Employment of peak area as instrumental datum for improving the voltammetric quantitative analysis of heavy metals in fresh and sea water in the presence of surfactants

Peak area instead of peak height is used for the simultaneous determination of Cu(II), Pb(II), Cd(II), and Zn(II) in fresh and sea water in the presence of anionic and cationic surfactants by differential pulse anodic stripping voltammetry. These species, if present, tend to make more irreversible the electrodic process of the metals. Because the employment of peak area for species having irreversible electrodic processes permits limits of detection about one or 2 orders of magnitude lower, this work shows the possibility of determining heavy metals at ultratrace level concentrations in the presence of surfactants, compounds which are always present in natural waters. The precision and accuracy of the analytical method were checked by the analysis of the standard reference materials (SRM) Fresh Water NIST-SRM 1643d, Sea Water BCR-CRM 403, and Estuarine Water BCR-CRM 505. The former, expressed as relative standard deviation (s(r)), and the latter, expressed as relative error (e), were satisfactory, being in all cases lower than 5%. The analytical procedure has been applied to fresh and sea water sampled in the Po river mouth area (Italy).     

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.     

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%.     

Determination of heavy metals in environmental bio-indicators by voltammetric and spectroscopic techniques

The determination of copper, lead, cadmium and zinc in matrices involved in the food chain as algae, species Ulva rigida, and clams, species Tapes philippinarum by differential pulse anodic stripping voltammetry (DPASV) was carried out. For the mercury determination in these matrices, a new accurate and precise method was developed employing a mixture of concentrated acids H₂SO₄-K₂Cr₂O₇ for digestion and subsequent cold vapor atomic absorption spectrometry (CV-AAS) by reduction with SnCl₂. The analytical procedures were verified for four reference standard materials: Ulva lactuca BCR-CRM 279, Lagarosiphon major BCR-CRM 060, Oyster tissue NBS-SRM 1566, Mussel tissue BCR-CRM 278. For all the elements the precision, expressed as relative standard deviation (s_r), and the accuracy, expressed as relative error (e), were in the order of 3 to 5%, while the detection limits were in the range 0.010–0.100 μg/g. The standard addition technique improved the resolution of the voltammetric method even in the case of very high element concentration ratios. The analytical procedure was used for real matrices sampled in the Adriatic Sea south to Po river mouth, in the zone “Goro bay”, and at open sea north to the Ravenna shore.     

Determination of heavy metals in environmental bio-indicators by voltammetric and spectroscopic techniques

The determination of copper, lead, cadmium and zinc in matrices involved in the food chain as algae, species Ulva rigida, and clams, species Tapes philippinarum by differential pulse anodic stripping voltammetry (DPASV) was carried out. For the mercury determination in these matrices, a new accurate and precise method was developed employing a mixture of concentrated acids H₂SO₄-K₂Cr₂O₇ for digestion and subsequent cold vapor atomic absorption spectrometry (CV-AAS) by reduction with SnCl₂. The analytical procedures were verified for four reference standard materials: Ulva lactuca BCR-CRM 279, Lagarosiphon major BCR-CRM 060, Oyster tissue NBS-SRM 1566, Mussel tissue BCR-CRM 278. For all the elements the precision, expressed as relative standard deviation (s_r), and the accuracy, expressed as relative error (e), were in the order of 3 to 5%, while the detection limits were in the range 0.010–0.100 μg/g. The standard addition technique improved the resolution of the voltammetric method even in the case of very high element concentration ratios. The analytical procedure was used for real matrices sampled in the Adriatic Sea south to Po river mouth, in the zone “Goro bay”, and at open sea north to the Ravenna shore. Received: 7 June 1998 / Revised: 2 November 1998 / Accepted: 5 November 1998     

Sequential voltammetric determination of trace metals in meals

An analytical procedure for the sequential determination of Zn(II), Cr(VI), Cu(II), Sb(III), Sn(II), Pb(II) by square wave anodic stripping voltammetry (SWASV) and Fe(III), Mn(II), Mo(VI) by square wave voltammetry (SWV) in matrices involved in foods and food chain as wholemeal, wheat and maize meal is described.The digestion of each matrix was carried out using a concentrated HCl–HNO₃–H₂SO₄ attack mixture, employing dibasic ammonium citrate buffer solution (pH 6.9 and 8.7) as supporting electrolytes. The analytical procedure was verified by the analysis of the standard reference materials Wholemeal BCR-CRM 189, Wheat Flour NIST-SRM 1567a and Rice Flour NIST-SRM 1568a.For all the elements in the certified matrix, the precision as repeatability, expressed as relative standard deviation (s_r) was of the order of 3–5%; the accuracy, expressed as relative error (e) was generally of the order of 3–6%.In presence of reciprocal interference, the standard addition method considerably improved the resolution of the voltammetric technique.Finally, the analytical procedure was transferred and applied to commercial meals sampled on market.A critical comparison with atomic absorption spectroscopic measurements is also discussed.     

Spatial and temporal distribution of inorganic species in water and sediments of the Tronto River ecosystem

Analytical results are reported for the determination of inorganic species in water and sediments sampled in the Tronto river ecosystem. The species determined are Cd, Co, Cr, Cu, Fe, Mn, Ni, Zn, Hg, F, NO3-, SO4-, Na, K, Ca, Mg, NH4+ in integrated water, and Cd, Co, Cr, Cu, Fe, Mn, Ni, 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 (Sr), and the latter, expressed as relative error (e), were good, being in all cases lower than 5%.     

Monitoring of inorganic species distribution in water and sediments of Aso river

Analytical results are reported for the determination of inorganic species in water and sediments sampled in the Aso river ecosystem. The species determined are Cd, Co, Cr, Cu, Fe, Mn, Ni, Zn, Hg, F-, NO3-, SO4--, Na, K, Ca, Mg, NH4+ in water, and Cd, Co, Cr, Cu, Fe, Mn, Ni, 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 (Sr), and the latter, expressed as relative error (e), were good, being in all cases lower than 6%.     

Measurement of voltammetric peak area and resolution of overlapping peaks in the simultaneous determination of copper, lead, cadmium, and nickel in environmental matrixes

Peak area was used for the simultaneous determination of copper(II), lead(II), cadmium(II), and nickel(II) in environmental matrixes by differential pulse voltammetry. The voltammetric measurements were performed with a conventional 3-electrode cell and an ammonia-ammonium chloride buffer, pH 9.1, as the supporting electrolyte. The analytical procedure was verified first in aqueous reference solutions and later by analysis of the standard reference materials Estuarine Sediment BCR-CRM 277 and River Sediment BCR-CRM 320. The precision and accuracy of the method, expressed as the relative standard deviation and the relative error, respectively, were <5% in all cases; the detection limit for each element under the experimental conditions used was in the range 1-5 microg/L. In the case of mutual interference between neighboring elements, an analytical procedure is proposed that is based on the standard additions technique, which allows the resolution of the overlapping voltammetric peaks.     

Determination of heavy metals in environmental matrices sampled inside the Park of the Po Delta

Analytical results are reported for the determination of heavy metals in environmental matrices, sampled in an ecosystem inside a protected area: the Park of the Po Delta, located near the thermoelectric power station ENEL of Porto Tolle, one of the greater in Italy. The elements determined, in sediments and superficial water, are Ni and V, linked to the fuel oil combustion. However, in order to obtain a complete picture enough of heavy metals polluting load in the study areas, the following elements: Cd, Co, Cr, Cu, Fe, Mn, Pb and Zn are also determined. For all the elements, in addition to the detection limits, precision and accuracy are also 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%.     

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。     

Determination of Se, As, Cu, Pb, Cd, Zn and Mn by anodic and cathodic stripping voltammetry in marine environmental matrices in the presence of reciprocal interference. Proposal of a new analytical procedure

Arsenic(III), selenium(IV), copper(II), lead(II), cadmium(II), zinc(II) and manganese(II) have been determined in environmental matrices by differential pulse cathodic (DPCSV) and anodic (DPASV) stripping voltammetry. The voltammetric measurements were carried out using a conventional three-electrode cell and the ammonia–ammonium chloride buffer (pH 9.4) as the supporting electrolyte. The analytical procedure was verified by the analysis of the standard reference materials: Sea Water BCR-CRM 403; Lagarosiphon Major BCR-CRM 060; and Cod Muscle BCR-CRM 422. The precision, expressed as relative standard deviation, and the accuracy, expressed as relative error, were, in all cases, lower than 5%; the detection limits, for each element in the experimental conditions employed, was approximately 10⁻⁹ M. The standard addition technique significantly improved the resolution of the voltammetric method, even in the case of very high metal concentration ratios.     

Heavy metal determination in aquatic species for food purposes

New analytical procedures and sample mineralizations are proposed regarding the determination of arsenic, selenium, copper, lead, cadmium, zinc and mercury in matrices involved in food chain as mussel, clams and fishes. As regard As, Se, Cu, Pb, Cd and Zn determinations, H2SO4-HNO3 acidic mixture is used for the digestion of each matrix. In the case of Hg the sample digestion is performed using a concentrated suprapure H2SO4-K2Cr2O7 mixture and the results are compared with those from other conventional methods. Differential pulse cathodic (DPCSV) and anodic stripping voltammetry (DPASV) are employed for determining simultaneously selenium, arsenic and copper, lead, cadmium, zinc, respectively, while mercury determination is carried out by the cold vapour atomic absorption spectrometry (CV-AAS) with reduction with SnCl2. The voltammetric measurements were performed using a conventional three-electrode cell and the ammonia-ammonium chloride buffer (pH 9.3) as supporting electrolyte. For all the elements, in addition to the detection limits, precision and accuracy data are also reported: the former, expressed as relative standard deviation (Sr), and the latter, expressed as relative error (e), are in all cases between 3 to 6%.     

松口蘑中微量元素的测定

采用火焰原子吸收法同时测定了松口蘑中K、Ca、Na、Mg、Fe、Pb、Cd、Co、Cr、Zn、Mn、Cu等12种元素的含量。方法的相对标准偏差在0.08％－2.32％范围,回收率在97.1%－108.3%范围。结果表明,在三种松口蘑样品中,除含有较高的K、Na、Ca、Mg和一定量的有害元素Cd、Pb外,其余6种对人体有益的微量元素较为丰富。     

Cathodic and anodic stripping voltammetry: simultaneous determination of As-Se and Cu-Pb-Cd-Zn in the case of very high concentration ratios

Arsenic(III), selenium(IV), copper(II), lead(II), cadmium(II) and zinc(II) are determined in environmental matrices. The voltammetric measurements were carried out using a conventional three-electrode cell and the ammonia-ammonium chloride buffer pH 9.3 as supporting electrolyte. The analytical procedure was verified by the analysis of the standard reference materials Estuarine Sediment BCR-CRM 277 and River Sediment BCR-CRM 320. The precision, expressed as relative standard deviation (s(r)), and the accuracy, expressed as relative error, were, in all cases, less than 5%; the detection limits, for each element and in the experimental conditions employed, were around 10(-9) M. The standard addition technique significantly improved the resolution of the voltammetric method, even in the case of very high metal concentration ratios.     

原子吸收光谱法测定皇冠草地上部分的7种微量元素

采用原子吸收光谱法测定了皇冠草地上部分所含微量元素铜、锰、锌、铁、镉、铅、铬.结果表明,皇冠草地上部分含有较丰富的铜、锰、锌、铁,RSD≤4.23％(n=4),加标回收率99.20％～103.00％.     

六极杆碰撞反应池–ICP–MS法测定海水中痕量金属元素

建立了直接稀释法测定海水中痕量金属元素Cr,Cu,Zn,Cd,Pb的方法。样品经稀释10倍后,使用基体匹配及内标校正,采用六极杆碰撞反应池–电感耦合等离子体质谱仪直接测定稀释后海水样品中的5种元素Cr,Cu,Zn,Cd,Pb。各元素在0.0~100μg/L范围内均呈现良好的线性关系,线性相关系数(r~2)均大于0.999 0,方法检出限为0.004~0.209μg/L。测定结果的相对标准偏差为2.4%~4.4%(n=6),加标回收率为92%~113%。该方法简单快捷,适用于近岸海水中痕量元素Cr,Cu,Zn,Cd,Pb的分析。     

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).     

Determination of trace elements in Antarctic krill samples by inductively coupled atomic emission and graphite furnace atomic absorption spectrometry

Analytical methods were developed for the determination of trace elements in Antarctic krill samples applying inductively coupled plasma atomic emission spectrometry (ICP-AES) and graphite furnace atomic absorption spectrometry (GF-AAS). Cu, Fe, Mn and Zn were determined by ICP-AES, while Cd and Pb by GF-AAS technique. Two microwave assisted digestion procedures were elaborated for the preparation of 0.5-g krill samples using open and closed vessel systems. The efficiency of the digestion processes was checked by measurements of the total organic carbon content of the solutions obtained. The deviations of the analytical data from the certified values and the relative standard deviations of the concentration measurements were lower for all six elements investigated applying the closed vessel digestion system.     

Heavy Metals in Matrices of Food Interest: Sequential Voltammetric Determination at Trace and Ultratrace Level of Copper,Lead, Cadmium,Zinc, Arsenic,Selenium, Manganese and Iron in Meals

The voltammetric methods are very suitable and versatile techniques for the simultaneous metal determination in complex matrices. The present work, regarding the sequential determination of Cu(II), Pb(II), Cd(II), Zn(II) by square‐wave anodic stripping voltammetry (SWASV), As(III), Se(IV) by square‐wave cathodic stripping voltammetry (SWCSV) and Mn(II), Fe(III) by square‐wave voltammetry (SWV) in matrices involved in foods and food chain as wholemeal, wheat and maize meal, are an interesting example of the possibility to sequentially determine each single element in real samples. Besides the set up of the analytical method, particular attention is aimed either at the problem of possible signal interference or to show that, using the peak area A_p as instrumental datum, it is possible to achieve lower limits of detection. The analytical procedure was verified by the analysis of the standard reference materials: Wholemeal BCR‐CRM 189, Wheat Flour NIST‐SRM 1567a and Rice Flour NIST‐SRM 1568a. Precision, as repeatability, and accuracy, expressed as relative standard deviation and relative error, respectively, were lower than 6% in all cases. In the presence of reciprocal interference, the standard addition method considerably improved the resolution of the voltammetric technique. Once set up on the standard reference materials, the analytical procedure was transferred and applied to commercial meals sampled on market for sale. A critical comparison with spectroscopic measurements is also discussed.