Distributions of major-to-ultratrace elements among the particulate and dissolved fractions in natural water as studied by ICP-AES and ICP-MS after sequential fractionation.

In order to elucidate the distributions of the elements among the particulate and dissolved fractions in pond water, major-to-ultratrace elements in different sizes of particles as well as in the filtrate passed through the 0.05 microm filter were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The different sizes of particle samples (ca. 100-300 microg each) were collected on the membrane filters with pore sizes of 10, 3.0, 1.2, 0.4, 0.2 and 0.05 microm, respectively, by sequential fractionation. As a result, about 40 elements in different sizes of particles could be determined by ICP-AES and ICP-MS, after acid digestion using HNO3/HF/HClO4. Then, the fractional distribution factors of major-to-ultratrace elements among the particulate and dissolved fractions were estimated from the analytical results. The total contents of Al, Fe, Ti, REEs (rare earth elements), Bi, Pb and Ag in the particulate fractions (larger than 0.05 microm) were more than 80-90%, while those of Ca, Sr, Cs, W, Ba, Mn and Co in the dissolved fraction, which corresponded to the filtrate passed through the 0.05 microm membrane filter, were more than 80%. It was further found that the fractional distributions of Cu and Zn in the dissolved fraction were ca. 50%. In addition, the enrichment factors (EFs) of the elements in the particulate fractions with particle sizes of 3.0-10 microm and 0.05-0.2 microm were estimated to elucidate their geochemical characteristics in natural water.     

Major-to-ultratrace elements in bone-marrow fluid as determined by ICP-AES and ICP-MS.

The major-to-ultratrace elements in human bone-marrow fluid were determined by ICP-AES (inductively coupled plasma atomic emission spectrometry), and ICP-MS (inductively coupled plasma mass spectrometry). The bone-marrow fluid sample was centrifuged prior to acid digestion to exclude the bone piece from bone marrow, and then digested with nitric acid. As a result, 20 elements could be determined over the concentration range from 1610 microg g(-1) for Na to 0.00043 microg g(-1) for W. It was found that Fe, Zn and Sb were enriched by ca. 264-, 7- and 15-fold, respectively, in bone-marrow fluid, compared to those in human blood serum. Alkali metals (K, Rb, Cs), except for Na, were also significantly enriched in bone-marrow fluid. Furthermore, the concentrations of various elements, such as Fe, P, Al, Zn, Cu, Se, Zr, Sn, Ag and W, were significantly higher than those in open seawater.     

Neutron activation analysis of bottom and fly oil ashes

The concentrations of 25 elements in 7 oil ash samples were determinedby computerized systematic instrumental absolute neutron activation analysis.In the oil ash samples, the following mean concentrations (in ppm) of elementswere found: Al: 39531, As: 109, Ba: 1391, Ca: 29701, Ce: 295, Co: 1294, Cr:1485, Cs: 7.9, Dy: 4.5, Eu: 1.2, Fe: 53094, Ga: 146, Hf: 2.2, La: 1534, Mn:547, Na: 40277, Sb: 360, Sc: 2.3, Sm: 21, Sr: 674, Ta: 15.8, V: 130548, W:4.1, Yb: 0.9 and Zn: 3125. These findings were compared with the concentrationsof elements found in coal ash samples. The concentrations of Co, Na and Vwere significantly higher in the oil ash samples, while the concentrationof Sc was lower. The purpose of this study has been to determine the backgroundlevels of different elements in oil ash, in order to evaluate its potentialimpact on the environment.     

Trace elements of coal,coal ashes and fly ashes by activation analysis with short-lived nuclides

On irradiation with neutrons, some of the interesting trace elements in coal, coal ash and fly ash produce short-lived nuclides which may be determined—together with some of the matrix elements—by activation analysis. This enables the characterization of samples. To find out the distribution of elements in the gaseous or aerosol exhaust of fossil-fired power plants, we simulated the combustion in a quartz apparatus containing a cold trap, using the combustion temperature (780 °C) employed for the standard ash determination. High Se values were found in the cold trap deposits from black coal from Poland. Halogens were also found in the deposits.     

ICP-AES法测定出口工业硅中11种杂质元素

利用ICP-AES分析技术,对试样溶解方法,元素分析谱线,共存元素干扰,仪器分析参数,无机酸介质影响等因素进行了研究,确定了最佳工作条件,建立了可同时测定出口金属硅中11种杂质元素的简单、快速和适用的分析方法,结果表明,该方法线性范围宽,检出限低,准确性高,操作步骤简单,11个元素测定回收率在85％～105％之间,相对标准偏差在1．9％～8．1％之间。     

The potential of downscaled dynamic column extraction for fast and reliable assessment of natural weathering effects of municipal solid waste incineration bottom ashes

There is a current worldwide interest for evaluating the potential reuse of municipal solid waste incineration (MSWI) bottom ash as a sub-base in road construction and secondary building material. Yet, there is a need for exploration of the physicochemical features of the bottom ashes to ensure environmental sustainability. To this end, batchwise water extraction as promulgated by the European norm EN 12457 or the German DIN 38414-S4 tests is commonly utilized to ascertain the impact of leachable trace elements in bottom ashes on biota. However, the above extraction protocols are not properly simulating the dynamic extraction conditions occurring in the nature, whereby the analytical information provided for risk assessment is debatable.In this work, a downscaled flow-through extraction method is proposed for mimicking the leaching of hazardous trace elements (namely, Pb, Zn, Cd, Cu and Cr) in MSWI bottom ashes by runoff waters more accurately than the manual counterparts. The flow assembly facilitates the full automation of standard and regulatory leaching tests by packing of a suitable amount of solid material into a column, whereupon the leaching reagent is continuously pumped through, thus yielding an accurate assessment of the environmentally significant water-extraction fraction with no effect from readsorption phenomena.The flow-through column system is exploited as a screening tool for fast evaluation of the influence of natural bottom ash weathering on the immobilization of hazardous elements to dictate the potential reuse of the solid waste. The dependence of sorption sites for humic substances on trace element leachability is also discussed. As compared to the steady-state approach, the dynamic method features the substantial shortening of the analytical extraction protocol from 24 h to just 30 min, better precision, with relative standard deviations (R.S.D.) <11% versus >20% R.S.D. for batchwise extraction, improved accuracy because of the absence of metal redistribution phenomena and minimization of manual operations as well as straightforward investigation of leaching rates for the suite of target elements.     

Application of a sequential extraction procedure to study the release of elements from municipal solid waste incineration bottom ash

The release of five elements (Cr, Cu, Mn, Pb and Zn) from a municipal solid waste incineration bottom ash (BA) under different extraction conditions has been investigated by performing the three-step sequential extraction procedure proposed by the Standards, Measurements and Testing Program of the European Union. A fourth step (strong acid attack) has been added in order to calculate the mass balance. The results of this study provide information on the potential mobility of the studied elements. Almost all of the Cr and part of the Mn are extracted with strong acid which indicates low potential mobility in the environment. Most of the Cu is extracted under oxidizing conditions. Pb and Zn are released under acidic condition, indicating the possibility of their mobilization by changes in pH. The reproducibility of the sequential extraction procedure is also discussed.     

Chemical characterization of airborne particulate matter in ambient air of Nagoya, Japan, as studied by the multielement determination with ICP-AES and ICP-MS.

The multielement determination of PM(10) (airborne particulate matter smaller than 10 microm) samples, which was collected by a high volume air sampler at the urban site of Nagoya City, was carried out by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The present analytical method was validated by analyzing urban particulate matter standard reference material of NIST SRM 1648. The analytical data for ca. 30 elements in PM(10) samples collected during a period from 8 September to 9 October, 2003, were obtained in the concentration range from sub-microg g(-1) to several-10 mg g(-1), but the data for 18 elements among ca. 30 elements were available for the characterization of PM(10) samples in ambient air, because of problems caused by the filter blanks. Then, the trends concerning the distributions of diverse elements in PM(10) samples were analyzed based on the enrichment factors and size distribution factors. The lithophile and siderophile elements were distributed more than 50% in coarse particle fraction (>2.1 microm), which was derived mainly from natural sources, such as soils and crustal minerals. On the other hand, chalcophile elements were distributed more than 50% in fine particle fraction (<2.1 microm), which was derived mostly from anthropogenic emission sources. The large enrichment of chalcophile elements in PM(10) samples as well as their mining influence factors (MIFs) suggested their wide use in industrial productions.     

Analysis of glass and glass melts during the vitrification of fly and bottom ashes by laser-induced plasma spectroscopy. Part II. Process analysis

Laser-induced plasma spectroscopy (LIPS) is employed for in situ and on-line process analysis of major glass constituents during a vitrification process for fly and bottom ashes from waste incineration. The system is based on an Nd:YAG laser for plasma ignition, while the elemental emissions from the plasma are detected time-resolved by an intensified multichannel analyzer. The perpendicular, single axis, imaging optics allow a remote sensing of the composition of the hot glass melt. Taking into account the plasma characteristics for calibration, good agreement between the LIPS analysis and the established reference analysis is achieved for the concentration ratios of SiO₂, Al₂O₃, and CaO. In addition, LIPS is applied to the analysis of aerosols generated by homogeneous nucleation during the heating-up of the investigated fly ashes. A distinctive temperature dependence of the heavy metal concentration of the aerosols is observed.     

利用旋风炉玻璃化处理垃圾焚烧飞灰实验研究

在自行设计的旋风炉实验台上对焚烧飞灰进行玻璃化熔融实验,系统研究了焚烧飞灰熔融前后微观形貌、灰渣中重金属特性和浸出特性。实验结果表明,焚烧飞灰旋风熔融后成黑色的脆硬玻璃态熔渣,表层呈浅黄色。在熔渣中N i、Cr的固溶率最高,均超过95%以上;低熔点重金属多数挥发至熔融烟气和熔融烟道飞灰颗粒中,Cd的固溶率仅有21%,Pb和Zn部分固溶于玻璃态熔渣中,两者固溶率可达42%以上。Cu和As的固溶率分别为37%和18%。熔融后的玻璃态熔渣重金属浸出率明显低于熔融前的焚烧飞灰,且均低于美国EPA的标准限值。     

垃圾焚烧飞灰中重金属的热稳定化条件及机理

研究了生活-农业混合型垃圾焚烧飞灰与单一生活垃圾焚烧飞灰（简称混合型飞灰与单一型飞灰）热处理过程中的重金属挥发特性与稳定化效果，并结合FT-IR、XRD检测手段对稳定化机理进行了探讨。结果表明，单一型飞灰中重金属的挥发性普遍高于混合型飞灰，垃圾源氯含量对重金属的挥发性有明显影响。飞灰中Mn、Cr不易挥发，Zn、Cu较易挥发，Pb、Cd挥发性很强，热处理温度超过1 000 ℃时挥发率都超过50%。800 ℃为相对最优的热处理温度，兼顾了热处理过程重金属稳定化与抑制挥发。800 ℃以上时飞灰形成了稳定的硅酸盐结构体系，是重金属热处理后难以浸出的主要机理。     

Multielement determination and speciation of major-to-trace elements in black tea leaves by ICP-AES and ICP-MS with the aid of size exclusion chromatography.

A multielement determination of major-to-trace elements in black tea leaves and their tea infusions was carried out by ICP-AES (inductively coupled plasma atomic emission spectrometry) and ICP-MS (inductively coupled plasma mass spectrometry). Tea infusions were prepared as usual tea beverage by brewing black tea leaves in boiling water for 5 min. About 40 elements in tea leaves and tea infusions could be determined over the wide concentration range in 8 orders of magnitude. The extraction efficiency of each element was estimated as the ratio of its concentration in tea infusions to that in tea leaves. From the experimental results for the extraction efficiencies, the elements in black tea leaves were classified into three characteristic groups: (i) highly-extractable elements (>55%): Na, K, Co, Ni, Rb, Cs and Tl, (ii) moderately-extractable elements (20-55%): Mg, Al, P, Mn and Zn, and (iii) poorly-extractable elements (<20%): Ca, Fe, Cu, Sr, Y, Zr, Mo, Sn, Ba and lanthanoid elements. Furthermore, speciation of major-to-trace elements in tea infusions was performed by using a combined system of size exclusion chromatography (SEC) and ICP-MS (or ICP-AES). As a result, many diverse elements were found to be present as complexes associated with large organic molecules in tea infusions.     

Determination of trace elements in coal and coal fly ash by joint-use of ICP-AES and atomic absorption spectrometry

Microwave-acid digestion (MW-AD) followed by inductively coupled plasma-atomic emission spectrometry (ICP-AES), graphite furnace atomic absorption spectrometry (GFAAS), and hydride generation atomic absorption spectrometry (HGAAS) were examined for the determination of various elements in coal and coal fly ash (CFA). Eight certified reference materials (four coal samples and four CFA samples) were tested. The 10 elements (As, Be, Cd, Co, Cr, Mn, Ni, Pb, Sb, and Se), which are described in the Clean Air Act Amendments (CAAA), were especially considered. For coal, the HF-free MW-AD followed by ICP-AES was successful in the determination of various elements except for As, Be, Cd, Sb, and Se. These elements (except for Sb) were well-determined by use of GFAAS (Be and Cd) and HGAAS (As and Se). For CFA, the addition of HF in the digestion acid mixture was needed for the determination of elements, except for As, Sb, and Se, for which the HF-free MW-AD was applicable. The use of GFAAS (Be and Cd) or HGAAS (Sb and Se) resulted in the successful determination of the elements for which ICP-AES did not work well. The protocol for the determination of the 10 elements in coal and CFA by MW-AD followed by the joint-use of ICP-AES, GFAAS, and HGAAS was established.     

Analysis of glass and glass melts during the vitrification process of fly and bottom ashes by laser-induced plasma spectroscopy. Part I: Normalization and plasma diagnostics

For laser-induced plasma spectroscopy (LIPS) analysis of the main components (Si, Al, and Ca) in glasses utilized for vitrification of ashes from waste incineration, a normalization procedure for line ratios is presented. Even in homogeneous glass samples, considerable pulse-to-pulse variations of the plasma electronic excitation temperature and electron density were observed because of changes in the material–laser interaction. A normalization procedure is outlined using Saha–Boltzmann equilibrium relationships to include the electronic excitation temperature and density in the calibration model. As a result of the normalization, the variation of the line ratios is reduced and linear calibrations for LIPS intensity ratios versus concentration ratios are achieved. For samples with high aluminum concentrations, the analysis was hampered by self-reversal effects.     

Evaluation of a mixed chelator as heavy metal stabilizer for municipal solid‐waste incineration fly ash: Behaviors and mechanisms

This paper compares the stabilization performances of three dithiocarbamate and three phosphate chemical stabilizing agents, selects the best agents from each group, combines them as a mixed heavy metal stabilizer for municipal solid‐waste incineration (MSWI) fly ash, and investigates the effectiveness of the mixed chelator in stabilizing heavy metals in MSWI fly ash from southwest China. The mechanism of stabilization is also analyzed. Results indicate that piperazine dithiocarbamate can stabilize Cd, Cu, and Ni effectively, while sodium dihydrogen phosphate can stabilize Pb better. With the addition of the mixed chelator (2% sodium dihydrogen phosphate and 1% piperazine dithiocarbamate), all the targeted heavy metal concentrations in the leachate were below the standards for pollution control on municipal solid waste landfill sites in China. The stabilizing agents combined with the heavy metals in fly ash could not generate insoluble crystals; however, the heavy metals could combine with the agents' effective groups, generating flocs in the pores or on the surfaces of the fly ash and offering significant densification. The mixed chelator could transfer heavy metals from unstable fractions to stable fractions, so the leaching of heavy metals from the fly ash was greatly decreased.     

电感耦合等离子体原子发射光谱法和电感耦合等离子体质谱法测定不同肥料产品中铊含量比对

铊是一种高毒性的微量元素,具有较强的富集能力,已被列为肥料的强制性检验项目。选择了水溶性肥料、复混肥料、有机肥料3种代表性的肥料样品,通过比对微波消解和电热板敞口消解前处理方式;分析电感耦合等离子体原子发射光谱(ICP-AES)法和电感耦合等离子体质谱(ICP-MS)法主要干扰来源;通过建立各自的标准工作曲线、比对方法检出限、精密度、加标回收率,探讨研究肥料产品中铊含量测定方法。研究结果表明：微波消解法和电热板敞口消解法各有优点,可以根据样品实际情况灵活选择。ICP-AES法主要干扰为光谱干扰,需要在前处理过程中除去Mn元素,而ICP-MS法主要干扰为基体效应,可以使用内标物加以校正。ICP-MS法的检出限低于ICP-AES法。由于微波消解-ICP-AES法无法除去消解液中的Mn元素带来的光谱干扰,因此不适合测定铊含量。而微波消解-ICP-MS法、电热板敞口消解-ICP-AES法和电热板敞口消解-ICP-MS法这三种方法测定结果无明显差异,测定标准化肥质控样品均在指定值范围内,加标回收率为86%-110%。实验室可以根据肥料样品的数量、组成、性质合理选择搭配前处理方式和测定方法。     

Heterogeneous electron-transfer kinetic parameters of metalloproteins as studied by channel-flow hydrodynamic voltammetry

Channel-flow hydrodynamic voltammetry was used to study the direct electron-transfer reactions of two metalloproteins, myoglobin and cytochrome c, under steady-state conditions at methyl viologen modified (MVM) gold foil electrodes. Utilization of a dual working electrode cell with this technique permitted determination of the heterogeneous electron-transfer kinetics for both the reduction and oxidation of myoglobin. The formal heterogeneous electron-transfer rate constants in pH 7.00 phosphate buffered solutions were found to be 8.9 (±1.5)×10⁻⁵ cm s⁻¹ for the reduction, and 7.7 (±1.2)×10⁻⁵ cm s⁻¹ for the reoxidation of myoglobin. The transfer coefficient values obtained were 0.21 (±0.01) for the reductive (α) and 0.82 (±0.01) for the oxidative (1−α) electrode reactions. Ionic strength and pH dependences were observed in these direct electron-transfer reactions. Collective current efficiency measurements in the myoglobin experiments indicated that an overall simple charge-transfer process occurred at the respective electrode interfaces. A formal rate constant of 3.4 (±0.2)×10⁻⁵ cm s⁻¹ with a transfer coefficient of 0.25 (±0.01) for the reduction (α) of cytochrome c was obtained by this hydrodynamic technique. The use of channel-flow hydrodynamic voltammetry in characterizing an electrode reaction as well as an interpretation of the data presented are discussed.     

电感耦合等离子体原子发射光谱(ICP-AES)法测定电镀废弃物中的七种元素

采用HCl-HNO3-HF-HClO4体系溶解试料,电感耦合等离子体原子发射光谱法测定电镀废弃物中的钙、铝、镉、钴、铁、锰、镁七种元素含量。通过加标回收实验,这几种元素的加标回收率为96.1%~102%,相对标准偏差均小于3%(n=7),此方法操作速度快、检测效率高,是一种理想的分析方法。     

Annual variations of the elemental concentrations of PM10 in ambient air of Nagoya City as determined by ICP-AES and ICP-MS.

PM10 samples were collected at an urban site of Nagoya City during September, 2003, to August, 2004, and annual variations of the concentrations of the elements in PM10 samples were examined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The annual concentration variations of ca. 30 elements in ambient air were in the range from sub-ng m(-3) to several microg m(-3). From an evaluation by the enrichment factors of the elements, elements such as Al, Ca, Fe, Mg, Ti, Mn, Ba, Sr, Ce, La, Nd, Co, Cs, and Pr, in PM10 samples were found to have originated mostly from natural sources, while the elements such as S, Zn, Pb, Cu, Ni, Sb, Sn, Cd, Bi, W, Tl, and In originated from anthropogenic emission sources. Furthermore, in seasonal variations of the elemental concentrations of PM10 samples in ambient air, the elements originated mostly from natural sources provided significantly high concentrations in spring during the "Kosa" period (the dust season from March to May). On the other hand, the elements mainly from anthropogenic emission sources provided relatively higher concentrations in autumn and winter, which may be explained by the fact that the urban atmospheric structure is stabilized by the temperature-inversion layer formed over the city in those seasons. In addition, all of the elements provided significantly low concentrations in the summer, due to the dilution effect of the oceanic winds as well as due to the convection of air mass up to the high levels.     

The application of ICP-MS and ICP-OES in determination of micronutrients in wood ashes used as soil conditioners

In the present paper, the elemental composition of wood ashes obtained by the combustion of wood in a fireplace was determined with the use of ICP-MS and ICP-OES techniques. Wood ashes may find a potential application as deacidifying agents and soil conditioners, since they contain calcium (in the form of CaCO₃ and CaO), potassium (in the form of K₂SO₄ and K₂CO₃) and significant levels of micronutrients. However, if applied to soil, it is important to assess the bioavailability of particular elements to plants. This process can be simulated by proper extraction procedures.

Various species of wood were combusted in a firestove in a single-family house. The ashes underwent multielemental analyses with ICP-MS Varian Ultra Mass 700 (Australia) and ICP-OES Vista-MPX from Varian (Australia) in order to determine the content of macro- and micronutrients as well as toxic elements. Ashes were also extracted with solutions of 0.1 M NaNO₃ and water in order to simulate the process of elemental transfer from ash (used as soil conditioner) to soil solution and consequently to plants. Also, the environmental impact of ash supplementation to soil was assessed in these experiments. Soil was supplemented with 0–20% of ash. After elution, the eluent underwent multielemental analysis by ICP-MS and ICP-OES techniques to determine the content of macronutrients (P, K, Mg), micronutrients (Fe, Mn, Co, Mo, Zn, Cu and Ti) and toxic elements (Hg, Pb, As and Cd).

It was shown that fireplace ashes can be applied for deacidification of homestead gardens. Ash may be described as a valuable soil conditioner with N:P:K formula 0:1:3. It is concluded therefore that in order to achieve full fertilization, additional supplementation with nitrogen fertilizer would be necessary.