Inductively coupled plasma optical emission spectrometric determination of trace element in PM10 airborne particulate matter collected in an industrial area of Argentina

Trace metals of relevance from the environmental and toxicological point of view were quantified in the city of Campana, Buenos Aires, Argentina. The collection of particulate matter was performed on ash-free fiber glass filters using high-volume samplers with a PM₁₀ sampling head, during a 3-month period in 2002. An acid leaching of elements deposited on the filters was adopted paying special attention to the recovery of volatile elements. Analysis was performed by inductively coupled plasma optical emission spectrometry (ICP OES) to ascertain the concentrations of 12 key elements, namely, Al, As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V and Zn. The validation of the procedure was performed by the analysis of the standard reference material NIST 1648, urban particulate matter, and good agreement between concentrations found and the reported certified values was achieved. Blank filters were spiked with the analytes investigated and the recoveries varied between 83% and 92%. Metal concentrations spanned the range 0.03 ng m⁻³ (equivalent to 0.42 μg g⁻¹) for Cd to 1.9 μg m⁻³ (equivalent to 29.7 mg g⁻¹) for Fe. The results obtained show that the pollutants of special environmental and health concern are As and Pb. Mean As concentration was higher than the guideline value associated with an excess cancer risk of 1:10⁻⁶, reported by the World Health Organization (WHO). Lead is the only element that showed higher concentrations than those recently measured in the large and heavily trafficked metropolitan area of Buenos Aires. Cadmium>Pb>As>Zn>Cu are the elements more enriched in airborne PM₁₀.     

Determination of water soluble trace metals in airborne particulate matter using a dynamic extraction procedure with on-line inductively coupled plasma optical emission spectrometric detection

A novel continuous-flow system for the dynamic extraction of water soluble metal fractions in airborne particulate matter (APM) with subsequent inductively coupled plasma optical emission spectrometric (ICP-OES) analysis of derived extracts is presented. The fully automated extraction system with on-line multi-element detection offers enhanced sensitivity when compared to batch-wise counterparts; additionally it provides information about the extraction process. With the developed procedure detection limits in the order of 1.5 (Ba) to 8.0 (Ni) ng extractable mass per investigated sample could be achieved, which translates to method detection limits for soluble metal concentrations in APM ranging from 0.2 ng m⁻³ (Ba) to 0.9 ng m⁻³ (Fe). Reproducibility of analysis was determined by replicate measurement (n = 6) of an APM sample with an aerodynamic diameter ≤10 μm (PM10), derived results varied between 3.5% (Mn) and 12.1% (Ni) relative standard deviation. Method validation was accomplished by comparison of extracted soluble and remaining non-soluble fractions with the total metal contents of the investigated PM10 samples, showing an excellent mass balance for all elements. Application of the developed procedure for the analysis of water soluble metal fractions in PM10 samples (n = 16) from Linz (Austria) indicated a high variability of extractable fractions ranging from 11.7 ± 7.2% (Fe) to 48.8 ± 15.4% (Mn) of the total metal contents.     

An off-line automated preconcentration system with ethylenediaminetriacetate chelating resin for the determination of trace metals in seawater by high-resolution inductively coupled plasma mass spectrometry

A novel automated off-line preconcentration system for trace metals (Al, Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb) in seawater was developed by improving a commercially available solid-phase extraction system SPE-100 (Hiranuma Sangyo). The utilized chelating resin was NOBIAS Chelate-PA1 (Hitachi High-Technologies) with ethylenediaminetriacetic acid and iminodiacetic acid functional groups. Parts of the 8-way valve made of alumina and zirconia in the original SPE-100 system were replaced with parts made of polychlorotrifluoroethylene in order to reduce contamination of trace metals. The eluent pass was altered for the back flush elution of trace metals. We optimized the cleaning procedures for the chelating resin column and flow lines of the preconcentration system, and developed a preconcentration procedure, which required less labor and led to a superior performance compared to manual preconcentration (Sohrin et al. [5]). The nine trace metals were simultaneously and quantitatively preconcentrated from ∼120 g of seawater, eluted with ∼15 g of 1 M HNO₃, and determined by HR-ICP-MS using the calibration curve method. The single-step preconcentration removed more than 99.998% of Na, K, Mg, Ca, and Sr from seawater. The procedural blanks and detection limits were lower than the lowest concentrations in seawater for Mn, Ni, Cu, and Pb, while they were as low as the lowest concentrations in seawater for Al, Fe, Co, Zn, and Cd. The accuracy and precision of this method were confirmed by the analysis of reference seawater samples (CASS-5, NASS-5, GEOTRACES GS, and GD) and seawater samples for vertical distribution in the western North Pacific Ocean.     

Simultaneous determination of suspended particulate trace metals (Co, Ni, Cu, Zn, Cd and Pb) in seawater with small volume filtration assisted by microwave digestion and flow injection inductively coupled plasma mass spectrometer

A new technique for the determination of suspended particulate trace metals (P-metals >0.2 μm), such as Co, Ni, Cu, Zn, Cd and Pb, in open ocean seawater has been developed by using microwave digestion coupled with flow injection inductively coupled plasma mass spectrometry (FI-ICP-MS). Suspended particulate matter (SPM) was collected from 500 mL of seawater on a Nuclepore filter (0.2 μm) using a closed filtration system. Both the SPM and filter were completely dissolved by microwave digestion. Reagents for the digestion were evaporated using a clean evaporation system, and the metals were redissolved in 0.8 M HNO₃. The solution was diluted with buffer solution to give pH 5.0 and the metals were determined by FI-ICP-MS using a chelating adsorbent of 8-hydroxyquinoline immobilized on fluorinated metal alkoxide glass (MAF-8HQ). The procedure blanks with a filter were found to be 0.048 ± 0.008, 10.3 ± 0.3, 0.27 ± 0.05, 3.3 ± 1.8, 0.02 ± 0.03 and 0.85 ± 0.09 ng L⁻¹ for Co, Ni, Cu, Zn, Cd and Pb, respectively (n = 14). Detection limits defined as 3 times the standard deviation of the blanks were 0.023, 0.90, 0.14, 5.3, 0.078 and 0.28 ng L⁻¹ for Co, Ni, Cu, Zn, Cd and Pb, respectively. Accuracy was evaluated using certified reference materials of chlorella (NES CRM No. 3) and marine sediment (HISS-1). The method was applied to the determination of vertical distributions for P-Co, Ni, Cu, Zn, Cd and Pb in the Western North Pacific.     

A pilot study for the production of a certified reference material for trace elements in honey

In the context of the general mandate of the European Union Community Reference Laboratory (CRL) for residues in living animals and their products established at the Istituto Superiore di Sanità, a pilot study was undertaken to assess the possibility of producing a new certified reference material (CRM) for trace elements in a matrix of honey. The elements considered were As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Sn, V and Zn. Their determination was performed by inductively coupled plasma (ICP)-based techniques. Data obtained with different ICP techniques were generally in good agreement. In light of these results, the next step was the effective production of a candidate CRM in a honey matrix. In the preliminary phase, two different types of honey, i.e., Eucalyptus (solid and sticky) and Robinia (viscous and sticky), were pretreated at the Institute for Reference Materials and Measurements, Joint Research Centre, European Commission (EC-JRC-IRMM) in order to produce the materials candidate for the certification process. Approximately 600 ampoules were thus produced for the Robinia honey and 450 ampoules for the Eucalyptus honey, each ampoule containing 5 g of an aqueous solution of honey (with 20% and 30% high purity water, respectively) and sealed under inert gas (Ar). A ring test to determine the levels of the chemical elements and a long-term study to evaluate the stability of the samples is in progress. Tentative figures for the analytes of interest are (in ng g⁻¹): Robinia, As, 1.28±0.09; Cd, 0.59±0.08; Cr, 2.36±0.21; Cu, 57.6±3.2; Fe, 209±9; Mn, 90.8±3; Ni, 18.1±0.6; Pb, 23±1.5; Sn, 8.10±0.35; V, 1.19±0.37; and Zn, 178±4; Eucalyptus, As, 3.18±0.21; Cd, 0.70±0.08; Cr, 2.73±0.22; Cu, 141±6; Fe, 926±16; Mn, 1905±81; Ni, 7.77±0.4; Pb, 138±4; Sn, 7.97±0.16; V, 3.47±0.15; and Zn, 405±9.     

Hair analysis and the early detection of imbalances in trace elements for members of expeditions in Antarctica

In the framework of the Human Biology and Medicine Project of the National Program for Research in Antarctica (Programma Nazionale di Ricerche in Antartide, PNRA) a study was undertaken to explore the suitability of trace element determination in human hair as a tool for the early detection of the impact of extreme environmental conditions on the health of members of the Italian and French expeditions. This study included three campaigns, namely, the 1995–1996 expedition to the Italian base of Terra Nova Bay, as well as the 1997–1998 and 1998–1999 expeditions to both the Italian base of Terra Nova Bay and the Italian–French base of Dome C. Sampling of hair of participants in the expeditions was carried out both prior to departure and at the end of the period spent at the bases. As regards storage, pre-treatment and analysis of hair samples they were performed in accordance with previously established procedures. Acid-assisted microwave digestion was adopted as the best approach for preparing solutions for subsequent analysis by inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry. In the first part of this study, only the elements Ca, Cu, Fe, Mg and Zn were selected, while at a later stage it was decided to also include Co, Cr, Mn, Mo and Ni. Experimental results were subjected to basic statistical analysis to detect possible significant differences in element concentrations that occurred during the sojourn at the bases, with a view to identify possible remedial action to minimize adverse consequences.     

黄芪口服液中8种重金属元素含量的测定

在2015年版《中国药典》的基础上,采用原子荧光光谱法和电感耦合等离子体质谱法对黄芪口服液中的铅、砷、镉、汞、铜、锌、镍和铬进行测定,并对所用试剂、器皿,赶酸时间,内标的种类和加入方式进行了优化。结果表明,在样品处理前对器皿采用硝酸(30%)处理,赶酸时间在1.5h以上,以手动方式加入单内标103 Rh溶液,可以得到较准确、稳定的测定结果,8种元素测定的相对标准偏差(RSD)均小于4%,Hg、As、Cu、Pb、Zn、Cd、Ni、Cr的检出限分别为0.089、0.21、0.45、0.15、0.45、0.025、0.35和0.39μg/L,8种元素的加标回收率在92.0%～114%。方法对于黄芪口服液中痕量元素的检测,结果稳定,过程简单,引入污染小。     

Source identification and long-term monitoring of airborne particulate matter (PM<Subscript>2.5</Subscript>/PM<Subscript>10</Subscript>) in an urban region of Korea

Summary For the identification of air pollution sources, about 500 airborne particulate matter (PM_2.5and PM₁₀) samples were collected by using a Gent air sampler and a polycarbonate filter in an urban region in the middle of Korea from 2000 to 2003. The concentrations of 25 elements in the samples were measured by using instrumental neutron activation analysis (INAA). Receptor modeling was performed on the air monitoring data by using the positive matrix factorization (PMF2) method. According to this analysis, the existence of 6 to 10PMF factors, such as metal-alloy, oil combustion, diesel exhaust, coal combustion, gasoline exhaust, incinerator, Cu-smelter, biomass burning, sea-salt, and soil dust were identified.     

A clean up step of fat content previous to trace metal characterization in mussel tissues by inductively coupled plasma mass spectrometry

Inductively coupled plasma mass spectrometry analysis of trace and major elements of mussel tissues can be quickly and accurately analyzed after cleaning up the interfering fat content before the sample is digested in a microwave oven. Making use of experimental designs, the clean up procedure was achieved by the extraction of 1 g of freeze-dried tissue sample stirred with 5 ml of dichloromethane during five minutes. The microwave assisted digestion of the fat free samples was carried out with 0.2 g of tissue sample, 15 ml of 7.0% nitric acid with a power of 980 W during 18 min. The analytical method efficiency (accuracy and precision) was evaluated with a CRM: (NIST 2977, mussel tissue) and real mussel samples analyzed previously. The results confirmed the accuracy of the analysis by agreement with the previous results but the precision was significantly improved. The developed method allows operating routinely permitting to large numbers of samples to be quickly screened for trace metals.     

Single-step microwave digestion with HNO(3) alone for determination of trace elements in coal by ICP spectrometry

A microwave digestion method with HNO₃ alone was conducted at a temperature as high as 250 °C for determination of 19 trace elements (Li, Be, V, Cr, Mn, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Cd, Cs, Ba, Hg, and Pb) in coal jointly by inductively coupled plasma optical emission spectrometry (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS), and flow injection ICP-MS (FI-ICP-MS). The validity of determination was assessed by using three standard coals, SRM 1632c, BCR 180, and SARM 19. It was found that the high-temperature digestion led to an extensive decomposition of the organic matrix and clay in coal, and no dissolved and solid carbon remained in the final solution after evaporation. Good recoveries were observed for all trace elements in three coals, with the exception of V, Rb, and Cs in high-ash SARM 19. Additionally, FI-ICP-MS combined with the present digestion without evaporation pretreatment was proved to be a rapid and efficient approach for determination of ultra-trace elements such as Se, Cd, and Hg in coal.     

Determination of Arsenic,Cadmium, Cobalt,Chromium, Nickel,and Lead in Cosmetic Face-Powders: Optimization of Extraction and Validation

An analytical method for the quantification of toxic metals in face-powders is presented and discussed. Acid digestion with HNO₃-H₂O₂ or HNO₃-HCl was performed and compared with total digestion by HF. The digestion with HNO₃-H₂O₂ was the most suitable for these purposes. Analyses were performed by inductively coupled plasma atomic emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS), whose performances were compared by analyzing three different certified reference materials. The analysis of five commercial face-powders revealed the presence of all the considered metals in the range 0.06–8.0 µg/g. To simulate the bioaccessibility of metals in physiological conditions, a digestion with a simulated sweat solution was performed. In this case, the analysis of the same face-powder samples provided results below the limit of quantification, suggesting low bioaccessibility of the considered trace elements.     

Levels of essential and potentially toxic trace metals in Antarctic macro algae

Eleven species of Antarctic algae were examined for their accumulation ability in the uptake of different metals and metalloids from the Antarctic aquatic environment. Macro algae were collected during the 2000 austral summer season at Jubany Station (Argentinean base) around Potter Cove, King George Island. The elements quantified were: As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Se, Sr, V, and Zn. An optimized microwave-assisted digestion procedure was used to digest the samples and the elements were determined by inductively coupled plasma optical emission spectrometry. A wide range of metal retention capacity among the different species was observed. The highest levels of trace elements were found in Monostroma hariotii and Phaeurus antarcticus, with concentrations up to 3095 μg g⁻¹ for Fe. On the basis of the levels of trace elements observed in Monostroma hariotii and its wide distribution in the Antarctic Peninsula, this organism accomplishes a number of prerequisites to be considered as an adequate biomonitor for future studies.     

微波消解-电感耦合等离子体质谱同时测定普里兹湾沉积物中微量元素

以HNO3-H2O2为消解体系,采用微波对沉积物进行消解,建立了普里兹湾沉积物中微量元素的电感耦合等离子体质谱(ICP-MS)测定方法。从样品分析数据可以看出:8个站位10种元素总量变化范围为493.41～1481.02μg/g,总量最大值是最小值的3.00倍。元素Ba、Mn在总量中占了很大比例,V次之,而As、Mo、Ag、Cd的含量很少。大部分元素检出限可达ng/L,仅Co、Mo 2种元素的检出限稍高;各元素线性良好,相关系数r2≥0.9997。方法的RSD<5.0%,适用于普里兹湾沉积物中微量元素的定量分析。     

Determination of trace elements in natural waters by inductively coupled plasma time of flight mass spectrometry after flow injection preconcentration in a knotted reactor

A flow injection on-line sorption system was developed for the separation and preconcentration of traces of Ag, Cd, Co, Ni, Pb, U and Y from natural water samples with subsequent detection by ICP TOF MS. Simultaneous preconcentration of the analytes was achieved by complexation with the chelating reagent 1-phenyl-3-methyl-4-benzoylpyrazol-5-one immobilized on the inner walls of a (200 cm × 0.5 mm) PTFE knotted reactor. The analytes were eluted and transported to an axial ICP TOF MS system with 1% (v/v) HNO₃ containing 0.3 μg l⁻¹ of Rh as an internal standard using ultrasonic nebulization. The detection limits (3σ) varied from 0.3 ng l⁻¹ for Y to 15.2 ng l⁻¹ for Ni and the precision (R.S.D.) was better than 4%. Using a loading time of 90 s and a sample flow rate of 4.5 ml min⁻¹, enhancement factors of 3-14 were obtained for the different analytes in comparison with their direct determination by ICP TOF MS with ultrasonic nebulization without preconcentration. The accuracy of the method was demonstrated by analysis of water based certified reference materials.     

Ultrasensitive determination of heavy metals at the sub-picogram per gram level in ultraclean Antarctic snow samples by inductively coupled plasma sector field mass spectrometry

Assessing changes in heavy metals concentrations in Antarctic snow dated from the last century is of high interest to determine to which extent the most remote regions of our planet are contaminated for these metals, and to have a better understanding into their long-range transport from the different natural and anthropogenic source areas to the Antarctic continent. Such investigations are unfortunately very difficult because the concentrations to be measured are exceedingly low, down to the sub-picogram per gram level. They require a strict control of contamination problems from field sampling to laboratory analysis, and the use of ultrasensitive analytical techniques.

We present here important advances in the analytical protocols for obtaining reliable data on the occurrence of heavy metals in Antarctic snow. Utmost precautions were taken to obtain a series of large size ultraclean snow blocks from the wall of a 8.3 m clean hand-dug pit at a remote site in Coats Land, Antarctica. These blocks were then sub-sampled inside a laminar flow clean bench in a cold room, using ultraclean protocols, to provide high-resolution heavy metal times series. V, Cr, Mn, Cu, Ag, Ba, Pb, Bi and U were then determined directly, without any pre-concentration step, by the ultrasensitive inductively coupled plasma sector field mass spectrometry (ICP-SFMS) technique in clean room conditions. Calibration of the instrument was performed using ultralow concentrations standards, and extreme precautions were taken to ensure the cleanliness of the instrument and its introduction system. The results show that it is possible to accurately measure a variety of heavy metals in Antarctic snow, down to the sub-picogram per gram level, using this approach. Examples of the data obtained for the Coats Land site are finally presented. For U, the observed concentrations range from 0.004 to 0.21 pg/g; they are the first data ever obtained for this metal for Antarctic snow and ice.     

Direct determination of toxic trace metals in honey and sugars using inductively coupled plasma atomic emission spectrometry

A rapid method for the determination of Pb, Cd, Cu, Cr, Co, Ni, Mn and Zn in honey and sugars without prior digestion or ashing of the sample was developed, using inductively coupled plasma atomic emission spectrometry (ICP-AES). The critical instrumental parameters such as sample flow rate and radio frequency incident power were thoroughly optimized. The effect of matrix type and its concentration was also examined for glucose/fructose, sucrose and honey matrices. The sensitivity was investigated using calibration curves obtained in presence of the above matrices. The obtained recoveries for Cd, Cu, Cr, Co, Ni and Mn at the μg l⁻¹ level were satisfactory and practically independent of the matrix used for the calibration standards. The recoveries of Pb and Zn were less sufficient. Various commercial samples of honey, sugar, glucose and fructose were analyzed with respect to their toxic metal content. The method can be applied for routine analysis, quality and environmental pollution control purposes at the μg l⁻¹ level of concentration, after suitable dilution of the samples.     

带八极杆碰撞/反应池的电感耦合等离子体质谱测定中药中的微量元素

建立了用带八极杆碰撞/反应池的电感耦合等离子体质谱仪(ICP-MS)测定中药中的多种微量元素的方法.八极杆碰撞/反应池技术的使用,有效地消除了多原子离子对待测元素的干扰,使Se、 As及其它微量元素的测试更为准确.方法对固体中药样品的检出限为0.002～0.085 μg/g,相对标准偏差为0.4%～3.1%,回收率为90%～110%.     

Determination of trace element in Italian virgin olive oils and their characterization according to geographical origin by statistical analysis

Multi-element analysis of organic virgin olive oils from different Italian regions was carried out by inductively coupled plasma mass spectrometry (ICP-MS) aiming at developing a reliable method in the traceability of the origin of oils. The data were processed by means of the chemiometric approach of linear discriminant analysis (LDA) that allows classifying unknown samples after checking possible differentiation of samples of known origin.An external calibration curve was build for the quantitative analysis. The calibration curves for each element were linear in the range between 0.01 and 100 ng mL⁻¹ and 0.2 to 2000 ng mL⁻¹, the correlation coefficients were ranging between 0.996 and 0.999. Results from spike and recovery experiments at levels of 30 and 65 ng mL⁻¹ were in the range of 91-119%, whereas the quantitation limits, based on 10 times standard deviation of the blank, were also in the range of 0.009-10.2 ng g⁻¹, for almost all the elements.     

Simultaneous determination of major to ultratrace elements in geological samples by fusion-dissolution and inductively coupled plasma mass spectrometry techniques

A method has been developed for the simultaneous quantification of major to ultratrace elements in geological samples using quadrupole ICP-MS techniques. The sample preparation involves fusion with LiBO₂ and dilution in HNO₃-HF which allows complete decomposition of refractory minerals and quantification of the elements of interest. The effects of high Total Dissolved Solids (TDS) and Li in the solution are minimized using a matrix-tolerant interface and conditioning the instrument with LiBO₂ solution. The signal drift is moreover controlled using conventional internal standards and specific Drift Correction Standards (DCS). A key issue of the technique is the external calibration using selected Certified Reference Materials (CRM). Depending on the sample type and analytes of interest three optimized programmable modes are used sequentially: Standard, Collision Cell (CCT) and Kinetic Energy Discrimination (KED) mode. The method allows to quantify more than 40 elements in concentrations from tens-of-percent to <0.1 ppm levels during a single experiment. The method has been validated through the analysis of different CRMs with recovery factors of ca. 100% and typical 2σ errors of <10%.     

Determination of cadmium, lead, iron, nickel and chromium in selected food matrices by plasma spectrometric techniques

In the frame of a study aimed at investigating the transfer of metal contaminants through the food chain and the effects of food processing, five elements, namely Cd, Pb, Fe, Ni and Cr, were accurately determined in (i) durum wheat grain and derived products, (ii) wheat-based reference materials, (iii) drinking water, used both as an ingredient and for technological purposes in the investigated industrial process. Microwave closed vessel digestion was selected as the dissolution technique for solid samples, whereas water samples were acidified with ultrapure nitric acid and analysed directly. As several analytes had to be quantified at trace or ultratrace levels, inductively coupled plasma mass spectrometry (ICP-MS) was resorted to for analytical determinations. Overall, this straightforward analytical approach enabled to detect the often small changes in element concentration associated with the different technological steps of processing. Nevertheless, detection of heavily interfered elements, especially Cr, as well as analyte quantification at ultratrace-level level in water, posed analytical challenges that required suited analytical solutions.Changes in the sample introduction system and complementary use of inductively coupled plasma atomic emission spectrometry (ICP-AES) straightforwardly overcame the difficulties in determining the analytes in the selected food matrixes. The benefits of ultrasonic nebulization in reducing the effects of problematic spectral interferences were demonstrated. Overall, a robust and high-throughput analytical method was outlined.