Sequential extraction procedure for speciation of inorganic selenium in emissions and working areas

A sequential extraction procedure for separating inorganic species of selenium in particulate matter of emissions and working areas, has been developed. The proposed procedure has been tested first on synthetic samples prepared in laboratory with the different selenium salts, then in the presence of atmospherical particulate matter sampled in a laboratory of the department of general chemistry, previously checked for the absence of selenium. Finally the speciation was tested on a reference material (urban particulate matter NIST SRM 1648), certified for the total selenium content. The sample was first treated with the proposed procedure, followed by an evaluation of matrix spiking and recovery analyses. The repeatability of the selenium speciation was assessed by performing multiple analyses of the spiked samples. Quantitative determinations have been made by AAS and voltammetry. The possible interferences of the most common ions have been investigated.     

Determination of inorganic beryllium species in the particulate matter of emissions and working areas

A sequential extraction procedure for separating and determining Be(0), soluble Be(II) inorganic compounds, BeO and beryllium silicates in samples such as particulate matter of emissions and working areas, has been developed. The proposed procedure has been tested on synthetic samples prepared with the inorganic beryllium compounds, in the presence of atmospherical particulate matter sampled in a laboratory of the Department, previously checked for the absence of beryllium. The speciation was then repeated on a sample of fly ash deriving from a solid waste incinerator and on a reference material (Coal Fly ash SRM 1633a, by NIST), followed by an evaluation of matrix spiking and recovery analyses. Performing multiple analyses of the spiked samples assessed the repeatability of the procedure. Quantitative determinations have been made by inductively coupled plasma optical emission spectrometry (ICP-OES) and electrothermal atomic absorption spectrometry (ETAAS). The possible interferences of the most common ions have been investigated. The selective sequential extractions allow one to separate and to determine different inorganic beryllium species, to which a different toxicity and therefore, a different risk are related: it is the case for example of metallic beryllium and beryllium oxide.     

Determination of inorganic nickel compounds in the particulate matter of emissions and workplace air by selective sequential dissolutions

A speciation method of inorganic nickel compounds in airborne particulate, based on selective sequential extractions, is described. It allows the separation and the determination of Ni(0), Ni(II) soluble salts such as sulphate and chloride, Ni insoluble compounds such as nickel oxide and sulphide, to which a different toxicity and therefore a different risk are related. The nickel concentration in each fraction was determined by Flame or Furnace Atomic Absorption Spectroscopy. The proposed procedure has been tested first, on synthetic samples prepared with the different nickel compounds, in the presence of atmospherical particulate matter not containing nickel, in order to take into account the possible matrix influence. The speciation was then repeated on four different samples (fly ash deriving from a solid waste incinerator and three RSMS from NIST: Coal Fly ash SRM 1633b, Urban Particulate 1648, Washington Dust 1649), followed by an evaluation of matrix spiking and recovery analyses. Performing multiple analyses of the spiked samples assessed the repeatability of the procedure.     

Selective sequential dissolution for the determination of inorganic indium compounds in the particulate matter of emissions and workplace air.

A speciation method was developed for the determination of inorganic indium compounds in the particulate matter of emissions and from the workplace, based on selective sequential extractions. The main inorganic indium compounds that are expected to be present in the atmospheric particulate matter involving the industrial production of indium and in the manufacture of indium compounds were separated and determined. The procedure has been tested on standard reference materials. The indium recovery was in the range 93 - 105%.     

Optimization of an urban particulate matter multi-element analysis method by inductively coupled plasma--atomic emission spectrometry (ICP-AES)

In the present work a method for simultaneous metals determination, in urban air particulate matter by ICP-AES has been set up. A large number of elements (18) has been analyzed, including major (Al, Fe, K, and Mg), minor (Na, Pb and Zn) and trace (As, Cd, Co, Cr, Cu, Hg, Mn, Ni, Sb, Sr and V) elements. The procedure consists of microwave sample acidic total digestion by HNO3/HF mixture and subsequent analysis by ICP-AES, using different assemblies depending on sample treatment procedure: a quartz Meinhard nebulizer/cyclonic chamber, if HF excess was eliminated, or a cross-flow nebulizer/plastic Scott chamber, suitable for application with HF. A cyclonic chamber for hydride generation was used for As, Sb and Hg determination. The procedure was tested with Standard Reference Materials 1648 NIST Urban Particulate Matter and Certified Reference Material No8 NIES "Vehicle Exhaust Particulates". Two sampling supports, quartz fibre and polycarbonate filters, have been examined in order to find the most suitable i.e. the one characterized by less interference. Some real samples of urban air particulate matter, TSP, PM10 and PM2.5 fractions, collected during an intercomparison campaign promoted by Regione Lombardia, have been analyzed with the procedure developed.     

Speciation of cadmium in seawater — a direct voltammetric approach

The present report deals with differential pulse anodic stripping voltammetry (DPASV) applied for the analysis of cadmium in open ocean seawater. Evaluation of different Cd species can generate information about distribution and speciation of Cd in the open ocean. Distribution of Cd was investigated in surface waters of the Atlantic Ocean over a wide geographical range as well as in the water column. Surface water sampling on board the research vessel Polarstern was performed from the bow boom of the ship as well as with a snorkel system which allowed continuous sample-taking. Two different Cd species could be differentiated in the voltammograms. UV-irradiation experiments allowed the identification of an inorganic and organic Cd form, the latter caused by the association between Cd and organic matter as e.g. humic substances (HS). Atlantic ocean surface seawater normally contains between 2 and 4 ng organically complexed Cd/kg and no detectable inorganic Cd. Some areas however showed readings of up to 14 ng inorganic Cd/kg in addition. Water column samples exhibited an enrichment of inorganic Cd by depth. Occurrence of inorganic Cd at the surface could be related to specific oceanographical conditions. Together with analytical results of trace metal contents in the particulate phases of surface seawater, new aspects could be established about the biogeochemical cycling of Cd in the sea.     

Determination of heavy metals in suspended matter in the storage lake “Bitterfelder Muldestausee”

Dissolved and particulate trace elements have been determined in 400 samples of both the inflow and the outflow waters of the storage lake “Bitterfelder Muldestausse” in order to investigate the sedimentation of 22 elements transported by the highly polluted Mulde River, an affluent of the river Elbe. Inductively coupled plasma mass spectrometry (ICP-MS) has been used to analyse filtered water samples because of its multielemental capabilities, the excellent detection limits, the wide linear calibration range and the high speed of analysis. A special leaching procedure has been employed for the very low amounts of the suspended matter collected from each water sample. The dissolved material has been also analysed by ICP-MS. Testing of the procedure employed by the analysis of a standard reference material (SRM BCR 146) and use of the standard addition method has resulted in both a good precision (1–7%) and accuracy. Despite the wide variation in the composition of the suspended matter samples the concentrations of the heavy metals in sediment samples and in the suspended matter have been found to be comparable. A balance of sedimentation has been calculated based on the mean values of concentrations of all elements investigated in both the water and suspended matter samples of the inflow and outflow. Results from this first study show that the storage lake acts as a sedimentation trap for Zn, Cu, Pb, Ni, Cr, Cd, U and Co.     

Copper Complexation with Soluble and Surface Freshwaters Ligands

Speciation of copper has been done using samples collected at different times of the year (December 92 and October 93) and in three sites of a polluted river (Este River, Northern Portugal). Filtered samples and the suspended particulate matter were titrated with metal ion and the labile metal concentrations measured by anodic stripping voltammetry (DPASV). An extra peak in the Cu voltammograms has been noticed when titrating filtered samples and its origin was investigated. Results have suggested that the extra peak is due to copper(I) stabilized by ligands adsorbed on the mercury electrode and a model for the electrochemical mechanism is proposed. From titrations of the same samples with zinc, cadmium and lead it has been concluded that there are two types of organics in the river water: macromolecules and small molecules with D_ML≈D_M with higher affinity for soft cations such as Cd(II) and Cu(I), that can be adsorbed on mercury electrode as anions.     

The determination of cadmium,copper, iron,lead and zinc in aerosols by atomic-absorption spectrometry

The determination of five elements in filter papers loaded with air particulate matter has been investigated. After a wet destruction of about 10 cm² of filter material by a standard procedure, analysis was carried out with a flame atomic absorption method for zinc and a flameless procedure for Cd, Cu, Fe and Pb. Furnace program parameters for each of the elements in different acid solutions are reported. The interferences of some common anions and the most abundant cations in aerosol material are described. For some urban and industrial samples, the results are compared with those obtained by energy-dispersive x-ray fluorescence. Accuracy was checked against standard samples.     

Direct determination of metals associated with airborne particulates using a graphite probe collection technique and graphite probe atomic absorption spectrometric analysis

A new analytical method has been developed for direct analysis of solid samples of airborne particulate matter by a graphite probe collection technique coupled with graphite furnace atomic absorption spectrometry. A porous graphite probe is used as a filter for air particles. The probe is then subjected to atomization by being inserted into a graphite furnace which has been pre-heated to a constant atomization temperature. Some aspects of the method have been tested by recovery studies using NBS Urban Particulate Matter, SR M No. 1648, and found to give recoveries of 91–107% for Pb, Cd, Ni, Cu and Mn. By combining a highly efficient filtering medium with the extremely high relative sensitivity of solid sampling, this method has the potential of monitoring sources of air particulate emission with sufficient temporal and spatial resolution for unequivocal identification of the pollution source (at least on a local scale).     

连续萃取法研究海湾养殖区沉积物中重金属形态

以连续萃取法研究海湾养殖区沉积物中重金属(Cd, Cu, Pb, Zn)的形态,将重金属分离为酸溶态、还原态、有机质结合态、硫化物结合态和残渣态.分别采用基体匹配法和内标法消除高盐基体对电感耦合等离子体光谱法(ICP-OES)和质谱法(ICP-MS)分析结果的影响.对海洋沉积物标准物质分析结果表明,样品稀释后测定值与标准值一致.比较了本连续萃取法和BCR法对沉积物样品中重金属形态的提取结果,并考察了萃取剂的选择性.实验表明,本方法可用于有机质污染和富营养化环境沉积物中重金属形态分析,特别是有机质结合态和硫化物结合态的分析.     

Determination of113mCd in natural water

A method has been developed for the determination of^113mCd from fallout in large-volume environmental water samples. In the analytical procedure a known amount of cadmium carrier is added to the sample and the cadmium is preconcentrated as insoluble hydroxide by coprecipitation with ferric hydroxide. The separated cadmium is purified from other interfering elements by an anion—exchange procedure. Finally, cadmium is coprecipitated with copper sulfide, and the radioactivity of^113mCd is measured in a lowbackground, gas-flow proportional beta counter. The cadmium recovery is established by determining the amount of Cd in the precipitate using an energy dispersive x-ray fluorescence spectrometer. For a 24hr counting period a lower limit of detection around 50μBq^113mCd/1 of sample has been attained. Samples of Lake Michigan water were analyzed: the concentration of^113mCd in 1980 was 177±5 μBq/l.     

The determination of trace amounts of zinc, cadmium, lead and copper in airborne particulate matter by anodic stripping voltammetry

The application of anodic stripping voltammetry, with a hanging mercury drop electrode, to the determination of zinc, cadmium, lead and copper in airborne particulate matter collected by filtration is discussed. This procedure allows for the destruction of the filter material followed by the complete dissolution (including silicates) of the collected particulate matter. A low-temperature ashing process is described and the recovery of cadmium in this procedure is studied. Analytical data obtained by anodic stripping and atomic absorption for zinc, cadmium, lead and copper are compared.     

Electroanalytical Device for Cadmium Speciation in Waters. Part 1: Development and Characterization of a Reliable Screen‐Printed Sensor

A reliable screen‐printed sensor for cadmium speciation analysis is presented here. Its development has been focused on the achievement of a reproducible and repeatable sensor. The electrode construction and its surface coating are discussed in detail. The optimized procedure has permitted to obtain very accurate sensors with detection limit of 0.2 μg (Cd) L^?1 using SWASV for only 60 s of deposition time. The electrochemically accessible, i.e. potentially bioavailable, fraction of the cadmium present in an untreated river water sample has been successfully quantified without degassing. These results give a glimpse of the potential of this membrane‐free sensor in real matrices.     

Troubleshooting in the trace analysis of organochlorine pesticides in water samples

Summary As a consequence of the high toxicity of organochlorine pesticides their presence in water for human consumption is limited by legislation. To determine these compounds at trace levels, an extraction procedure and a highly sensitive analytical technique is necessary. In this work we have used laminar disks for the solid-phase extraction of 21 organochlorine pesticides from water. The analytical technique selected is gas chromatography with electron-capture detection. A solid-phase extraction procedure is proposed, and some problems has been encountered. Low recovery of some pesticides has been obtained, because of their adsorption by the walls of containers. To prevent this adsorption, addition of 20% methanol before the sampling step is proposed. Adsorption of pesticides by the organic matter present in water samples was also observed. Pesticides can be adsorbed by the membrane filters usually used to remove suspended particulate matter from water samples. Different kinds of filters have been tested, and the occurrence of the problem has been confirmed. The use of laminar disks in this work has overcome this problem.     

Open-framework cadmium succinates of different dimensionalities

Open-framework cadmium succinates, [CN(3)H(6)](2)[Cd(2)(C(4)H(4)O(4))(Cl)(2)], I; [CN(3)H(6)](2)[Cd(C(4)H(4)O(4))(2)], II; Cd(2)(C(4)H(4)O(4))(2)(C(4)N(2)H(8))(H(2)O)(3), III; [C(4)N(2)H(12)][Cd(2)(C(4)H(4)O(4))(3)].4H(2)O, IV; Cd(C(4)H(4)O(4))(H(2)O)(2), V; and Cd(3)(C(4)H(4)O(4))(2)(OH)(2)], VI, of different dimensionalities have been synthesized by hydrothermal procedure by employing two different strategies, one involving the reaction of Cd salts with organic-amine succinates and the other involving the hydrothermal reaction of Cd salts with a mixture of succinic acid and the organic amine. While the latter procedure yields structures without any amine in them, the former gives rise to amine templated cadmium succinates with open architectures. By employing guanidinium succinate we have obtained I and II, and with piperazinium succinate we obtained III and IV. Of these I has a one-dimensional chain structure, IV has a layered structure, and II and III have three-dimensional architectures. The two cadmium succinates without incorporation of amine, V and VI, possess layered and three-dimensional structures, respectively. The three-dimensional structures II and III exhibit interpenetration similar to that in diamondoid and alpha-polonium type structures, respectively.     

Distribution of mercury in soil organic matter fractions obtained by dissolution/precipitation method

Sequential multistep procedure, usually used for the fractionation and characterization of soil organic matter was tested for Hg content in the individual steps and fractions. Under general laboratory conditions serious problems have arosen during the attempt in the Hg mass balance calculation. Several sources of Hg contamination were recognized. The most serious was the background concentration of Hg even in research grade chemicals (what is in general not declared) and laboratory air. The work on operational Hg speciation as non-humic bound, humic acid, fulvic acid bound proceeds from the established status-quo on distribution of mercury of soil organic matter.     

Speciation of antimony in airborne particulate matter using ultrasound probe fast extraction and analysis by HPLC-HG-AFS

A fast extraction procedure has been developed for Sb(III) and Sb(V) oxoanions speciation in airborne particulate matter samples. Different extraction media (diammonium tartrate, hidroxilammonium clorhidrate, citric acid + ascorbic acid, phosphoric acid and citrate solutions) were tried, with assistance of an ultrasonic probe. The operation power and time of extraction were also optimized. The higher extraction recoveries were obtained with a 100 mmol L⁻¹ hidroxilammonium clorhidrate aqueous solution assisted by the ultrasound probe operated at 50 W during 3 min. The extracts were analyzed by HPLC-HG-AFS. The chromatographic separation of Sb(III) and Sb(V) was also optimized using diammonium tartrate and phthalic acid as mobile phases. The separation of both Sb species was performed in less than 3 min under isocratic conditions, using a 200 mmol L⁻¹ diammonium tartrate solution. The proposed extraction procedure and the HPLC-HG-AFS instrumental coupling have been successfully applied to airborne particulate matter samples, with high Sb content, collected in heavy traffic streets from Buenos Aires (Argentina). The results showed the presence of both Sb species at similar concentrations in the ng m⁻³ level. The extraction yield was higher than 90% for all the analyzed samples.     

Determination of trace elements in ambient aerosol samples

A microwave-assisted digestion procedure using HNO₃, HF, and H₂O₂ has been developed for analysis of elements in ambient particulate matter (PM). The samples are collected on cellulose filters and analyzed by inductively coupled plasma mass spectrometry (ICP-MS). The ICP-MS is calibrated with external standards, and recovery of analytes is tested with NIST SRM 1648 Urban Dust. This method has been used to quantify the airborne concentrations of a large number of elements, including Ag, As, Ba, Be, Ca, Cd, Ce, Co, Cr, Cs, Cu, Fe, Ga, K, Li, Mg, Mn, Mo, Ni, Pb, Rb, Se, Sb, Sr, Ti, Tl, V, and Zn. For the majority of these elements, recovery of the NIST SRM is within 15% of the certified values.