Exchange of Mn compounds between bottom sediments and water: 1. Mn flux from water to the bed

Formation mechanisms of Mn flux from water into bottom sediments in the form of particulate matter are considered. Data characterizing Mn concentration in particulate matter, its transformation features, and the size of Mn-containing suspensions are given. Information about Mn fluxes from water to the bed of water bodies and the processes governing them are generalized.     

Manganese in the North Pacific

A quantitative and precise method for determination of dissolved Mn at the nanomole(nmol)/kg level in seawater has been developed and used to study the distribution of Mn in the northeast Pacific. Mn concentrations in the surface mixed layer decrease from 1.0 to 0.6 nmol/kg between the central gyre and the western boundary of the California Current, then increase to values from 2 to 6 nmol/kg near the coastal boundary (in contrast to the distribution of²¹⁰Pb). Particulate Mn in the surface waters accounts for only about 1% of the total.Vertical distributions of Mn are characterized by surface maxima, minima near 300 m, maxima at mid-depth coinciding with the oxygen minimum and the labile nutrient maxima, and concentrations in Pacific bottom waters of approximately 0.2 nmol/kg. The oceanic distribution of Mn appears to be dominated by external inputs superimposed upon overall scavenging which can lead to Mn maxima in (1) the surface waters due to riverine and atmospheric sources; (2) the deep ocean as a result of hydrothermal injection and/or sediment resuspension; and (3) the oxygen minimum region resulting from in-situ breakdown of organic matter, in-situ MnO₂ reduction, and/or advective-diffusive transport of dissolved Mn from anoxic slope sediments.     

Cosmogenic radioisotopes in the Dhajala chondrite: implications to variations of cosmic ray fluxes in the interplanetary space

Activities of a suite of radioisotopes ranging in half-life from 5.6 days (⁵²Mn) to 3.7 m.y. (⁵³Mn) have been measured in the Dhajala chondrite. The results show that all the radioactivities are close to the expected levels except⁵⁴Mn and ²²Na. Their activities are higher than those based on the interplanetary fluxes at 1 A.U. near the ecliptic, expected immediately before the fall of Dhajala, corresponding to the time of solar minimum. Furthermore, activity ratios of ⁵⁴Mn/⁵³Mn and ²²Na/²⁶Al are higher by 30–50% than expected. The departure from the expected values is discussed in terms of spatial variations of cosmic rays based on the computed orbital parameters of the meteoroid. If the galactic cosmic ray fluxes in the equatorial region (±15°) are assumed to be the same as in the ecliptic plane then these results suggest higher fluxes by 33 ± 7% at heliographic latitudes 15–40°S, during solar minimum.     

Reconstructing the iron cycle from the horizontal distribution of metals in the sediment of Baldeggersee

In Baldeggersee, the distributions of solid phase Fe, Mn, V, Cr, As and Mo were determined in different sediment strata, deposited under various deep-water oxygen conditions. Iron concentrations are correlated with water depth when an anoxic sediment is in contact with an oxic water column. Benthic redox gradients trigger iron transport towards the deepest site (geochemical focusing) and loss of iron from the shallower parts through the outflow. Fe cycling in the lake is inhibited by oxygen penetration into the sediment. Vanadium and arsenic can be used as tracers for the internal Fe cycle. Their distribution patterns are highly correlated with iron. In case of a stable oxycline in the deep water, Mo is enriched in the sediment and correlates with Mn. The horizontal distribution patterns of Fe, V, As and the correlation of Fe and Mn with trace metals are promising proxy indicators for the reconstruction of deep-water oxygen conditions during deposition.     

Effects of the Santorini (Thera) eruption on manganese behavior in Holocene sediments of the eastern Mediterranean

The explosive eruption on the island of Santorini in ∼1630 B.C. in Minoan times had a large environmental impact over the eastern Mediterranean region. It has even been suggested that the Mn-enriched layer (the “Marker Bed”) above the most recent sapropel (S1) in sediments of a crestal area of the Mediterranean Ridge gained Mn from a hydrothermal source related to the Santorini eruption. Radiocarbon dating of two cores from this area sampled at high resolution demonstrate that this large Mn peak in fact pre-dates the Santorini event by ∼2.8 ky and forms part of a pattern seen in Mn profiles from all over the eastern Mediterranean. This same Mn profile shape is altered in areas that experienced substantial deposits of either the tephra layer emitted by the Santorini eruption or the turbidites that were triggered by it. Evidence of both of these perturbations is readily identified from compositional element/Al and Sr/Ca profiles that are distinct from those of the enclosing sediments. In one core with a 37 cm thick Santorini ash layer an oxidation front succeeded in penetrating the whole ash layer after emplacement to form a Mn peak but is now retreating. In cores where thin (< 15 cm) Santorini turbidites or ash layers lie above S1, oxidation fronts initially form additional Mn peaks on top of the turbidites and subsequently alter the characteristic double peaked Mn profile shape usually observed above sapropel S1.     

The chemistry of hydrothermal mounds near the Galapagos Rift

Samples dredged from the sediment mounds have a unique chemistry and mineralogy which reveals details of the hydrothermal processes that produce these deposits. The mounds form primarily by deposition of Fe, Mn and Si from hydrothermal fluids which circulate through the basalt crust and the overlying sediments. The Mn, Fe and Si are strongly fractionated in the process; the Fe and Si precipitate within the mounds under slightly reducing conditions as nontronite, while the Mn is deposited as Mn oxyhydroxides at the seawater-sediment interface. The nontronite is exceptionally well crystallized, and contains less than 200 ppm Al. The Mn minerals, todorokite and birnessite, also have exceptional crystallinity and the distribution of trace elements Cu, Ni, Zn, Co, Ca and Ba in these phases agrees with predictions made on the basis of models of their crystal structure. The environment of deposition which produces this suite of minerals — slow percolation of hydrothermal fluids through pelagic sediments — may not be unique to the Galapagos Rift, as the same suite of minerals has been found in similar setting in the Gulf of Aden and on the Mid-Atlantic Ridge.     

On the depth-dependent production of long-lived spallogenic53Mn in the St. Severin chondrite

The contents of spallogenic⁵³Mn and target elements for its production were determined in 80- to 400-mg samples from 13 different locations of the LL6 chondrite St. Severin, along the 34.8-cm drill core AIII. The⁵³Mn content increases from the surface to the center of the stone by ≈30%. The variation with depth is satisfactorily described by several models, presuming that appropriate primary and secondary particle fluxes are chosen. The⁵³Mn saturation activities (⁵³Mn^*) are linearly correlated with the spallogenic³He/²¹Ne and²²Ne/²¹Ne ratios, which suggests the possibility to eliminate uncertainties in the determination of⁵³Mn cosmic ray exposure ages arising from depth effects and terrestrial residence times.     

Removal fluxes of Mn and Fe from the nearshore waters along the west coast of Taiwan

Dissolved and particulate Mn and Fe in the nearshore waters were determined at 27 stations along the west coast of Taiwan during 19-23 November 2004. The latitudinal distributions of Mn and Fe were very similar; however, the concentration in the dissolved phase was lower, whereas that in the particulate phase was higher in the northern regime. The higher percentage of Fe than Mn that was associated with particles resulted in a two-order of magnitude higher particle-water partition coefficient for Fe, K_d(Fe), than that for Mn, K_d(Mn). The removal fluxes of Mn and Fe could be estimated by multiplying the particulate ²³⁴Th removal flux with the Mn/²³⁴Th and Fe/²³⁴Th ratios in suspended particles, which ranged from 0.1 to 3.8 mmol m⁻² d⁻¹ for Mn, and from 3.4 to 194.5 mmol m⁻² d⁻¹ for Fe. Residence times ranged from 1 to 20 days for Mn and Fe were estimated in the nearshore.     

Heavy Metals in the Water and Bottom Sediments of the Selenga River Delta

The overall concentration of Cu, Pb, Zn, Cr, Mn, and Fe are determined in the water and bottom sediments of the Selenga River delta. The concentration of Cu, Pb, and Zn is found to decrease in the lower course of the river, at the delta outlet. The concentration of Mn and Fe is found to decrease in the downstream direction from the river's upper course along the investigated delta arms, whereas the concentration of Zn and Cr in certain arms exceeds their concentration in the upper section of the delta.     

Variability of zinc and manganese concentrations in relation to sex and season in the bivalve Donax trunculus

Females of Donax trunculus L. show higher concentrations of Mn and Zn than males. Differences are very high for Mn which also shows very large monthly fluctuations. Both the metals present higher contents during the period of gonadic maturation. Some high values of manganese found in the period when gonads are resting suggest the influence of sharp environmental variations in the area where bivalves have been collected.     

Major element composition of phyllosilicates in the Orgueil carbonaceous meteorite

Phyllosilicates in Orgueil are depleted in Ca, Mn and Fe relative to the bulk meteorite. Partition of Fe and Mn was apparently established in the oxidized state and may reflect a late-stage redistribution, possibly after accretion of the parent body. Mineralogical identity of phyllosilicate species cannot be completely specified but an upper limit of 30% may be placed on the proportion of montmorillonite-like species.     

The geochemistry of manganese in the Dead Sea

The most important source of dissolved manganese, Mn(II), to the Dead Sea is by upward diffusion from bottom sediments. This source contributes about 80 tons of Mn(II) each year. The concentration of dissolved manganese in the Dead Sea is extraordinarily high (7.03 mg 1^?1). It appears that the content (some 1.026 × 10⁶ tons) of dissolved manganese in the sea has remained constant during 1977–1979, although oxygen was introduced into deeper layers during the deepening of the pycnocline (1977–1978) and during the overturn of its water masses in the winter of 1978/79. The rate of oxidation of Mn(II) in Dead Sea water is extremely slow hence Mn(II) may practically be considered as the stable form of Mn in Dead Sea waters. Dilution by fresh water causes a pH rise and may facilitate faster oxidation of the dissolved divalent manganese. It is shown here that the shape of the Mn(II) profile, observed in the lake during 1963, may have developed by oxidation of Mn(II) in the more diluted upper layers and subsequent reduction of the oxidation products in the anoxic and more saline deeper layers during 260 years of continuous meromixis.     

Dynamics of particulate major and trace elements in the lower reaches of the Daugava River and adjacent area of the Gulf of Riga (Baltic Sea)

Suspended particulate matter (SPM) was collected in the freshwater-seawater mixing zone in the lower reaches of the Daugava River (Latvia) and adjacent marine area, during five cruises in 1998-2001. The study focused on biogeochemical phase exchange processes. SPM in the freshwater was found to be mainly allochthonous with a high content of organic matter, Mn and sorbed phosphate. Property-salinity plots suggested flocculation of humic-Fe complexes across the salinity gradient. The variability of sorbed phosphate was related to particulate Fe, although no dependence on pH and ionic strength was observed. The Mn contents of SPM mainly follow conservative mixing, but there are also indications of interface exchange of Mn in the mixing zone. The geochemical behaviour of particulate Al appears to differ from that of Fe. In early spring, trace element contents in SPM (Cr, Ni, Cu, Zn, Cd, Pb) correlate tightly with particulate organic matter, whose distribution is linked to phytoplankton distributions.     

Copper,zinc, cadmium,nickel, iron and manganese in the Southern Bight of the North Sea

Ni, Cd, Cu, Zn, and Fe were determined in water and suspended matter samples and Mn in suspended matter samples from the Southern Bight region of the North Sea. Four distinct areas, comprising the Rhine estuary, the Dutch coastal waters, the centre of the Bight, and the English coastal water can be distinguished on the basis of the distribution of the trace metals. The total concentrations of all metals were high in the Rhine estuary, decreased in a seaward direction to reach very low values, comparable to continental shelf water, in the centre of the Bight, and increased again towards the English coast. Elevated concentrations of dissolved Cu, Ni, Cd and Zn near the English coast are not only due to river inputs. Over the entire region, the fraction of Cd, Ni and Zn in solution was consistently more important than the fraction in the suspended particulate phase. In contast, the fraction of Fe and Mn in the solid phase was consistently greater than the fraction in solution. Total concentrations of Fe, Mn and Cu are more dictated by the suspended particulate matter concentration than Cd, Ni and Zn.     

鄱阳湖湿地土壤中Fe、Mn的迁移特征及其与水位周期变动的关系

对鄱阳湖地区蚌湖水下沉积物、滩地草甸土柱状样品不同深度土壤的酸度、氧化还原电位进行了现场测定;对剖面各层次的Ｆｅ、Ｍｎ总量,还原性Ｆｅ、Ｍｎ含量,以及有机质等进行了分析。实验表明：鄱阳湖湿地土壤中Ｆｅ、Ｍｎ有其独特的分布规律和迁移特征。元素Ｆｅ仅在水土界面轻微富集,Ｍｎ则向界面和深层双向富集;还原性Ｆｅ、Ｍｎ受氧化还原边界层的控制呈垂向分布。另外,元素Ｆｅ、Ｍｎ的水平迁移与水位变动相关,退水时Ｆｅ     

Comparison of Salix Genotypes for Co-Phytofiltration of Iron and Manganese from Simulated Contaminated Groundwater in a Floating Culture System

Groundwater contamination with iron (Fe) and manganese (Mn) is directly related to drink water safety. It remains challenging to simultaneously remove Fe and Mn from groundwater by conventional physical and chemical methods. Willows (Salix spp.) show promise for co-phytofiltration of Mn and Fe from groundwater. Here, a floating culture system was developed using willows for co-phytofiltration of Mn and Fe from simulated groundwater. Genotypic differences of willows were evaluated in terms of their tolerance to and accumulation of a mixture of Fe and Mn. The results showed that the growth responses of eight genotypes significantly differed to a mixture of Fe and Mn, ranging from growth inhibition to enhancement. Tolerance index analysis further indicated wide variation in the responses of willows. Tissue-specific analysis also revealed genotypic variation in the capacity of willows for translocation and accumulation of Fe and Mn. Compared with other genotypes, SB7 (Salix babylonica) and J842 (S. babylonica × Salix alba) demonstrated higher co-phytofiltration potentials for Fe and Mn based on tolerance, tissue metal concentrations, and shoot metal contents. Thus, both SB7 and J842 are candidates for co-phytofiltration of Fe and Mn from groundwater.     

Distribution of dissolved and labile particulate trace metals in the overlying bottom water in the vistula river plume (southern Baltic Sea).

Overlying bottom water samples were collected in the Vistula River plume, southern Baltic Sea, (Poland) and analysed for dissolved and labile particulate (1 M HCl extractable) Cu, Pb, Zn, Mn, Fe and Ni, hydrological parameters being measured simultaneously. Particulate organic matter (POM), chlorophyll a and dissolved oxygen are key factors governing the chemical behaviour of the measured metal fractions. For the dissolved Cu, Pb, Zn, Fe and Ni two maxima, in the shallow and in the deeper part of the river plume, were found. In the shallow zone desorption from seaward fluxing metal-rich riverine particles account for markedly increased metal concentrations, as confirmed also by high particulate metal contents. For Pb, atmospheric inputs were also considered to have contributed to the elevated concentrations of dissolved Pb adjacent to the river mouth. In the deep zone desorption from detrital and/or resuspended particles by aerobic decomposition of organic material may be the main mechanism responsible for enrichment of particle-reactive metals (Cu, Pb, Zn) in the overyling bottom waters. The increased concentrations of dissolved Fe may have been due to reductive dissolution of Fe oxyhydroxides within the deep sediments by which dissolved Ni was released to the water. The distribution of Mn was related to dissolved oxygen concentrations, indicating that Mn is released to the water column under oxygen reduced conditions. However, Mn transfer to the dissolved phase from anoxic sediments in deeper part of the Vistula plume was hardly evidenced suggesting that benthic flux of Mn occurs under more severe reductive regime than is consistent with mobilization of Fe. Behaviour of Mn in a shallower part has been presumably affected by release from porewaters and by oxidization into less soluble species resulting in seasonal removal of this metal (e.g. in April) from the dissolved phase. The particulate fractions represented from about 6% (Ni) and 33% (Mn, Zn, Cu) to 80% (Fe) and 89% (Pb) of the total (labile particulate plus dissolved) concentrations. The affinity of the metals for particulate matter decreased in the following order: Pb > Fe > Zn > or = > Cu > Mn > Ni. Significant relationships between particulate Pb-Zn-Cu reflected the affinity of these metals for organic matter, and the significant relationship between Ni-Fe reflected the adsorption of Ni onto Fe-Mn oxyhydroxides. A comparison of metal concentrations with data from other similar areas revealed that the river plume is somewhat contaminated with Cu, Pb and Zn which is in agreement with previous findings on anthropogenic origin of these metals in the Polish zone of southern Baltic Sea.     

Correlating the concentration of mobile manganese with redox- and acid–base properties in sediment column of the Mozhaisk Reservoir in the period of its formation (1970-1975)

Data of 1970-1971 and 1974-1975 for six layers of the Mozhaisk Reservoir were used to analyze the within-year relationships between Mn concentration and silt Eh and pH. The character of these relationships is explained. For the first time, a critical Eh zone, where Mn concentration abruptly changes, was identified. The redox processes involving Mn were shown to gradually stabilize over time.     

Biogeochemical control on the temporal variability of trace element concentrations in the Oubangui river (Central African Republic)

Dissolved Ba, Cd, Co, Mn, Mo, Ni, Rb, Sb, Sr, U and V were measured in the Oubangui river (Central African Republic) during a complete flood period. The dissolved concentrations vary by factors ranging from 1.4 to 8.2 as a function of river discharge: Sr, Ba, Rb and Mo concentrations decrease with rising stage; Ni, U, Sb, Cd, V and Mn concentrations increase with rising stage. These distributions are explained by a mixing of quick flow, mostly surface runoff with delayed flow, mostly groundwater. The dual origin of stream waters is demonstrated by the major element ratios, which are close to a silicate end-member during the high-flow period and trend towards a carbonate end-member during the low-flow period. Moreover, geological heterogeneities in the Oubangui basin may play a role in the variation of concentrations observed at the basin outlet. The previously indicated presence of a subsurface carbonate sequence in the lower part of the basin is confirmed. Cd, V, Mn and Co show peak concentrations during decreasing stage. We suggest that biological processes such as release from phytoplanktonic material and dissolution of oxides or carbonate phases may explain this maximum.     

Iron and Manganese in Groundwater: Using Kriging and GIS to Locate High Concentrations in Buncombe County,North Carolina

For health, economic, and aesthetic reasons, allowable concentrations (as suggested by the United States Environmental Protection Agency) of the secondary contaminants iron (Fe) and manganese (Mn) found present in drinking water are 0.3 and 0.05 mg/L, respectively. Water samples taken from private drinking wells in rural communities within Buncombe County, North Carolina contain concentrations of these metals that exceed secondary water quality criteria. This study predicted the spatial distribution of Fe and Mn in the county, and evaluated the effect of site environmental factors (bedrock geology, ground elevation, saprolite thickness, and drinking water well depth) in controlling the variability of Fe and Mn in groundwater. A statistically significant correlation between Fe and Mn concentrations, attributable to bedrock geology, was identified. Prediction models were created using ordinary kriging and cokriging interpolation techniques to estimate the presence of Fe and Mn in groundwater where direct measurements are not possible. This same procedure can be used to estimate the trend of other contaminants in the groundwater in different areas with similar hydrogeological settings.