstrated its practical utility.     

Simultaneous determination of Cd, Pb, Cu, Sb, Bi, Se, Zn, Mn, Ni, Co and Fe in water samples by differential pulse stripping voltammetry at a hanging mercury drop electrode

A highly sensitive and selective voltammetric procedure is described for the simultaneous determination of eleven elements (Cd, Pb, Cu, Sb, Bi, Se, Zn, Mn, Ni, Co and Fe) in water samples. Firstly, differential pulse anodic stripping voltammetry (DPASV) with a hanging mercury drop electrode (HMDE) is used for the direct simultaneous determination of Cd, Pb, Cu, Sb and Bi in 0.1 M HCI solution (pH = 1) containing 2 M NaCl. Then, differential pulse cathodic stripping voltammetry (DPCSV) is used for the determination of Se in the same solution. Zn is subsequently determined by DPASV after raising the pH of the same solution to pH 4. Next, the pH of the medium is raised to pH 8.5 by adding NH3/NH4Cl buffer solution for the determination of Mn by DPASV. Ni and Co are determined in the same solution by differential pulse adsorptive stripping voltammetry (DPAdSV) after adding DMG (1 x 10(-4) M). Finally, 1 x 10(-5) M 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) is added to the solution for the determination of Fe by DPAdSV. The optimal conditions are described. Relative standard deviations and relative errors are calculated for the eleven elements at three different concentration levels. The lower detection limits for the investigated elements range from 1.11 x 10(-10) to 1.05 x 10(-9)M, depending on the element determined. The proposed analysis scheme was applied for the determination of these eleven elements in some ground water samples.     

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.     

Solvent extraction of metals with potassium-dihydro-bispyrazolyl-borate

The extraction of Cu(II), Ni(II), Co(II), Cd(II), Zn(II), Pb(II) and Mn(II) with potassium-dihydro-bispyrazolyl-borate (H(2)BPz(2)(-)) in dichloromethane has been studied. Extraction constants (logK(ex)) have been calculated for all metal systems and were compared with those obtained with dibenzoylmethane (DBM), thenoyltrifluoroacetone (HTTA) and 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (HPMBP). The method has been used for the determination of Cu(II), Co(II), Cd(II), Zn(II), Pb(II) and Mn(II) in standard alloys and for preconcentration of metal ions in synthetic samples.     

Determination of trace metal ions by AAS in natural water samples after preconcentration of pyrocatechol violet complexes on an activated carbon column

A simple preconcentration method is described for the determination of Cu, Mn, Co, Cd, Pb, Ni and Cr in water samples by flame AAS. Trace metal ions in water were sorbed as pyrocatechol violet complexes on activated carbon column at the pH range of 4–8, then eluted with 1 M HNO₃ in acetone. The effect of major cations and anions of the natural water samples on the sorption of metal ions has been also investigated. The concentration of the metal ions detected after preconcentration was in agreement with the added amount. The present method was found to be applicable to the preconcentration of Cu, Mn, Co, Cd, Pb, Ni and Cr in natural water samples with good results such as R.S.D. from 3 to 8% (N=10) and detection limits under 70 ng l⁻¹.     

Certified reference material for the quality control of cadmium,copper nickel and zinc determination in estuarine water (CRM 505)

Analyses of estuarine water samples are routinely carried out by a number of laboratories to monitor the level of environmental contamination by toxic substances, e.g. heavy metals. A series of interlaboratory studies has been organised by the Community Bureau of Reference, BCR (now renamed Standards, Measurements and Testing Programme) to improve the quality of the determinations of selected trace metals in estuarine water samples. The improvement achieved allowed to produce a reference material (CRM 505) which was certified for its content of Cd, Cu, Ni and Zn. Further improvements were considered to be necessary for the certification of other trace elements, e.g. Pb. This material was collected in the Tagus Estuary, carefully prepared (filtered and acidified) and its homogeneity and long term stability were verified. This paper presents the work performed for the certification of Cd, Cu, Ni and Zn. Indicative values are reported for As, Co, Fe, Mn, Pb and V.     

Determination of trace metals in Nile River and ground water by differential pulse stripping voltammetry

The determination of trace metals in river water and ground water by DPSV is seriously disturbed by the presence of organic complexes. The influence of these substances can be eliminated by acidification of the samples with acids. Cd, Pb and Cu were determined at pH 1.1 (HNO₃ medium) and Zn, Cd, Pb and Cu at pH 2 (HCl medium), in both the Nile river and ground water. Zn was determined at pH 3.5 in HCl and pH 4.5 in HNO₃, after neutralizing the samples with NH₃/NH₄Cl buffer. Manganese could then be determined, after further addition of ammoniacal buffer solution up to pH 7.5 and 8.5. Ni and Co were determined in the adsorptive mode after formation of dimethylglyoximates at pH 9.2. The effect of pH on the stripping peaks of manganese was studied. Good agreement was observed between DPSV and AAS results for Zn, Cd, Pb, Cu and Mn, but the concentrations of Ni and Co were below the detection limits for AAS. Good agreement was obtained between DPSV results in HCl and HNO₃ for Ni and Co. The results indicate that decomposition of organic complexes by acidification with HNO₃ is better than in the case with HCl for Zn, Pb, Cu, Ni and Co, but HCl is better than HNO₃ for Cd and Mn.