Biological manganese removal from acid mine drainage in constructed wetlands and prototype bioreactors

Mine drainage waters vary considerably in the range and concentration of heavy metals they contain. Besides iron, manganese is frequently present at elevated concentrations in waters draining both coal and metal mines. Passive treatment systems (aerobic wetlands and compost bioreactors) are designed to remove iron by biologically induced oxidation/precipitation. Manganese, however, is problematic as it does not readily form sulfidic minerals and requires elevated pH (>8) for abiotic oxidation of Mn (II) to insoluble Mn (IV). As a result, manganese removal in passive remediation systems is often less effective than removal of iron. This was found to be the case at the pilot passive treatment plant (PPTP) constructed to treat water draining the former Wheal Jane tin mine in Cornwall, UK, where effective removal of manganese occurred only in one of the three rock filter components of the composite systems over a 1-year period of monitoring. Water in the two rock filter systems where manganese removal was relatively poor was generally 相似文献   

A study of the cycling of manganese and other elements in a seasonally anoxic lake, Rostherne Mere, U.K.

The vertical distribution of sulphate, dissolved sulphide, alkalinity, pH, total iron and manganese, Fe(II) and Mn(II) and humic substances was monitored for a year in a seasonally anoxic lake, Rostherne Mere, U.K. During summer stratification Mn(II), probably of sediment origin, accumulated in the hypolimnetic bottom waters to a concentration of 50μm. Release occurred in two stages and appeared to be related to the supply of organic material to the sediment. No ferrous iron or dissolved sulphide were detected in the water column, although they were measured in the interstitial waters of the sediment. Ferrous sulphide formation in the sediment controls the iron(II) and dissolved sulphide concentrations and so minimises the concentration gradients at the sediment-water interface. Electron acceptors other than oxygen are capable of oxidising ferrous and sulphide ions in the water column. pH and alkalinity were the only other chemical components to show appreciable variation with depth, reflecting the biological processes of photosynthesis, respiration and decomposition. Iron and humic substances simultaneously increased in the surface waters after a major flood indicating that they are both present in the solution in contact with the soils of the catchment.     

黄土对锰离子的吸附特性及机理研究

重金属污染事件频发引起了很多学者的关注,锰是一种重金属痕量元素,人体通过食物链摄入过量的锰会产生中毒效应。研究了Mn(II)的浓度、反应温度、土水比、pH值等因素对Mn(II)在黄土上吸附特性的影响。黄土对Mn(II)的吸附容量可达7.84 mg/g,等温吸附模型Langmuir、Freundlich和D-R模型都能很好地解释Mn(II)在黄土上的吸附性能。热动力学分析表明Mn(II)在黄土上的吸附是一个自发的过程,升高温度可促进吸附作用的进行。增大土水比可提高Mn(II)的去除效率,但单位黄土上Mn(II)的吸附量有个最优值。Mn(II)的初始浓度越大单位黄土的最大吸附量越小,达到最大吸附量所需的土水比越高。溶液的酸碱度是影响Mn(II)去除效果的一个重要因素,pH>10.7时Mn(II)几乎完全被去除。通过X光衍射图谱和红外光谱分析,探讨了黄土与Mn(II)的结合机理,黄土中的黏土矿物、有机质成分对重金属Mn(II)的吸附起重要作用。     

Kinetic modeling of pyruvic acid ozonation in aqueous solutions catalyzed by Mn(II) and Mn(IV) ions

The ozonation of pyruvic acid (2-ketopropionic acid) in aqueous solutions, catalyzed by Mn(II) and Mn(IV) ions, has been studied at three different pH values (pH = 1.1, 2.0 and 3.0). A mathematical model of the unsteady operation of the experimental reactor has been developed, which takes into account the reactions occurring in the liquid phase and the ozone mass transfer from the gas bubbles. Those reactions have been described with two alternative kinetic models, both made out of four elementary steps. The two kinetic models correlate the experimental data with a fair accuracy, respectively at the lowest and at the highest pH examined. In particular, at pH = 3.0, the ozonation results are inhibited by the acetate ions produced by the reaction itself. This effect has been correctly described in the terms of a complex formed with the low oxidation-state manganese, which successively reacts with the dissolved ozone.     

Potential kinetic availability of metals in sulphidic freshwater sediments

The insolubility of metal sulphides is believed to limit the bioavailability of trace metals in sulphidic sediments. However, if non-equilibrium conditions are important, metals may be more available than simple thermodynamic calculations suggest. To investigate the possible dynamic supply of Cu, Ni and Zn in a sulphidic freshwater sediment, they were measured, along with iron, manganese and sulphide, by the technique of diffusive gradients in thin-films (DGT). DGT measures the supply of solute from sediment to solution in response to a local solute sink. Release of Mn, Cu, Zn and Ni was observed at the sediment surface and attributed to the supply from reductive dissolution of manganese oxides. The depth profile of simultaneously extractable metals (SEM) for Cu and Ni followed the shape of the Mn profile more closely than the profiles of either acid volatile sulphur (AVS) or Fe, again consistent with supply from Mn oxides. Solubility calculations for a mesocosm of homogenised sediment indicated supersaturation with respect to the sulphides of Fe, Cu, Ni and Zn, yet DGT measurements demonstrated a substantial supply of both trace metals and sulphide from the solid phase to the pore waters. Ratios of metals measured in pore waters by DGT were consistent with their release from iron and manganese oxides, indicating that supply, as much as removal processes, determines the pseudo-steady state concentrations in the pore waters. The observations suggest that trace metals are not immediately bound in an insoluble, inert form when they are in contact with sulphide. This has consequences for modelling metal processes in sediment, as well as for uptake by some biota.     

Biological treatment of Mn(II) and Fe(II) containing groundwater: kinetic considerations and product characterization

In the present article, the treatment of groundwater containing Mn(II) and Fe(II) has been investigated. The biological oxidation of Mn(II) and Fe(II) in upflow filtration units comprised the applied experimental technique. The oxidation processes were mediated by specific bacteria, namely the Leptothrix ochracea and Gallionella ferruginea, which belong to the general category of manganese and iron oxidizing bacteria. This work was focused on the characterization of the products of biological oxidation and to the examination of the kinetics of Mn(II) removal as compared with Fe(II) removal from groundwaters. The products of biological oxidation were characterized using the spectroscopic techniques XRD, XPS and SEM-EDS and comprised a mixture of biogenic hydrous manganese and iron oxides. The oxidation state of manganese in the precipitates was found to be between 3 and 4. Iron oxides were mainly in the form of amorphous ferrihydrite. The kinetic results indicated that the rates of manganese and iron oxidation were several orders of magnitude greater than the respective for abiotic oxidation. The bacterially mediated oxidation of iron was faster than manganese oxidation, presenting half-lives of reaction 0.9 and 3.98 min, respectively.     

高锰酸盐预氧化去除太湖原水中稳定性铁、锰

太湖B支流河水属于低浊、高藻、高铁锰、高色度和高耗氧量水质，其中铁、锰主要以溶解态和胶体态（铁、锰化合物胶体）存在。胶体态铁、锰被有机物膜包裹，和溶解态铁、锰形成了高稳定性铁、锰，采用常规给水工艺处理时难于去除。为此，开展了高锰酸盐（PPC）预氧化去除该原水中稳定性铁、锰的研究。结果表明，高锰酸盐对稳定性铁、锰的去除效果好，但受预氧化时间、pH值、水中本底成分的影响较大。在预氧化时间为30min、原水锰含量〈0．67mg／L时，对锰的去除率接近100％；在预氧化时间为60min、原水铁含量〈0．5mg／L时，对铁的去除率约为100％。当原水为酸性和碱性时，预氧化对铁、锰的去除率较高，在中性条件下去除率则相对较低。     

Manganese micro-nodules on ancient brick walls

Romans, Jews, Arabs and Christians built the ancient city of Toledo (Spain) with bricks as the main construction material. Manganese micro-nodules (circa 2 microm in diameter) have grown under the external bio-film surface of the bricks. Recent anthropogenic activities such as industrial emissions, foundries, or traffic and housing pollution have further altered these old bricks. The energy-dispersive X-ray microanalyses (XPS) of micro-nodules show Al, Si, Ca, K, Fe and Mn, with some carbon species. Manganese atoms are present only as Mn(4+) and iron as Fe(3+) (FeOOH-Fe(2)O(3) mixtures). The large concentration of alga biomass of the River Tagus and the Torcón and Guajaraz reservoirs suggest manganese micro-nodules are formed either from water solutions rich in anthropogenic MnO(4)K in a reduction environment (from Mn(7+) to Mn(4+)) or by oxidation mechanisms from dissolved Mn(2+) (from Mn(2+) to Mn(4+)) linked to algae biofilm onto the ancient brick surfaces. Ancient wall surfaces were also studied by scanning electron microscopy (SEM-EDS) and X-ray diffraction (XRD). Chemical and biological analyses of the waters around Toledo are also analysed for possible sources of manganese. Manganese micro-nodules on ancient brick walls are good indicators of manganese pollution.     

Spatio-temporal change of water chemical elements in Lake Dianchi, China

Lake Dianchi is a large lake, which is listed in the 'Three Important Lakes Restoration Act in China'. The water quality has deteriorated from class II in the 1970s to class V today, with an attendant increase in the frequency and intensity of the formation of blue algae blooms. From 2003 to 2006, a water quality monitoring programme was implemented for eight regional zones in Lake Dianchi. It monitored the following substances: carbon (C), nitrogen (N), phosphorus (P), sulphur (S), calcium (Ca), magnesium (Mg), iron (Fe), potassium (K), sodium (Na), zinc (Zn), copper (Cu), manganese (Mn) and chlorine (Cl), together with water temperature, pH, total hardness and total salt content. Data were analysed using regression models to determine the impacts of these substances and conditions for the formation of blue algae bloom, and to assess their relationship with chlorophyll a . The results showed a significant relationship between chlorophyll a and C, P, N, Cl, Fe, Mg, water temperature, pH, total hardness and total salt. There was no significant relationship between chlorophyll a and total manganese (TMn), Mn, sulphate (SO₄²⁻), soluble total manganese STMn, Ca, Zn, K, Na and Cu. The study showed that the concentration of chlorophyll a in different regions of the lake was different, indicating that the mix of chemicals in a region has a different impact on pollution levels throughout Lake Dianchi.     

Manganese removal during bench-scale biofiltration

As biological manganese (Mn) removal becomes a more popular water treatment technology, there is still a large gap in understanding the key mechanisms and range of operational characteristics. This research aimed to expand on previous bench-scale experiments by directly comparing small filtration columns inoculated with indigenous biofilms from a Mn filtration plant and filtration columns inoculated with a liquid suspension of Leptothrix discophora SP-6. Batch tests found that in the absence of manganese oxidizing bacteria Mn was not removed by air alone, whereas a mixed population and Leptothrix strain achieved greater than 90% removal of Mn. The bench-scale biofiltration experiments found that biological filters can be inoculated with a pure culture of L. discophora SP-6 and achieve a similar removal of indigenous biofilm. While Mn oxidizing bacteria (MOB) seem to be necessary for the auto-catalytic nature of these biological filters, Mn removal is achieved with a combination of adsorption to Mn oxides and biological oxidation. Additionally, it was demonstrated that biological Mn removal is possible over a broader “field of activity” (e.g., Mn removal occurred at a pH level as low as 6.5) than has previously been reported. The ability of this treatment technology to work over a broader range of influent conditions allows for more communities to consider biological treatment as an option to remove Mn from their drinking water.     

Chemistry of trace elements in coalbed methane product water

Extraction of methane (natural gas) from coal deposits is facilitated by pumping of aquifer water. Coalbed methane (CBM) product water, produced from pumping ground water, is discharged into associated unlined holding ponds. The objective of this study was to examine the chemistry of trace elements in CBM product water at discharge points and in associated holding ponds across the Powder River Basin, Wyoming. Product water samples from discharge points and associated holding ponds were collected from the Cheyenne River (CHR), Belle Fourche River (BFR), and Little Powder River (LPR) watersheds during the summers of 1999 and 2000. Samples were analyzed for pH, Al (aluminum), As (arsenic), B (boron), Ba (barium), Cr (chromium), Cu (copper), F (fluoride), Fe (iron), Mn (manganese), Mo (molybdenum), Se (selenium), and Zn (zinc). Chemistry of trace element concentrations were modeled with the MINTEQA2 geochemical equilibrium model. Results of this study show that pH of product water for three watersheds increased in holding ponds. For example the pH of CBM product water increased from 7.21 to 8.26 for LPR watershed. Among three watersheds, the CBM product water exhibited relatively less change in trace element concentrations in CHR watershed holding ponds. Concentration of dissolved Al, Fe, As, Se, and F in product water increased in BFR watershed holding ponds. For example, concentration of dissolved Fe increased from 113 to 135 microg/L. Boron, Cu, and Zn concentrations of product water did not change in BFR watershed holding ponds. However, concentration of dissolved Ba, Mn, and Cr in product water decreased in BFR watershed holding ponds. For instance, Ba and Cr concentrations decreased from 445 to 386 microg/L and from 43.6 to 25.1 microg/L, respectively. In the LPR watershed, Al, Fe, As, Se, and F concentrations of product water increased substantially in holding ponds. For example, Fe concentration increased from 192 to 312 microg/L. However, concentration of dissolved Ba, Mn, Cr, and Zn decreased in holding ponds. Geochemical modeling calculations suggested that observed increase of Al and Fe concentrations in holding ponds was due to increase in concentration of Al(OH)(4)(-) and Fe(OH)(4)(-) species in water which were responsible for pH increases. Decreases in Ba, Mn, Cr, and Zn concentrations were attributed to the increase in pH, resulting in precipitates of BaSO(4) (barite), MnCO(3) (rhodochrosite), Cr(OH)(2) (chromium hydroxide), and ZnCO(3) (smithsonite) in pond waters, respectively.     

Manganese and land-use in upland catchments in Scotland

Manganese (Mn) in surface waters is a micronutrient, but elevated concentrations are toxic to fish and impair drinking water quality. In Scotland, undesirable Mn concentrations (> 0.05 mg l(-1)) occur predominantly in upland freshwaters because the acidic pH and organic nature of catchment soils favour Mn mobilisation. The relationship between upland land-use in Scotland and Mn concentrations in surface waters is reviewed. Conifer afforestation is associated with enhanced Mn in runoff. Mn is leached from conifer foliage and litter, and mature conifers enhance acid deposition and loss of Mn from acidified catchment soils. After harvesting, increased soil pools of water-soluble Mn and elevated Mn concentrations in runoff have been observed. Liming, fertiliser addition, drainage ditch construction and ploughing to improve upland pastures, and muirburn on grouse moors may also increase Mn concentrations in runoff, but the evidence is less clear-cut. The extent to which land-use influences Mn concentrations in upland catchments in Scotland is modified by catchment hydrology and soil type. Catchment geology, instream processes and standing water stratification are probably lesser influences on Mn concentrations in surface waters of upland catchments in Scotland. The location of land-use in upland catchments, especially in the riparian zone, is critical in determining its effect on Mn in runoff. Climate change is expected to increase Mn concentrations in runoff from upland catchments in Scotland because of predicted changes in soil hydrology.     

Mn(II)、Cr(III)在黄土上共存吸附特性研究

重金属是土体污染中最重要的污染物质之一,土中的重金属污染往往是复合污染的形式。通过一系列室内试验,研究了锰铬重金属共存时在黄土上的吸附特性。在Mn(II)、Cr(III)重金属复合体系中,Mn(II)在黄土上的吸附明显受到抑制,吸附量减小14.6%~46.5%,而Cr(III)在黄土上的吸附基本不受Mn(II)的影响。Mn(II)的吸附能较好地符合Langmuir模型,受Cr(III)的抑制而不能很好地符合Fredunlich、D-R模型,Cr(III)的吸附仍能较好地符合Fredunlich、D-R模型。在pH=5~7酸性条件下Cr(III)促进了Mn(II)在黄土上的吸附,Mn(II)对Cr(III)的吸附稍有抑制;在碱性条件下,Cr(III)基本不受影响能完全被去除,而Mn(II)的吸附受到很大的抑制作用。重金属本身的物理属性比如水解常数大小以及黄土中的矿物成分都对Mn(II)、Cr(III)在黄土上吸附特性发挥了重要作用。     

负锰滤料去除地下水中锰的影响因素研究

通过锥形瓶静态实验,研究不同参数下负锰滤料对水中锰（Mn2＋）的去除效果.实验表明：滤料粒径为2mm时,Mn2＋的去除率及实际应用效果最佳;随着负锰滤料投加量的增加,Mn2＋的去除率也随之增加;随着溶液pH值的升高,滤料对水中的Mn2＋的去除率也随之增加;若体系中有Fe2＋存在,不利于负锰滤料对Mn2＋的吸附;负锰滤料对Mn2＋吸附等温线更符合Langmuir吸附模型,属于单分子层吸附.     

Variation of manganese, dissolved oxygen and related chemical parameters in the bottom waters of Lake Mendota, Wisconsin

The increase of Mn concentration and the simultaneous depletion of dissolved oxygen in the bottom waters (hypolimnion) of Lake Mendota, Wisconsin were studied in situ. Considerably higher Mn concentrations were found in the hypolimnion compared to Fe, despite a sedimentary Fe/Mn weight ratio of 19 : 1. Laboratory equilibration studies under anoxic conditions indicated that pH was an important parameter involved in the release of Mn from the sediments. This was also implied by the Mn and pH data measured in situ. Possible mechanisms involved in the release of Mn from the sediments including desorption of Mn from oxide substrates, reduction of Mn oxides and dissolution of carbonates and sulfides are discussed.     

Complexation analysis of fresh waters by equilibrium diafiltration

Equilibrium ultrafiltration has been employed to determine the extent of Cu, Ni, Co, Fe, Mn and Zu chelation in oxic waters from mineralized terrains. Concentrations of Cu, Ni and Co were determined in different organic fractions separated by various Amicon ultrafilters. Titrations of fresh water samples with metal ions were made, and “free” metal concentration measured by equilibrium diafiltration. Experiments were made at concentrations and pH at which metals and ligands occur in natural waters. Conditional stability functions ranged from 10^6.72 at pH 6.5 to 10^7.07 at pH 7.6 for Ni and 10^6.85 at pH 6.8 to 10^6.97 at pH 7.6 for Co. At low metal concentrations (8 × 10⁻⁷ M) only one complexing class of major importance for natural water environments was observed. The order of metal complexing ability was found to be Cu > Ni > Co > Zn > Mn with Cu showing a preference towards the higher MW organic fractions.     

Removal of metal ions by modified Pinus radiata bark and tannins from water solutions

Pinus radiata bark and tannins, chemically modified with an acidified formaldehyde solution were used for removing metal ions from aqueous solutions and copper mine acidic residual waters. The adsorption ability to different metal ions [V(V), Re(VII), Mo(VI), Ge(IV), As(V), Cd(II), Hg(II), Al(III), Pb(II), Fe(II), Fe(III), Cu(II)] and the factors affecting their removal from solutions were investigated. Effect of pH on the adsorption, desorption, maximum adsorption capacity of the adsorbents, and selectivity experiments with metal ion solutions and waste waters from copper mine were carried out. The adsorbents considerably varied in the adsorption ability to each metal ion. The adsorption depends largely upon the pH of the solution. Modified tannins showed lower adsorption values than the modified bark. For the same adsorbent, the maximum capacity at pH 3 for the different ions were very different, ranging for modified bark from 6.8 meqg⁻¹ for V to 0.93 meqg⁻¹ for Hg. Waste waters were extracted with modified bark as adsorbent and at pH 2. The ions Cu(II) (35.2 mgL⁻¹), Fe(III) (198 mgL⁻¹), Al(III) (83.5 mgL⁻¹) and Cd(II) (0.15 mgL⁻¹) were removed in 15.6%, 46.9%, 83.7% and 3.3%, respectively, by using 1 g of adsorbent/10 mL of waste water. In general, a continuous adsorption on a packed column gave higher adsorbed values than those observed in the batchwise experiment.     

Potential of dandelion (Taraxacum officinale) as a bioindicator of manganese arising from the use of methylcyclopentadienyl manganese tricarbonyl in unleaded gasoline

Methylcyclopentadienyl manganese tricarbonyl (MMT) is an organic manganese (Mn) compound currently added to unleaded gasoline in Canada. It has been suggested that the combustion of MMT containing Mn could cause various deleterious health effects in animals and humans at very high concentrations. This study evaluates the potential of dandelions (Taraxacum officinale) as bioindicators of Mn environmental contamination. Samples were picked at three different distances from a highway: a highly exposed site (E++), a lightly exposed site (E+) and a control site (E), located respectively at 10, 50 and 100 m. The total Mn, Mg, Ca, Al, Fe and Zn concentrations were measured in the soils and in the plants (flower, stem, leaves and root) by neutron activation analysis. Exchangeable Mn was measured in soils by atomic absorption spectrophotometry. Mn concentrations of the different parts of the plant and exchangeable Mn in soils were not correlated with distance from the roadway and, thus, do not seem to be a sensitive indicator of Mn contamination. Soil Mn concentrations were correlated with distance from the roadway. This suggests the hypothesis that the environmental fate of Mn from MMT sources could be associated with an increased total Mn in soil but does not lead to an increase in exchangeable Mn.     

Sorption of lead ions on diatomite and manganese oxides modified diatomite

Naturally occurring diatomaceous earth (diatomite) has been tested as a potential sorbent for Pb(II) ions. The intrinsic exchange properties were further improved by modification with manganese oxides. Modified adsorbent (referred to as Mn-diatomite) showed a higher tendency for adsorbing lead ions from solution at pH 4. The high performance exhibited by Mn-diatomite was attributed to increased surface area and higher negative surface charge after modification. Scanning electron microscope pictures revealed a birnessite structure of manganese oxides, which was featured by a plate-like-crystal structure. Diatomite filtration quality was improved after modification by manganese oxides. Good filtration qualities combined with high exchange capacity emphasised the potential use of Mn-diatomite in filtration systems.     

Motor alterations associated with exposure to manganese in the environment in Mexico

Overexposure to manganese (Mn) causes neurotoxicity (a Parkinson-like syndrome) or psychiatric damage ("manganese madness"). Several studies have shown alterations to motor and neural behavior associated with exposure to Mn in the workplace. However, there are few studies on the effects of environmental exposure of whole populations. We studied the risk of motor alterations in people living in a mining district in Mexico. We studied 288 individual people (168 women and 120 men) from eight communities at various distances from manganese extraction or processing facilities in the district of Molango. We measured manganese concentrations in airborne particles, water, soil and crops and evaluated the possible routes of Mn exposure. We also took samples of people's blood and determined their concentrations of Mn and lead (Pb). We used "Esquema de Diagnóstico Neuropsicológico" Ardila and Ostrosky-Solís's neuropsychological battery to evaluate motor functions. Concentrations of Mn in drinking water and maize grain were less than detection limits at most sampling sites. Manganese extractable by DTPA in soils ranged between 6 and 280 mg kg(-1) and means were largest close to Mn extraction or processing facilities. Air Mn concentration ranged between 0.003 and 5.86 microg/m(3); the mean value was 0.42 microg/m(3) and median was 0.10 microg/m(3), the average value (geometric mean) resulted to be 0.13 microg/m(3). Mean blood manganese concentration was 10.16 microg/l, and geometric mean 9.44 microg/l, ranged between 5.0 and 31.0 mcrog/l. We found no association between concentrations of Mn in blood and motor tests. There was a statistically significant association between Mn concentrations in air and motor tests that assessed the coordination of two movements (OR 3.69; 95% CI 0.9, 15.13) and position changes in hand movements (OR 3.09; CI 95% 1.07, 8.92). An association with tests evaluating conflictive reactions (task that explores verbal regulations of movements) was also found (OR 2.30; CI 95% 1.00, 5.28). It seems from our results that people living close to the manganese mines and processing plants suffer from an incipient motor deficit, as a result of their inhaling manganese-rich dust.