The solubility of rhodochrosite (MnCO3) and siderite (FeCO3) in anaerobic aquatic environments

Jensen, Dorthe Lærke; Boddum, Jens K.; Tjell, Jens Christian; Christensen, Thomas Højlund

doi:10.1016/s0883-2927(01)00118-4

Cited by 149 publications

(103 citation statements)

References 28 publications

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“…The ongoing decrease of Fe(III) is consistent with observations (compare observed Fe(III) for 1993-1995 versus 2006-2008 in Figure 10a). The favored form of sorbed over precipitated Fe(II) in the model is consistent with slow kinetic precipitation rates measured for siderite in low temperature anaerobic aquifers [Jensen et al, 2002]. If conditions change in the future to favor remobilization of sorbed Fe, then the dominance of sorbed over precipitated Fe phases may affect the long-term secondary water quality impact of Fe.…”

Section: /2015wr016964supporting

confidence: 76%

“…Siderite has been detected in the reduced zones of the Bemidji plume [Baedecker et al, 1992;Tuccillo et al, 1999;Zachara et al, 2004], but saturation indices of siderite and rhodochrosite, using the PHREEQC-2 database dissolution log K values of 210.89 and 211.13 for siderite and rhodochrosite, respectively, are often above zero within the plume (Figure 3). This may suggest a kinetically limited precipitation model [Jensen et al, 2002], but we choose instead to apply in-plume saturation indices determined with the original database (Figure 3) to adjust the dissolution log K values upward (Table 4). Because Mn reoxidation is significantly slower than Fe reoxidation [Martin, 2005], we do not allow it in the model implementation.…”

Section: Solid Phase Processesmentioning

confidence: 99%

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Reactive transport modeling of geochemical controls on secondary water quality impacts at a crude oil spill site near Bemidji, MN

Bekins

Cozzarelli

et al. 2015

Water Resources Research

131

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Anaerobic biodegradation of organic amendments and contaminants in aquifers can trigger secondary water quality impacts that impair groundwater resources. Reactive transport models help elucidate how diverse geochemical reactions control the spatiotemporal evolution of these impacts. Using extensive monitoring data from a crude oil spill site near Bemidji, Minnesota (USA), we implemented a comprehensive model that simulates secondary plumes of depleted dissolved O 2 and elevated concentrations of Mn 21 , Fe 21 , CH 4 , and Ca 21 over a two-dimensional cross section for 30 years following the spill. The model produces observed changes by representing multiple oil constituents and coupled carbonate and hydroxide chemistry. The model includes reactions with carbonates and Fe and Mn mineral phases, outgassing of CH 4 and CO 2 gas phases, and sorption of Fe, Mn, and H 1 . Model results demonstrate that most of the carbon loss from the oil (70%) occurs through direct outgassing from the oil source zone, greatly limiting the amount of CH 4 cycled down-gradient. The vast majority of reduced Fe is strongly attenuated on sediments, with most (91%) in the sorbed form in the model. Ferrous carbonates constitute a small fraction of the reduced Fe in simulations, but may be important for furthering the reduction of ferric oxides. The combined effect of concomitant redox reactions, sorption, and dissolved CO 2 inputs from source-zone degradation successfully reproduced observed pH. The model demonstrates that secondary water quality impacts may depend strongly on organic carbon properties, and impacts may decrease due to sorption and direct outgassing from the source zone.

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Section: /2015wr016964supporting

confidence: 76%

Section: Solid Phase Processesmentioning

confidence: 99%

Reactive transport modeling of geochemical controls on secondary water quality impacts at a crude oil spill site near Bemidji, MN

Bekins

Cozzarelli

et al. 2015

Water Resources Research

131

View full text Add to dashboard Cite

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“…3, demonstrate the consumption of TEAs in order of decreasing nominal en- Although relatively low concentrations of Fe 2+ (up to 71 µM) were measured in solution, 0.5 M HCl extractions revealed that significantly greater Fe 2+ was produced during each anoxic cycle than was measured in the aqueous phase. Fe 2+ generated by dissimilatory iron reduction has been shown to sorb to mineral surfaces in sediment (Gehin et al, 2007;Klein et al, 2010;Liger et al, 1999) or precipitate as ferrous carbonate (Jensen et al, 2002), ferrous sulfide or other mixed ferrous/ferric phases (Rickard and Morse, 2005). The 0.5 M HCl extractions targeted this sorbed or poorly crystalline freshly precipitated Fe 2+ .…”

Section: Experimental Redox Oscillation: Aqueous Chemistrymentioning

confidence: 99%

Sediment phosphorus speciation and mobility under dynamic redox conditions

Parsons¹,

Rezanezhad²,

O’Connell³

et al. 2017

Biogeosciences

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Abstract. Anthropogenic nutrient enrichment has caused phosphorus (P) accumulation in many freshwater sediments, raising concerns that internal loading from legacy P may delay the recovery of aquatic ecosystems suffering from eutrophication. Benthic recycling of P strongly depends on the redox regime within surficial sediment. In many shallow environments, redox conditions tend to be highly dynamic as a result of, among others, bioturbation by macrofauna, root activity, sediment resuspension and seasonal variations in bottom-water oxygen (O 2 ) concentrations. To gain insight into the mobility and biogeochemistry of P under fluctuating redox conditions, a suspension of sediment from a hypereutrophic freshwater marsh was exposed to alternating 7-day periods of purging with air and nitrogen gas (N 2 ), for a total duration of 74 days, in a bioreactor system. We present comprehensive data time series of bulk aqueous-and solidphase chemistry, solid-phase phosphorus speciation and hydrolytic enzyme activities demonstrating the mass balanced redistribution of P in sediment during redox cycling. Aqueous phosphate concentrations remained low (∼ 2.5 µM) under oxic conditions due to sorption to iron(III) oxyhydroxides. During anoxic periods, once nitrate was depleted, the reductive dissolution of iron(III) oxyhydroxides released P. However, only 4.5 % of the released P accumulated in solution while the rest was redistributed between the MgCl 2 and NaHCO 3 extractable fractions of the solid phase. Thus, under the short redox fluctuations imposed in the experiments, P remobilization to the aqueous phase remained relatively limited. Orthophosphate predominated at all times during the experiment in both the solid and aqueous phase. Combined P monoesters and diesters accounted for between 9 and 16 % of sediment particulate P. Phosphatase activities up to 2.4 mmol h −1 kg −1 indicated the potential for rapid mineralization of organic P (P o ), in particular during periods of aeration when the activity of phosphomonoesterases was 37 % higher than under N 2 sparging. The results emphasize that the magnitude and timing of internal P loading during periods of anoxia are dependent on both P redistribution within sediments and bottom-water nitrate concentrations.

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“…Equilibrium and supersaturation with respect to siderite (FeCO 3 ) and rhodochrosite (MnCO 3 ) were also observed but may likewise suffer from inaccuracies in pH measurement, unaccounted complexation of, respectively, Fe 2+ and Mn 2+ by DOC, and from kinetic hindrances (Jensen et al 2002). Nevertheless, the presence of postdepositional manganous siderites in various aquifers in the Netherlands (Huisman 1998) suggests that its dissolution or precipitation is feasible.…”

Section: A Critical Look At Mineral Saturation Indicesmentioning

confidence: 99%

Benefits and hurdles of using brackish groundwater as a drinking water source in the Netherlands

Stuyfzand

Raat

2009

Hydrogeol J

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The production of fresh drinking water from brackish groundwater by reverse osmosis (BWRO) is becoming more attractive, even in temperate climates. For successful application of BWRO, the following approach is advocated: (1) select brackish source groundwater with a large volume and a composition that will yield a concentrate (waste water) with low mineral saturation; (2) maintain the feed water salinity at a constant level by pumping several wells with different salinities; (3) keep the permeate-to-concentrate ratio low, to avoid supersaturation in the concentrate; (4) keep the system anoxic (to avoid oxidation reactions) and pressurized (to prevent formation of gas bubbles); and (5) select a confined aquifer for deep well injection where groundwater quality is inferior to the membrane concentrate. This approach is being tested at two BWRO pilot plants in the Netherlands. Research issues are the pumping of a stable brackish source water, the reverse osmosis system performance, membrane fouling, quality changes in the target aquifer as a result of concentrate disposal, and clogging of the injection well. First evaluations of the membrane concentrate indicate that it is crucial to understand the kinetics of mineral precipitation on the membranes, in the injection wells, and in the target aquifer.

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The solubility of rhodochrosite (MnCO3) and siderite (FeCO3) in anaerobic aquatic environments

Cited by 149 publications

References 28 publications

Reactive transport modeling of geochemical controls on secondary water quality impacts at a crude oil spill site near Bemidji, MN

Reactive transport modeling of geochemical controls on secondary water quality impacts at a crude oil spill site near Bemidji, MN

Sediment phosphorus speciation and mobility under dynamic redox conditions

Benefits and hurdles of using brackish groundwater as a drinking water source in the Netherlands

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