Determination of Trace Element Stability in Sediments Using Redox Gel Probes: Probe Construction and Theoretical Performance

A simple and inexpensive technique is described that can be used to assess the stability of redox-sensitive compounds in the sediments of wetlands and other shallow water environments. In this method, solid redox-sensitive compounds, such as manganese dioxide (MnO 2 ), are incorporated into agar gels held in rigid plastic holders. One surface of the gel remains exposed along the length of the resulting probe. The probes are pushed vertically into sediments and are left in situ for a period of time (days to weeks), after which they are visually inspected and chemically analyzed. The diffusion of nonreactive solutes (e.g., sulfate) in 2% (wt/vol) agar was unaffected by the presence of immobilized MnO 2 particles. The rate of dissolution of particulate MnO 2 in agar gels in the presence of an external diffusing reductant (L-ascorbic acid) could be quantified by digital analysis of pixel density on gel images. Redox gel probes incubated in the sediment of a wetland built to remove manganese from circumneutral pH coal mine drainage demonstrated different patterns of depth-dependent MnO 2 stability along a 15-m transect. MnO 2 gel probe results were consistent with data obtained using sediment cores and porewater diffusion samplers.     

Redox processes of sulfur and manganese in a constructed wetland

Constructed wetlands are very popular in terms of wastewater treatment today. Formation of redox potential gradients inside such a system strongly influences the wastewater-treatment efficiency. Individual oxidation forms of sulfur, and dissolved and precipitated manganese forms were determined in the vegetation bed of the constructed wetland. The aim of the speciation analysis was to contribute to the characterization of its redox properties. Sulfur was mostly oxidized at the inflow. The concentration of sulfates at the inflow varied from 25 to 55 mg/l, while concentration of sulfides was always lower than 6.0 mg/l and mostly even lower than 1.0 mg/l. However, sulfates were reduced during the pretreatment and the wastewater flow through the vegetation bed. The concentration of total manganese varied from 0.2 to 0.8 mg/l. Approximately 60% of Mn was precipitated at the inflow. The content of precipitated Mn forms declined to ca. 40-50% at the inflow zone, this content was almost constant across the vegetation bed to the outflow when water was sampled from 60-cm depth. However, the content of precipitated Mn forms increased to ca. 74% for samples from 20-cm depth. With respect to the aeration of the system, manganese can be precipitated as MnO2 in these samples.     

Transport of iron and manganese in relation to the shapes of their concentration-depth profiles

A model is presented which describes the transport of iron and manganese in the vicinity of a redox boundary. It is based on input of a particulate component, to form a point source, from which soluble species diffuse along a concentration gradient. The shapes of concentration-depth profiles in marine and freshwater sediments and water columns are reviewed and discussed in terms of the model. Transport, either entirely within a water column or within the sediment, may be simply treated because the rate of vertical transport can be regarded as constant. The discontinuity in the rate of vertical transport which occurs at the sediment-water interface can provide a complicated example of the model, especially when it coincides with the redox boundary. Authigenic mineral formation processes can modify the model, sometimes to such an extent that it becomes invalid. This is particularly true for soluble iron profiles in organically rich marine sediments. Sampling interval is critical to the resultant profile shape and must be relevant to the particular environment, e.g. metres in water columns and millimetres in sediments. The differences in the rates of reduction and oxidation of iron and manganese tend to modify both the position of the profile with respect to the redox-cline and its stage of development in a seasonally anoxic system. It is these factors which determine why most of the iron which reaches a sediment is permanently incorporated whereas manganese is re-released. This mechanism determines the average ratio of iron to manganese in sedimentary rocks. The development of peaked profile shapes in water columns implies that under certain conditions dissolved iron and manganese may be transported from the water column to the pore waters of the sediment.     

Bacteria in gel probes: comparison of the activity of immobilized sulfate-reducing bacteria with in situ sulfate reduction in a wetland sediment.

A novel method was used to examine the microbial ecology of iron-rich wetland sediments receiving neutral-pH coal mine drainage. Gel probes inserted into the sediments allowed analysis of the distribution and activity of bacterial sulfate reduction (BSR). A mixed population of sulfate-reducing bacteria enriched from anoxic wetland sediments was immobilized in low temperature-gelling agarose held in grooved rods or probes. The probes were inserted vertically into sediments and were allowed to incubate in situ for 48 h. After their retrieval, the gels were sectioned and analyzed for residual BSR activity and were compared to in situ BSR rates and chemical porewater profiles. The depth distribution of residual BSR activity in the immobilized cell gel probes differed significantly from the BSR measured in situ. Approximately 51% of the total integrated residual sulfate reduction activity measured in the gel probes occurred between 0 and 7 cm of the upper 20 cm of sediment. In contrast, ca. 99% of the integrated in situ BSR occurred between 7- and 20-cm depth, and only 1% of the total integrated rate occurred between 0- and 7-cm depth. Lactate-enriched bacteria immobilized in the gel may have been atypical of the majority of sulfate-reducing bacteria in the sediment. Agarose-immobilized sulfate-reducing bacteria might also be able to proliferate in the otherwise inhospitable zone of iron reduction, where sulfate and labile carbon compounds for which they are usually outcompeted can diffuse freely into the gel matrix. Gel probes containing particulate iron monosulfide (FeS) indicated that FeS remained stable in sediments at depths greater than 2 to 3 cm below the sediment-water interface, consistent with the shallow penetration of oxygen into surface sediments.     

Geochemical processes of iron and manganese in a seasonally stratified lake affected by coal-mining drainage in China

Lake water, pore water, and sediments were sampled in a seasonally stratified lake affected by coal-mining drainage. Contrasting geochemical processes of iron and manganese in summer were investigated by studying the seasonal distributions of iron and manganese species in the water column, pore water, and sediments. The results show that iron buildup in the water during summer was mainly from the gradual dissolution of particulate matter due to the pH decrease, whereas manganese oxide reduction and manganese-bound carbonate dissolution near the sediment–water interface were mainly responsible for manganese accumulation in the stratified hypolimnion. The geochemical processes of iron and manganese in the sediments during early diagenesis were also discussed in terms of the possible influence on the overlying water. Received: November 29, 1999 / Accepted: June 30, 2000     

Influence of Manganese Dioxide and Manganic Ions on the Production of Two Proteins in Arthrobacter sp.

The production by Arthrobacter sp. of a 30-kDa surface protein and a 25-kDa cytoplasmic protein was increased by the presence of MnO2 in the medium. This high production was also observed in the presence of MnO4- (Mn VII). N-terminal and partial internal sequences of the 30-kDa surface protein have shown no homology with other known proteins. The role of this protein is still unknown, but its highly induced synthesis is possibly related to the binding or the processing of manganic ion by the cells. The 25-kDa cytoplasmic protein has been identified by its N-terminal matching sequence as a superoxide dismutase isoenzyme (Mn-SOD). SOD activity measurements performed on cytoplasmic fractions are related to the protein amounts observed by gel electrophoresis. Arthrobacter sp. synthesized and exhibited SOD activity in both aerobic and anaerobic conditions, thus suggesting other or additional physiological functions for this enzyme.     

Formation of manganese oxyhydroxides on the Dead Sea coast by alteration of Mn-enriched carbonates

Manganese enriched carbonates preferentially accumulate in near-shore, shallow water sediments of the Dead Sea. These carbonates are formed by coprecipitation of Mn with authigenic aragonite, as well as by direct precipitation of Mn-carbonate from the pore water of the shallow sediments. The primary source of the Mn that accumulates as carbonates is allochthonous Mn-enriched oxides that are eroded from the nearby coasts and become buried within the near-shore shallow water sediments. Due to the decline in the level of the Dead Sea between 1960–1990, bands of sediments (parallel to the current shoreline) which were previously submerged, became exposed to air and consequently desiccated. We suggest that in order to approach new hydraulic equilibrium in some of those coastal areas, the decline in the level of the lake was followed by a lakeward advance of fresher groundwater from the shallow coastal aquifer. Those fresher waters are characterized by a higher pH than the interstitial brine, and therefore a new state of water-rock interaction is established which results in oxidative alteration of Mn-carbonates to Mn-oxides. In addition, manganese-oxidizing bacteria, shown to be active in water with lower salinity than that of the Dead Sea, may also play a part in oxidation of divalent manganese released from the sediment. As a result, some segments of the Dead Sea coast are characterized by black Mn-enriched sediments that in places form crusts over the surface.     

Stabilization ofd-amino-acid oxidase fromTrigonopsis variabilis by manganese dioxide

Stabilization of immobilized D-amino-acid oxidase was achieved as follows. Yeast Trigonopsis variabilis producing D-amino-acid oxidase was used to deaminate cephalosporin C to glutaryl-7-aminocephalosporanic acid. Permeabilized cells were co-immobilized with manganese dioxide by entrapment in (poly)acrylamide gel so that hydrogen peroxide, liberated in the reaction, could be partially deactivated and both the enzyme and the substrate could be stabilized. Activity of entrapped cells was determined by HPLC and enzyme flow microcalorimetry. The process was evaluated in terms of activity, immobilization yield, storage stability and oxo-product formation by immobilized preparations. The storage stability of immobilized biocatalysts with MnO2 was nearly doubled and production of 2-oxoadipyl-7-aminocephalosporanic acid was 2-3-fold higher than by entrapped cells without MnO2. Glutaryl-7-aminocephalosporanic acid can be easily obtained from the resulting oxo-product by a non-enzymic reaction via externally added hydrogen peroxide.     

Spatial pattern, patch dynamics and successional change: chironomid assemblages in a Lake Erie coastal wetland

1. Distribution patterns in 1994 and 1995 of chironomid larvae in the sediments of wetlands on Presque Isle, Pennsylvania were used to determine whether relationships exist among species composition and wetland age, position or environmental characteristics. Canonical correspondence analysis was used to relate wetland age, degree of isolation, vegetation abundance and water chemistry to species composition.
2. Of forty-two chironomid taxa collected, Tanytarsus lugens group, Paratanytarsus sp. and Cladotanytarsus mancus group were the most widespread, but Lauterborniella agrayloides , Stictochironomus sp. and Cryptochironomus sp. were locally abundant in several sampling sites.
3. The canonical ordination based on all site characteristics was statistically significant and accounted for 54.9% of the variance in the species data and 69.5% of the variance in the species–environment relationship. The variables that contributed significantly to the ordination model were macrophyte abundance, conductivity and wetland area.
4. Partial canonical ordination based on environmental conditions with wetland age and position effects as covariables showed that environmental conditions explain a significant proportion of the variance in species composition among sites. Neither wetland age nor position variables explain a significant proportion of the variance in species composition.     

Spatial pattern, patch dynamics and successional change: chironomid assemblages in a Lake Erie coastal wetland

1. Distribution patterns in 1994 and 1995 of chironomid larvae in the sediments of wetlands on Presque Isle, Pennsylvania were used to determine whether relationships exist among species composition and wetland age, position or environmental characteristics. Canonical correspondence analysis was used to relate wetland age, degree of isolation, vegetation abundance and water chemistry to species composition.
2. Of forty-two chironomid taxa collected, Tanytarsus lugens group, Paratanytarsus sp. and Cladotanytarsus mancus group were the most widespread, but Lauterborniella agrayloides , Stictochironomus sp. and Cryptochironomus sp. were locally abundant in several sampling sites.
3. The canonical ordination based on all site characteristics was statistically significant and accounted for 54.9% of the variance in the species data and 69.5% of the variance in the species–environment relationship. The variables that contributed significantly to the ordination model were macrophyte abundance, conductivity and wetland area.
4. Partial canonical ordination based on environmental conditions with wetland age and position effects as covariables showed that environmental conditions explain a significant proportion of the variance in species composition among sites. Neither wetland age nor position variables explain a significant proportion of the variance in species composition.     

The fate of stormwater-associated bacteria in constructed wetland and water pollution control pond systems

The performances of a constructed wetland and a water pollution control pond were compared in terms of their abilities to reduce stormwater bacterial loads to recreational waters. Concentrations of thermotolerant coliforms, enterococci and heterotrophic bacteria were determined in inflow and outflow samples collected from each system over a 6-month period. Bacterial removal was significantly less effective in the water pollution control pond than in the constructed wetland. This was attributed to the inability of the pond system to retain the fine clay particles (< 2 microm) to which the bacteria were predominantly adsorbed. Sediment microcosm survival studies showed that the persistence of thermotolerant coliforms was greater in the pond sediments than in the wetland sediments, and that predation was a major factor influencing bacterial survival. The key to greater bacterial longevity in the pond sediments appeared to be the adsorption of bacteria to fine particles, which protected them from predators. These observations may significantly affect the choice of treatment system for effective stormwater management.     

Manganese as an ecological factor in salt marshes

The plant available manganese concentration (Mn²⁺) of salt-marsh sediments was compared to that of acidic and neutral soils. The mean soil-manganese concentration was higher in the top 1 cm of salt-marsh soil than in the neutral soil and comparable to that of the acidic soil (0–5 cm). A peak in the soil-manganese concentration in the upper marsh was observed one week after the spring tide but this effect was not evident in the lower marsh. Despite these differences, there was no correlation between mean manganese concentration and position on the marsh.The response to manganese of salt-marsh halophytes was studied by measuring growth and root elongation in a range of Mn²⁺ concentrations with and without sodium chloride. Although there was a differential response to manganese between salt-marsh species, manganese resistance was not related to position on the marsh. Most of the species investigated were tolerant of Mn²⁺ at concentrations higher than normally recommended for plant growth. Moreover a salt-marsh ecotype of Festuca rubra was found to have a higher manganese resistance than an inland ecotype of the same species.When sodium chloride was included in the growth medium, salt-marsh plants had a greatly increased resistance to manganese associated with a reduced uptake. This effect is reflected in the tissue-manganese concentration which was lower than in Deschampsia flexuosa although both groups of plants were exposed to a similar range of Mn²⁺ concentrations. It is concluded that sodium chloride markedly reduces the phytotoxicity of manganese in salt marshes.Nomenclature following Clapham, Tutin & Warburg (1968). Flora of the British Isles.The work was carried out while one of us (C. E. Singer) was in receipt of an SERC studentship, which is gratefully acknowledged.     

Changes in biotic communities developing from freshwater wetland sediments under experimental salinity and water regimes

1. Reduction in diversity of both freshwater aquatic and terrestrial ecosystems has been attributed to salinity increase and such increases are a symptom of changes to land use. Hydrological alteration to ground and surface water are likely to be associated with salinity increase and its influence on biodiversity. However the combined effects of salinity and hydrology on aquatic biodiversity have not been elucidated fully in either field or experimental situations. 2. The effect of salinity and water regime on the biota in sediments from seven wetlands from inland south‐eastern Australia was tested experimentally using germination of aquatic plant seeds (five salinity and two water levels) and emergence of zooplankton eggs (five salinity levels). Salinity levels were <300, 1000, 2000, 3000, 5000 mg L^?1 and water regimes were damp (waterlogged) and submerged. 3. Aquatic plant germination and zooplankton hatching was not consistent for all seven wetland sediments. Four of the wetland sediments, Narran Lakes, Gwydir Wetlands, Macquarie Marshes and Billybung Lagoon showed similar responses to salinity and water regime but the other three wetland sediments from Lake Cowal, Great Cumbung Swamp and Darling Anabranch did not. 4. As salinity increased above 1000 mg L^?1 there was a decrease in the species richness and the abundance of biota germinating or hatching from sediment from four of the wetlands. 5. Salinity had a particularly strong effect in reducing germination from sediments in damp conditions when compared to the flooded conditions. In parallel, salts accumulated in the sediment in damp conditions but did not in flooded conditions. 6. There is potential for increasing salinity in freshwater rivers and wetlands to decrease the species richness of aquatic communities and thus of the wetland community as a whole, resulting in loss of wetland biodiversity. This reduction in diversity varies between wetlands and is at least partly related to hydrology. For aquatic plants the reduction in diversity will be more marked for plants germinating from seed banks at the edges of wetlands where plants are not completely submerged than for the same seed bank germinating in submerged conditions.     

Manganese bioleaching from pyrolusite: Bacterial properties reliable for the process

Abstract: Technological exploitation of biohydrometallurgy for industrial metal recovery starts with batch and lab scale researches aimes at defining the basic information on microbiological and physico-chemical conditions influencing the process. An Italian ore having MnO₂ as the most relevant component (27%) was subjected to bioleaching under different conditions, both in batch and lab scale fermenters. The results show that microbial solubilization of MnO₂ in batch cultures requires MnO₂ to be reduced to Mn²⁺. The process is influenced by several factors, e.g. nature, amount of organic matter and specific granulometry of the mineral. Quite surprisingly, aerobic conditions are required for manganese solubilization which, on the contrary, accumulates in a reduced chemical form. In a lab scale fermenter, multifactorial analysis of both data and physico-chemical factors indicates that an almost general correlation is found between the extent of sucrose expenditure and pyrolusite solubilization when different concentrations of sucrose and MnO₂ are applied.     

Prion protein fate governed by metal binding

The conversion of the normal cellular prion protein to an abnormal isoform is considered to be causal to the prion diseases or transmissible spongiform encephalopathies. The prion protein is a copper binding protein but under some conditions may bind other metals. In particular, the binding of manganese has been suggested to convert the prion protein (PrP) to a protease resistant isoform. Therefore, the differences in the way the protein binds copper and manganese might be revealing in terms of the mechanism of conversion of the protein or its normal cellular activity. We report the use of near-infrared spectroscopy for studies on aqueous solutions of prion protein binding Cu or Mn. These alloforms of the protein were analyzed by spectral data acquisition and multivariate analysis. Our results indicate that PrP binds both Mn and Cu differently. Analyses of Cu binding suggest that the PrP-Cu complex protected Cu from the water increasing protein stability. PrP-Mn does not protect Mn from water interactions. A real-time study of the protein alloforms showed that PrP-Cu remains stable in solution, but that PrP-Mn underwent highly different changes that led to fibril formation.     

Biotransformation of manganese oxides by fungi: solubilization and production of manganese oxalate biominerals

The ability of the soil fungi Aspergillus niger and Serpula himantioides to tolerate and solubilize manganese oxides, including a fungal-produced manganese oxide and birnessite, was investigated. Aspergillus niger and S.?himantioides were capable of solubilizing all the insoluble oxides when incorporated into solid medium: MnO(2) and Mn(2) O(3) , mycogenic manganese oxide (MnO(x) ) and birnessite [(Na(0.3) Ca(0.1) K(0.1) )(Mn(4+) ,Mn(3+) )(2) O(4) ·1.5H(2) O]. Manganese oxides were of low toxicity and A.?niger and S.?himantioides were able to grow on 0.5% (w/v) of all the test compounds, with accompanying acidification of the media. Precipitation of insoluble manganese and calcium oxalate occurred under colonies growing on agar amended with all the test manganese oxides after growth of A.?niger and S.?himantioides at 25°C. The formation of manganese oxalate trihydrate was detected after growth of S.?himantioides with birnessite which subsequently was transformed to manganese oxalate dihydrate. Our results represent a novel addition to our knowledge of the biogeochemical cycle of manganese, and the roles of fungi in effecting transformations of insoluble metal-containing compounds in the environment.     

Design and application of rRNA-targeted oligonucleotide probes for the dissimilatory iron- and manganese-reducing bacterium Shewanella putrefaciens.

A 16S rRNA-targeted oligonucleotide probe specific for the iron (Fe3+)- and manganese (Mn4+)-reducing bacterium Shewanella putrefaciens was constructed and tested in both laboratory- and field-based hybridization experiments. The radioactively labeled probe was used to detect S. putrefaciens in field samples collected from the water column and sediments of Oneida Lake in New York and its major southern tributary, Chittenango Creek. S. putrefaciens was quantified by (i) hybridization of the probe to bulk RNA extracted from field samples and normalization of the S. putrefaciens-specific rRNA to total eubacterial rRNA, (ii) a colony-based probe hybridization assay, and (iii) a colony-based biochemical assay which detected the formation of iron sulfide precipitates on triple-sugar iron agar. The results of field applications indicated that the three detection methods were comparable in sensitivity for detecting S. putrefaciens in water column and sediment samples. S. putrefaciens rRNA was detected in the surficial layers of the lake and creek sediments, but the levels of S. putrefaciens rRNA were below the detection limits in the lake and creek water samples. The highest concentrations of S. putrefaciens rRNA, corresponding to approximately 2% of the total eubacterial rRNA, were detected in the surficial sediments of Chittenango Creek and at a midlake site where the Oneida Lake floor is covered by a high concentration of ferromanganese nodules. This finding supports the hypothesis that metal-reducing bacteria such as S. putrefaciens are important components in the overall biogeochemical cycling of iron, manganese and other elements in seasonally anoxic freshwater basins.     

韭菜线粒体锰超氧化物歧化酶纯化及性质研究

经硫酸铵沉淀、ＤＥＡＥ－Ｓｅｐｈａｃｅｌ层析和Ｓｅｐｈａｄｅｘ Ｇ－２００凝胶过滤,将韭菜线粒体ＳＯＤ纯化到均一程度。从６０００ｇ韭菜叶片线粒体中纯化得到２．５ｍｇ酶,酶比活力达１２００Ｕ／ｍｇ蛋白。该酶对ＫＣＮ和Ｈ２Ｏ２都不敏感,热稳定性弱 外光区吸收峰在２８０ｎｍ,凝胶过滤法测得其分子量为８２００Ｄ,ＳＯＳ－ＰＡＧＥ法测定其亚基分子量的２２０００Ｄ,ＤＮＳ法测得其Ｎ－末端氨基酸为缬氨酸。上述结     

Phytoremediation in Wetland Ecosystems: Progress,Problems, and Potential

Assessing the phytoremediation potential of wetlands is complex due to variable conditions of hydrology, soil/sediment types, plant species diversity, growing season, and water chemistry. Conclusions about long-term phytoremediation potential are further complicated by the process of ecological succession in wetlands. This review of wetlands phytoremediation addresses the role of wetland plants in reducing contaminant loads in water and sediments, including metals; volatile organic compounds (VOC), pesticides, and other organohalogens; TNT and other explosives; and petroleum hydrocarbons and additives. The review focuses on natural wetland conditions and does not attempt to review constructed wetland technologies. Physico-chemical properties of wetlands provide many positive attributes for remediating contaminants. The expansive rhizosphere of wetland herbaceous shrub and tree species provides an enriched culture zone for microbes involved in degradation. Redox conditions in most wetland soil/sediment zones enhance degradation pathways requiring reducing conditions. However, heterogeneity complicates generalizations within and between systems. Wetland phytoremediation studies have mainly involved laboratory microcosm and mesocosm technologies, with the exception of planted poplar communities. Fewer large-scale field studies have addressed remediation actions by natural wetland communities. Laboratory findings are encouraging with regards to phytoextraction and degradation by rhizosphere and plant tissue enzymes. However, the next phase in advancing the acceptance of phytoremediation as a regulatory alternative must demonstrate sustained contaminant removal by intact natural wetland ecosystems.     

塔里木河下游湿地面积时序变化及对生态输水的响应

及时了解和定量分析荒漠区河岸带湿地月度时序变化趋势及对生态输水过程的响应, 对认识湿地生态修复过程, 改进生态输水策略, 维护湿地生态系统稳定具有重要意义。该文基于Landsat ETM+/TM/OLI和Sentinel 2形成的月尺度的密集长时序遥感数据, 分析2000-2018年塔里木河下游英苏-阿拉干之间的湿地时序变化特征, 并评估湿地变化对生态输水过程的响应。结果表明: 近19年来湿地面积持续增加, 其中2011-2013年和2017-2018年是面积快速增加的时段。不同的单、双通道输水方式和输水量大小解释了喀尔达依湿地与博孜库勒湿地在不同时段增长的快慢。对湿地面积与生态输水量、地下水埋深关系的分析表明, 累计生态输水量的持续增加是近20年来塔里木河下游河岸带湿地扩张的重要因素, 每年大于3.5亿m ³的双通道生态输水, 地下水埋深维持在-5.0- -3.5 m是湿地持续稳定增长的关键。