河套地区盐碱化和砷氟中毒问题探讨

内蒙古河套地区多目标地球化学调查表明，河套地区总体上为无公害、绿色土地。作为我国北方重要的粮食生产基地可以为全国生产出优质的绿色产品；但河套地区也具有比较严重的生态地球化学问题，首先是土壤的盐渍化制约了河套地区农业的发展，其次是全区以砷氟中毒为主的地方病比较严重，极大地影响了该区人民的身体健康。此外，包钢尾矿坝作为一个局部性的生态问题，对包头市民产生重大的影响，对其周围的居民身体健康造成严重危害。     

湄公河下游地下水域中的砷

通过对亚洲东南部多数冲积含水层的水进行调查，更进一步加强了人们对砷的认识，其调查结果使人们增加了对湄公河流域下游地下水水域中砷的关注。本文作者对此进行了新的研究并且回顾了许多以前小规模研究，提供了柬埔寨和越南Cuu Long三角洲含水层中砷的综合概况。天然砷一般起源于湄公河流域的下游，而不是起源于某一有地质特征的地区，而且发现浓度介于8ppm和16ppm（干重）之间的砷广泛分布于土壤中。与天然冲积层的砷相比，工业和农业用的砷是有限的。含水层地下水的砷浓度不低于10μgL^-1，但是，在离散的反常区域，砷的浓度在10-30μgL^-1也是常见的，有时也可能有暂时的砷异常，砷浓度可达到600μgL^-1，。最严重的是，洪积平原中的铁和富含有机质的沉积物容易受到洪水水位大的波动的影响，在氧化条件下．产生不稳定的毒砂。而一般情况下，地下水中高浓度的砷，由于受到吸附和解吸的袭夺作用，在还原和带轻微碱性的条件下，砷适宜释放。在水位埋深浅的含水层和100—200米较深的含水层中，地下水的砷浓度高。砷蔓延的过程没有明显的迹象，但是砷对健康有严重的局部危害，而且通过间接方式（诸如通过污染的稻米和水产品）摄取低浓度砷也存在着一定的风险。土壤中含砷几乎是普遍存在的，加之将来地下水抽取量的快速增加的可能性，这就要求在整个区域开发水资源时要持续保持警惕性。     

砷的原位去除——Danida公众健康工程部试点项目回顾

通过试验来确定两种公认的铁去除技术去除砷的效率。一种方法是以原位沉淀为原理，另一种方法是传统的铁去除技术。初步分析结果显示，当地下水中砷的浓度小于0.1mg/L时，通过利用这两种技术能够把地下水中砷的浓度降至符合孟加拉国的饮用水标准，然而，当地下水中砷的初始浓度较高时，通过使用这两种技术仅能把砷浓度减少50%。在大多数砷污染地区，在所有受砷污染的管井中，有50%的管井井水中砷的浓度低于0.1mg/L。利用这两种技术能够有效地缓解孟加拉国的砷污染问题。这两种砷去除技术有可能被公众完全接受，然而，仍需要对这两种砷去除技术进行进一步改进，以便更有效地处理初始砷浓度较高的地下水。     

土壤环境中砷元素的生态效应

论述了各环境介质中砷元素的分布特点,指出土壤第Ⅱ环境中的砷主要来源于人为活动。砷主要富集于土壤表层,且主要以稳定矿物形式存在;但当土壤砷总量高时其可溶性砷量亦相应高,砷在土壤中易形成Fe、Al、Ca型砷化物而被固定;当土壤pH值增高至中性或碱性时,砷易转化为迁移能力更强、毒性更大的三价砷。砷对作物、人体生态系统危害作用明显,砷通过蔬菜对人体的危害甚于谷物,应采取有效措施防治土壤中砷污染。     

黔西南高砷煤的元素地球化学特征

通过分析黔西南高砷煤的元素地球化学特征,探索高砷煤中微量元素、稀土元素的地球化学行为,从而揭示了高砷煤的形成机理。分析表明,高砷煤与非高砷煤在微量元素含量方面存在较大差异,金、汞、铊矿石与龙潭煤系中的砷具有同源性,龙潭煤系页岩与峨眉山玄武岩在稀土元素组成上具有继承性。     

Association between multi-level inorganic arsenic exposure from drinking water and skin lesions in Inner Mongolia, China

Arsenic is one of the most important single-substance toxicants in the environment. In Inner Mongolia of China, 300000 residents are believed to drink water containing 〉50 μg/L. Skin lesions have been known as the most common consequences resulting from chronic exposure to arsenic. To clarify the prevalence of arsenic-induced skin lesions, it is important to assess the impact of this problem on the target population, and to make future planning. We evaluated the association between multi-level inorganic arsenic exposure from drinking water and skin lesions in an arsenic-affected area in Inner Mongolia, China. 109 and 32 subjects fi＇om high-level arsenic-affected （〉5 μg/L） village and low-level （≤50 μg/L） village were recruited and had detailed physical examination with special emphasis on arsenic-related skin lesions. Arsenic exposure was measured for each participant with As concentration of primary well and the duration of using the well was recorded. Arsenic-induced skin lesions including keratosis, pigmentation, and/or leucomelanosis were diagnosed in 56 and 3 subjects in the two villages, respectively. Logistic regression was conducted to calculate prevalence-odd ratios of skin lesions by levels of arsenic exposure with adjustment of sex, age group, smoking and duration of exposure. A consistent dose-response relationship between arsenic exposure level and skin lesion risk was observed.     

XANES analysis of the mechanisms of arsenic removal in biological iron and manganese treatment unit

Biological iron and manganese removal utilizing indigenous iron and manganese oxidizing bacteria （IRB hereafter） in groundwater can also be applied to arsenic removal according to our pilot-scale test. The arsenic removal probably occurred through sorption and complexation of arsenic to iron and manganese oxides formed by enzymic action of IRB. We investigated the chemical properties of iron and manganese oxides in IRB floc and the valence state of arsenic sorbed to the floc to clarify the mechanisms of the arsenic [especially As （Ⅲ）] removal. The floc samples were collected from two drinking water plants using IRB （Jyoyo and Yamatokoriyama, Japan）, and our pilot - scale test site where arsenic and iron removal using IRB is under way （Mukoh, Japan）. The Jyoyo and Yamatokoriyama IRB floc samples were subjected to As （Ⅲ） and As（Ⅴ） sorption experiments. The elemental composition of the floc samples was measured. XANES spectra were collected on As, Fe and Mn K-edges at synchrotron radiation facility Spring 8 （Hyogo, Japan）. FT-IR and the X-ray diffraction spectra of the samples were also obtained. The IRB floc contained ca. 35 % Fe, 0.3%-3.5% Mn and 2%-6% P. The samples were highly amorphous and contained ferrihidrites and hydrated iron phosphate. According to XANES analyses of IRB, As associated with IRB was in ＋5 valence state when As （Ⅲ） （or As （Ⅴ）） was added in laboratory sorption test, Fe in ＋3 valence state, and Mn a mixture of＋3 and ＋4 valence states. Small shift was observed in the XANES spectra of IRB on As K-edge as the equilibration time of the sorption experiment was increased. Gradual oxidation of a small amount of As （Ⅲ） associated with IRB or change in arsenic binding with sorption site were the probable mechanism.     

Possibility of degradation of phenylarsonic acid in the presence of ferrihydrite

Although inorganic species are predominant in natural systems, but there are many kinds of organoarsenic species such as methylated and phenylated arsenic compounds. Phenylarsonic acid （PA） is a degradation product of organoarsenics used for chemical warfare agents, which has been detected in well water at the disposal site of the agents in Japan. There are few reports studying behavior of PA in soil. In this study, PA was adsorbed onto ferrihydrite and its chemical forms were determined using high performance liquid chromatography connected to inductivity-coupled plasma mass spectrometry （HPLC-ICP-MS）. 100 mg/kg of PA was mixed with 0.03 g of 2-line ferrihydrite. For each suspension, pH was adjusted by HNO3 or NaOH. Each sample was incubated for more than 19 hours and the final pH was measured. After filtration, the chemical form of arsenic in the filtrate was measured using HPLC-ICP-MS. In addition, ferrihydrite separated by filtration was dissolved by 3 ml of 0.5 M HCI and the arsenic species in the solution was detected by HPLC-ICP-MS （column： Tosoh TSKgel SuperlC-AP, eluent： 0.01 M HNO3）. It was verified that PA is not degraded by heating in 0.5 M HCl solution. At pH 3.1, any arsenic compounds were not detected from the solution, because almost all arsenic species were adsorbed onto ferrihydrite at lower pH. At pH= 12, however, 7%-10% of inorganic arsenic was detected in the solution. In solid phase, there are some problems to determine the precise ratio of inorganic and organic species. When the solution includes Fe ion at 0.01 M level, the retention time of arsenic species drifted compared to those in standard solution, which makes it difficult to determine precisely the arsenic species adsorbed on ferrihydrite. Therefore, more study is needed to determine the ratio of inorganic and organic species in the system.     

Geochemistry of porewater and sulfate-reducing bacteria in sediment cores from the Chianan Plain, Taiwan

High concentrations of arsenic and humic substances in groundwater from the southwestern coastal plain of Taiwan were well known for their probable relationships with black-foot disease. In order to realize the relationships between the concentrations of humic substances and arsenic in this area, 24 well water samples were analyzed. After filtered through 0.45 μm glass fiber membrane in the field, samples were kept in the dark at 4℃ and then separated into six fractions with varying range of molecular weight （〈0.5, 0.5-1, 1-5, 5-10, 10-50 and 〉50 k Da） by ultrafiltration apparatus （Molecular/Por Stirred Cell system） in the lab. Concentrations of humic substances were measured by fluorescence spectrometer （HITACHI F-2000, ex=370, em=445） and arsenic by FIAS-AA （Perkin Elmer AAnalyst 100, FIAS-400）. On average, only 6.2% of the total arsenic in water existed in the fraction of 〉0.5 k Da. and the others were complexed with humic substances （including humic acid and fulvic acid）. The results demonstrated a distinct positive correlation between the concentrations of humic substances and arsenic.     

新型氢化物发生技术--可移动还原床氢化物发生器Ⅰ.可移动还原床氢化物发生器的结构及特征

发展了一种新型的氢化物发生技术--可移动还原床氢化物发生器,可以实现微升级样品的分析而不需要对样品进行酸化和使用气-液分离器.给出了装置的结构、操作,试验并优化了固体还原剂与有机酸的质量配比、反应腔体体积、进样量等反应条件.该技术易于实现自动化,可作为液相色谱、毛细管电泳和其他色谱分离技术与光谱检测技术之间的接口.