Thiolated arsenicals in arsenic metabolism: Occurrence, formation, and biological implications

Arsenic (As) is a notoriously toxic pollutant of health concern worldwide with potential risk of cancer induction, but meanwhile it is used as medicines for the treatment of different conditions including hematological cancers. Arsenic can undergo extensive metabolism in biological systems, and both toxicological and therapeutic effects of arsenic compounds are closely related to their metabolism. Recent studies have identified methylated thioarsenicals as a new class of arsenic metabolites in biological systems after exposure of inorganic and organic arsenicals, including arsenite, dimethylarsinic acid (DMAV), dimethylarsinous glutathione (DMAIIIGS), and arsenosugars. The increasing detection of thiolated arsenicals, including monomethylmonothioarsonic acid (MMMTAV), dimethylmonothioarsinic acid (DMMTAV) and its glutathione conjugate (DMMTAVGS), and dimethyldithioarsinic acid (DMDTAV) suggests that thioarsenicals may be important metabolites and play important roles in arsenic toxicity and therapeutic effects. Here we summarized the reported occurrence of thioarsenicals in biological systems, the possible formation pathways of thioarsenicals, and their toxicity, and discussed the biological implications of thioarsenicals on arsenic metabolism, toxicity, and therapeutic effects.     

吉非罗齐在热活化过硫酸盐体系中的降解机制研究

以降血脂药物吉非罗齐(GEM)为目标污染物,研究其在热活化过硫酸盐体系中的降解机制.结果表明,GEM的降解过程符合准一级反应动力学规律,增加过硫酸盐初始浓度或升高反应溶液温度都可以显著提高GEM的降解速率常数(kobs),其反应的表观活化能Ea为133.14k J·mol~(-1).酸性和中性条件下GEM的降解效果要好于碱性条件.自然水体中的腐植酸(HA)和HCO_3~-对GEM的降解有明显的抑制作用.自由基清除实验表明,在酸性和中性条件下,SO_4~(·-)对GEM的降解起主导作用,而在碱性条件下,HO·成为体系主要的氧化物种.利用HPLC-MS/MS技术共检测到11种中间产物,推测GEM的降解路径涉及苯环的羟基化和醛基化反应、苯环侧链的环化作用和脱羧反应以及醚支链的断裂.     

双酚AF诱导乳腺癌细胞增殖的分子机制

从细胞水平上研究不同浓度双酚AF （BPAF）对MCF-7人乳腺癌细胞系的细胞增殖能力、细胞凋亡、细胞周期等终点的影响;以新型雌激素膜受体GPER1介导的PI3K/Akt和ERK1/2信号通路为靶点,研究低浓度BPAF对该信号通路相关基因表达的影响,以及其在诱导乳腺癌细胞增殖中的作用,评估其增殖效应机制.结果表明,低浓度BPAF （0.001~1μmol/L）能够诱导MCF-7细胞的增殖,使S期细胞比例升高,并且激活雌激素信号通路相关基因mRNA的表达;在较高浓度时（>10μmol/L）能抑制细胞活力,诱导细胞凋亡.通过特异性靶点抑制剂发现GPER1在mRNA层面上激活了PI3K/Akt和ERK1/2信号通路,并且该信号通路的激活可能是BPAF引起MCF-7细胞增殖的关键机制,并且ERα也在其中起到了重要的作用.     

Microbial degradation of the benzonitrile herbicides dichlobenil, bromoxynil and ioxynil in soil and subsurface environments--insights into degradation pathways, persistent metabolites and involved degrader organisms

The benzonitriles dichlobenil, bromoxynil and ioxynil are important broad-spectrum or selective herbicides used in agriculture, orchards and public areas worldwide. The dichlobenil metabolite 2,6-dichlorobenzamide is the most frequently encountered groundwater contaminant in Denmark, which suggests that the environmental fate of these three structurally related benzonitrile herbicides should be addressed in detail. This review summarises the current knowledge on microbial degradation of dichlobenil, bromoxynil and ioxynil with particular focus on common features of degradation rates and pathways, accumulation of persistent metabolites and diversity of the involved degrader organisms.     

Environmental risk assessment of metals contaminated soils at silvermines abandoned mine site,Co Tipperary,Ireland

A centuries long history of mining and mineral processing has resulted in elevated Cd, Pb and Zn soil concentrations in the vicinity of the Silvermines abandoned mine site (AMS), Co. Tipperary, Ireland. A process for preliminary evaluation of environmental risk was developed and implemented. Potential pathways of metal compound transport and deposition were mapped and used to optimise the subsequent site investigation. Elevated soil metals are shown to be predominantly in areas where metal deposition in soil is associated with water related pathways (surface runoff, seasonal groundwater seepage and floodplains). Extensive areas of soil in the surrounding district are classified as contaminated on the basis of Cd, Pb and Zn concentrations, both total and potential bioavailable (EDTA-extractable). The most affected areas, with metal concentrations in soil comparable with that within the AMS, were floodplains located 2–3 km downstream from the site. Assessment of the sequential effects on grass and grazing animals indicates that Pb poses the greatest risk due to its high toxicity and high concentrations in soil (more than 10 000 mg kg^–1). Within floodplain areas grazing cattle may intake a lethal dose of Pb. On the basis of the investigation an approach to risk assessment was developed which allowed quantified assessment of the risks related to individual metals, areas of contamination and contamination targets.     

常州市冬季大气污染特征及潜在源区分析

为了解常州市冬季大气污染特征,对2013—2015年常州市冬季PM_2.5、PM₁₀、SO₂、NO₂、CO数据进行分析,并结合HYSPLIT 4.9模式研究不同气团来源对常州市各污染物浓度的影响及潜在污染源区分布特征.结果表明,常州市冬季以PM_2.5污染为主,其占冬季首要污染物的90%以上,冬季PM_2.5小时浓度对应的空气质量级别以良和轻度污染出现频次最多,冬季的ρ（PM_2.5）对ρ（PM_2.5）年均值的贡献率高达37.4%,不完全燃烧是颗粒物的一个重要来源.冬季ρ（PM_2.5）、ρ（PM₁₀）、ρ（SO₂）、ρ（NO₂）和ρ（CO）的日变化均呈双峰分布,两个峰值分别出现在交通的早高峰和晚高峰附近.ρ（NO₂）在晚高峰明显大于早高峰,而ρ（SO₂）和ρ（CO）表现为早高峰大于晚高峰.常州市CO/NO_x和SO₂/NO_x的分析结果表明,常州市交通源的贡献明显,点源对常州市的空气质量的影响也较大.1和6 h的ρ（PM_2.5）梯度变化可判识细颗粒物的爆发性增长.冬季常州市受到西北、西和西南等地区的大陆性气流影响较大,其对应的ρ（PM_2.5）、ρ（PM₁₀）、ρ（SO₂）、ρ（NO₂）和ρ（CO）平均值相对较高,且对应的污染轨迹出现概率较大.偏东方向的气流由于移动速度慢,不利于污染物扩散易造成污染累积,导致ρ（PM_2.5）、ρ（SO₂）和ρ（NO₂）相对较高.WPSCF（源区分布概率）高值区（>0.5）集中于从芜湖至上海的长江中下游区域和杭州湾区域.PM_2.5、PM₁₀、SO₂、NO₂和CO潜在源区存在较大差异性,NO₂、SO₂和CO本地化的潜在贡献较PM_2.5和PM₁₀更明显.此外,受船舶等影响海洋源区对NO₂、SO₂和CO的潜在贡献较大.研究显示,长三角区域的大气污染物以本地污染为主,但远距离污染输送贡献也不容忽视.      

Adaptation pathways in planning for uncertain climate change: Applications in Portugal,the Czech Republic and the Netherlands

Adaptation pathways are developed to design adaptive policies to handle climate change uncertainty. Use of this tool varies across planning practices and adaptation challenges and adjusting the tool to particular practices can foster its adequate use. To gain insight into the use of adaptation pathways, we compared four initiatives (one each in Portugal and the Czech Republic and two in the Netherlands) with regard to design choices made. We found six design choices which need to be considered when adjusting adaptation pathways. Design choices about the geographic scale, inclusion of sectors, the generation and delineation of adaptation options, specification of possible pathways, the related performance metrics and the type of assessment are interdependent, but they are also influenced by contextual aspects. Analysis of the institutional diversity, planning culture and framing shows that the use of adaptation pathways is flexible enough to be adjusted for diverging planning practices. However, the tool is best suited to deliver local adaptation solutions, and adequate use depends on consensus about the adaptation problem, setting objective thresholds and determining uncertainty about future change. We conclude that understanding the customised use of tools for local planning practices is essential for adaptive policy design.     

Towards phosphorus sustainability in North America: A model for transformational change

Global food production and security rely heavily on finite reserves of newly mined phosphate for fertilizers. However, systemic inefficiencies result in the deposition in aquatic ecosystems of much of the phosphorus mined for food production causing costly eutrophication problems that damage aquatic ecosystems and human health. The Sustainable Phosphorus Alliance (SPA, formerly named North American Partnership for Phosphorus Sustainability) was created to implement sustainable phosphorus solutions through active engagement of stakeholders in both the private and public sectors. This paper describes a conceptual model of transformative change to a sustainable phosphorus system for the North American region. The model emerged from discussions at a series of formal and informal meetings held in conjunction with a ‘Future of Phosphorus’ event (National Science Foundation’s Phosphorus Sustainability Research Coordination Network) and an inaugural SPA Board meeting. Model development drew on the multi-level perspective of socio-technical transitions to develop a series of pathways to a transformed phosphorus system. The uses of the model and transition pathways are discussed in terms of their potential to form an important first step towards the development of a regional vision for improved phosphorus sustainability. The process provides an example of how research in sustainability science can contribute to action on environmental improvement.     

Soils Characteristics of The Bassendean and Spearwood Sands of the Gnangara Mound (Western Australia) and their Controls On Recharge, Water Level Patterns and Solutes of The Superficial Aquifer

The flow pathways of water in the soils of the Gnangara Mound are highly irregular and depend upon the moisture content, the repellency and preferential wettability potential of the soils. The occurrence of preferential flow is more evident in dry soils. As the soil wets during the rainy season, the water repellence and differential wettability decreases, the fingering and the preferential flow paths disappear. Most of the agricultural sites in the Spearwood Sands which showed more irregular flow than the Bassendean Sands are under continuous irrigation during cultivation season. As the repellency problems are chemically treated, it is therefore expected that the flow will be more uniform all the year round. Landuse is mainly responsible for variation in recharge rates; however, the hydraulic properties control aquifer response and water level pattern to a greater degree. Water levels in the mid 1970s were in a semi steady state. Since that time, a combination of increasing water use by pine plantations, heavy pumping from private boreholes in market gardens and private homes and intensive pumping from the Gnangara Mound for the metropolitan water supply have caused water levels to continually decline in the Superficial aquifer. Nitrate and phosphate concentrations in the regional Superficial aquifer are generally very low. None of the tested pesticides (atrazine, diazinon, dimethoate, endosulfan, fenamiphos, iprodione, malathion and chlorpyrifos) were detected in the groundwater samples collected from the monitoring bores.     

山地农业种植结构演变特征及其调控途径分析——以贵州省为例

为分析山地农业种植结构的演变特征及其主要驱动因子,制定种植结构的调控途径,采用C-PCA耦合模型(典型主成分分析)对贵州省1949~2013年种植结构演变的15个驱动因子进行分析。结果表明:(1)贵州省1949~2013年种植结构逐渐向市场导向型转变,经济作物比重上升,粮食作物比重下降,粮食作物和经济作物产量分别以7.24%和2.95%的速率增长;(2)通过C-PCA耦合模型的贡献率得出种植结构演变的主要驱动因子为总人口、城市化水平、仓储运输业比重、年均气温、年降水量和农业人口比重,其对应累计贡献率达86.04%;(3)调控山地农业种植结构,不仅需要发展山地高效复合型农业,提高种植系统抗灾能力,还需借助农产品生产、加工、销售云平台实现农业的可持续发展,从而为山地农业经济的发展提供重要支撑。