异化Mn(IV)还原菌激活及其对有机药物去除

以嘉陵江沉积物为菌源,利用荧光绝对定量（qPCR）技术探究了不同碳源（葡萄糖和乙酸钠）和不同形态的锰氧化物（δ-MnO₂和锰矿粉）对异化Mn（IV）还原菌激活效果的影响.在此基础上,研究了激活效果最佳的异化Mn（IV）还原菌对卡马西平、布洛芬、萘普生、雌激素和双氯芬酸5种有机药物的去除效果.结果表明,葡萄糖作为碳源,δ-MnO₂作为电子受体时激活效果最佳,Mn²⁺10d累计生成浓度达416.03mg/L,TOC消耗率达88.24%.激活后的异化金属还原菌在有无外加碳源时对卡马西平和布洛芬均无明显去除,对萘普生在外加碳源时能实现11.88%的去除.雌二醇和双氯芬酸可以作为异化Mn（IV）还原菌唯一碳源,其去除率可达75.70%和58.25%.     

硫素对水稻吸收砷的生物有效性及其在土壤中形态影响

采用外源砷污染水稻土进行水稻盆栽实验,研究不同形态硫肥(单质硫和石膏)对水稻吸收砷的有效性及其在土壤中赋存形态的影响.结果表明,在水稻不同生育期内,土壤溶液pH平均值范围为7.38~7.45,且AsS0和AsS1处理的高于AsS2处理;土壤溶液氧化还原电位Eh值变化在200 mV左右,且AsS0处理高于AsS1和AsS2处理;从不同生育期水稻根系、地上部茎叶及籽粒干物重来看,施用S肥(单质硫及石膏)能提高水稻的干物质质量,单质硫和石膏处理的差异不显著;水稻根表胶膜以Fe膜为主,含量达到10~30 g·kg-1,Mn膜相对较少,含量仅为0.1~1.3 g·kg-1,根系吸附的铁锰胶膜含量的差异主要表现在分蘖期,单质硫处理能比石膏硫处理的能促进水稻根系表面铁锰胶膜的形成;水稻根表胶膜吸附As量分蘖期为583~719 mg·kg-1,孕穗期为466~621 mg·kg-1,扬花期和成熟期为310~384 mg·kg-1,这与铁锰胶膜形成厚度一致;施用S肥能明显降低水稻根系、地上部茎叶以及籽粒中As的含量,且施用石膏硫效果更好,这可能与孕穗期铁锰胶膜吸附As有关.根据土壤砷的赋存形态,非专性吸附态和专性吸附态As是最有活性的,在分蘖期AsS1处理它们之和显著低于AsS2处理的As含量2.85 mg·kg-1,而在扬花期AsS1处理Asnea+Asea之和高于AsS2处理的As含量0.77 mg·kg-1,或许有更多的As溶解于土壤溶液中,造成处理AsS1的生物有效性高于处理AsS2.     

Mn-Ce/分子筛的脱汞特性研究

采用浸渍法在分子筛载体上负载活性锰、铈组分得到一种复合催化剂,在小型实验台架上考察了催化剂的脱汞性能,并对改性前后的样品进行XPS表征以研究制备的催化剂的活性组分的变化.结果表明负载锰、铈组分的催化剂在300~450℃内有较高的氧化单质汞的能力,特别是在450℃时单质汞的氧化效率仍保持在80%以上.催化剂具有较多的利于单质汞氧化的官能团,其主要靠化学吸附脱汞.烟气中的SO2与NO对单质汞的氧化有一定的抑制作用.     

锰污染土壤对超富集植物木荷生长及生理的影响

采用土培的方法,以广西桂林市未受污染土壤(CK)为对照,研究了贺州市某锰矿区的未开采区(U)、探矿区(P)、恢复区(R)、采矿区(M)土壤和尾砂(W)对锰超富集植物木荷(Schima superba)的生长、锰的吸收及生理的影响。结果表明,从CK~W处理,木荷根茎叶中Mn含量依次增加,木荷的株高和株重随锰处理浓度的增加呈先上升后下降的趋势,表明一定浓度的锰能促进木荷的生长,增加木荷的生物量。植株Mn含量的增加引起了木荷生理特征的变化,显著增加了叶片中硝酸还原酶(NR)及氨酸脱氢酶(GDH)的活性(P0.05),降低了叶片中铵态氮的累积(P0.05),抑制了谷氨酰胺合成酶(GS)和谷氨酸合成酶(GOGAT)的活性(P0.05),在R和M处理时NR、GDH活性最高,分别为对照的2.15和1.34倍,在W处理时GS、GOGAT分别比对照降低了66.1%、43.1%;硝态氮在U处理时达到最大值,从U-W处理呈下降的变化趋势。Mn处理同时还引起了木荷叶片中渗透调节物质的变化,随着Mn处理浓度的增加,游离脯氨酸、可溶性蛋白质、可溶性糖和还原性糖含量均有不同程度的增加,苹果酸含量则呈先上升后下降的趋势,表明为了适应锰胁迫,木荷可通过改变渗透调节物质的含量来维持体内的渗透压和正常生理功能。     

电解锰企业生产废水循环模式优化

通过对贵州省电解锰行业生产废水循环模式的调查,针对水质、水量特征进行改造:电解锰生产冷却循环水的强制排污水可降级作为电解产品和阴极板的冲洗水使用,处理后的含铬锰废水可作为制液氨水和电解清槽用水。进行以上优化后,电解锰生产废水闭路循环是可以实现的。     

Induced transformation of antimony trioxide by Mn(II) oxidation and their co-transformed mechanism

Antimony (Sb) is a toxic and carcinogenic element that often enters soil in the form of antimony trioxide (Sb₂O₃) and coexists with manganese (Mn) in weakly alkaline conditions. Mn oxides such as birnessite have been found to promote the oxidative dissolution of Sb₂O₃, but few researches concerned the co-transformations of Sb₂O₃ and Mn(II) in environment. This study investigated the mutual effect of abiotic oxidation of Mn(II) and the coupled oxidative dissolution of Sb₂O₃. The influencing factors, such as Mn(II) concentrations, pH and oxygen were also discussed. Furthermore, their co-transformed mechanism was also explored based on the analysis of Mn(II) oxidation products with or without Sb₂O₃ using XRD, SEM and XPS. The results showed that the oxidative dissolution of Sb₂O₃ was enhanced under higher pH and higher Mn(II) loadings. With a lower Mn(II) concentration such as 0.01 mmol/L Mn(II) at pH 9.0, the improved dissolution of Sb₂O₃ was attributed to the generation of dissolved intermediate Mn(III) species with strong oxidation capacity. However, under higher Mn(II) concentrations, both amorphous Mn(III) oxides and intermediate Mn(III) species were responsible for promoting the oxidative dissolution of Sb₂O₃. Most released Sb (∼72%) was immobilized by Mn oxides and Sb(V) was dominant in the adsorbed and dissolved total Sb. Meanwhile, the presence of Sb₂O₃ not only inhibited the removal of Mn(II) by reducing Mn(III) to Mn(II) but also affected the final products of Mn oxides. For example, amorphous Mn oxides were formed instead of crystalline Mn(III) oxides, such as MnOOH. Furthermore, rhodochrosite (MnCO₃) was formed with the high Mn(II)/Sb₂O₃ ratio_, but without being observed in the low Mn(II)/Sb₂O₃ ratio. The results of study could help provide more understanding about the fate of Sb in the environment and the redox transformation of Mn.     

碱锰型电解二氧化锰生产环境影响与环保措施

主要以某公司9000t/a碱锰型电解二氧化锰技改项目环境影响评价为例,结合验收监测数据,简要介绍碱锰型电解二氧化锰生产的环境影响与环保措施.该公司采用氧化锰矿和硫铁矿混合硫酸溶液浸出--电解的生产工艺生产碱锰型电解二氧化锰,生产过程中大气污染源主要有锅炉排放的烟气,化合、电解工序产生的硫酸雾;生产废水主要有锅炉除尘废水、漂洗水及炭黑生产废水;废渣主要是压滤锰渣.     

An Environmental Application of Regional Geochemical Mapping in Understanding Enzootic Geophagia of Calves in the Reivilo Area, South Africa

A specific enzootic form of geophagia (the deliberate ingestion of soil) occurs in young cattle and sheep in restricted areas of the Barkley-West, Postmasburg and Vryburg Districts of the Northern Cape- and North West Provinces of the Republic of South Africa. It results in severe, subacute to chronic hepatitis and jaundice, with a high mortality rate in untreated cases. An association between the disease and high concentrations of manganese in soils was shown since all the affected farms are situated on outcrops of the Reivilo Formation of the Campbell Rand Subgroup, which consists mainly of manganiferous dolomite. Furthermore high concentrations of manganese were found in the analysis of liver specimens from affected calves and the characteristic microscopic pathological changes in the liver could be induced experimentally in a calf and lamb by oral administration of manganese sulphate. The highest incidence of geophagia occurs at 7 to 14 days, whereas calves older than about 2 months are rarely affected. The symptoms usually start with intermittent, progressive geophagia, followed by constipation, dehydration and death within ca. 7–10 days in untreated cases. Young calves and lambs display an insatiable appetite for soil and sometimes lick iron poles. The treatment of calves by the parenteral injection of commercial iron-dextran- and vitamin B₁₂ preparations at 1 to 2 days after birth, and at 14 days of age, at the registered therapeutic doses, appeared to have a marked preventative effect on the occurrence of geophagia and its complications. Regional geochemical maps show a northeast–southwest trending anomaly in MnO, Zn and Pb, visually correlating with the distribution of the affected farms. Anomalously high distributions of Pb and Zn are also spatially related to the Pering (Pb,Zn) Mine. In this study, two farms were selected for comparative purposes. Gam, a farm situated on the Reivilo Formation of the Campbellrand Subgroup was chosen where a high incidence of geophagia occurred, as well as the farm Holpan on the Lyttelton Formation of the Malmani Subgroup where the problem was not known to be present. The farm Holpan was chosen as a control area, and is situated close to an old manganese mine on dolomite with a high MnO content. Geographically, Holpan is situated in an area with a high rainfall, with leaching and the formation of deep red soils on the dolomite, together with a hilly relief and low soil pH_{H 2 O}. Gam is situated in an area with lower rainfall, where precipitation would be less than evapotranspiration. The dolomite of the Malmani Subgroup and the Reivilo Formation are significantly different in their soil geochemistry. The MnO, Fe₂O₃ ^T and Co contents are significantly higher in the soils of the Malmani Subgroup than in the Reivilo Formation. The MnO, Zn and Pb contents on Gam are higher than on Holpan, whereas the Fe₂O₃ ^T and Co contents are lower. Soil on Holpan contains iron-minerals such as haematite, while no iron minerals were detected in the soils of Gam. The concretions, found in the soils on both farms, differs remarkably in iron-contents. Concretions on both farms have similar high concentrations of MnO, whereas the FeO content are low for the concretions on Gam and high for Holpan. Preliminary comparative analytical results of the colostrum, sampled from cows with new born calves within three days of birth, do not entirely reflect the soil geochemistry of the different farms. Whereas the soils on Gam have higher MnO, Zn and Pb, and lower Fe₂O₃ ^T and Co than Holpan, the colostrum produced on Gam has lower Mn, Fe and Co than on Holpan. The Pb and Zn concentrations in the colostrum on both farms do not differ significantly. The comparative regional geochemical soil data, together with the colostrum data, suggest that young calves on the farm Gam probably suffer from Fe and Co deficiency. Conversely, it was illustrated that the Fe and Co content in the soils are high and the Fe is abundant in the concretions on the farm Holpan. These findings, together with the apparent absence of geophagia at Holpan, as well as the observed effect of iron and cobalt supplementation in the prevention of geophagia on the farm Gam, suggests an association of geophagia with iron and cobalt deficiencies on the farm Gam.     

锰超积累植物——水蓼

超积累植物筛选是重金属污染土壤植物修复的基础和核心问题,同时也是重金属污染环境植物修复的难点及前沿。本文通过野外调查与营养液模拟试验相结合的方法,初次发现并证实水蓼(Polygonum hydropiper L)是一种锰超积累植物。野外调查结果表明,生长在土壤锰含量为2000mg·kg-1的水蓼,叶部锰的富集量可达3675.89mg·kg-1,且转移系数为1.37。营养液模拟培养试验证实,当营养液中锰的浓度为5000μmol·L-1时,水蓼植株生长正常,但叶中锰含量超过了10000mg·kg-1,达到了锰超积累植物应达到的临界含量标准,水蓼地上部富集系数高达19.41(大于1),转移系数为1.05(也大于1)。当营养液中锰的浓度为15000μmol·L-1时,水蓼叶、根和茎三部分的锰含量均达到最大值,分别为24447.17mg·kg-1、11574.47mg·kg-1和10343.52mg·kg-1。这一发现为锰污染土壤和水体的植物修复提供了一种新的可能的种质资源。     

土壤锌铁铜锰形态分布及其有效性

各土壤微量元素的形态分布特性有相似的规律，每个微量元素的各种形态都可以根据其对植物的有效性划分为两组．第一组形态分布百分率与植物有效性指数呈显著或极显著相关．第二组则呈显著或极显著负相关．因而第一组的形态为主要的有效养分源，第二组的形态很难为植物提供有效养分．减少相应元素转化成为第二组的形态和增加第一组各形态的储备容量是调节和控制土壤营养的重要措施．