土壤中植物有效锰的形态分级

用4种方法测定土壤有效态锰含量,并加以比较和评价,从而确定出最优的土壤有效锰测定方法。研究结果表明,采用一种顺序浸提的方法能比较准确地反映土壤的供锰状况,锰组分及其相应浸提剂为易溶态锰(O.05mol／LCa(NO     

Elevated manganese concentrations at the cores of clupeid otoliths: possible environmental,physiological, or structural origins

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to investigate the distribution of manganese (Mn) in Atlantic herring (Clupea harengus L.) otoliths. An unusual pattern of Mn concentration, which has not previously been reported in fish otoliths, was observed. Time-resolved plots (time roughly equivalent to ablation depth) of the Mn signal recorded in the ICP-MS detector during ablation of otoliths contained a distinct peak, suggesting that elevated Mn concentrations were specific to certain regions. Ablation inside and outside of the otolith core revealed that the region of high Mn concentration coincided with the ablation of the core. It was initially suggested that Mn from the gravel substrate on which herring eggs are incubated is incorporated into the otolith core, producing elevated Mn concentrations in this region. It was hypothesised that otoliths from fish whose eggs are not incubated in gravel will not contain high Mn concentrations at the core. To test this, otoliths of sprat (Sprattus sprattus), which have a pelagic embryological stage, and from reared herring, which were incubated on glass plates, were analysed using LA-ICP-MS. Peaks in the Mn signal were observed during the ablation of cores from some sprat and reared herring otoliths, indicating that incubation on a gravel substrate is not necessary for the accumulation of Mn at the otolith core and that otoliths from both pelagic and demersally spawning fish species can contain elevated Mn concentrations. The results suggest that Mn concentrations at the otolith core do not reflect the external environment of the developing embryo. Two other hypotheses are considered. A dramatic increase in Mn concentrations in the egg, associated with embryological development, may produce elevated Mn levels at the otolith core. Alternatively, the high levels of Mn observed at the otolith core may reflect spatial variation in the crystal structure of the calcium carbonate portion of the otolith. The possible influence of physiological or structural factors on the chemical composition of the otolith core may confound the environmental signal in this region of the otolith. This has important implications for the interpretation of otolith chemistry data.Communicated by J.P. Thorpe, Port Erin     

土壤中锰氧化物的形态及其化学提取方法综述

土壤中锰元素主要来自于成土母质,风化后的锰主要以锰氧化物形式存在于土壤中.锰氧化物因具有比表面积大、表面电荷低、对金属的亲合力强、氧化还原电位高等特性,对土壤中痕量金属的环境行为存在重要影响.化学提取方法是研究土壤中不同固相组分的重要手段.本文首先从土壤中锰的来源及主要存在形态出发,介绍了不同价态锰(+2、+3、+4)...     

不同锰处理对镉胁迫下2种油菜重金属累积和根系形态的影响

采用水培试验,研究Cd胁迫(10μmol·L~(-1))条件下,不同浓度Mn(0,0.1,1,10,100μmol·L~(-1))处理对2种镉累积能力不同的油菜生物量、Cd和Mn含量以及根系形态参数的影响。结果表明,与正常营养处理Mn1相比,缺Mn和Mn过量处理显著降低2种油菜的地上部和镉低积累油菜"华骏"的根部生物量,而对普通油菜"寒绿"的根部生物量没有显著影响。与Mn1处理相比,缺Mn处理下2种油菜的Cd累积总量和"华骏"地上部Cd含量显著降低;Mn过量处理下2种油菜根部和地上部Cd含量均呈升高趋势,2种油菜的Cd累积总量无显著变化或显著降低。随Mn处理浓度升高,2种油菜地上部和根部Mn含量显著升高,缺Mn处理下2种油菜根部的Mn含量低于Mn缺乏的临界值。与Mn1处理相比,缺Mn处理下"华骏"的根长、表面积、体积、平均直径和根尖数显著降低;Mn过量处理下"寒绿"的根长以及"华骏"的根系表面积、体积显著降低;缺Mn处理下2种油菜细根表面积所占的比例增加,粗根表面积比例降低;Mn过量时,"寒绿"的粗根表面积比例增加,细根比例降低,而"华骏"则相反。总的来看,缺Mn处理影响油菜根系和地上部生长,减少地上部Cd含量和植株Cd累积总量;Mn过量处理下油菜生长也受到抑制,但是油菜地上部和根部Cd含量有所升高;2种油菜的根系形态学参数在不同Mn处理下变化规律不同,表现出不同的响应策略。     

4种蔬菜对土壤Mn转运累积特征及食用安全性研究

为探究土壤中锰(Mn)污染对蔬菜食用安全性的影响,以上海市常见的4种蔬菜(青椒,CA;黄瓜,CS;豇豆,VU;菠菜,SO)为试验材料,采用温室盆栽土培试验方法研究了不同土壤Mn含量梯度下的蔬菜生物量变化以及各部位Mn转运累积特征,并基于各蔬菜食用安全分析了土壤中Mn的安全阈值。研究结果表明,Mn对4种蔬菜的生长均表现出低含量促进、高含量抑制现象,SO和VU对Mn的耐受度强于CA和CS。Mn主要富集在SO的茎叶,以及CA、CS和VU的茎叶和根部,可食部分中Mn含量大小排序为SO>VU>CS>CA。SO可食部分Mn含量与土壤Mn含量呈显著对数相关(P<0.01),其他3种蔬菜的可食部分Mn含量与土壤Mn含量均呈显著指数相关(P<0.01)。依据新鲜蔬菜中Mn食用安全限量值,推导出各蔬菜对应的土壤Mn安全阈值预测区间为:SO 992.5～1 097.3 mg·kg~(-1),VU 2 607.5～2 910.0 mg·kg~(-1),CS 3 147.5～3 494.6 mg·kg~(-1),CA3 618.0～3 921.5 mg·kg~(-1)。Mn污染土壤的安全利用应优先选择种植CA、CS和VU等低累积品种。     

Sequestration of heavy metals from soil with Fe–Mn concretions and nodules

In recent years, heavy metal contamination has become a major environmental issue in many parts of the world. Fe and Mn oxides, oxyhydroxides and hydroxides have long been recognized as scavengers playing an important role in controlling the location, mobility and bioavailability of metal contaminants in soils. Fe–Mn concretions and nodules are discrete bodies made of soil or sediment materials cemented together under the influence of Fe and Mn oxides. Here metals sorption by Fe–Mn concretions and nodules are surveyed and critical reviewed. Valuable available literature data demonstrate that the formation of Fe–Mn concretions and nodules is the most efficient and durable process for metal contaminants sequestration in the soils. The papers discussed in this review show that the application of Fe–Mn concretions and nodules, as geochemical scavengers for remediating metal contaminated soils, is strongly recommended.     

锰胁迫对青葙生长及叶绿素荧光特性的影响

通过温室水培实验,研究在不同锰质量浓度（2.5、50、100、150、200、300 mg·L-1）胁迫下青葙（Celosia argentea Linn.）的叶绿素含量、叶绿素荧光参数的变化,及对其生长的影响,探究青葙对锰毒的耐性。结果表明,随着Mn2＋质量浓度的升高,青葙叶片的叶绿素含量和叶绿素荧光参数值都出现不同程度下降。当Mn处理浓度大于50 mg·L-1时,叶绿素a、叶绿素b含量和总叶绿素含量显著下降,但在Mn质量浓度为100-300 mg·L-1的范围内,叶绿素b含量变化不明显（p〉0.05）。青葙的最大光化学量子产量（Fv/Fm）、最大荧光产量（Fm）、最小荧光产量（Fo）、光合量子产量（EQY）、表观光合电子传递速率（ETR）、光合化学淬灭系数（qP）均随Mn2＋质量浓度的增加显著降低,说明锰胁迫抑制了青葙的电子传递过程。但在150、200、300 mg·L-1质量浓度锰处理下ETR、EQY、qP下降趋势变缓,且ETR、EQY不存在显著差异。青葙株高与ETR、EQY的变化规律基本相似,根长则与对照组相比下降不显著,到300 mg·L-1才出现明显降低。试验结果证明青葙对锰毒具有耐性。     

Co-present Pb(II) accelerates the oxidation of organic contaminants by permanganate: Role of Pb(III)

• Simultaneous removal of organic contaminants and Pb(II) was achieved by Mn(VII). • Pb(II) enhanced Mn(VII) oxidation performance over a wide pH range. • Pb(II) did not alter the pH-rate profile for contaminants oxidation by Mn(VII). • Mn(VII) alone cannot oxidize Pb(II) effectively at pH below 5.0. • Pb(III) plays important roles on enhancing Mn(VII) decontamination process. The permanganate (Mn(VII)) oxidation has emerged as a promising technology for the remediation and treatment of the groundwater and surface water contaminated with the organic compounds. Nonetheless, only a few studies have been conducted to explore the role of the heavy metals (especially the redox-active ones) during the Mn(VII) oxidation process. In this study, taking Pb(II) as an example, its influence on the Mn(VII) decontamination performance has been extensively investigated. It was found that, with the presence of Pb(II), Mn(VII) could degrade diclofenac (DCF), 2,4-dichlorophenol, and aniline more effectively than without. For instance, over a wide pH range of 4.5–8.0, the dosing of 10 μmol/L Pb(II) accelerated the DCF removal rate from 0.006–0.25 min⁻¹ to 0.05–0.46 min⁻¹ with a promotion factor of 1.9–9.4. Although the UV-vis spectroscopic and high resolution transmission electron microscopy analyses suggested that Mn(VII) could react with Pb(II) to produce Mn(IV) and Pb(IV) at pH 6.0–8.0, further experiments revealed that Pb(II) did not exert its enhancing effect through promoting the generation of MnO₂, as the reactivity of MnO₂ was poor under the employed pH range. At pH below 5.0, it was interesting to find that, a negligible amount of MnO₂ was formed in the Mn(VII)/Pb(II) system in the absence of contaminants, while once MnO₂ was generated in the presence of contaminants, it could catalyze the Pb(II) oxidation to Pb(IV) by Mn(VII). Collectively, by highlighting the conversion process of Pb(II) to Pb(IV) by either Mn(VII) or MnO₂, the reactive Pb(III) intermediates were proposed to account for the Pb(II) enhancement effect.     

3种水生植物对锰污染水体修复作用的研究

通过静态水培试验,研究了3种水生植物水葫芦（Eichhornia crassipes（Mart.）Solms）、水浮莲（Pistia stratiotes L.）、水花生（Atlernanthera philoxeroides）在55、155mg L-1锰（Mn）质量浓度下的生物量、Mn质量分数、富集系数、转运系数,以及对2种Mn质量浓度水体的修复作用。结果表明,水浮莲的鲜质量、干质量、相对生长率、Mn质量分数、富集系数随着取样时间的延长而显著增加（P〈0.05）。2种Mn质量浓度下,水葫芦与水浮莲的鲜质量与相对生长率显著高于水花生。植物茎叶的Mn质量分数依次为水浮莲〉水葫芦〉水花生（P〈0.05）,其中155mg L-1Mn处理水浮莲与水葫芦茎叶Mn质量分数均高于10000mg kg-1,分别为12431.05mg kg-1、11238.28mg kg-1。3种植物茎叶、根的富集指数均显著大于1,且茎叶的富集系数依次为水浮莲〉水葫芦〉水花生（P〈0.05）,根富集指数依次为水浮莲≈水葫芦〉水花生（P〈0.05）。在10,21d这2个取样时期,水浮莲的转运系数要高于其它植物,其中在155mg L-1处理下,水浮莲的转运系数要高于1,分别为1.04、1.01。种植3种水生植物后,2种Mn处理水体的Mn质量浓度随着取样时间的延长而降低。水葫芦、水浮莲、水花生收获时,55mg L-1Mn处理的水体Mn质量浓度分别降低了31.84%、31.44%、18.47%;155mg L-1Mn处理则降低了12.02%、18.53%、7.57%。可见,水浮莲符合超积累植物对Mn质量分数、富集系数、转运系数的要求,其在Mn污染水体修复方面有很好的应用前景。     

Exogenously applied oxalic acid assists in the phytoremediation of Mn by Polygonum pubescens Blume cultivated in three Mn-contaminated soils

• The OA supply significantly increased the water-extractable Mn in all soils. • All OA supply levels promoted plant growth in unexplored soil. • Low OA supply level promoted plant growth in explored and tailing soils. • OA amendment increased the Mn concentrations and total Mn in P. pubescens. • P. pubescens experienced less Mn stress in unexplored soil than in the other two soils. The current study evaluated the effects of oxalic acid (OA) application on the growth and Mn phytoremediation efficiency of Polygonum pubescens Blume cultivated in three different manganese (Mn)-contaminated soils sampled from an unexplored area (US), an explored area (ES) and a tailing area (TS) of the Ertang Mn mine, South China. The supplied levels of OA were 0 (control), 1 (low level), 3 (medium level), and 9 (high level) mmol/kg, referred to as CK, OA1, OA3 and OA9, respectively. The results revealed that the average water-extractable Mn concentrations US, ES and TS amended with OA increased by 214.13, 363.77 and 266.85%, respectively. All OA supply levels increased plant growth and Mn concentrations in US. The low OA supply level increased plant growth in ES and TS; however, contrasting results were found for the medium and high OA supply levels. Plant Mn concentrations and total Mn increased in ES and TS in response to all OA supply levels. Total Mn in the aerial parts increased by 81.18, 44.17 and 83.17% in US, ES and TS, respectively; the corresponding percentages for the whole plants were 81.53, 108.98 and 77.91%, respectively. The rate of ·O₂⁻ production and malondialdehyde (MDA) concentrations increased in response to OA amendment, especially the medium and high OA supply levels in ES and TS. In general, antioxidant enzymes might play a vital role in alleviating Mn stress in plants cultivated in US, while non-enzymatic antioxidants might be the main factor for plants cultivated in ES and TS.     

Ce(x)Mn/TiO2-y催化剂低温NH3-SCR脱硝性能

以锐钛矿TiO₂(P25)为载体采用原位生长法负载锰氧化物制备了Mn/TiO₂催化剂,再以等体积浸渍-煅烧法对该催化剂掺杂氧化铈制备Ce(x)Mn/TiO₂-y催化剂用以烟气低温SCR脱硝.在固定锰负载量(质量分数为8%)的基础上,考察了铈掺杂量(铈锰摩尔比)、煅烧温度对催化剂SCR脱硝性能的影响.采用TEM、BET、XRD和XPS等手段表征了催化剂的理化结构特性.结果发现,当Ce/Mn的摩尔比例为1.0,煅烧温度为300℃时,Ce(1.0)Mn/TiO₂-300催化剂在150—300℃温度范围内、10500—27000 h^-1的空速范围内,能够保持90%以上的NO转化率.理化性能分析结果表明,煅烧温度对催化剂的微观形貌影响显著,随着煅烧温度的升高,Ce(1.0)Mn/TiO₂-500催化剂活性物种颗粒集聚明显、比表面积降低,且锰氧化物价态分布偏向于低价态;铈的掺杂有助于Ce(1.0)Mn/TiO₂-300催化剂活性物种在载体表面的均匀分散,可以促进产生更多的Mn4+物种和更多的吸附氧,有利于催化剂低温SCR脱硝性能的提升.     

Manganese-catalyzed degradation of phosphonic acids

The non-biodegradable and chemically very stable phosphonates are used in a variety of industrial applications including cooling waters, oil production and textile industry. We show here that they are degraded in the presence of Mn(II) and oxygen. The half-life for the reaction is 9 min near neutral pH. The presence of other cations such as Ca(II) and Zn(II) considerably slows down the reaction by competition with Mn(II) for the phosphonate. The reaction involves the oxidation of complexed Mn(II) by oxygen to Mn(III) and the subsequent oxidation of phosphonate by Mn(III) thus yielding two stable phosphonic acid breakdown products. The oxidation also proceeds in the presence of the mineral manganite (Mn(III)OOH), and yields the same breakdown products. The use of a newly developed chromatographic method revealed the presence of the breakdown products in wastewater. The results show that manganese-catalyzed oxidation might be an important pathway for phosphonate degradation in natural waters. Electronic Publication     

Manganese toxicity in Drosophila melanogaster: extension of the life span by resveratrol

The effect of resveratrol was studied on the life span and motor activity of Drosophila melanogaster treated with manganese (Mn). Two days after emerging from the pupa, male wild type D. melanogaster were fed for 13 days with corn media containing 15?mM Mn. Thereafter, Drosophila were divided into six groups of 300 flies each: (1) the flies remained treated with Mn; (2) began treatment with 0.43?mM resveratrol (Mn-resveratrol group); (3) received no additional treatment (Mn-no treatment group); (4) simultaneously fed with Mn and resveratrol (Mn?+?resveratrol group). In addition, a control (5) with no treatment and another group (6) fed only with resveratrol after emerging from the pupa were included. All Mn-treated flies (group 1) were dead on the 25th day. The life span in the resveratrol group was 91?±?0.33 days (mean?±?S.E.M.) and in Mn-resveratrol flies was 83?±?2 days. These two values were significantly higher than those detected in the control (5) and Mn-no treatment (group 3) flies whose life span were 68?±?0.33 and 67?±?2.31 days, respectively. The Mn?+?resveratrol-fed flies had a markedly higher life span (31?±?1.53 days) than Mn-fed flies (23?±?0.88 days). In the flies that received Mn (Mn and Mn?+?resveratrol groups), the motor activity decreased significantly with respect to control (groups 5) and the Mn–resveratrol and resveratrol groups. In conclusion, resveratrol increased significantly the life span of Mn-treated D. melanogaster.     

Concentration of polyvalent metals by seaweeds in Vostok Bay,Sea of Japan

Spectrophotometric methods were used to measure the contents of the polyvalent metals Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo and Zn in 16 species of red, brown, and green seaweeds and 2 species of higher water plants collected from the intertidal and sublittoral zones of Vostok Bay, Sea of Japan. Some of the species displayed a unique capability for increased accumulation of groups of several metals. We have termed this ability specific group concentration. Thus, Ptilota filicina concentrates Ti, V, Mn, Fe, Ni, Cu, Zn, and Mo; Polysiphonia japonica Ti, V, Mn, Fe, Zn, Mo, and Cr; Rhodomela larix Ti, V, Mn, Fe, Ni, Zn, and Cr; Agarum cribrosum Ti, V, Mn, Fe, Ni, Zn, and Cr; Ulvaria splendens Ti, V, Mn, Fe, Ni, and Cu; Ulva fenestrata Mn, Fe, Ni, and Cu; Enteromorpha prolifera Mn, Co, Zn, Mo, and Cr; codium yessoensis V, Mn, Fe, Ni, and Cr; Zostera asiatica Ti, Mn, Ni, and Mo; Phyllospadix iwatensis Ti, V, Mn, Fe, and Zn. Specific group concentration makes possible a new approach to the study of active transport of polyvalent metals, physiologically significant for live organisms, through cell membranes, and the study of the formation of complex metal compounds inside the cell, i.e., the study of the processes that determine the degree of element concentration. The contents of the metals studied in sea water and the accumulation coefficients were also determined. The variation range is extremely high both for the seaweed species and metals investigated. Maximum coefficients were noted for Mn: 1.8·10⁵; Ti: 4.4·10⁴; Fe: 2.4·10⁴; Cr: 1.2·10⁶.     

Crop demand of manganese

The objectives of this study were to evaluate some of the popular rotation crops grown in Hungary for tolerance to low external Mn(2+) levels and to determine the critical tissue concentration of Mn(2+) deficiency during early stages of growth. The minimum Mn(2+) concentration required in soil nutrient contents was 42.5 mg kg(-1) for sunflower, 24.3 mg kg(-1) for tobacco and 10.2 mg kg(-1) for triticale. Sunflower, tobacco and triticale achieved optimum growth at 48.0-65.0 mg Mn(2+) kg(-1), 24.9-32.1 mg Mn( n+) kg(-1) and 28.7 to 29.6 mg Mn(2+) kg(-1), respectively. Critical shoot Mn(2+) concentration at early stages of growth was 53.6 mg kg(-1) in sunflower, 458.0 mg kg(-1) in tobacco and 193.8 mg kg(-1) in triticale. Our results demonstrate that the tolerance to low external Mn(2+) (triticale: <30.2 mg kg(-1); sunflower: <56.2 mg kg(-1); tobacco: <69.3 mg kg(-1)) and the critical tissue Mn(2+) levels for deficiency varied significantly between crop species tested.     

强化高锰酸钾氧化体系中自由基的产生与利用研究进展

高锰酸钾在水处理行业中的应用已趋于成熟,但与臭氧、芬顿及其他高级氧化技术相比,高锰酸钾与难降解有机污染物的反应速率较低,需要与其它方法联用来强化自身的氧化能力.近年来随着对强化高锰酸钾氧化机理研究的不断深入,人们发现该体系中产生的自由基对有机污染物的降解有显著的促进作用.为此本文综述了强化高锰酸钾氧化体系中各类无机与有机自由基的产生路径和促进有机污染物降解的机制,提出了后续的研究展望,以期为强化高锰酸钾氧化技术的进一步推广提供理论依据.     

Visible light induces bacteria to produce superoxide for manganese oxidation

● Term of manganese-oxidizing microorganisms should be reconsidered. ● Visible light induces heterotrophic bacteria to produce superoxide. ● Heterotrophic bacteria oxidize Mn(II) ions with a fast oxidation rate. ● Superoxide oxidizing Mn(II) ions is an unintended side reaction of bacteria. ● Superoxide is an important oxidation force of Mn(II) in the environment. Manganese oxides are widely distributed in soils and sediments, affecting the migration and transformation of heavy metals and organic pollutants. The microbial conversion of soluble Mn(II) into insoluble Mn(III/IV) oxides is considered to be the initial source of manganese oxides in the environment; however, whether this process is related to a physiological role remains unclear. Here, we explored the microbial manganese oxidation process under visible light by using coastal surface seawater microorganisms. Visible light greatly promotes the oxidation rate of Mn(II), and the average rate reaches 64 μmol/(L·d). The generated manganese oxides were then conducive to Mn(II) oxidation, thus the rapid manganese oxidation was the result of the combined action of biotic and abiotic, and biological function accounts for 88 % ± 4 %. Extracellular superoxide produced by microorganisms induced by visible light is the decisive factor for the rapid manganese oxidation in our study. But the production of these superoxides does not require the presence of Mn(II) ions, the Mn(II) oxidation process was more like an unintentional side reaction, which did not affect the growth of microorganisms. More than 70 % of heterotrophic microorganisms in nature are capable of producing superoxide, based on the oxidizing properties of free radicals, all these bacteria can participate in the geochemical cycle of manganese. What’s more, the superoxide oxidation pathway might be a significant natural source of manganese oxide.     

Speciation of particulate trace metals in sediments of Anarbe reservoir∗

Total concentration and chemical forms of heavy metals in samples of sediment from a drinking water reservoir have been analysed. The result of total metal contest shows Fe and Mn concentration increase along the reservoir, from 4.4% in Fe and 0.07% in Mn in the end part to 6.4% Fe and 0.22% Mn at the dam. However, a decrease in organic matter along the reservoir is observed. In order to test the accuracy of the digestion methods used, a standard reference material was also analysed.

Trace metal concentrations, with exception of Cadmium, Pb and Mn, found in fraction 5 are higher than those observed in the others extractions, Fe, Ni, Zn, Cr and Cu content in non‐residual fraction is found mainly in moderately reducible fraction, but the percentage of this fraction in each metal is very different.     

Sequence of the main geochemical controls on the Cu and Zn fractions in the Yangtze River estuarine sediments

Metal speciation can provide sufficient information for environmental and geochemical researches. In this study, based on the speciation determination of Cu and Zn in the Yangtze Estuary sediments, roles of eight geochemical controls (i.e., total organic carbon (TOC), clay, Fe/Mn in five chemical fractions and salinity) are fully investigated and sequenced with correlation analysis (CA) and principal components analysis (PCA). Results show that TOC, clay and Fe/Mn oxides are key geochemical factors affecting the chemical speciation distributions of Cu and Zn in sediments, while the role of salinity appears to be more indirect effect. The influencing sequence generally follows the order: TOC>clay>Mn oxides>Fe oxides>salinity. Among the different fractions of Fe/Mn oxides, residual and total Fe content, and exchangeable and carbonate Mn exert the greatest influences, while exchangeable Fe and residual Mn show the poorest influences.     

选择性萃取方法在生物膜上铁、锰氧化物分离中的应用

1　IntroductionSurfacecoatings (biofilmsandassociatedminerals)existonallkindsofsolidphasesinnaturalaquaticenvironments.FeandMnoxideswerefoundedtobethemostimportantcomponentsofsur facecoatingsfortheirhighadsorptioncapacity[1—3].Tostudytherelativeroleofdif…