Mn In Pore Water Research Articles

Controlling exposure to As and Cd from rice via irrigation management

Irrigation management controls biogeochemical cycles in rice production. Under flooded paddy conditions, arsenic becomes plant-available as iron-reducing conditions ensue, while oxic conditions lead to increased plant availability of Cd in acidic soils. Because Cd enters rice through Mn transporters, we hypothesized that irrigation resulting in intermediate redox could simultaneously limit both As and Cd in rice grain due to As retention in soil and Mn competition for Cd uptake. In a 2 year field study, we used 6 irrigation managements that varied in extent and frequency of inundation, and we observed strong effects of irrigation management on porewater chemistry, soil redox potentials, plant As and Cd concentrations, plant nutrient concentrations, and methane emissions. Plant As decreased with drier irrigation management, but in the grain this effect was stronger for organic As than for inorganic As. Grain organic As, but not inorganic As, was strongly and positively correlated with cumulative methane emissions. Conversely, plant Cd increased under more aerobic irrigation management and grain Cd was negatively correlated with porewater Mn. A hazard index approach showed that in the tested soil with low levels of As and Cd (5.4 and 0.072 mg/kg, respectively), irrigation management could not simultaneously decrease grain As and Cd. Many soil properties, such as reducible As, available Cd, soil pH, available S, and soil organic matter should be considered when attempting to optimize irrigation management when the goal is decreasing the risk of As and Cd in rice grain.

Arsenic mobilization across the sediment-water interface of the Three Gorges Reservoir as a function of water depth using DGT and HR-Peepers, a preliminary study

The artificial regulation of the Three Gorges Reservoir (TGR) creates large water level fluctuation zones (WLFZ) that may change the behavior of metals and metalloid in sediment, particularly redox sensitive elements. Mobilization of As, Fe and Mn across the sediment-water interface (SWI) in the TGR as a function of different water depth (periodically and permanently submerged sediments, respectively) was in situ determined by diffusive gradients in thin films (DGT) and high-resolution dialysis technique (HR-Peeper), respectively. The results showed that the mobilization of As was significantly affected by Fe/Mn especially Mn, across the SWI. Duo to the oxic-anoxic transitional state in near bottom water, the reduced Fe and Mn in sediment pore water could be oxidized and precipitated again, leading to the co-precipitation of As with Fe/Mn oxides (hydroxides). Consequently, concentrations of As, Fe and Mn in labile phases and pore water were generally low across the SWI, then they sharply increased at a few centimeters below the SWI. Considering different water depth, various trends were found in labile phase, whereas concentrations of As, Fe and Mn in pore water in permanently submerged sediments were significantly higher than those in periodically submerged sediments. The dry-re-wetting alternation processes in the WLFZ may play vital roles in the resupply capacity of sediments as it was found that periodically submerged sediments with longer re-wetting time had higher Fe/Mn resupply capacity than those with shorter re-wetting times and permanently submerged sediments.

Spatial Distribution and Factors Influencing the Various Forms of Iron in Alluvial–Lacustrine Clayey Aquitard

The compression release of pore water in clayey aquitards has a significant impact on groundwater quality. Iron is an active variable element that mediates biochemical reactions in groundwater systems, but its transformation mechanisms in clayey aquitards remain unclear. The sediment and pore water samples from the shallow clayey aquitard (thickness = ~20 m) in the Chen Lake area of China were collected in three boreholes. The spatial distribution and influencing factors of Fe occurrence in the aquitard were revealed using hierarchical extraction, statistical analysis, and simulation calculations. The results indicate that the background value of alluvial–lacustrine sediments primarily affects the Fe concentration of clayey sediments. The dissimilatory reduction in free Fe oxide was the main source of Fe ions in pore water, resulting in a major percentage of Fe2+ in the total Fe concentration (0.07−5.91 mg/L). The abundant organic matter in organic-rich clay promoted a dissimilatory reduction in Fe (III) oxides, while the Fe concentrations of sediment and pore water were lower in the sand-rich stratum because of its weak adsorption capacity. The impact of human reclamation activities on the aquitard was mainly concentrated in the shallow layer (>−3 m), resulting in water drainage and O2 and CO2 input, which induced the crystallization of poorly crystalline Fe oxides. The input of reactive organic matter from reclaimed crops promoted the dissimilatory reduction in Fe oxides and the enrichment of Fe in deep pore water. The copious Fe2+ in deep stratum pore water tended to interact with CO32− and S2− to form coprecipitation with Fe (II). The concentrations of As, Cr, Sr, Zn, and Mn in pore water followed a similar variation trend to the Fe ion concentration, and their release could be attributed to the reduction dissolution of sediment Fe (III) oxides.

Iron and Manganese Oxidation States, Bonding Environments, and Mobility in the Mining-Impacted Sediments of Coeur d’Alene Lake, Idaho: Core Experiments

The mobility of a metal in mining-impacted sediments is determined by the environmental conditions that influence the metal’s oxidation state and bonding environment. Coeur d’Alene Lake, USA, has been impacted by legacy mining practices that allowed the hydrologic transport of mining waste to the lakebed, resulting in substantial amounts of redox-sensitive Fe and Mn along with Ag, As, Cd, Cu, Hg, Pb, Sb, and Zn. Future lake conditions may include algal blooms and additional algal detritus at the sediment–water interface, which may alter Fe and Mn forms that can influence their, and other metal(loid)s, mobility during seasonal anoxia. Cores of the lakebed sediments were exposed to anoxic and anoxic + algal detritus conditions for 8 weeks. Sediment samples were collected biweekly for analysis of Fe and Mn oxidation states and bonding environments by synchrotron-based X-ray absorption spectroscopy. Over the 8-week period and at a location 12.5 cm deep in the sediments, anoxic and anoxic + algae conditions produced limited changes in Fe and Mn oxidation states and bonding environments. At a location 2.5 cm below the sediment–water interface, the anoxic condition promoted a relatively stable environment in which Fe and Mn oxidation states and bonding environments did not vary greatly during the experiment. At the 2.5 cm depth, the anoxic + algae condition substantially altered the Mn oxidation state distribution and bonding environment, but this condition did not strongly influence the Fe oxidation state distribution or bonding environment. The anoxic + algae condition increased the presence of Mn3+, produced Mn4+ at select times, altered the Mn bonding environment, and temporarily increased the release of Mn into porewater. The algae influence on sediment and porewater Mn likely occurred because of the increased formation of organo-Mn complexes produced during algae-enhanced enzymatic processes. The lack of influence of algal detritus on sediment and porewater Fe and the formation of soluble organo-Mn complexes may limit the potential increase in the mobility of other metal(loid)s with future lake conditions.

A mechanistic investigation of the coral Mn/Ca-based trade-wind proxy at Kiritimati

Tropical Pacific trade-wind behavior is linked to the El Niño-Southern Oscillation and Pacific Decadal Variability, which modulate the rate of climate change. Despite their importance, high-resolution trade-wind observations span only the past 30–40 years and are too sparse to assess decadal wind variability and long-term trends. Previous work demonstrated that reef-building corals growing at the tropical Pacific island of Tarawa (2°N, 165°E) exhibit spikes in the manganese-to-calcium ratio (Mn/Ca) of their skeleton in response to a reversal of trade winds (i.e., westerly winds). Records of Mn/Ca from long-lived corals therefore hold great promise as indicators of past trade-wind variability. However, at other nearby islands with west-facing lagoons, there is a lag between westerly winds and coral Mn/Ca spikes and a significant difference in the magnitude of spikes between corals. To address uncertainties in how winds are recorded by coral Mn/Ca, we assess the reservoirs of Mn in the sediment, sediment pore spaces (porewater), and water column of Kiritimati’s lagoon and inland lakes (1.9°N, 157.5°W). We find that insoluble dustborne Mn, once buried in lagoon sediments, becomes reduced and more soluble, leading to its accumulation in the sediment porewater. This Mn reservoir is then released into the water column when strong westerly wind events cause sufficient water-column mixing to reach lagoonal sediments. While this mechanism is consistent with what was previously proposed at Tarawa, the concentration of dissolved porewater Mn at Tarawa is nearly 20 times greater than at Kiritimati. We attribute this difference to the water depth of the sediment core from which porewater was sampled and the time elapsed between the most recent westerly wind event and core sampling, which both influence the “recharge time” of the porewater Mn reservoir. As such, lagoon bathymetry and morphology modulate lagoon water and sediment porewater Mn concentrations, which impact how westerly winds imprint their signal onto coral Mn/Ca. Armed with an improved understanding of the mechanism behind this coral Mn/Ca-trade wind relationship, we can better assess the reliability of this coral proxy through space and time and identify optimal sites for Mn/Ca-based wind reconstructions, paving the way for critical new insights into the role of winds in future climate change.

Effect of applying persulfate on the accumulation of arsenic in rice plants grown in arsenic-contaminated paddy soil

Arsenic is known to be a notorious human carcinogen and rice consumption is becoming the primary human exposure route for As, especially in many Asian countries. As one of redox-sensitive elements in soil, sulfur plays an indisputable role in controlling As behaviors. However, information on the effects of persulfe (PS) on the toxicity and accumulation of As in rice plant under flooded conditions is limited. Therefore, a pot experiment was conducted to investigate the effects of PS amendment on the growth and accumulation of As species in rice plants grown in As-contaminated paddy soil. Results revealed that PS application increased the As, Fe, and Mn in porewater at the early stage, and then declined. Application of PS increased the biomass of stem and root, while inhibited the formation of iron plaque on the root surface. The As translocation from root to rice above tissues and accumulation of As species in brown rice were declined by amendment with PS. The inorganic arsenic (iAs) and DMA were the two main species in brown rice, and decreased by 13~26% and 40~60% respectively upon PS application. The results suggested that amendment with PS might be feasible for reducing the accumulation of As in rice grains grown in As-contaminated paddy soil. However, further detailed studies on the potential soil biogeochemical and physiological mechanisms are recommended.

Phosphorus release from intact soil monoliths of manure-amended fields under simulated snowmelt flooding.

Anaerobic conditions developed in soils with flooding can enhance the release of soil P to overlying water, but little information is available for soils with a long history of manure application. We examined the P release from manure-amended soils under simulated snowmelt flooding. Intact monoliths from manured (solid swine manure [SSM] or liquid swine manure [LSM]) and unamended (control) field plots were collected from Carman, Manitoba. Monoliths were frozen for 7 d, thawed, flooded, and incubated at 4±1°C. Redox potential, pH, and concentrations of dissolved reactive P (DRP), Ca, Mg, Fe, and Mn in pore water and floodwater were determined weekly up to 56 d after flooding (DAF) and at 84 DAF. Redox potential decreased with DAF with a greater and more rapid decrease in SSM (from ∼300 to<0mV by 84 DAF) compared with LSM and control (∼100mV by 84 DAF). Pore water and floodwater DRP concentrations were significantly greater in manured treatments than in the control at all DAFs and in SSM than in LSM for most DAF. Whereas floodwater DRP concentrations remained relatively stable in the control treatment, concentrations in manured treatments increased substantially from the onset of flooding to 35-42 DAF (threefold to fourfold increase) and remained relatively stable thereafter. Significantly greater P release from SSM- than from LSM-treated monoliths was due to greater input of P and the higher organic matter content in SSM-treated soils. These favored the rapid development of anaerobic conditions that further induced P release.

Rapid Shifts in Chemical and Isotopic Compositions of Sediment Pore Waters in the Amami Sankaku Basin in Response to Initial Arc Rifting in the Mid‐Oligocene

AbstractPore waters were recovered from the sediment cores drilled in the back‐arc Amami Sankaku Basin (ASB) during the International Ocean Discovery Program Expedition 351. The sediment sequence is composed of the recent mud and ooze from late Oligocene/early Miocene accumulated at 7 m/Ma and rapid deposition of thick volcaniclastic sequence at 50 m/Ma. Such variations are reflected in the evolutions of chemical and isotopic compositions of pore waters. Cl and Ca concentrations in pore waters increased rapidly with depth and became enriched in the deep portion. Before arc rifting, extremely high deposition rates of volcaniclastic gravity‐flow sediments from the nearby Kyushu‐Palau arc into the ASB resulted in strong alteration, removing Mg and Si from pore waters. Mg concentrations were initially almost zero but abruptly shifted to substantial increases after ~29.5 Ma, indicating extended rifting of the active volcanic axis from the ASB. The δ18O and δD values of pore waters also evolved from more depleted and wide range to more positive and narrow range as a response to reduced alteration and increasing influence of seawater. Concentrations of Si and Mn in pore waters rapidly increased since ~29.5 Ma but suddenly declined at ~17.5 Ma due to the cessation of input of volcaniclastic materials. Covariations of Ca and Mg in pore waters are very similar to those in the back‐arc West Philippine Basin but significantly different from those in the Izu‐Bonin fore‐arc basin. Variations in chemical and isotopic compositions of pore waters can assist the reconstruction of tectonic activities.

Controls on the shuttling of manganese over the northwestern Black Sea shelf and its fate in the euxinic deep basin

Manganese (Mn) is an essential micronutrient for phytoplankton and its cycling interacts with that of iron (Fe). Continental shelf sediments are a key but poorly quantified source of Mn to marine waters. In this study, we investigate Mn release from shelf sediments, its lateral transport (“shuttling”) in the oxic water column over the northwestern Black Sea shelf and its fate in the adjacent euxinic deep basin. We find a high release of Mn from organic-rich, bioirrigated coastal sediments, but negligible mobilization and release of Mn from sediments in offshore shelf regions, because of a low input of organic matter. Most Mn in the water column is present in dissolved form. We suggest that this dissolved Mn is released from coastal sediments and subsequently transported offshore through physical processes. Surface sediments at open shelf and shelf edge stations are highly enriched in Mn when compared to coastal and deep basin stations. Only part of the surface enrichment can be explained by oxidation of porewater Mn. The remainder of this enrichment is likely the result of oxidative removal of dissolved Mn from the water column and deposition as Mn oxides. Using X-ray spectroscopy we show that Mn in surface sediments in this area predominately consists of Mn(IV) oxides (phyllo- and/or tectomanganates). A key difference between Mn versus Fe shuttling is the form in which the metal is transported: while dissolved Mn dominates in the water column over the shelf, most Fe is present in particulate form. Sediment trap data indicate that the vertical transport of both Mn and Fe through the euxinic water column is correlated and is associated with the sinking flux of biogenic particulate matter following the spring and fall phytoplankton blooms. In the sediments of the euxinic basin, Mn is enriched when compared to a detrital Mn background and its burial correlates with that of Fe. This suggests that Mn could be incorporated in pyrite in the euxinic water column. Our results highlight the critical role of organic matter input as a driver of Mn and Fe shuttling over the Black Sea continental shelf and particulate matter as the carrier of Mn and Fe into the euxinic basin.

The Specific Features of the Microcomponent Composition of Pore Solutions in the Rocks of the Bazhenov Formation, Western Siberia

The results of experimental studies of the macrocomponent and microcomponent compositions of pore solutions in the bituminous siliceous shales of the Bazhenov Formation (BF) in Western Siberia with total organic carbon (TOC) contents up to 12.63% (“normal rocks”) and the silty sandstones of the “anomalous” section of the BF with TOC contents no higher than 0.63% (“anomalous” rocks) are presented. The studies of water extracts from core samples were performed. It was found that the pore solutions in the rocks of the “normal” BF rocks are sodium sulfate–bicarbonate, whereas the solutions in the “anomalous” rocks are sodium bicarbonate–chloride. The following tendencies were noted in the pore solutions of both “normal” and “anomalous” rocks compared with the oceanic water: (a) increase in Mn, Co, Ni, Cu, Zn, Mo, Sb, Cd, Ba, V, and Cr concentrations to varying degrees; (b) elevated Cs, Pb, and Ti concentrations in pore solutions of “anomalous” rocks only; (c) reduced Li, B, Rb, and Sr concentrations. A direct correlation between Li, B, Ba, Sr, U, Mo, Cd, Sb, and Ni concentrations in the pore water and total organic carbon (TOC) contents in the rocks was established. The concentrations of V, Cs, Sb, Rb, Ti, and Mn in pore waters display a close to inverse correlation with TOC content in rocks. The content of Ba in the pore solutions of the “normal” BF rocks equals or exceeds the Sr content, which is abnormal compared with formation water in most oil fields and with ocean water and is attributable to the specific features of organic-rich mudstone accumulation, considering that the Sr content in the “anomalous” rocks of the BF is two times higher than the Ba content, which is closer to their usual ratios in most natural waters.

Features of the microcomponent composition of pore solutions of rocks of the Bazhenov Formation in Western Siberia

The results of experimental studies of the macro- and microcomponent composition of pore solutions of bituminous clay-siliceous rocks of the Bazhenov Formation (BS) of Western Siberia, containing up to 12.63% Corg (“normal rocks”), as well as silt-sandstones from the “anomalous” section are presented. BS with a Corg content of up to 0.63% (“abnormal” rocks) obtained on the basis of a study of aqueous extracts from core samples. It has been established that pore solutions of “normal” BS rocks have a sulfate-bicarbonate-sodium composition, and “abnormal” ones have a hydrocarbonate-sodium chloride composition. In pore solutions of both “normal and“ abnormal ”rocks relative to ocean water, the following were noted: a) concentration of Mn, Co, Ni, Cu, Zn, Mo, Sb, Cd, Ba, V, Cr of various degrees of intensity; b) increased content of Cs, Pb, Ti only in pore solutions of “abnormal” rocks; c) reduced content of Li, B, Rb, Sr. A direct relationship was found between the contents of Li, B, Ba, Sr, U, Mo, Cd, Sb, and Ni with the content in the Corg rock. For V, Cs, Sb, Rb, Ti, Mn in pore waters, the relationship with the amount of Corg in the rocks is close to the inverse relationship. In the pore solutions of “normal” BS rocks, the Ba content is equal to or higher than the Sr content, which is anomalous with respect to the stratal waters of most oil fields and ocean water and, apparently, is associated with the peculiarities of the accumulation of organic clay deposits, since in “anomalous” rocks The BS content of Sr is two times higher than the Ba content, which is closer to the usual for most natural waters.

Gypsum Amendment Reduces Redox-Induced Phosphorous Release from Freshly Manured, Flooded Soils to Floodwater.

The effectiveness of gypsum in reducing runoff P losses from soils and the mechanisms responsible are well documented; however, gypsum amendment effects in reducing redox-induced P losses from flooded soils are less researched and documented. We examined the effect of gypsum amendment on P release from freshly manured soils to pore water and floodwater with continuous flooding for 56 d in the laboratory. Three soils (Pembina, Denham, and Dencross series) collected from Manitoba, Canada, were preincubated with liquid swine manure. Each preincubated manured soil was packed into vessels with or without recycled wallboard gypsum in triplicates and flooded for 56 d, during which pore water and floodwater were sampled weekly and analyzed for pH and dissolved reactive P (DRP), Ca, Mg, Fe, and Mn concentrations. Change in soil redox potential (Eh) with flooding was also monitored. Wallboard gypsum amendment significantly decreased the pore water and surface floodwater DRP concentrations in all three soils for most days after flooding (DAF). The Dencross soil, which had Olsen P about fivefold greater than the other soils, showed the greatest magnitude decrease in DRP concentration with gypsum amendment, by 1.27 mg L on 49 DAF and 0.99 mg L on 21 DAF for pore water and floodwater, respectively. Gypsum amendment (i) delayed the Eh reduction with flooding beyond +200 mV, (ii) decreased pore water pH, and (iii) increased concentrations of Ca, Mg, and Mn in pore water favoring precipitation of P, all of which may have directly or indirectly reduced the P release from flooded soils to overlying floodwater.

Massive Mn carbonate formation in the Landsort Deep (Baltic Sea): Hydrographic conditions, temporal succession, and Mn budget calculations

The sediments of the Landsort Deep and Gotland Basin in the central Baltic Sea are strongly enriched in Mn carbonate. However, conceptual models attempting to explain the intense Mn carbonate precipitation in both basins are in part conflicting. In the Gotland Basin model, deposited Mn oxides are converted to Mn carbonate after the oxygenation of euxinic bottom waters enriched in dissolved Mn by major Baltic inflows (Huckriede and Meischner, 1996). By contrast, according to the Landsort Deep model, Mn carbonate precipitation occurs independent of oxygenation events below a euxinic water column (Lepland and Stevens, 1998; Lenz et al., 2015). In this study, we investigated Mn solid-phase signatures in recent/sub-recent well-dated sediments from the Landsort Deep and compared them to long-term observations to identify the hydrographic conditions favoring Mn carbonate formation. The comparisons of water column O2 and sulfide time series with sedimentary Mn carbonate enrichments identified long-lasting bottom water oxygenation as an important environmental factor in the enhancement of Mn carbonate precipitation (up to 32wt% Mn) in the Landsort Deep. Thus, by preventing the escape of dissolved Mn from still reducing sediments into the open water column, these conditions allow the accumulation of large amounts of Mn-oxide particles at the sediment/water interface, with their subsequent conversion to Mn carbonate. The euxinic conditions that have prevailed almost continuously in the Landsort Deep since roughly AD 2000 do not favor Mn enrichment (maximum 0.9wt% Mn), highlighting the importance of the recurring oxygenation of bottom water, most likely via medium-intensity inflows. The Mn abundances in seven sediment cores from water depths of 190–437m together with Mn balance calculations indicated that the Mn inventory in the water column in response to porewater Mn reflux and detrital Mn input is sufficient for Mn carbonate enrichment only in the deepest part of the basin.

Benthic foraminiferal Mn / Ca ratios reflect microhabitat preferences

Abstract. The Mn / Ca of calcium carbonate tests of living (rose-Bengal-stained) benthic foraminifera (Elphidium batialis, Uvigerina spp., Bolivina spissa, Nonionellina labradorica and Chilostomellina fimbriata) were determined in relation to pore water manganese (Mn) concentrations for the first time along a bottom water oxygen gradient across the continental slope along the NE Japan margin (western Pacific). The local bottom water oxygen (BWO) gradient differs from previous field study sites focusing on foraminiferal Mn / Ca and redox chemistry, therefore allowing further resolution of previously observed trends. The Mn / Ca ratios were analysed using laser ablation inductively coupled plasma-mass spectrometer (ICP-MS), allowing single-chamber determination of Mn / Ca. The incorporation of Mn into the carbonate tests reflects environmental conditions and is not influenced by ontogeny. The inter-species variability in Mn / Ca reflected foraminiferal in-sediment habitat preferences and associated pore water chemistry but also showed large interspecific differences in Mn partitioning. At each station, Mn / Ca ratios were always lower in the shallow infaunal E. batialis, occupying relatively oxygenated sediments, compared to intermediate infaunal species, Uvigerina spp. and B. spissa, which were typically found at greater depth, under more reducing conditions. The highest Mn / Ca was always recorded by the deep infaunal species N. labradorica and C. fimbriata. Our results suggest that although partitioning differs, Mn / Ca ratios in the intermediate infaunal taxa are promising tools for palaeoceanographic reconstructions as their microhabitat exposes them to higher variability in pore water Mn, thereby making them relatively sensitive recorders of redox conditions and/or bottom water oxygenation.

Manganese and iron release from mangrove porewaters: A significant component of oceanic budgets?

Mangrove porewater can be highly enriched in dissolved manganese (Mn), iron (Fe), and other trace metals. As a result, porewater exchange may release dissolved metals to surface waters. This study assessed dissolved Mn exchange with the coastal ocean in four mangroves ecosystems, and whether porewater exchange represents a major driver of the oceanic exchange along a latitudinal gradient in Australia (from 28° S to 12° S). Dissolved Fe was also determined but concentrations were below detection in most surface water samples, preventing any flux estimates. Average concentrations of Mn in porewater were approximately an order of magnitude greater than surface waters at all sites, resulting in average porewater-derived Mn fluxes of 441kmolkm−2year−1 at the four sites. Time series surface water observations indicate that average Mn concentrations decrease at lower latitudes. The average dissolved Mn export rate from the four mangrove systems to the coastal ocean was 88kmolkm−2year−1. Porewater-derived Mn inputs were greater than surface water exports, which may be explained by dissolved Mn precipitation, oxidation or flocculation at the sediment water interface. While the removal of Mn at the sediment-water interface brings about uncertainties in the estimated porewater fluxes, it has no impact on estimated surface water exports to the coastal ocean. If our surface water export estimates are representative of the global mangrove area (140,000km2), mangroves may deliver 12Gmolyear−1 of dissolved Mn to the coastal ocean. These fluxes are greater than the estimated flux from global riverine (5.4Gmolyear−1) and atmospheric (11Gmolyear−1) sources, demonstrating that mangroves may be a major player in the oceanic cycle of Mn.

Combining benthic foraminiferal ecology and shell Mn/Ca to deconvolve past bottom water oxygenation and paleoproductivity

The Mn/Ca of carbonate tests of living deep-sea foraminifera (Hoeglundina elegans, Bulimina aculeata, Uvigerina peregrina and Melonis barleeanus) were determined together with pore water manganese along a bottom water oxygen gradient across the lower boundary of the Arabian Sea oxygen minimum zone. Although Mn has long been considered an indicator for contamination, new cleaning protocols and high-resolution laser ablation ICP-MS now allow the reliable analyses of test-associated Mn. Within locations, Mn incorporation between species varies as a function of their in-sediment depth preferences and associated pore water chemistry. Under well-oxygenated bottom water conditions, shallow infaunal species incorporate little Mn in their test, whereas the species collected from deeper habitats show elevated Mn concentrations. With decreasing oxygen contents pore water Mn concentrations and benthic foraminiferal in-sediment distribution change. Whereas Mn/Ca in shallow infaunal species responds moderately to bottom water oxygenation, Mn/Ca of the infaunal species M. barleeanus correlates well to oxygenation. Although high productivity results in a shallower redox cline within the sediment, pore water Mn is retained as long as the bottom water remains oxygenated. Under reduced bottom water oxygen conditions, Mn escapes to the overlying water column and test-associated Mn/Ca decreases also in the infaunal species. By combining pore water chemistry of Mn, calcitic Mn/Ca and foraminiferal ecology, a new conceptual model is presented (TROXCHEM3) that provides a framework for deconvolving past organic matter input and bottom water oxygenation.

Manganese, iron, and sulfur cycling in Louisiana continental shelf sediments

Sulfate reduction is considered the primary pathway for organic carbon remineralization on the northern Gulf of Mexico Louisiana continental shelf (LCS) where bottom waters are seasonally hypoxic, yet limited information is available on the importance of iron and manganese cycling in the region. Sedimentary manganese, iron, and sulfur cycling were investigated on the LCS using a combined chemical analysis and sediment diagenesis modeling approach. Three stations situated 320km across the LCS along the 20m isobath were sampled up to five times between the spring of 2006 and summer of 2007. Bottom water oxygen levels at the stations ranged from 203mmolm−3 in spring to 2.5mmolm−3 in summer. Porewater Mn and Fe2+ concentrations (up to 275 and 300μmolL−1, respectively), sulfate reduction rates (1.0–8.4mmolm−2d−1), and the fraction of total oxalate extracted iron obtained as Fe(II) (0.25–0.52) differed between station and season. Sediments at station Z02 on the eastern LCS, south of Terrebonne Bay, had higher organic matter content and sulfate reduction rates than sediments at Z03, 160km further west. Sulfate reduction rates were higher in summer than spring at station Z02 but not at Z03 where porewater Mn and Fe concentrations were highest in summer. Porewater Fe2+ concentrations, solid phase oxalate-extractable Fe concentrations, and sediment incubation experiments suggested iron reduction at Z03 may account for 20% or more of organic carbon remineralization. LCS Fe(III) concentrations decreased and sulfate reduction rates increased in model simulations by lowering interfacial dissolved oxygen levels and increasing the rates of organic matter deposited on the sediment surface. Results from this study demonstrate that LCS sedimentary metal oxide cycling may be more important in organic carbon mineralization pathways than previously recognized.

Abundant Porewater Mn(III) Is a Major Component of the Sedimentary Redox System

Soluble manganese(III) [Mn(III)] can potentially serve as both oxidant and reductant in one-electron-transfer reactions with other redox species. In near-surface sediment porewater, it is often overlooked as a major component of Mn cycling. Applying a spectrophotometric kinetic method to hemipelagic sediments from the Laurentian Trough (Quebec, Canada), we found that soluble Mn(III), likely stabilized by organic or inorganic ligands, accounts for up to 90% of the total dissolved Mn pool. Vertical profiles of dissolved oxygen and dissolved and solid Mn suggest that soluble Mn(III) is primarily produced via oxidation of Mn(II) diffusing upwards from anoxic sediments with lesser contributions from biotic and abiotic reductive dissolution of MnO2. The conceptual model of the sedimentary redox cycle should therefore explicitly include dissolved Mn(III).

Benthic geochemistry of manganese in the Bay of Biscay, and sediment mass accumulation rate

Manganese is a major redox reactive element of benthic metabolism. We have built a database of existing knowledge on the benthic geochemistry of Mn in the Bay of Biscay, in order to comprehensively assess the behaviour of Mn in a variety of environments during early diagenesis. The database contains vertical profiles of particulate and dissolved Mn species of 59 cores collected during 17 cruises between 1997 and 2006 at nine stations positioned between 140 and 4,800 m water depths. At all studied stations, Mn species follow the conventional distribution, where Mn(III,IV) species are enriched in the oxic layer, and dissolved Mn is present in the anoxic sediments. A minor part of Mn-oxides originates from sedimenting particles. The major part is of diagenetic origin, and derives from the oxidation of upward-diffusing dissolved Mn(II). Mn-oxide inventories are higher at the deeper stations than at the shallower ones. This difference cannot be attributed to different sources of sedimenting particles, but it must depend on sedimentation rate and diagenetic processes. At depth, dissolved Mn(II) concentrations are constant. This probably reflects equilibrium with an authigenic Mn(II) phase, which is the ultimate phase into which Mn is fossilized. The Mn content of deeper anoxic sediments is similarly low in all the cores studied, associated with corresponding trends of Mn content in sedimenting particles of the Bay of Biscay. Bioturbation, rather than redox oscillations, can convey Mn(III,IV) species downwards into the anoxic sediments where they are reduced, associated with a peak of dissolved Mn. Because dissolved Mn(II) is re-oxidized when it diffuses towards the oxic layer, the inventory of the diagenetic Mn(III,IV) phase remains at steady state, especially at stations where the oxic layer is thick. It then becomes possible to calculate the residence time of diagenetic Mn(III,IV) particles within the oxic layer, using the upward-directed flux of pore water Mn(II). By applying this residence time to the accumulation of sediments within the oxic layer, we obtain the sediment mass accumulation rate. The values calculated for the sediments of the Bay of Biscay fit well with accumulation rates obtained from radionuclides or sediment traps. The method has also been validated with data collected in other marine sedimentary environments.

Monitoring and modelling of the solid-solution partitioning of metals and As in a river floodplain redox sequence

For a period of 2 a, pore water composition in a heavily contaminated river floodplain soil was monitored in situ. Pore water samples were collected 12 times over all seasons in a profile ranging from aerobic to sulphidic redox conditions, and As, Cd, Cr, Cu, Pb, Zn, Mn, Fe, Ca, Cl, SO4. DOC,IOC and pH were determined. The variability of pH, IOC, DOC and Ca was found to be rather small during the year and within the profile (rsd <0.04, 0.16. 0.24 and 0.22, respectively). The temporal variability of the metal and As concentrations was small, too, whereas changes with depth were distinct. Under sulphidic conditions, concentrations were below 1 mu g L-1 (Cd, Cu, Pb) or 10 mu g L-1 (Zn, As). The data set was compared with results from a geochemical model that was fully parameterised from literature data and included equilibrium speciation, sorption and mineral dissolution. The general pattern of the solid-solution partitioning of Cd, Cu, Zn and As in the profile was predicted well by mechanistic geochemical modelling on the basis of solid phase composition. Metals strongly bound to organic matter Such as Cd and Cu were predicted better than metals mainly present within a mineral. Detailed information regarding the presence of colloidal Fe and Mn in pore water might improve the prediction of the solid-solution partitioning of a number of metals. The study also indicates that the chemical behaviour of Pb is still not understood sufficiently. (c) 2008 Elsevier Ltd. All rights reserved.