Analysis of Rates of Geochemical Reactions

Brantley, Susan L.; Conrad, Christine F.

doi:10.1007/978-0-387-73563-4_1

Cited by 20 publications

(14 citation statements)

References 23 publications

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“…Fe(II)-catalyzed Ni release from NiHem and NiGoe in the presence and absence of oxoanions is consistent with a second-order rate reaction, in agreement with past research of oxoanion-free systems . The second-order rate reaction describing the Ni release data in the current paper was confirmed following the integral method (Brantley and Conrad, 2008). The kinetic fit parameters (Table 2) show that the overall amount of Ni released is less for NiHem than for NiGoe in the absence of oxoanions (with 1.3% and 9% of substituted Ni released, respectively), consistent with past research (Frierdich et al, 2011;.…”

Section: Sulfate and Phosphate Coadsorption With Nisupporting

confidence: 82%

Effect of phosphate and sulfate on Ni repartitioning during Fe(II)-catalyzed Fe(III) oxide mineral recrystallization

Hinkle

Catalano

2015

Geochimica et Cosmochimica Acta

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Dissolved Fe(II) activates coupled oxidative growth and reductive dissolution of Fe(III) oxide minerals, causing recrystallization and the repartitioning of structurally-compatible trace metals. Phosphate and sulfate, two ligands common to natural aquatic systems, alter Fe(II) adsorption onto Fe(III) oxides and affect Fe(III) oxide dissolution and precipitation. However, the effect of these oxoanions on trace metal repartitioning during Fe(II)-catalyzed Fe(III) oxide recrystallization is unclear. The effects of phosphate and sulfate on Ni adsorption and Ni repartitioning during Fe(II)-catalyzed Fe(III) oxide recrystallization were investigated as such repartitioning may be affected by both Fe(II)-oxoanion and metal-oxoanion interactions. In most systems examined, phosphate alters Ni repartitioning during Fe(II)-catalyzed recrystallization to a larger extent than sulfate. Phosphate substantially enhances Ni adsorption onto hematite but decreases (nearly inhibiting) Fe(II)-catalyzed Ni incorporation into and release from this mineral. In the goethite system, however, phosphate suppresses Ni release but enhances Ni incorporation in the presence of aqueous Fe(II). In contrast, sulfate has little effect on macroscopic Ni adsorption and release of Ni from Fe(III) oxides, but substantially enhances Ni incorporation into goethite. This demonstrates that phosphate and sulfate have unique, mineral-specific interactions with Ni during Fe(II)-catalyzed Fe(III) oxide recrystallization. This research suggests that micronutrient bioavailability at redox interfaces in hematite-dominated systems may be especially suppressed by phosphate, while both oxoanions likely have limited effects in goethiterich soils or sediments. Phosphate may also exert a large control on contaminant fate at redox interfaces, increasing Ni retention on iron oxide surfaces. These results further indicate that trace metal retention by iron oxides during lithification and later repartitioning during diagenesis may be substantially altered in the presence of oxoanions.2

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Section: Sulfate and Phosphate Coadsorption With Nisupporting

confidence: 82%

Effect of phosphate and sulfate on Ni repartitioning during Fe(II)-catalyzed Fe(III) oxide mineral recrystallization

Hinkle

Catalano

2015

Geochimica et Cosmochimica Acta

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“…Based on the proposed simple hydrogeochemical model discussed above, we modeled the release of Mg 2+ by weathering and its transport between the low‐flow and high‐flow zones using Eq. [5] for a series of three well‐mixed “stepped flow” reactors (Hill, 1977; Brantley and Conrad, 2008) along the hillslope. Each reactor is considered to be 25 m long given the distance between the SPRT and SPVF is about 75 m. The rectangular boxes shown in Fig.…”

Section: Discussionmentioning

confidence: 99%

Opening the “Black Box”: Water Chemistry Reveals Hydrological Controls on Weathering in the Susquehanna Shale Hills Critical Zone Observatory

Jin

Andrews

Holmes

et al. 2011

Vadose Zone Journal

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114

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We investi gated variati ons of Mg concentrati on, δD and δO in precipitati on, soil water along a planar hillslope, groundwater, and fi rst-order stream water at the Susquehanna Shale Hills Criti cal Zone Observatory (SSHO). Water fl ows verti cally in the unsaturated zone of the hillslope, but hydrological saturati on periodically causes lateral fl ow along interfaces of permeability contrast between the A-B and B-C soil horizons. Changes in soil water Mg concentrati on respond to hydrological changes and are ulti mately controlled by the kineti cs of clay mineral dissoluti on, but are buff ered by the soil exchange capacity. Clay dissoluti on predominantly occurs within the A and B horizons, and Mg released from these zones of "low-fl ow" diff uses or fl ows into the "high-fl ow" zones at horizon interfaces. The Mg concentrati ons are low in these high-fl ow zones because fresher (younger) water fl ows in through macropores. The amplitude of seasonal variati ons in water isotopes (data from 2008-2010) decreases in the following order: precipitati on (δD: 286‰) >> soil water (δD: 86‰) > shallow groundwater (δD: 26‰), indicati ng water becomes progressively older along the fl owpath. Fractures and preferenti al high-fl ow paths make the watershed hydrologically responsive: the average ti me water stays in the shallow subsurface is inferred to be <2 yr. The stream water chemistry is aff ected by inputs of old groundwater that is relati vely high in Mg concentrati on but relati vely limited in range in δD, as well as by inputs from young soil water that is relati vely low in Mg concentrati on with a wide range in δD. The relati ve contributi ons of these two sources to the stream change seasonally. Abbreviati ons: BLS, below land surface; DOC, dissolved organic carbon; GW, groundwater; LMWL, local meteoric water line; NADP, Nati onal Atmospheric Depositi on Program; SH, stream at the headwater; SM, stream at the mid-point; SPMS, south planar middle slope site; SPRT, south planar ridge top site; SPVF, south planar valley fl oor site; SSHO, Susquehanna Shale Hills Criti cal Zone Observatory; SW, stream at the weir.Chemical weathering converts bedrock into soils to provide nutrients to support the terrestrial ecosystems on the Earth's surface (e.g., Chorover et al., 2007;Amundson et al., 2007). Th ese weathering reactions are governed by dissolution kinetics, as well as the rate and direction of water fl ow. For example, the intensity and amount of rainfall are known to impact weathering rates and elemental release by initiating water-rock interaction, transporting reaction products, and shift ing equilibrium with respect to primary and secondary mineral phases (e.g., White and Blum, 1995;Maurice et al., 2002;Asano et al., 2003Asano et al., , 2006Jarvis et al., 2008;Goddéris et al., 2010;Williams et al., 2010). Th e mechanisms and pathways of infi ltration and runoff determine the fl uxes of solute and particles that are transported out of catchments (e.g., Pearce et al., 1986;Maurice et al., 2002). Th e residence ti...

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“…In the system, carbonate rock served as the solid phase for dissolution or precipitation; the liquid and gas filled in the porosity served as the fluid. The main factors influencing the interaction between solid and liquid are temperature, pressure, pH, fluid/solid ratio, mineral surface structure, reaction surface area, and so on [21]. The burial depth determines the temperature and pressure of the system.…”

Section: Methodsmentioning

confidence: 99%

Experiment of Carbonate Dissolution: Implication for High Quality Carbonate Reservoir Formation in Deep and Ultradeep Basins

Ding

Yujin

et al. 2017

Geofluids

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As the most frontiers in petroleum geology, the study of dissolution-based rock formation in deep carbonate reservoirs provides insight into pore development mechanism of petroleum reservoir space, while predicting reservoir distribution in deep-ultradeep layers. In this study, we conducted dissolution-precipitation experiments simulating surface to deep burial environments (open and semiopen systems). The effects of temperature, pressure, and dissolved ions on carbonate dissolution-precipitation were investigated under high temperature and pressure (∼200 ∘ C; ∼70 Mpa) with a series of petrographic and geochemical analytical methods. The results showed that the window-shape dissolution curve appeared in 75∼150 ∘ C in the open system and 120∼175 ∘ C in the semiopen system. Furthermore, the dissolution weight loss of carbonate rocks in the open system was higher than that of semiopen system, making it more favorable for gaining porosity. The type of fluid and rock largely determines the reservoir quality. In the open system, the dissolution weight loss of calcite was higher than that of dolomite with 0.3% CO 2 as the reaction fluid. In the semiopen system, the weight loss from dolomitic limestone prevailed with 0.3% CO 2 as the reaction fluid. Our study could provide theoretical basis for the prediction of high quality carbonate reservoirs in deep and ultradeep layers.

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Analysis of Rates of Geochemical Reactions

Cited by 20 publications

References 23 publications

Effect of phosphate and sulfate on Ni repartitioning during Fe(II)-catalyzed Fe(III) oxide mineral recrystallization

Effect of phosphate and sulfate on Ni repartitioning during Fe(II)-catalyzed Fe(III) oxide mineral recrystallization

Opening the “Black Box”: Water Chemistry Reveals Hydrological Controls on Weathering in the Susquehanna Shale Hills Critical Zone Observatory

Experiment of Carbonate Dissolution: Implication for High Quality Carbonate Reservoir Formation in Deep and Ultradeep Basins

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