THE FRACTIONAL PRECIPITATION OF BARIUM AND RADIUM CHROMATES<sup>1</sup>

Henderson, L. M.; Kracek, F. C.

doi:10.1021/ja01402a017

Cited by 122 publications

(29 citation statements)

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“…When dripwater reaches void spaces within the epikarst (or the main cave chamber itself), degassing of CO 2 drives the water to supersaturation (X P 1) with respect to calcite, and then Ca is removed from solution by precipitation of calcite via PCP (Pilson, 1998;Fairchild et al, 2000). As PCP proceeds, other minor elements such as Mg and Sr are continually enriched in the residual solution because their solid-solution distribution coefficients ½D x ¼ ðX=CaÞ calcite =ðX=CaÞ H 2 O (Henderson and Kracek, 1927) are less than 1.0. Under the condition that initial dripwater composition remains constant (no changes in seasalt input or dripwater flow paths through different lithology), PCP drives co-varying increases in Mg/Ca and Sr/Ca ratios in an approximately straight-line relationship governed by their distribution coefficients (Eq.…”

Section: Identifying Prior Calcite Precipitationmentioning

confidence: 99%

A two-year automated dripwater chemistry study in a remote cave in the tropical south Pacific: Using [Cl−] as a conservative tracer for seasalt contribution of major cations

Tremaine

Sinclair

Stoll

et al. 2016

Geochimica et Cosmochimica Acta

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Stalagmite Mg/Ca and Sr/Ca ratios are commonly interpreted as proxies for past hydrologic conditions and are often used to supplement carbon and oxygen stable isotope records. While the processes that control these element ratios, including water-rock interaction, dripwater residence time, and upstream precipitation of calcite, are well understood in continental caves, there have been few investigations of dripwater Element/Ca (X/Ca) evolution in coastal marine caves where seasalt can have a strong influence on the incoming Mg/Ca ratio.We instrumented a marine cave on the remote South Pacific island of Niue to record daily cave microclimate, as well as weekly-integrated drip rates, dripwater oxygen and hydrogen isotopes, and dripwater chemistry over a period of twenty-two months. Using chloride as a conservative tracer for sea-spray, we calculate that seasalt input accounts for a large portion of dripwater Na, SO 4 , and Mg (89%, 93%, and 85% respectively) and a smaller portion of the Ca and Sr (19% and 17%). During the second year of this study a gradual decrease (by $18%) in dripwater chlorinity was observed, suggesting that an epikarsthosted seasalt aerosol inventory was being diluted over time. Minor element to calcium ratios for B, K, Cl, SO 4 , Mg, Na, Sr, and Fe all strongly covary over the observation period, suggesting that although sea-spray plays a significant role in modulating incoming drip chemistry, prior calcite precipitation (PCP) dominates chemical evolution within the epikarst. During a prolonged drought episode, evaporative enrichments in dripwater dD and d 18 O (+4‰ and 0.5‰, respectively) were observed to coincide with increased cation and anion concentrations, strong Ca removal via PCP, and increases in Sr/Ca and Mg/Ca ratios (28% and 34%, respectively), suggesting that concomitant enrichment in speleothem d 18 O and X/Ca ratios may be interpreted as multi-proxy evidence for dry climate conditions. We use modern dripwater chemistry and empirical water-calcite distribution coefficients to predict a range of stalagmite X/Ca ratios. We then forward model a number of scenarios that could modulate stalagmite chemistry, including increased/decreased seasalt input and changing dripwater flow path through calcite, dolomite, and aragonite bedrock. One major implication from this study is that even if PCP and flow path lithology remain constant over time, changing seasalt input can drive stalagmite Mg/Ca and Sr/Ca ratios away from PCP-controlled covariation, and lead to strongly varying http://dx. ScienceDirect Geochimica et Cosmochimica Acta 184 (2016) 289-310Sr/Mg ratios. Thus in order to interpret coastal cave stalagmite X/Ca records accurately, it is necessary to estimate seasalt input and analyze parent drip and bedrock chemistry to quantify the influence of each contributing process.

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Section: Identifying Prior Calcite Precipitationmentioning

confidence: 99%

A two-year automated dripwater chemistry study in a remote cave in the tropical south Pacific: Using [Cl−] as a conservative tracer for seasalt contribution of major cations

Tremaine

Sinclair

Stoll

et al. 2016

Geochimica et Cosmochimica Acta

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“…The partition coefficient for Sr in the solid phase is best represented for our experimental data by the molar ratio of the concentration in the solid phase (dolomite, "dol") over that in the fluid ("bmi"), which is expressed as D Sr dol = Sr dol / Sr bmi using the Nernst partition coefficient (1891). However, all previous studies have defined the Sr partition coefficient for natural dolomites (Baker and Burns, 1985;Vahrenkamp and Swart, 1990) and recrystallization of dolomite (Malone et al, 1994(Malone et al, , 1996 using the equation of Henderson and Kracek (1927), where D Sr dol is the homogeneous partition coefficient for the homogeneous incorporation of Sr in dolomite. These authors assume that: (1) Sr/Ca of the solid (dolomite) and Sr/Ca ratio of the solution from which dolomite precipitates are in equilibrium and (2) Sr homogeneously replaces Ca in the crystal lattice.…”

Section: Sr Partition Coefficient For Dolomite D Sr Dolmentioning

confidence: 99%

Experimentally determined biomediated Sr partition coefficient for dolomite: Significance and implication for natural dolomite

Sánchez‐Román

McKenzie

Wagener

et al. 2011

Geochimica et Cosmochimica Acta

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“…Using the K sp fromRai et al (1988), a W of Ϫ370 cal/mol was calculated for the binary BaSO 4 -BaCrO 4 solution Henderson and Kracek (1927). measured a K D of 15.5 for fractional precipitation of Ba-RaCrO 4 .…”

mentioning

confidence: 99%

Coprecipitation in the barite isostructural family: 1. binary mixing properties

Zhu¹

2004

Geochimica et Cosmochimica Acta

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THE FRACTIONAL PRECIPITATION OF BARIUM AND RADIUM CHROMATES¹

Cited by 122 publications

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A two-year automated dripwater chemistry study in a remote cave in the tropical south Pacific: Using [Cl−] as a conservative tracer for seasalt contribution of major cations

A two-year automated dripwater chemistry study in a remote cave in the tropical south Pacific: Using [Cl−] as a conservative tracer for seasalt contribution of major cations

Experimentally determined biomediated Sr partition coefficient for dolomite: Significance and implication for natural dolomite

Coprecipitation in the barite isostructural family: 1. binary mixing properties

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THE FRACTIONAL PRECIPITATION OF BARIUM AND RADIUM CHROMATES1

Cited by 122 publications

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A two-year automated dripwater chemistry study in a remote cave in the tropical south Pacific: Using [Cl−] as a conservative tracer for seasalt contribution of major cations

A two-year automated dripwater chemistry study in a remote cave in the tropical south Pacific: Using [Cl−] as a conservative tracer for seasalt contribution of major cations

Experimentally determined biomediated Sr partition coefficient for dolomite: Significance and implication for natural dolomite

Coprecipitation in the barite isostructural family: 1. binary mixing properties

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THE FRACTIONAL PRECIPITATION OF BARIUM AND RADIUM CHROMATES¹