施用改良剂对岩溶地区矿山污染农田土壤中锌生物有效性的影响

以玉米（ZeamaysL．）为研究对象,采用盆栽试验,观测在重金属锌污染的土壤（总锌含量为1412．1mg·kg0）上施用不同改良剂（石灰、石灰＋泥炭、石灰＋胡敏酸钠、石灰＋泥炭＋硅肥、石灰＋胡敏酸钠＋硅肥,分别简称S、SN、SH、SNG、SHG）对土壤锌形态、生物有效性及其在作物中富集的影响。结果表明,施用各种改良剂均显著提高土壤pH值,显著降低土壤弱酸可溶态锌和可还原态锌含量,提高可氧化态锌和残渣态锌含量;提高玉米生物量和产量,增产效果为SHG〉SNG〉SH〉SN〉S。施人改良剂可显著降低锌在玉米不同部位的吸收和转运,植株根、茎、叶、籽粒锌富集明显下降,以SHG、SNG的效果最明昂．S的效果最小。     

Treatment of metal-chloride-enriched wastewater by simulated constructed wetlands

The ability of surface flow and subsurface flow simulated wetlands to remove heavy metals from a NaCI-enriched wastewater was examined, employing bulrush (Scirpus validus) and cattail (Typha angustifolia) plants, and two organically amended substrates (mixtures of mushroom compost and leaf litter,with topsoil) with a limestone liner. A simulated wastewater solution containing Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn as chloride salts was added to the wetlands at a rate of 0.3 l h^–1. During 12 weeks of surface flow, Fe was retained most efficiently (74%), and Mn the least (24%). Most metal retention occurred in residual forms, primarily in the upper 5 cm of the substrate. A subsequent 10 week subsurface flow treatment exhibited greater removal efficiencies for all metals, probably due to increased contact with the highly buffered lower substrate. During both treatments, bioaccumulation occurred in plants, but accounted for a very small portion of the total metal removal. Plant species did not significantly influence wetland performance with respect to metal retention. Substrate type did not affect removal efficiency for most metals, but did influence the forms of the metals retained in the wetland.To whom correspondence should be addressed.     

广东某铀废石堆周边土壤中铀污染特征及其环境有效性

铀（U）矿冶过程中产生了大量铀废石。通常认为其放射性核素含量低,大多沿山谷露天自然堆放,一般不对堆场做防渗漏处置,对铀废石可能产生的潜在环境影响尚未引起重视。以广东某花岗岩型铀矿山的一个废石堆周边土壤为研究对象,在废石堆上、下游方向分别采集了2条（即BP1和BP2,视作背景土壤,距离废石堆的距离分别为10和20 m）和3条土壤剖面（即WP1、WP2和WP3,视作潜在U污染土壤,距离废石堆的距离分别为50、100和180 m）。通过对剖面间U分布特征的对比,定量估算了受污染土壤中外源U的输入通量;结合逐级化学提取技术,分析了U在土壤剖面的赋存形态及其环境有效性。结果表明：1）铀废石堆对周边土壤产生了显著的放射性污染,废石堆下游方向由近及远的3条U污染剖面（WP1、WP2和WP3）中U平均质量分数比背景剖面分别富集了634.6、10和3.7倍,其外源U的平均输入通量分别为4840.36、86.72和20.46μg·g-1。距污染源（废石堆）愈近,土壤中外源U的输入通量愈大;2）在近源区,大量的外源U优先在土壤表层聚集,随着远离污染源,逐渐转变为优先在剖面的深部淀积;3）与U 污染剖面相比,背景剖面（BP2）的惰性态 U（晶质铁锰氧化物/氢氧化物结合态+残渣态）所占比例最大,活性态 U（可交换态（包括水溶态）+碳酸盐结合态）所占比例最小,说明U污染土壤的外源U输入更倾向于对活性态U的贡献,这是对植物影响最直接的部分。另外,距污染源由近及远,U污染土壤中活性态U所占比例增大,潜在活性态U（有机质结合态+无定形铁锰氧化物/氢氧化物结合态）所占比例降低;4）3条U污染剖面中,平均90%以上的U（活性态和潜在活性态）对生态系统构成了威胁。因此,铀废石堆对周边环境产生的风险应得到充分重视。本研究为开展铀矿冶地域的放射性环境影响评价和土壤修复提供了有益的参考。     

Seasonal variation of total dissolved arsenic and arsenic speciation in a polluted surface waterway

Seasonal differences in the dissolved arsenic concentration and speciation in a contaminated urban waterway in northwest England have been determined using a coupled ion chromatography-inductively coupled plasma-mass spectrometry (IC-ICP-MS) technique. Waters sampled in the vicinity of an industrial works during relatively dry conditions in April 2000 were found to contain total arsenic concentrations (As) of up to 132 g L^–1, more than an order magnitude greater than the 4 g L^–1 maximum found in December 2000. The difference in As between the April and December sampling periods is speculated to be largely due to the irregular anthropogenic supply of arsenic to the watercourse. For both sampling periods, the dissolved arsenic was exclusively inorganic in nature and had an As(V)/As ratio of between 0.6 and 0.8. Analysis of samples taken downstream of the industrial site, after the confluence with a relatively As-poor stream, revealed that As(III), As(V) and As concentrations were lower than would be expected from conservative mixing. The As(V)/As ratio was also observed to decrease markedly. The loss of arsenic from solution is thought to be due to adsorption on the iron oxyhydroxide-rich sediment observed to coat the riverbed downstream of the confluence. The reduction in the As(V)/As ratio is believed to be due to the more rapid adsorption of As(V) compared to that of As(III). Deviations from conservative behaviour were more marked during the relatively dry April 2000 sampling period and suggest the increased importance of adsorption processes controlling arsenic availability during this time.     

Effect of natural organic matter on arsenic release from soils and sediments into groundwater

Arsenic (As) contamination in groundwater has received significant attention recently. Natural and anthropogenic sources contribute to the worldwide occurrence of As contamination. As speciation is an important factor related to its toxic and mobile behavior. The release of As from soils and sediments into groundwater is governed by several geophysicochemical processes, of which, As sorption behavior is of principle significance. This review paper summarizes existing information regarding the effects of natural organic matter (NOM) on the fate and mobility of As species in the environment. NOM may enhance the release of As from soils and sediments into the soil solution, thereby facilitating As leaching into the groundwater. The main influencing mechanisms include competition for available adsorption sites, formation of aqueous complexes, and/or changes in the redox potential of site surfaces and As redox speciation. NOM may also serve as binding agents, thereby reducing As mobility. However, comparably little research has been performed on this aspect. Since most investigations have been done on purified minerals under laboratory conditions, further research involving various geological materials under natural environmental conditions is required. Development of proper geochemical conceptual models may provide means of predicting the role of NOM in arsenic leaching and/or immobilization.     

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.     

模拟酸雨条件下降尘中Cu,Pb,Zn,Cr各形态的溶出和转化研究

本文用Ｔｅｓｓｌｅｒ方法，研究了模拟酸雨条件下，降尘中Ｃｕ，Ｐｂ，Ｚｎ，Ｃｒ各形态的溶出和相互转化。试验表明：（１）降尘中Ｃｕ，Ｃｒ的溶出量随酸雨酸度的增大而增加；Ｐｂ，Ｚｎ没分别在ＰＨ＝３．５和ＰＨ＝４．５时溶出量最大，溶出的金属多源于可交换态和碳酸盐结合态，说明这两种形态的稳定性较差。（２）在模拟酸雨条件下，Ｃｕ，Ｐｂ，Ｚｎ，Ｃｒ各形态的含量发生了较大变化；Ｃｕ从其优势形态有机结合态向可交换态