铊的环境地球化学研究进展

铊（Tl）作为一种高毒害性的元素越来越受到人们的关注。大量含Tl矿物的开采和冶炼、化石燃料的燃烧等人类活动,导致Tl及其化合物进入环境,进而通过食物链进入生物体,从而对动植物特别是人类健康造成严重的危害。文章对铊在各环境介质中的存在、迁移、转化,以及Tl的生物效应研究进展进行了概述。Tl在岩石中的平均质量分数为0.5~10 mg.kg-1,在大气中的平均质量浓度为0.22~1.0 ng.m-3,在天然水体中的平均质量浓度为0.001~1.264μg.L-1,在土壤中的平均质量分数为0.01~3.0 mg.kg-1,在植物中的平均质量分数为0.02~0.25 mg.kg-1。大气中的铊可随大气迁移,导致全球Tl污染;土壤中Tl的迁移主要受pH影响,pH越小其迁移能力越强,而水中溶解态的铊迁移能力最强。植物对Tl具有较强的富集能力,而动物实验则表明Tl具有一定的致畸性,可能存在一定的致癌性,并且职业暴露是人体Tl中毒的主要原因。尽管有关有Tl的地球化学以及生态毒理学方面的研究取得了一定的进展,但有关Tl在环境介质之间的界面化学机理、Tl在分子水平上吸附机理、不同形态的Tl在生物体中的致毒代谢机理以及铊的同位素在环境介质中的变化等方面仍有待于进一步的研究。     

Thallium(I) and thallium(III) induce apoptosis in isolated rat hepatocytes by alterations in mitochondrial function and generation of ROS

Environmental metal toxins, generated through diverse anthropogenic activities, constitute one of the major contaminants that have led to global dispersion of these toxic metals in the ecosystem. Thallium is one of these widely dispersed metals that produce severe adverse effects on human and biological systems. The influence of thallium(I) and thallium(III) on the early events that trigger apoptosis signaling were examined in freshly isolated rat hepatocytes. In addition, the role of oxidative stress, and mitochondria in the induction of apoptosis were also investigated. Incubation of thallium(I) and thallium(III) with isolated rat hepatocytes generated reactive oxygen species (ROS), collapse of mitochondrial membrane potential, activation of caspases cascade, and appearance of apoptosis phenotype. Mitochondrial permeability transition (MPT) pore sealing agents (cyclosporine A and carnitine) and ATP generators (L-glutamine, fructose, and xylitol) inhibited the activation of caspase-3 and apoptosis, indicating that both the cations activated apoptosis signaling via mitochondrial pathway. Pretreatment of hepatocytes with antioxidants (α-tocopherol or deferoxamine) also blocked caspase-3 activation induced by these cations, suggesting that oxidative stress may be directly involved in a mitochondrial MPT pore opening and activation of caspases cascade. These findings contribute to a better understanding of the mechanisms that mediate thallium-induced apoptosis in isolated rat hepatocytes.     

水体中铊对泥鳅外周血红细胞的遗传毒性的时效性

铊(T1)是剧毒的重金属元素,会对生态环境和人体健康造成威胁.目前各国铊的环境安全标准存在差异.本文利用泥鳅红细胞微核技术,研究泥鳅Misgurnus anguillicaudatus红细胞微核率和核异常率与铊污染时间的关系,为该技术在铊毒理研究中的可行性和铊环境安全标准提供依据.结果表明:水体铊质量浓度为0.5μg·L~(-1)下,随处理时间的延长,泥鳅红细胞微核率、核异常率显著增加,并与时间呈显著的正相关,其中微核率、核异常率分别在处理24 h和48 h时达到最大值;随后两指标逐步下降,与时间呈显著的负相关.在此铊质量浓度和处理时间内,核异常率与微核率均显著高于空白无铊对照处理,表明水体铊质量浓度0.5 μg·L~(-1)对泥鳅血红细胞具有遗传毒性.     

In vitro assessment of genotoxic and oxidative effects of zinc borate

Zinc borate is used as flame retardant for plastics and cellulose fibers, paper, rubber, and textiles. Despite its wide industrial use, there is limited information concerning its toxicity. The aim of the present study was to investigate the concentration dependence (0–280 mg L^?1) of its genotoxic activity on cultured human lymphocytes by using sister chromatid exchange and chromosomal aberration assays. Total antioxidant capacity and the extent of oxidative stress were also determined. Zinc borate was found to be non-genotoxic at all tested concentrations. It exhibited antioxidant activity at concentrations lower than 40 mg L^?1, and total oxidative stress levels were not changed at any applied concentration of zinc borate.     

Toxic Effect of a Pesticide, Diflubenzuron on Freshwater Microinvertebrate (Tetrahymena pyriformis)

Harmful bugs affect food production,directly by the qualitativeor quantitative reduction of the harvests,or indirectly while servinglike vectors of several illnesses of the plants and human[1].Many chemical products are used by human for a long time inthe…     

Thallium in the Environment and Health Effects

Thallium is present in the natural environment in low concentration, being found most frequently in the sulphide ores of a number of heavy metals. Atmospheric emission and deposition from industrial sources has resulted in raised levels in the vicinity of mineral smelters, coal burning power plants, brick works and cement plants. In contaminated areas, raised levels are found in vegetables, fruit and in farm animals. Thallium is used industrially in small quantities, with uses in electronics, in the production of certain glasses and crystals and in medical diagnostics. It has in the past been commonly used as a rodenticide, but its use has now been banned in many countries. Thallium salts are now considered to be amongst the most toxic compounds known. With regard to population exposure, an epidemiological study in an area with high thallium concentrations in soil and garden vegetables centred on a cement plant, has found evidence of a dose response relationship between thallium concentration in urine and a number of non-specific subjective symptoms. Much further research is required to investigate the possible adverse health effects of thallium following population exposure.     

邻苯二甲酸二乙基己酯对蚕豆根尖微核及幼苗超氧化物歧化酶的影响

为了初步探讨邻苯二甲酸二乙基己酯(Di-(2-ethylhexyl)phthalate,DEHP)对植物的毒害作用,采用不同浓度的DEHP溶液对蚕豆根部进行处理(终含量0、0.2、2、20、200mg·kg-(1细沙)),检测根尖微核率和对幼苗茎、叶SOD活性的影响.结果表明:对蚕豆根尖进行短期(6h)处理后,各DEHP处理组微核率随DEHP含量的升高呈显著上升趋势(与对照比较,p<0.05或p<0.01).处理7d后,随DEHP含量的升高(0～20mg·kg-(1细沙)),蚕豆幼苗茎、叶SOD活性均呈逐渐升高趋势;DEHP含量在20～200mg·kg-(1细沙)时,SOD活性均略有下降.以上结果表明DEHP对蚕豆种子具有遗传毒性,且能够对蚕豆幼苗产生氧化损伤.     

对化学品登记要求的数据解释：皮肤致敏重复染毒及致变

本文对化学品登记所要求的部分健康效应数据——皮肤致敏、重复经口染毒、致变做了解释.涉及到的测试参数包括:皮肤致敏、重复(14/28天)经口啮动物毒性、基因突变、染色体畸变和DMA效应.     

农药氰戊菊酯和三氟氯氰菊酯对蚕豆根尖细胞的遗传损伤

采用蚕豆根尖微核技术研究了农药氰戊菊酯、三氟氯氰菊酯对蚕豆根尖细胞的遗传损伤.测定了不同浓度氰戊菊酯、三氟氯氰菊酯(5×10-10～5×10-2g·L-1)诱导下的蚕豆根尖细胞微核率、有丝分裂指数和染色体畸变率.结果表明,氰戊菊酯、三氟氯氰菊酯均能诱发较高的微核率,在一定浓度范围内,微核率随两种农药处理浓度的升高而增加,但随着处理浓度的进一步升高微核率反而呈下降趋势;两种农药均可使蚕豆根尖细胞有丝分裂指数增大;并能诱导蚕豆根尖细胞产生较高频率、多种类型的染色体畸变.氰戊菊酯和三氟氯氰菊酯对蚕豆根尖细胞具有明显的遗传毒性.     

Genotoxic Effect of Phenol on the Cells of Onion (Allium cepa) Roots

The roots of onion (Allium cepa) stand out for having cells with large size and small number of chromosomes.These characteristics make them useful in bioassays for the measurement of a variety of cytogenetic and morphological parameters , in which they can be used as toxicity indicators of the induction and formation of micronuclei and chromosomal aberrations.Based on this background , the potential genotoxic effect of phenol concentration on cells of A.ceparoots was investigated either in terms of induced aberrations or micronuclei formation.The results demonstrated that the higher the concentration of phenol , the higher the incidence of abnormalities , thus confirming the genotoxicity of this pollutant.     

Combined Fenton process and sulfide precipitation for removal of heavy metals from industrial wastewater: Bench and pilot scale studies focusing on in-depth thallium removal

Addition of alkali to pH 10 is effective for precipitation of precipitable metals. Fenton treatment is effective for substantial removal of Tl, Cd, Cu, Pb, and Zn. Sulfide precipitation is a final step for removal of trace Tl, Cd, Cu, Pb, and Zn. Bench and pilot studies demonstrated the effectiveness of this combined technique. Thallium (Tl) in industrial wastewater is a public health concern due to its extremely high toxicity. However, there has been limited research regarding Tl removal techniques and engineering practices to date. In this investigation, bench and pilot studies on advanced treatment of industrial wastewater to remove Tl to a trace level were conducted. The treatment process involved a combination of hydroxide precipitation, Fenton oxidation, and sulfide precipitation. While hydroxide precipitation was ineffective for Tl+ removal, it enabled the recovery of approximately 70%–80% of Zn as Zn hydroxide in alkaline conditions. The Fenton process provided good Tl removal (>95%) through oxidation and precipitation. Tl was then removed to trace levels (<1.0 µg/L) via sulfide precipitation. Effective removal of other heavy metals was also achieved, with Cd<13.4 µg/L, Cu<39.6 µg/L, Pb<5.32 µg/L, and Zn<357 µg/L detected in the effluent. X-ray photoelectron spectroscopy indicated that Tl2S precipitate formed due to sulfide precipitation. Other heavy metals were removed via the formation of metal hydroxides during hydroxide precipitation and Fenton treatment, as well as via the formation of metal sulfides during sulfide precipitation. This combined process provides a scalable approach for the in-depth removal of Tl and other heavy metals from industrial wastewater.     

Indium tin oxide nanoparticles-mediated DNA fragmentation and cell death by apoptosis in human lung epithelial cells

Indium tin oxide (ITO) nanoparticles (NP) have extensive applications in industrial fields, and concerns regarding their potential toxicity in humans and environmental impact have increased. Since exposure to ITO NP is mainly via skin and inhalation, this study was conducted utilizing human lung epithelial (A549) cell line. Cells were exposed to different concentrations of the ITO NP for 24 and 48 hr. A severe cytotoxic response of ITO NP was observed as evident by the (3-4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide and neutral red uptake assays after 48 hr exposure. ITO NP significantly reduced glutathione levels with a concomitant increase in lipid hydroperoxide levels, superoxide activity, and reactive oxygen species (ROS) generation after exposure. A significant induction in caspase activity and formation of condensed chromosomal bodies was also observed after ITO NP (10 or 25 µg/ml) exposure. Furthermore, a significant induction in DNA damage was observed by the Comet assay in cells exposed to ITO NP. Our data demonstrate that ITO NP display cytotoxic and genotoxic potential. However, increase in ROS levels and oxidative stress leading to oxidative DNA damage and condensed chromosomal bodies formation, suggests involvement of apotosis. Thus, ITO NP-mediated effects on cell viability indicate cytotoxicity, and therefore, exposures need to be carefully monitored in the industrial sector.     

Product identification and toxicity change during oxidation of methotrexate by ferrate and permanganate in water

• Oxidation of methotrexate by high-valent metal-oxo species was first explored. • Fe(VI) presented a higher reactivity to MTX than Mn(VII) at pH 8.0. • Ketonization and cleavage of peptide bond were two initial reaction pathways. • Products of MTX were not genotoxic, neurotoxic, or endocrine-disrupting chemicals. • The less biodegradable products exhibited developmental and acute/chronic toxicity. Accompanying an annual increase in cancer incidence, the global use of anticancer drugs has remarkably increased with their worldwide environmental prevalence and ecological risks. In this study, the oxidation of methotrexate (MTX), a typical anticancer drug with ubiquitous occurrence and multi-endpoint toxicity, by ferrate(VI) (Fe(VI)) and permanganate (Mn(VII))) was investigated in water. Fe(VI) exhibited a higher reactivity with MTX (93.34 M⁻¹ s⁻¹) than Mn(VII) (3.01 M⁻¹ s⁻¹) at pH 8.0. The introduction of Cu(II) and Fe(III) at 1.0 mM improved the removal efficiency of 5.0 μM MTX by 100.0 μM Fe(VI) from 80% to 95% and 100% after 4 min, respectively. Seven oxidized products (OPs) were identified during oxidative treatments, while OP-191 and OP-205 were characterized as specific products for Fe(VI) oxidation. Initial ketonization of the L-glutamic acid moiety and cleavage of the peptide bond of MTX were proposed. Additionally, a multi-endpoint toxicity evaluation indicated no genotoxicity, neurotoxicity, or endocrine-disrupting effects of MTX and its OPs. Particularly, serious developmental toxicity in zebrafish larvae was observed in the treated MTX solutions. Based on the acute and chronic aquatic toxicity prediction, OP-190, OP-192, OP-206, and OP-208 were deemed toxic or very toxic compared to harmful MTX. Furthermore, the reduced biodegradability index from 0.15 (MTX) to −0.5 to −0.2 (OP-192, OP-206, and OP-468) indicated the formation of lower biodegradable OPs. Overall, this study suggests that Fe(VI) and Mn(VII) oxidation are promising treatments for remediating anticancer drug-contaminated water. However, the environmental risks associated with these treatments should be considered in the evaluation of water safety.     

Zero-valent manganese nanoparticles coupled with different strong oxidants for thallium removal from wastewater

• Nano zero-valent manganese (nZVMn, Mn⁰) is synthesized via borohydrides reduction. • Mn⁰ combined with persulfate/hypochlorite is effective for Tl removal at pH 6-12. • Mn⁰ can activate persulfate to form hydroxyl and sulfate radicals. • Oxidation-induced precipitation and surface complexation contribute to Tl removal. • Combined Mn⁰-oxidants process is promising in the environmental field. Nano zero-valent manganese (nZVMn, Mn⁰) was prepared through a borohydride reduction method and coupled with different oxidants (persulfate (S₂O₈²⁻), hypochlorite (ClO⁻), or hydrogen peroxide (H₂O₂)) to remove thallium (Tl) from wastewater. The surface of Mn⁰ was readily oxidized to form a core-shell composite (MnO_x@Mn⁰), which consists of Mn⁰ as the inner core and MnO_x (MnO, Mn₂O₃, and Mn₃O₄) as the outer layer. When Mn⁰ was added alone, effective Tl(I) removal was achieved at high pH levels (>12). The Mn⁰-H₂O₂ system was only effective in Tl(I) removal at high pH (>12), while the Mn⁰-S₂O₈²⁻ or Mn⁰-ClO⁻ system had excellent Tl(I) removal (>96%) over a broad pH range (4–12). The Mn⁰-S₂O₈²⁻ oxidation system provided the best resistance to interference from an external organic matrix. The isotherm of Tl(I) removal through the Mn⁰-S₂O₈²⁻ system followed the Freundlich model. The Mn⁰ nanomaterials can activate persulfate to produce sulfate radicals and hydroxyl radicals. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy suggested that oxidation-induced precipitation, surface adsorption, and electrostatic attraction are the main mechanisms for Tl(I) removal resulting from the combination of Mn⁰ and oxidants. Mn⁰ coupled with S₂O₈²⁻/ClO⁻ is a novel and effective technique for Tl(I) removal, and its application in other fields is worthy of further investigation.     

Introduction of cob(I)alamin as an analytical tool: application to reaction-kinetic studies of oxiranes

The strongly nucleophilic cob(I)alamin, i.e. Vitamin B₁₂ with Co(III) reduced to Co(I), is introduced as a trapping agent in the determination of concentrations of electrophilic reagents. This compound was applied, in comparison with the previously used moderately reactive nicotinamide (H.J.C.F. Nelis and J.E. Sinsheimer (1981). Anal. Biochem., 115, 151.). Oxiranes, metabolites of 1-alkenes, were chosen as model electrophiles. The reagents (nicotinamide and cob(I)alamin) were evaluated in the determination of the rates of reaction toward valine methylamide, a model of N-terminal valines in hemoglobin often used for monitoring of doses in vivo of genotoxic carcinogens. The rate constants for reaction at 37°C with valine methylamide (k _VMA) determined by the cob(I)alamin and nicotinamide procedure, respectively, were for ethylene oxide (1.6, 1.7), propylene oxide (0.9, 1.1), 1,2-epoxybutane (0.7, 0.8) and 1,2-epoxyoctane (0.5, 0.6) M^?1?h^?1, decreasing with increasing number of carbons of the oxirane. Concentrations of oxiranes trapped with nicotinamide are underrated in reaction mixtures containing valine methylamide due to consumption by reaction with the competing nucleophile, a disturbance that is not observed in trapping with cob(I)alamin which reacts about 10⁵ times faster than nicotinamide. Cob(I)alamin which was demonstrated to be an efficient nucleophile for trapping of electrophiles, also in the presence of competing nucleophiles, is promising as an analytical tool in toxicological studies of reactive compounds. Furthermore, cob(I)alamin can be used to detect, measure and compare electrophilic reactivity of chemical substances, a property that is associated with genotoxic potency.     

Genotoxicity and mutagenicity of electronic waste leachates using animal bioassays

Human exposure to electronic waste (e-waste) is increasing, especially in developing nations. This has potential short and chronic adverse health risks. Information is currently scarce on potential genotoxicity of e-waste leachate. In this study, the potential mutagenic and genotoxic effects of leachates from e-waste dumpsites at two electronic markets in Lagos, Nigeria, were investigated. The assays utilized were: bone marrow micronucleus (MN) and chromosome aberration (CA), spermatogonia CA, sperm morphology, and sperm count in mice. Experiments were carried out at concentrations of 1%, 5%, 10%, 25%, and 50% (v/v; leachate: distilled water) of leachate samples. MN analysis showed a concentration-dependent induction of micronucleated polychromatic erythrocytes (MNPCE) across the treatment groups. In the CA tests (bone marrow and spermatogonia), there was concentration-dependent significant reduction in mitotic index and induction of different types of CA. Assessment of sperm shape showed a significant increase in sperm abnormalities with significant decrease in mean sperm count in treated groups. Heavy metals analyzed in the tested samples are believed to contribute significantly to the observed genetic damage. This indicates that e-waste contains potential genotoxic agents; and constitutes a genetic risk in exposed human population.     

不同价态铬在不同水分条件下的生物有效性及其对水稻的毒性

氧化还原过程在铬的形态转化中起了重要作用,而铬形态的转化能够影响其生物有效性及毒性。通过温室土培试验研究了六价铬(Cr(Ⅵ))与三价铬(Cr(Ⅲ))在淹水与不淹水条件下在土壤溶液中的动态变化及水稻对其吸收的变化。结果表明,土壤中添加Cr(Ⅲ)时,土壤溶液中检测不出Cr;而随着土壤中添加Cr(Ⅵ)浓度的增加,土壤溶液中Cr(Ⅵ)的浓度增加,但是溶液中检测不出Cr(Ⅲ);淹水处理总体上降低了土壤溶液中Cr(Ⅵ)的浓度。而土壤添加Cr(Ⅲ)、Cr(Ⅵ)和水分处理对土壤溶液p H没有显著影响,p H在7.08.0之间变动。土壤添加Cr(Ⅵ)处理的水稻中,只有90 mg·kg-1Cr(Ⅵ)淹水处理的水稻成活,而其余处理水稻没有成活。土壤中添加Cr(Ⅲ)处理,水稻幼苗生物量随Cr(Ⅲ)浓度的增加而显著降低;除了200mg·kg-1Cr(Ⅲ)处理外,其余淹水处理的水稻幼苗生物量明显高于不淹水处理的。土壤添加Cr(Ⅲ)处理的水稻,在不淹水条件下水稻空壳率比较高,淹水条件下,随着土壤中添加Cr(Ⅲ)浓度水平的增加,水稻各部位Cr含量有增加的趋势,但增加不显著,秸秆最高Cr含量达到33.80 mg·kg-1,籽粒中Cr含量最高0.30 mg·kg-1。土壤固定Cr(Ⅲ)的能力远强于Cr(Ⅵ),添加Cr(Ⅵ)处理的土壤溶液中Cr(Ⅵ)的浓度很高,对水稻表现出较强的生长抑制。     

A study on genotoxicity of textile dyeing industry effluents from Rajshahi,Bangladesh, by the Allium cepa test

Textile dye effluents are believed to be toxic as they might exert various harmful effects on living organisms including genotoxicity. These effluents are the main source of direct and continuous input of pollutants into the aquatic ecosystems. In this study, dye effluents from a local silk dyeing industry were analysed for their genotoxic potential by the Allium cepa genotoxicity test. The A. cepa test is characterised as a genotoxicity test where the roots of A. cepa are grown in different concentrations of the test material. The macroscopic results clearly showed that the toxicity of the dye effluents prompted A. cepa root growth inhibition, and this effect increased with higher concentrations of the effluents. At the cellular level, no dividing cells were found at higher concentrations such as 60%, 80% and 100% of the effluents. However, at a lower concentration of 20%, dividing cells were identified, although the mitotic index was much lower than that of the control. Microscopic analysis showed that the dye effluents induced chromosomal aberrations at significant levels. Taken together, these results revealed that the textile dyeing industry effluents are toxic to eukaryotic cells and these dyes have genotoxic properties that can potentially lead to cancer development and adverse health conditions.     

从HPRT和CD59基因的变化研究石英（MQZ）的诱变效应

通过用３１，６２．５，１２５和２５０μｇ／ｍＬ的ＭＱＺ剂量处理人与中国仓鼠杂交ＡＬ细胞２４ｈ，探讨石英对细胞生长、存活和突变效应。研究发现，细胞对ＭＱＺ微粒的吞噬作用随着处理剂量的增加而增大。吞噬的ＭＱＺ微粒多位于细胞质中。细胞的存活率与处理剂量成正比。基因突变率研究显示，ＭＱＺ的致突变效应并不强，对于ＨＰＲＴ基因位点，其最高处理剂量（ρ＝５００μｇ／ｍＬ）的基因突变率略高于４Ｇｙ的γ射线的突变频     

The toxic and environmental evaluation of pyrolytic liquids by Allium cepa test

In this study, liquid products obtained from the pyrolysis of hazelnut shell (HS), with and without ultra-high molecular weight polyethylene (UHMWPE), were subjected to the Allium cepa test system. Pyrolysis in conjunction with the A. cepa test is a promising technology not only from the perspective of energy savings and a source of precious material, but in terms of the removal of hazardous material from the environment in safe manner. Dosages of pyrolytic liquids dissolved in water were determined according to lethal dose (LD₅₀), with three different solution concentrations. The preparates were dyed with acetocarmine. The mitotic index decreased and chromosomal aberration, especially stickiness and c-mitosis, increased with dosage and time. The addition of UHMWPE to HS in the pyrolysis process resulted in less harmful chemical agents, as observed by the relatively higher mitotic index and lower levels of chromosomal aberration.