Speciation of heavy metals in suspended particulates in urban air†

An anayltical procedure based on a sequential extraction scheme is applied to samples of suspended particulates from an urban area of Barcelona. This area presents high levels of air pollution owing to automotive emissions and industrial activity.

The procedure allows the partitioning of particulate trace metals into four fractions: soluble and exchangeable, bound to carbonates and iron‐manganese oxides, bound to organic matter and residual. In this work, the chemical associations of Fe, Pb, Cu, Mn, Cr and Cd have been investigated.

In the analysed samples, only the cadmium is predominantly in the first fraction whereas the other metals are largely associated to carbonates and Fe‐Mn oxides.     

Speciation and carcinogenic classification—some limits of assessment and prevention procedures—the case of “nickel”

The speciation of nickel is of the highest importance for the definition of lists of substances for regulatory activity in terms of prevention, regarding possible cancer risk. A review is made of the different attitudes of outstanding administrations in front of nickel speciation. Some of them show a maximum of care in chemical definition, others reflect a lack of scientific rigor leading to generic classifications, more or less abusive. The great complexity of the chemistry and physicochemistry of nickel imposes the “two‐level speciation concept” (chemical and physicochemical), at least for compliance with the “Good Laboratory Practice” as far as experimental toxicology is concerned. Recommendations are exposed for the attention of toxicologists and regulators who have been for some years now extremely solicited for prevention aims.     

Polarographic investigations on the complexation of cadmium and zinc by thiol peptides

Complex formation of Cd²⁺ and Zn²⁺ with thiol derivatives has been investigated by differential pulse polarography. The binding of Cd²⁺ and Zn²⁺ with cysteine (CySH), glutathione (GSH) and the model peptide N‐acetyl‐cysteine‐methylamide (ASH) reveals different stoichiometry. Thus, Cd²⁺ forms 1:1 and 1:2 complexes with CySH while 1:2 and 1:4 complexes have been observed with GSH and ASH, respectively. Overall formation constants of Cd²⁺ with CySH (Iogβ ₂ 15.3) and with GSH (Iogβ5₂ 14.4) have been estimated using competitive complexation with nitrilotriacetic acid (NTA). Investigation of competition between Zn²⁺ and Cd²⁺ for the thiol complexation has underlined the role played by the amino group in CySH for the stabilization of Zn complexes in contrary to Cd complexes.     

Determination of metallic cobalt in the atmosphere

Due to the fact that, among the different chemical species, metallic cobalt is characterized by the highest toxicity, in this paper is proposed a procedure for its determination in the atmospheric paniculate. The air is filtered on a cellulose or glass fiber membrane, to collect the paniculate containing among the other species, metallic cobalt: the determination is based on a selective dissolution of the metallic cobalt possibly present followed by its determination by atomic absorption spectroscopy. The typical interferences that can be present in the matrix are discussed and suggestions for their minimisation are proposed. By the following procedure is also possible to determine separately the sum of the insoluble and water soluble cobalt compounds.     

Bioavailability of copper and cadmium in sediment of nanjing section of Changjiang river to aquatic organisms

Bioavailabilities of metals in sediment to aquatic organisms depend on the strength of metal bonding to particulates. The accumulation tests of Cu and Cd in carp and in snails have been studied in vitro with the solution containing semisynthetic sediment samples in which the contents of various speciation of metal in sediment have been extended. For carp, the accumulation of Cu and Cd is related to the concentration of dissolved metal which in turn is affected by the distributions of speciations in sediment under given environmental conditions. It is another pattern for snails, various speciations of metal in sediment can contribute indirectly to metal accumulation. The contribution ratio, or relative importance of various speciations of metal in sediment can be expressed by multiple linear regression formulas. The contribution of ion‐exchangable speciation and coprecipition with carbonate speciation is 10⁵ times larger than that of residue speciation in sediment.     

洞庭湖沉积物不同形态氮赋存特征及其释放风险

为了揭示湖泊沉积物中氮的空间分布特征及其释放风险,采用连续分级提取法研究了洞庭湖表层沉积物中EN(可交换态氮)、HN(酸解态氮)及NHN(非酸解态氮)的赋存特征;同时,结合BN(生物可利用态氮)的含量和释放通量的大小,探讨了各形态氮对BN的贡献及与释放通量的相关关系. 结果表明,受水动力和湖盆地形的影响,沉积物中各形态氮含量空间差异较大. 全湖w(TN)在735.91~2846.51mg/kg之间,平均值为1371.85mg/kg,东洞庭湖、西洞庭湖、南洞庭湖、洞庭湖出口w(TN)的平均值分别为1513.43、1173.14、1262.76和1363.31mg/kg. 从各形态氮含量占w(TN)的比例来看,w(HN)最高,平均占66.74%;其次是w(NHN),平均占21.46%;w(EN)最小,仅占11.80%. 东洞庭湖、西洞庭湖、南洞庭湖、洞庭湖出口w(BN)的平均值分别为189.31、170.16、152.87和139.51mg/kg,其值大小主要受w(EN)和w(HN)的影响. 东洞庭湖、西洞庭湖、南洞庭湖、洞庭湖出口沉积物中NH₄+-N释放通量的平均值分别为6.32、7.03、7.78和146.96mg/(m2·d),沉积物中NH₄+-N释放通量主要受EN控制,其中尤其受可交换态NH₄+-N的控制,而沉积物中的HN和TN尚不是影响沉积物氮释放的主要因素.      

模拟酸雨对街道灰尘重金属淋溶的累积释放特征与释放模型

以泉州市交通繁忙区街道灰尘为研究对象,采用模拟酸雨动态淋溶实验和改进的BCR四步提取法研究街道灰尘中重金属元素在不同酸度(pH=3.5、4.5、5.6)模拟酸雨淋溶下的溶出规律及形态变化.结果表明,街道灰尘中重金属元素的累积释放量均随模拟酸雨pH的降低而增加,当pH值为3.5和4.5时,Cu、Pb、Mn、Ni、V、As和Co的释放过程为快速释放阶段,Cr、Zn和Fe的释放过程分为快速释放和相对平稳释放两个阶段;当pH值为5.6时,除Co、V为快速释放过程外,其余重金属都处于相对慢速的释放过程.动力学方程拟合结果表明,双常数速率方程能更好地描述上述重金属元素的累积释放特征.尘样经模拟酸雨淋溶后,弱酸可溶态中Co、Cu、Mn、Zn、Ni百分含量有所增加,Cr、Fe、Pb百分含量变化不明显;可还原态中Cr、Pb、Cu、Ni百分含量有所增加,Mn、Zn、Co百分含量有所下降;可氧化态中上述各元素的百分含量均有所降低;残渣态中除Ni、Mn百分含量有所下降外,其它元素百分含量变化均不显著.     

Acidity of machine-made snow and its effect on pH and aluminum speciation in New England streams during spring thaw

The pH of machine-made snow and its effect on an acid-sensitive watershed in Vermont were studied. Spring runoff from snowmaking was found to be less acidic and to contain less dissolved inorganic aluminum. Dissolved inorganic aluminum has been associated with damage to aquatic life. The extensive use of machine-made snow by the ski industry in most of the northeast region of the US may be beneficial to aquatic life.     

Distribution and speciation of heavy metals in Apulian coastal sediments

In the framework of the Interreg II Project Italy–Greece, distribution and speciation of trace metals in surface coastal sediments of Apulian regions were studied. A sequential extraction technique was used to determine the chemical association of heavy metals (Zn, Pb, Ni, Fe, Cr, Mn, Cu and Cd) with major sedimentary phases (acid soluble phases, easily reducible fraction and oxidizable matter). The relationship between the metals' content and the grain-size composition of the sediments was also considered: generally the elements resulted associated with the fine fraction, even if in some cases (Cu in the oxidizable phase) the opposite behaviour was observed. The studied area is not particularly polluted, except for some defined zones, as for example Brindisi's harbour. Speciation analysis revealed that the major part of the heavy metals are not easily mobilizable and bioavailable. Even in this case, there are some exceptions to the general behaviour: Cu and Pb in several samples are largely present in the oxidizable phase, which even if not immediately available can become a source of associated elements when redox conditions change.     

食品烹调处理过程中砷的浓度、形态和生物可给性研究进展

食品作为人体砷暴露的主要途径,其砷的含量和形态备受关注。由于食品原料通常要经过烹饪加工后才会被人食用,因此,食品的烹调处理过程及方式对砷的形态及生物有效性的影响在砷的健康风险评价研究中,需要作为重要因素进行研究。通过综述不同食品烹调处理前后砷浓度、形态和生物可给性变化的相关研究,分析了砷变化的特征,探讨了相关机理,并得出如下结论:烹调处理能使食品中砷的浓度发生升高或降低;高温烹调能使食品中砷形态发生变化,目前研究结果确定的变化主要是砷甜菜碱的分解,烹调中食品砷形态变化的机理尚不明确。不同烹调方式下,食品中砷的生物可给性差异较大,砷的形态变化可能是其生物可给性差异的主要原因。烹调特别是高温烹调下食品砷浓度升高及形态变化导致的健康风险值得进一步关注。