HPLC—ICP—MS法测定农业废水中有机砷与无机砷的方法研究

建立了应用高效液相色谱（HPLC）和电感耦合等离子质谱（ICP—Ms）联用技术测定农业水环境样品中三价砷（Aslll）、一甲基砷（MMA）、二甲基砷（DMA）、五价砷（AsV）4种砷形态的分析方法。试验表明,4种砷形态的线性范围宽（1-300μg·L-1）,相关系数（r）均大于0．9990,方法检出限低（0．7～0．98μg·L-1）,精密度好,重复测定7次结果的RSD均小于5％。通过计算加标回收率验证方法的准确性,加标回收率为94％～112％。实际样品的测定结果显示,农田废水中砷的主要存在形态为As（V）,其次为As（Ⅲ）。     

煤中砷及燃煤固砷技术研究

对煤中砷的含量、分布、赋存状态等地球化学特征进行了综述,分析了煤炭燃烧过程中砷的迁移转化行为与释放特性,指出煤中砷的燃烧释放不仅与砷的物理化学性质有关,更取决于煤中的浓度、赋存状态及燃烧工况等因素。进一步讨论了天然钙基材料燃煤固砷技术及燃煤砷污染控制的研究现状。     

饮用水中砷去除技术综述

自从1996年孟加拉国和印度报道慢性砷中毒事件以来，饮用水砷污染和砷中毒问题就受到全世界的关注。如何解决这一难题，研究人员进行了大量研究。本文综述了饮用水中砷的去除方法，包括混凝／沉淀、吸附、离子交换技术等，对各种除砷技术进行了总结和比较。     

攀西蔬菜基地蔬菜砷、汞污染安全性评价

系统研究了攀西地区主要蔬菜基地的瓜类、茄果类、根菜类、叶菜类、豆类等五类蔬菜中砷、汞污染及其累积情况。结果表明，这五类蔬菜砷、汞含量都未超过相应产品限量标准，超标率为0％，污染程度都为安全，污染水平为清洁。各蔬菜对As的吸附能力为叶菜类〉根菜类〉豆类〉瓜类=茄果类；各蔬菜对Hg的吸附能力为叶莱类〉瓜类〉茄果类〉根菜类〉豆类。以叶菜类对As，Hg的富积能力最强，综合污染指数明显高于其他蔬菜。     

原子荧光法测废水中砷的主要影响因素探讨

原子荧光法因其分析灵敏度高、基体干扰少、线性范围宽、操作简便快速,是目前测砷最好的方法之一。但原子荧光法在测定砷过程中存在很多因素影响测定结果的准确度。文章通过实验从载流、还原剂、加入硫脲-抗坏血酸混合液的量和稳定时间及仪器预热时间几方面对影响原子荧光法测定废水中砷的主要因素进行探讨,从而确定最佳工作条件。并通过对相对标准偏差和检出限及标准样品的测定,证明了采用此方法能保证测量结果的准确可靠。     

黄河上游水体中砷的来源及迁移初探

在对黄河上游水体及沿岸表层土壤、底泥中的砷进行监测分析的基础上,对水体中砷的来源、迁移过程进行了初步探索。结果表明:黄河上游沿岸土壤中砷的含量偏高,水体中的砷来源于沿岸的土壤。     

检测实验室方法确认技术应用

基于实验室认可和资质认定评审准则对新开项目（或新建分析方法）必须要进行方法确认的要求,通过对标准土壤样品、能力验证样品、土壤及废弃泥浆样品分析对比,验证了原子荧光光谱法测定土壤中总砷方法的检出限、准确度、精密度、加标回收率等技术指标的符合性。     

中药川附子痕量砷的测定

本文报道了以ＨＮＯ３ － ＨＣｌＯ４ 混酸消化、Ｈ２ＳＯ４ － ＫＩ－ Ｔｅ（ Ⅳ） 体系极谱法测定中药川附子中的砷。该方法使样品消化过程的砷损失大为减少并简化了分析过程。样品中砷含量在０－２ ～０－６μｇ·ｇ－ １ ,回收率８４ ％ ～１０８ ％ 。     

不同操作条件对纳滤膜去除水中五价砷的研究

采用纳滤膜（NF90）过滤自配含砷水,研究在不同操作条件下纳滤膜对水中砷去除效果的影响。本实验探讨膜进水浓度、水的pH值、膜进水温度、操作压力、水中天然有机物浓度等对膜除砷效率的影响。结果表明：纳滤膜对水中五价砷（As（Ⅴ））的去除率很高,最高去除率能达到99%,在实验的前2.5个小时内,砷的去除率均在90%以上。但是,纳滤膜除砷效率随着时间变化,去除率会降低。不同的操作条件对纳滤膜除砷的影响很大,研究不同条件的影响对应用很有意义。     

Effects of arsenic concentrations and forms on arsenic uptake by the hyperaccumulator ladder brake

Ladder brake (Pteris vittata L.) is a newly discovered arsenic hyperaccumulator. No information is available about arsenic effects on ladder brake. This study determined the effects of different arsenic concentrations (50 to 1000 mg kg(-1)) or forms (organic vs. inorganic and arsenite vs. arsenate) applied to soils on growth and arsenic uptake by ladder brake. Young plants were grown in a greenhouse for 12 or 18 wk. Ladder brake was highly tolerant of arsenic and survived in soil containing up to 500 mg As kg(-1). The fact that addition of arsenate up to 100 mg As kg(-1) increased fern biomass by 64 to 107%, coupled with higher arsenic concentration in younger fronds at low soil arsenic concentrations and older fronds at high soil arsenic concentrations, implies that arsenic may be beneficial for fern growth. Addition of 50 mg As kg(-1) was best for fern growth and arsenic accumulation, resulting in the highest fern biomass (3.9 g plant(-1)), bioconcentration factor (up to 63), and translocation factor (up to 25). With an exception of FeAsO4 and AlAsO4, which had the lowest effects due to their low solubility, little difference was observed among other arsenic forms mainly because of arsenic conversion in soil. Aboveground biomass was mostly responsible for accumulation of arsenic by plant (75-99%). Up to 26% of the added arsenic was removed by ladder brake, showing the high efficiency of ladder brake in arsenic removal. The results suggest that ladder brake may be a good candidate to remediate arsenic-contaminated soils.     

Iron and aluminium based adsorption strategies for removing arsenic from water

Arsenic is a commonly occurring toxic metal in natural systems and is the root cause of many diseases and disorders. Occurrence of arsenic contaminated water is reported from several countries all over the world. A great deal of research over recent decades has been motivated by the requirement to lower the concentration of arsenic in drinking water and the need to develop low cost techniques which can be widely applied for arsenic removal from contaminated water. This review briefly presents iron and aluminium based adsorbents for arsenic removal. Studies carried out on oxidation of arsenic(III) to arsenic(V) employing various oxidising agents to facilitate arsenic removal are briefly mentioned. Effects of competing ions, As:Fe ratios, arsenic(V) vs. arsenic(III) removal using ferrihydrite as the adsorbent have been discussed. Recent efforts made for investigating arsenic adsorption on iron hydroxides/oxyhydroxides/oxides such as granular ferric hydroxide, goethite, akaganeite, magnetite and haematite have been reviewed. The adsorption behaviours of activated alumina, gibbsite, bauxite, activated bauxite, layered double hydroxides are discussed. Point-of-use adsorptive remediation methods indicate that Sono Arsenic filter and Kanchan™ Arsenic filter are in operation at various locations of Bangladesh and Nepal. The relative merits and demerits of such filters have been discussed. Evaluation of kits used for at-site arsenic estimation by various researchers also forms a part of this review.     

Arsenic and chromium removal by mixed magnetite–maghemite nanoparticles and the effect of phosphate on removal

Adsorption of arsenic and chromium by mixed magnetite and maghemite nanoparticles from aqueous solution is a promising technology. In the present batch experimental study, a commercially grade nano-size ‘magnetite’, later identified in laboratory characterization to be mixed magnetite–maghemite nanoparticles, was used in the uptake of arsenic and chromium from different water samples. The intent was to identify or develop a practical method for future groundwater remediation. The results of the study showed 96–99% arsenic and chromium uptake under controlled pH conditions. The maximum arsenic adsorption occurred at pH 2 with values of 3.69 mg/g for arsenic(III) and 3.71 mg/g for arsenic(V) when the initial concentration was kept at 1.5 mg/L for both arsenic species, while chromium(VI) concentration was 2.4 mg/g at pH 2 with an initial chromium(VI) concentration of 1 mg/L. Thus magnetite–maghemite nanoparticles can readily adsorb arsenic and chromium in an acidic pH range. Redox potential and pH data helped to infer possible dominating species and oxidation states of arsenic and chromium in solution. The results also showed the limitation of arsenic and chromium uptake by the nano-size magnetite–maghemite mixture in the presence of a competing anion such as phosphate. At a fixed adsorbent concentration of 0.4 g/L, arsenic and chromium uptake decreased with increasing phosphate concentration. Nano-size magnetite–maghemite mixed particles adsorbed less than 50% arsenic from synthetic water containing more than 3 mg/L phosphate and 1.2 mg/L of initial arsenic concentration, and less than 50% chromium from synthetic water containing more than 5 mg/L phosphate and 1.0 mg/L of chromium(VI). In natural groundwater containing more than 5 mg/L phosphate and 1.13 mg/L of arsenic, less than 60% arsenic uptake was achieved. In this case, it is anticipated that an optimum design with magnetite–maghemite nanoparticles may achieve high arsenic uptake in field applications.     

土壤As动态影响下枸杞质量评价及环境风险预测

选择柴达木盆地诺木洪农场3种类型农田进行20 cm表层土壤砷（As）含量检测。第1种为新开垦原生地,第2种为20年耕种地,第3种为50年耕种地,检测As含量分别为16.29、14.90、14.04 mg·kg^-1。3种土壤As含量均达到无公害食品标准（25 mg· kg^-1）和绿色食品标准（20 mg·kg^-1）。多年耕种并没有造成农田表层土壤As积累。农田灌溉用河水中未检出As。生产中使用的22种农药、肥料均检测到As,其中15种杀虫剂、杀真菌剂、除草剂、植物激素等,每年输入土壤As 4513.59 mg·hm^-2;7种肥料每年输入土壤As 258015.24 mg·hm^-2。施肥是土壤中As输入的重要来源,最主要的输入源是磷酸二铵,占到50％;其次为复合肥、鸡粪和有机肥。每年随作物输出As总量为4380 mg·hm^-2。模拟田间灌溉,进行土壤柱淋漓试验,农田20 cm表层土壤每年随灌溉淋漓输出As为245230.65 mg·hm^-2,这与随着肥料、农药输入量几乎相等。表层土壤As处在一个输入、输出相对稳定的动态平衡状态。从土壤中输出的As,随灌溉水输入到水系统中,继而造成水系统As的积累,最终将影响到地区农业的可持续发展。     

Concentrations of additive arsenic in Beijing pig feeds and the residues in pig manure

The swine industry in China has grown rapidly over last two decades. Great amount of pig manure is generated in China, which can be used as organic fertilizers on agricultural lands. Meanwhile, the organic arsenic compounds have been used as feed additives for swine disease control and weight improvement. Once the excessive additives are released in the environment, arsenic may compromise food safety and environmental quality. There is a growing public concern about the arsenic residues accumulation in pig manure, however, little work has been done to investigate the exact arsenic content in pig feed and the residues in manure in China This study investigates the concentrations of arsenic in 29 pig feed samples and 29 manure samples collected from eight pig farms in the Chaoyang district, Beijing city. The detected rate of arsenic in 29 couples of samples was 100%. The concentrations of arsenic in pig feeds and manures ranged from 0.15 to 37.8 mg/kg and 0.42 to 119.0 mg/kg, respectively. The result showed that arsenic concentration in pig manure will be greatly elevated when the arsenic in pig feed was largely increased. The loading rates of pig manure in fourteen Beijing counties and districts were in the range of 2.7–57.2 t/ha yr. Accordingly, the potential soil arsenic increase rates resulting from land application of pig manure might range between 11.8 and 78.9 μg/kg yr. Despite these findings, it is too early to draw the conclusion that arsenic pollution from pig manure is serious in Beijing farmland; therefore, longitudinal studies about the chemical form transformation and the environmental behaviors of pig manure arsenic are required in order to come up with more definitive conclusions.     

Chemical extraction methods to assess bioavailable arsenic in soil and solid media

Soil ingestion by children is an important pathway in assessing public health risks associated with exposure to arsenic-contaminated soils. Soil chemical methods are available to extract various pools of soil arsenic, but their ability to measure bioavailable arsenic from soil ingestion is unknown. Arsenic extracted by five commonly used soil extractants was compared with bioavailable arsenic measured in vivo by immature swine (Sus scrofa) dosing trials. Fifteen contaminated soils that contained 233 to 17 500 mg kg(-1) arsenic were studied. Soil extractants were selected to dissolve surficially adsorbed and/or readily soluble arsenic (water, 1 M sodium acetate, 0.1 M Na2HPO4/0.1 M NaH2PO4) and arsenic in Fe and Mn oxide minerals (hydroxylamine hydrochloride, ammonium oxalate). The mean percent of total arsenic extracted was: ammonium oxalate (53.6%) > or = hydroxylamine hydrochloride (51.7%) > phosphate (10.5%), acetate (7.16%) > water (0.15%). The strongest relationship between arsenic determined by soil chemical extraction and in vivo bioavailable arsenic was found for hydroxylamine hydrochloride extractant (r = 0.88, significant at the 0.01 probability level). Comparison of the amount of arsenic extracted by soil methods with bioavailable arsenic showed the following trend: ammonium oxalate, hydroxylamine hydrochloride > in vivo > phosphate, acetate > water. The amount of arsenic dissolved in the stomach (potentially bioavailable) is between surficially adsorbed (extracted by phosphate or acetate) and surficially adsorbed + nonsurficial forms in Fe and Mn oxides (extracted by hydroxylamine hydrochloride or ammonium oxalate). Soil extraction methods that dissolve some of the amorphous Fe, such as hydroxylamine hydrochloride, can be designed to provide closer estimates of bioavailable arsenic.     

Arsenic accumulation in the hyperaccumulator Chinese brake and its utilization potential for phytoremediation

The unique property of arsenic hyperaccumulation by the newly discovered Chinese brake (Pteris vittata L.) fern is of great significance in the phytoremediation of arsenic-contaminated soils. The objectives of this study were to (i) examine arsenic accumulation characterized by its distribution pattern in Chinese brake, and (ii) assess the phytoextraction potential of the plant. Young ferns with five or six fronds were transferred to an arsenic-contaminated soil containing 98 mg As kg-1 and grown for 20 wk in a greenhouse. At harvest, the Chinese brake produced a total dry biomass of 18 g plant-1. Arsenic concentration in the fronds was 6000 mg kg-1 dry mass after 8 wk of transplanting, and it increased to 7230 mg kg-1 after 20 wk with a bioconcentration factor (ratio of plant arsenic concentration to water-soluble arsenic in soil) of 1450 and a translocation factor (ratio of arsenic concentration in shoot to that in root) of 24. The arsenic concentrations increased as the fronds aged, with the old fronds accumulating as much as 13,800 mg As kg-1. Most (approximately 90%) of the arsenic taken up by the Chinese brake was transported to the fronds, with the lowest arsenic concentrations in roots. About 26% of the initial soil arsenic was removed by the plant after 20 wk of transplanting. Our data suggest that the arsenic hyperaccumulating property of the Chinese brake could be exploited on a large scale to remediate arsenic contaminated soils.     

Biological filtration for removal of arsenic from drinking water

The main objective of the study was to find a suitable iron to arsenic ratio in water to reduce arsenic to 5 μg/L or lower through sand filtration. Experiments were conducted by varying the quantity of iron(II) while keeping the arsenic concentration at 100 μg/L. A mixture of iron (II) and arsenic at different ratios (10:1, 20:1, 30:1 and 40:1) was pumped to the sand filters in a down flow mode and effluent arsenic and iron were analyzed. It was found that a ratio of iron to arsenic of 40:1 was necessary to ensure an effluent arsenic concentration of 5 μg/L or lower. Iron in the filtrate was found to be below 0.1 mg/L at all times.     

土壤-植物系统中磷和砷相互作用关系的研究进展

砷元素导致的环境污染问题日益突出，施磷已成为植物修复砷污染土壤过程中必要强化措施之一。土壤-植物系统中磷和砷的相互作用关系是非常复杂的，研究表明：磷和砷在土壤中往往是共生的，但又存在竞争吸附关系；磷和砷在不同植物中的相互作用关系主要有拮抗效应和协同效应；有必要通过分子生物学手段对磷和砷表达基理进行深入研究，获得对砷具有超积累能力的植株。