{"refrec":{"BRefID":404422,"RR":"<b>Karancz, S.; Uchikawa, J.; de Nooijer, L.J.; Wolthers, M.; Conner, K.A.; Hite, C.G.; Zeebe, R.E.; Sharma, S.K.; Reichart, G.-J.</b> (2024). Constraining sulfur incorporation in calcite using inorganic precipitation experiments. <i>Geochim. Cosmochim. Acta 381</i>: 116-130. <a href=\"https://dx.doi.org/10.1016/j.gca.2024.07.034\" target=\"_blank\">https://dx.doi.org/10.1016/j.gca.2024.07.034</a>","BEntID":402213,"PublicFlag":1,"CheckedFlag":0,"wosflag":1,"vabbflag":1,"RefStringPartII":". <i>Geochim. Cosmochim. Acta 381</i>: 116-130. <a href=\"https://dx.doi.org/10.1016/j.gca.2024.07.034\" target=\"_blank\">https://dx.doi.org/10.1016/j.gca.2024.07.034</a>","DocTypID":8,"DocType":"Journal article","MarineFlag":0,"FreshFlag":0,"BrackishFlag":0,"TerrestrialFlag":0,"Authorstring":"Karancz, S.; Uchikawa, J.; de Nooijer, L.J.; Wolthers, M.; Conner, K.A.; Hite, C.G.; Zeebe, R.E.; Sharma, S.K.; Reichart, G.-J.","OrigTitleTranslFlag":0,"Authorstringtrunc":"Karancz, S. <i>et al.</i>","Englishabstract":"The sulfur over calcium ratio (S/Ca) in foraminiferal shells was recently proposed as a new and independent proxy for reconstructing marine inorganic carbon chemistry. This new approach assumes that sulfur is incorporated into CaCO3 predominantly in the form of sulfate (SO42−) through lattice substitution for carbonate ions (CO32–), and that S/Ca thus reflects seawater [CO32–]. Although foraminiferal growth experiments validated this approach, field studies showed controversial results suggesting that the potential impact of [CO32–] may be overwritten by one or more parameters. Hence, to better understand the inorganic processes involved, we here investigate S/Ca values in inorganically precipitated CaCO3 (S/Ca(cc)) grown in solutions of CaCl2 − Na2CO3 − Na2SO4 − B(OH)3 − MgCl2. Experimental results indicate the dependence of sulfate partitioning in CaCO3 on the carbon chemistry via changing pH and suggest that faster precipitation rates increase the partition coefficient for sulfur. The S/Ca ratios of our inorganic calcite samples show positive correlation with modelled [CaSO40](aq), but not with the concentration of free SO42− ions. This challenges the traditional model for sulfate incorporation in calcite and implies that the uptake of sulfate potentially occurs via ion-ion pairs rather than being incorporated as single anions. Based on the [Ca2+] dependence via speciation, we here suggest a critical evaluation of this potential proxy. As sulfate complexation seems to control sulfate uptake in inorganic calcite, application as a proxy using foraminiferal calcite may be limited to periods for which seawater chemistry is well-constrained. As foraminiferal calcite growth is modulated by inward Ca2+ flow to the site of calcification coupled to outward H+ pumping, sulfate incorporation as CaSO40 ion-pair in the foraminifer’s shell also provides a mechanistic link for the observed relationship between S/Ca(cc) and [CO32–].","AbstractOtherLang":null,"BibLvlCode":"AS","StandardTitle":"Constraining sulfur incorporation in calcite using inorganic precipitation experiments","OrigTitleLangCode":"en","OrigTitleLangCodeExtended":"eng","OrigTitleLangID":15,"DateLastModified":{"date":"2026-06-10 01:32:59.511835","timezone_type":1,"timezone":"+02:00"},"UserAccessRight":null,"UserAccID":null,"AuthorKeywords":"Calcite growth experiment; Sulfate incorporation; Ion-pair formation; Inorganic carbon chemistry; Proxy","OtherDescriptors":null,"Notes":null,"AnaPub":2024,"MonPub":null,"DateUpdate":"2024-11-26","DateCreate":"2024-11-26","SecASFANote":null,"ConfID":null,"PeerRev":1,"VlizCoreFlag":1,"WoScode":null,"VABBcode":null,"OpenAcc":1,"DOI":"10.1016/j.gca.2024.07.034"},"refs":null,"anarec":{"AnaID":404422,"PubliDate":2024,"Pagination":"116-130","XtraPublOfAnaID":null,"ISBN":null,"Volume":"381","Issue":null,"BRefMon":null,"BRefMonRR":null,"BRefXtra":null,"BRefXtraRR":null,"SerBRefID":42901,"SerRR":"Geochimica et Cosmochimica Acta. Elsevier: Oxford,New York etc..  ISSN 0016-7037; e-ISSN 1872-9533","StandardTitleSer":"Geochimica et Cosmochimica Acta","ISSN":"0016-7037","AbbrevSer":"Geochim. Cosmochim. 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