Methylated and thiolated arsenic species for environmental and health research——A review on synthesis and characterization

Hundreds of millions of people around the world are exposed to elevated concentrations of inorganic and organic arsenic compounds, increasing the risk of a wide range of health effects. Studies of the environmental fate and human health effects of arsenic require authentic arsenic compounds. We summarize here the synthesis and characterization of more than a dozen methylated and thiolated arsenic compounds that are not commercially available. We discuss the methods of synthesis for the following14 trivalent(Ⅲ) and pentavalent() arsenic compounds: monomethylarsonous acid(MMA~Ⅲ), dicysteinylmethyldithioarsenite(MMA~Ⅲ(Cys)_2), monomethylarsonic acid(MMA~Ⅴ),monomethylmonothioarsonic acid(MMMTAⅤ) or monothio-MMA~Ⅴ, monomethyldithioarsonic acid(MMDTA~Ⅴ) or dithio-MMA~Ⅴ, monomethyltrithioarsonate(MMTTA~Ⅴ) or trithio-MMA~Ⅴ,dimethylarsinous acid(DMA~Ⅲ), dimethylarsino-glutathione(DMA~Ⅲ(SG)), dimethylarsinic acid(DMA~Ⅴ), dimethylmonothioarsinic acid(DMMTA~Ⅴ) or monothio-DMAⅤ, dimethyldithioarsinic acid(DMDTA~Ⅴ) or dithio-DMA~Ⅴ, trimethylarsine oxide(TMAO~Ⅴ), arsenobetaine(AsB), and an arsenicin-A model compound. We have reviewed and compared the available methods,synthesized the arsenic compounds in our laboratories, and provided characterization information. On the basis of reaction yield, ease of synthesis and purification of product, safety considerations, and our experience, we recommend a method for the synthesis of each of these arsenic compounds.     

絮体改质剂对清水剂处理油田含聚污水效果的影响

分别以胺基质子型离子液体(PIL)、非离子有机胺聚氧乙烯聚氧丙烯醚(NAPPE)、增效氧化剂(AO)、低分子量阴离子聚合物(AP)为絮体改质剂,考察絮体改质剂对大分子聚季铵盐(CWC)清水剂处理海上油田含聚污水的絮凝效果及絮体性质的影响。实验结果表明:PIL和AO对絮凝速率、絮凝起效时间、絮体层厚度无影响,可部分改善絮体黏附性;NAPPE虽可有效改善絮体黏附性,但影响清水剂絮凝效果,絮凝速率;相比较而言,当AP加入量为100 mg/L、CWC加入量为300 mg/L时,AP对清水剂絮凝速率和絮凝起效时间影响小,且水色清澈,可有效避免黏性油泥问题。     

High-recycled-content hydraulic cements of alternative chemistry for concrete production

Sustainable hydraulic cements based on alkali aluminosilicate chemistry were developed with market-limited wastes acting as the primary aluminosilicate precursors. Two sets of formulations were developed with waste brick or impounded coal ash used at relatively large volume as aluminosilicate precursors. Supplementary materials were used to produce raw materials of viable chemistry. Blends of raw materials were transformed into hydraulic cements by input of mechanical energy without resorting to elevated temperatures. The resultant hydraulic cements exhibited viable strength development characteristics. FTIR, SEM, EDS and NMR analyses were conducted in order to gain insight into the structure of the hydraulic cements and their hydration products. The results pointed at the prevalence of calcium aluminosilicate hydrates among the products of hydration which thoroughly bound the non-hydrated cores of cement particles.     

Aluminium: The Need for a Re-Evaluation of Its Toxicity and Solubility in Mature Forest Stands

Aluminium (Al) is a key element in critical loadcalculations for forest. Here, we argue for re-evaluating theimportance of Al. Effects of two levels of enhanced Alconcentrations and lowered Ca:Al ratios in the soil solutionin a field manipulation experiment in a mature spruce stand(1996–1999) on tree vitality parameters were tested. Inaddition, Al solubility controls were tested. Various loads ofAl were added to forest plots by means of an irrigationsystem. Potentially toxic Al concentrations and criticalratios of Ca to inorganic Al were established. The ratio of Cato total Al was not a suitable indicator for unfavourableconditions for plant growth. No significant effects on crowncondition, tree growth and fine root production were observedafter three years of treatment. In 1999, foliar Mg content inthe highest Al addition treatment had declined significantly.This agreed with the known response to Al stress of seedlingsin nutrient solution experiments. No support was found forusing the chemical criterion Ca:Al ratio in soil solution,foliar and root tissue as an indicator for forest damage dueto acidification. Al solubility was considerably lower thanimplied by the assumption of equilibrium with gibbsite,particularly in the root zone. The gibbsite equilibrium iscommonly used in critical load models. Substitution of thegibbsite equilibrium with an Al-organic matter complexationmodel to describe Al solubility in soil water may have largeconsequences for calculation of critical loads. The resultsindicate that critical load maps for forests should bereconsidered.     

多环芳烃光解活性的量子化学研究

应用量子化学从头算HF／6-311 G(d)和B3LYP／6-311 G(d)方法计算了16种PAHs的多种量子化学参数,选取六种参数为分子结构的描述符,采用最小二乘法对16种PAHs的光解半衰期进行逐步多元线性回归分析,得到两个PAHs光解半衰期的QSAR模型,模型具有较高的相关系数,可有效地用于预测PAHs的光解半衰期,结果表明,HF方法所得模型优于B3LYP方法所得的模型,所得模型与基于半经验PM3算法的QSAR模型相比较,HF从头算方法所建立的QSAR模型比半经验PM3算法的结果要好,在所考查的诸多参数中,分子最高占有轨道特征值EHOMO对PAHs光解半衰期起着决定作用,最后,运用所得模型预测了3种PAHs的光解半衰期。     

The chemistry and behaviour of antimony in the soil environment with comparisons to arsenic: A critical review

This article provides a critical review of the environmental chemistry of inorganic antimony (Sb) in soils, comparing and contrasting findings with those of arsenic (As). Characteristics of the Sb soil system are reviewed, with an emphasis on speciation, sorption and phase associations, identifying differences between Sb and As behaviour. Knowledge gaps in environmentally relevant Sb data for soils are identified and discussed in terms of the limitations this imposes on understanding the fate, behaviour and risks associated with Sb in environmental soil systems, with particular reference to mobility and bioavailability.     

3D simulation of hydrogen ignition in a rapid compression machine

Low-temperature (at T < 900–950 K) ignition delays of hydrogen–air mixtures are mainly measured in rapid compression machines (RCM). This communication is aimed at numerical simulation of ignition delays of hydrogen–air mixtures in the RCM by means of a coupled three-dimensional (3D) Unsteady Reynolds-Averaged Navier–Stokes (URANS) – Particle Method (PM) simulation of RCM operation capable of catching turbulence–chemistry interaction. The study indicates that the time history of piston motion in an RCM affects the final state of a test mixture at the end of compression stroke and therefore influences the phenomena relevant to test mixture ignition. More specifically, the calculations show that different laws of piston motion at a fixed average piston velocity (i.e., fixed piston displacement and fixed compression time) and fixed compression ratio result in different evolution of mean pressure, temperature and velocity fields in the RCM test section leading to different ignition behavior. The reasons for the arising differences lie in the fact that the local instantaneous piston velocity determines the roll-up vortex structure, strength and turbulence dissipation in it, heat transfer in test-section walls, and mass leakage through piston rings.     

油田采出水膜法处理技术应用研究进展

油田采出水的处理回用是一种必然的趋势.膜法处理技术可以解决传统水处理中存在的问题,有效地去除采出水中的油类、细菌、硬度,防止油层堵塞、结垢和外排水的环境污染,对于促进油气田可持续发展、水资源再利用和环境保护具有非常重要的意义.微滤、超滤和纳滤、反渗透膜技术在油田采出水处理中已有较多的应用研究.超滤在除油和除浊方面表现出...     

超薄型钢结构防火涂料的热解动力学研究

利用岛津DTG-60H型热重分析仪,在氮气气氛、升温速率为15 ℃/min条件下,对自行配制的一种超薄型钢结构防火涂料的热分解过程进行了分析,发现该防火涂料的热解过程可分为5个阶段.用Coats-Redfern积分方法分阶段对TG曲线数据进行了处理,并用常见的12种反应机理方程进行拟合,发现各阶段反应机理不尽相同: 第一阶段属于一维扩散反应机理D1,第二、第三阶段为1.5级化学反应模型RO(1.5),第四阶段为二级化学反应模型RO(2),第五阶段为一级化学反应模型RO(1).同时,求解出了各阶段的热解动力学参数及动力学方程.     

蜂蜜中氯霉素残留的检测及净化方法研究

建立了反相高效液相色谱-离子阱质谱法检测蜂蜜中氯霉素残留的方法.前处理采用改良的QuEChERS方法进行快速提取和净化.采用初级次级胺进行固相分散净化,可有效吸附蜂蜜中的糖类及有机色素等杂质.提取物在流动相甲醇:水(0.2%乙酸胺)=45:55(体积比)中,用整体色谱柱进行快速分离和质谱检测.并对MS检测中2种离子化方式(电喷雾ESI及大气压化学APCI)、各种离子化方式下正负离子模式及离子检测方法(总离子检测TIC和选择性离子监测MRM)进行了综合比较,最终确定采用电喷雾电离法(ESI)负离子模式、多反应离子监测(MRM)对氯霉素进行定性定量分析.在0.2～200μg/kgg添加浓度下,添加回收率水平在78%～93%间,变异系数在3.9%以下.该方法的检出限为0.1μg/kg,在0.1～100 μg/L浓度范围内,线性方程为y=58.753x 34867,相关系数R2=0.999 5.