表面酸碱2步改性对活性炭吸附Cr(Ⅵ)的影响

研究了酸碱2步改性对活性炭吸附水相中Cr(Ⅵ)的影响.将活性炭(AC₀)在HNO₃溶液中氧化(AC₁),然后在NaOH和NaCl的混合液中处理(AC₂).分别采用平衡和连续吸附试验,测试Cr(Ⅵ)的吸附特征.以Boemh滴定法定量检测活性炭表面酸性官能团数量,结合元素分析结果定量表征活性炭的表面含氧官能团变化;以低温液氮(N₂/77K)吸附法分析活性炭的比表面积和孔径结构.结果表明:活性炭经2步改性后,其Cr(Ⅵ)的吸附容量和吸附速度均显著改变.吸附容量和吸附速度大小依次为AC₂>AC₁>AC₀.改性活性炭表面积下降,表面含氧酸性官能团数量增加.HNO₃液相氧化处理可使活性炭表面生成带正电含氧酸性官能团,第2步改性后活性炭表面酸性官能团H⁺部分被Na⁺取代,使活性炭表面酸性降低.表面较多的含氧酸性官能团(与AC₀相比)、适宜的表面pH(与AC₁相比)是AC₂所表现出较高Cr(Ⅵ)吸附容量的主要原因.     

铬渣-煤矸石砖中Cr(Ⅵ)解毒机理研究

铬渣因所含Cr(Ⅵ)具有强氧化性而会对环境造成严重污染.本文采用自养煤矸石砖焙烧技术对铬渣进行无害化治理,对不同铬渣掺量的铬渣-煤矸石砖,进行铬的浸出毒性分析.通过试验得出,除铬渣掺量为15%的砖中六价铬浸出浓度超标外,其余铬的浸出浓度均小于国标规定,铬的解毒率都在95%以上.此技术对Cr的还原解毒为,在高温熔融条件下,煤矸石中的碳及随后产生的CO、H2、CH4等还原性物质与Cr(Ⅵ)化合物发生反应.铬渣、煤矸石及砖的X-粉晶衍射物相分析表明,砖中Cr(Ⅵ)被还原为Cr(Ⅲ)后,以类质同相方式进入辉石、尖晶石、铝硅酸盐等稳定物相,得以固化解毒.因此,还原后Cr的存在形式稳定,可以经受恶劣自然环境而不会重新溶出和造成二次污染,作为建材,可以安全利用.     

Role of GSH in the amelioration of chromium-induced membrane damage

Membrane damage is one of the important consequences of chromium (Cr), an environmental toxicant, induced cytotoxicity. Reduced glutathione (GSH), a membrane protectant may be used to reduce the Cr-induced membrane damage. In the present study, the impact of Cr in presence and absence of GSH was studied on plasma membrane of the liver and kidneys in male Wistar rats. Significant increases in membrane cholesterol levels as well as significant decreases in membrane phospholipid levels in Cr exposed (0.8 mg per 100 g body weight, i.p., for 28 days) animals suggest structural alterations in both the liver and kidney plasma membranes. Alkaline phosphatase (ALP), total ATPase, and Na⁺–K⁺–ATPase activities of plasma membrane were significantly decreased in both the liver and kidneys after Cr treatment. This treatment also produced significant weight loss and increased Cr content in the liver and kidneys. However, GSH (8 mg per 100g body weight, i.p., daily at an interval of 6 h after injection of Cr for a period of 28 days) supplementation restored alterations induced by Cr in plasma membrane of both the liver and kidneys but was not able to eliminate the deposited Cr from the liver and kidney tissues.     

1,3,5-triazine-triethylenetetramine polymer: an efficient adsorbent for removal of Cr(VI) ions from aqueous solution

The synthesis of 1,3,5-triazine-triethylenetetramine (TATETA), its characterization by infrared spectroscopy and elemental analysis, and its application for removal of Cr(VI) ions from aqueous solution is reported. The effects of pH, contact time, initial concentration of Cr(VI), sorbent dose, and temperature on adsorption were investigated and optimized by batch adsorption experiments. Adsorption was highest at acidic conditions with an equilibration time of 25 min. The adsorption followed a Langmuir model, with an adsorption capacity of 303 mg g^?1, was second order in its kinetics, and exothermic and thus spontaneous.     

Application of electrochemical reactor divided by cellulosic membrane for optimized simultaneous removal of phenols,chromium, and ammonia from tannery effluents

The post treatment of simulated tannery wastewater was evaluated in an electrochemical oxidation process under galvanostatic conditions. A continuous flow reactor divided by a cellulosic membrane consisted of Ti/SnO₂–Sb anodes and iron cathodes was used. Central composite design and response surface methodology (RSM) were applied to investigate the effects of six operational parameters, namely initial concentration of total phenols (TPh), total chromium (TCr), total ammonia nitrogen (TAN), flow rate (Q), current intensity (I), and electrode surface area (A). Effectiveness of the innovative cellulosic membrane was proven by considerable pH variations in the anolyte and catholyte chambers. A faster removal rate was observed for TPh and TAN, followed by TCr. The treatment level was very sensitive to Q and I in the studied ranges. RSM showed the removal efficiencies of 78.14%, 63.42%, and 86.09% for TPh, TCr, and TAN, respectively, are achieved under optimal conditions with consumption of only 9.03 kWh m^?3 electrical energy. Chlorinated compounds such as chloroform, 2,4-dichlorophenol, and chlorobenzene were detected as the degradation intermediates. According to the obtained results, electrolysis in the divided cell with cellulosic membrane is a practical, cost-effective method for advanced treatment of tannery effluents.     

Comments on the Carcinogenicity and Mutagenicity of metals and their compounds†

The carcinogenicity of metals has received extensive study, both epidemiologically and in the laboratory. These have included case reports of occasional human occurrence or clusters of cancer cases as well as extensive epidemiologic studies; in addition, there has been significant laboratory research on the whole animals and in vitro systems. This body of information will be examined selectively.

I will not in this paper attempt a comprehensive review of the mutagenicity and carcinogenicity of metals and their compounds. Rather, I will attempt to set forth some historical perspectives, and to comment on some current gaps and needs.

Other papers in this workshop have presented thorough and very current reviews of most of the topics briefly noted in this presentation and do not require repetition here.

The cancer issue has been studied and reported on far more extensively than that relating to heritable mutations. There has been in recent years increasing interest in the use of short term tests for mutagenicity and cell transformation. These, however, are primarily with respect to their relationship to cancer production rather than to germ cell injury. Interest in cancer from metal compounds goes back a long time; in fact, one of the earliest reports was on the carcinogenicity of arsenic not many decades after the pioneering report of Sir Perceval Pott on cancer in chimney sweeps. Since then cancer has been definitely associated in humans with chromium compounds, nickel, and with less assurance but probably definitely with beryllium and cadmium. The confirmation of these findings in laboratory animals has been uneven. In the case of arsenic, for example, there has been only limited success in the production of cancer in laboratory animals with arsenic.

Many other metals have been found in laboratory studies to produce cancer, although with most of these, evidence of production of cancer in humans is either absent or extremely uncertain.

The extensive body of recent information relating to the testing of metals with a variety of short term tests will be briefly reviewed.     

The use of the embryo‐culture techniques in the research on the Teratogenic and Mutagenic properties of metals†

Actually, embryos can be cultured from the one‐cell stage up to the blastocyst stage, and their development can be easily monitored at any time: severe effects caused by toxic compounds are traduced by rapid embryonic death, less pronounced effects can be expressed by a lowered cleavage activity or by an arrest of the development from a particular stage. The system can be improved by transferring the embryos at the blastocyst stage in another more complete medium where they can “implant”; and form an inner cell mass with differentiated ectoderm and endoderm. Since last years, it has also become possible to culture postimplantation rodent embryos for short periods involving a number of particularly critical stages of organogenesis, such as the formation and closure of the anterior neuropore. Embryo‐culture also represents a useful system to study cytogenetic effects of chemicals which are often linked to lethal or teratogenic effects. These different possibilities are illustrated by examples of studies already performed with metals, and dealing with their teratogenic and/or cytogenetic effects on pre‐ and postimplantation rodents.     

Occupational exposures,delivered doses and exposure limits for chromium and nickel†

The interaction of HCH (50 mg/kg) and dietary protein levels on microsomal drug metabolizing enzymes system and liver lipids were studied in the rats for 90 days. The results indicated that rats fed a lower protein diet and HCH has a higher rate of mortality, lower rate of growth and an increased liver weight. A significant induction in the hepatic microsomal aminopyrine‐N‐demethylase, p‐nitroanisole‐O‐dealkylase, benzo(a)pyrene hydroxylase and glutathione‐S‐transferase activity was observed in pesticide treated animals as compared to control animals. The pathological changes observed in liver of HCH treated animals consisted mainly of necrosis and fatty degeneration of hepatocytes. HCH also induced the significant accumulation of cholesterol, triglycerides, phospholipid and total lipid in liver in low protein diet animals. Protein accelerates the metabolism of HCH, resulting in a decrease of HCH concentration with the increase of dietary protein level. A close correlation existed between lipid accumulation, induction of drug metabolizing enzyme system and deposition of HCH in liver.     

Biochemical speciation in chromium genotoxicity

The biochemical speciation of chromium compounds in mammalian cells is discussed with respect to uptake, metabolism, DNA binding and damaging. Whereas soluble hexavalent chromium is taken up rapidly and accumulated intracellularly after its reduction, compounds of trivalent chromium penetrate biomembranes about three orders of magnitude slower. Cr(VI) after its uptake is metabolised by electron donating compounds via Cr(V) to Cr(III) compounds. Chromium from various Cr(III) compounds, but not chromate, binds to chromatin in isolated cell nuclei. The DNA‐protein crosslinks and DNA strand breaks observed in rat liver and kidney after chromate administration are also found in vitro, when Cr(III) compounds (but not chromate) interacts with isolated nuclei. In the Chinese Hamster cell HGPRT mutation assay, three out of four tested Cr(III) complexes were found to be mutagenic. In a direct DNA strand break assay with supercoiled bacteriophage PM 2 DNA, neither chromate nor the four Cr(III) compounds tested caused nicks. However, the combined action of chromate plus glutathione as well as the isolated complex of pentavalent chromium, Na₄Cr(glutathione)₄, did cause DNA breaks. Reactive oxygen species are inferred to be the ultimate DNA nicking agents in this assay. In conclusion there appear to be two mechanisms of chromate genotoxicity; one with direct DNA damage caused by Cr(V) species and one via DNA‐protein crosslinks formed with Cr(III), the final reduction state of chromate.     

Preliminary Evaluation of the Use of Phosphogypsum for Reef Substrate. I. A Laboratory Study of Bioaccumulation of Radium and Six Heavy Metals in an Aquatic Food Chain

Phosphogypsum (PG), a solid by-product of phosphoric acid production, contains radionuclides and trace metals in concentrations which may pose a potential hazard to human health and the environment. to investigate the possibility of bioaccumulation of radium and six heavy metals over time when aquatic organisms experience both trophic and environmental exposure to PG, we designed a laboratory experiment representing three levels of an aquatic food chain. During the 135 day experiment, a meiobenthic copepod species (Amphiascoides atopus) was cultured in the presence of PG. the copepods were subsequently fed to grass shrimp (Palaemonetes vulgaris and P. pugio) which were in turn fed to gulf killifish (Fundulus grandis); both the grass shrimp and the killifish also experienced an environmental PG exposure. Other than elevated radium levels in the experimental grass shrimp, the experiment demonstrated little effect of environmental or trophic exposure to PG on microinvertebrates, macroinvertebrates, or fishes that could be attributed to PG. in all cases where increased concentrations were indicated within the experimental group, roughly equivalent increases in metal concentrations also occurred in the control group.