小球藻表面酯基屏蔽对钙锶生物矿化的影响

生物矿化作用是在有机基质全程参与调控与诱导下形成矿物的过程。本文以钙锶为研究对象,通过小球藻对钙锶的生物矿化诱导,探索钙锶形成稳定矿化体的条件和方法。通过SEM,FT-IR和XRD来考察小球藻表面基团酯基屏蔽前后对钙锶生物矿物的影响。结果表明:1锶离子浓度较高时,晶体更易生成文石结构;2钙离子浓度偏高时,则更偏爱方解石;3在小球藻的作用下,晶体的取向更易受浓度较大的离子的影响;4当屏蔽小球藻表面基团酯基后,钙离子及锶离子对晶体的成核取向上的调控能力减弱。简言之,小球藻表面基团酯基能促进晶型的转换,并且对晶体的形貌具有一定的调控能力     

基于石灰石粉钙源的微生物固化砂土试验研究

微生物诱导碳酸钙沉积（MICP）作用是一种新型的土体改良技术。钙源作为MICP反应中重要的反应物,对微生物诱导碳酸钙沉积的效果有重要的影响。目前应用最广泛的钙源——氯化钙（CaCl2）,具有成本高,环境污染性大的缺点。为此,文章提出利用石灰石粉提取钙源,通过在石灰石粉中加入乙酸溶液,释放钙离子用于微生物固化土体。通过开展无侧限抗压强度试验以及微观结构的扫描电镜观测、碳酸钙含量测定等分析,验证利用石灰石粉提取的钙源用于微生物诱导碳酸钙沉积作用固化土体的可行性,同时与醋酸钙和氯化钙固化砂柱进行了对比分析。研究结果表明：（1）石灰石粉用于微生物固化土体具有可行性,固化后砂柱的强度和碳酸钙含量较高,结构完整性高;（2）不同钙源固化砂柱的力学特性不同但均呈典型的脆性破坏模式,其中醋酸钙固化砂柱的无侧限抗压强度略高于石灰石钙源固化砂柱,氯化钙固化砂柱的无侧限抗压强度则远低于前两者且表面更加粗糙,孔隙更多,破坏后的完整性更低;（3）不同钙源固化砂柱的碳酸钙含量不同。醋酸钙和石灰石钙源固化砂柱的碳酸钙含量相近,而氯化钙固化砂柱中碳酸钙含量较低。不同钙源固化砂柱的碳酸钙含量和无侧限抗压强度基本呈正相关关系;（4）醋酸钙和石灰石钙源固化砂柱中砂土颗粒的表面和接触点间均沉积大量碳酸钙,碳酸钙晶体主要为薄片状堆叠的方解石。氯化钙固化砂柱中碳酸钙沉积量低于前两者,碳酸钙晶体主要为六面体状的方解石;（5）不同钙源主要通过影响微生物成矿过程的晶型、晶貌、晶体含量、晶体分布及胶结特征来改变固化效果。     

白云鄂博的碳锶铈矿

在对白云鄂博碳酸岩中稀土矿物的研究中,发现了锶-稀土含水复碳酸盐矿物。根据电子探针分析结果,其化学成分相当于碳锶铈矿(Ancylite-Ce)、钙碳锶铈矿(Calcioancylite),前者Sr>Ca,后者Ca>Sr。计算得到的化学式分别为:(Sr0.62,Ca0.18)0.8(Ce0.5,Nd0.36,La0.17,Pr0.02,Sm0.02)1.2(CO3)2(OH1.04,F0.14)1.2H2O、(Ca0.73,Sr0.28,Ba0.17)1.2(Ce0.46,Nd0.15,La0.15,Pr0.04,Sm0.01)0.8(CO3)2(OH0.75,F0.06)0.8H2O,简化为:(Sr,Ca)2-xCex(CO3)2.(OH,F)2-x.H2O,接近理论化学式(Sr,Ca)Ce(CO3)2(OH)H2O,但附加阴离子除OH—外,还含有少量F-。两者均为几微米至十几微米的微小晶体,呈浸染状产出,且仅见于晚期方解石或方解石—白云石交生体中。     

低温环境下两种氨基酸对碳酸钙矿化影响的研究

黄龙景区高寒冷水型钙华沉积地貌环境中生存着大量的嗜冷微生物。为了探究这些微生物在低温及高浓度Ca~(2+)和HCO_3~-水环境中的代谢产物对钙华沉积的影响,本实验选取黄龙嗜冷细菌的两种特征代谢产物L-苯丙氨酸和L-半胱氨酸,通过模拟低温、含较高浓度的Ca~(2+)和HCO_3~-的实验环境,并利用X射线衍射仪(XRD)、傅里叶变换红外光谱仪(FT-IR)、扫描电子显微镜(SEM)等分析方法,来探讨氨基酸对矿化体系中碳酸钙沉积速率及其晶型和形貌的影响。实验结果表明:在特定模拟环境条件下,(1)L-苯丙氨酸和L-半胱氨酸均能促进碳酸钙的沉积。L-苯丙氨酸对晶型影响不大,产物均为方解石型碳酸钙,但是L-苯丙氨酸能抑制方解石晶面棱边的生长,使得晶体出现多面不规则的立方体形态;(2)L-半胱氨酸除诱导并促进方解石型碳酸钙的合成外还可以诱导文石型碳酸钙的合成。该结果可为黄龙地区钙华的生物成因研究提供一定的基础数据。     

磷灰石和方解石微生物风化作用的锶同位素示踪

为研究微生物对磷灰石和方解石的差异风化作用,将一株黑曲霉(Aspergillus niger)和一株青霉(Penicillium sp.)分别培养在含有方解石和磷灰石混合物的培养基中,按不同时间取培养基上清液样品,测定其Ca2+、Sr2+含量及Sr同位素比值.测试结果显示培养基上清液的Sr同位素比值介于端元组分方解石与磷灰石的Sr同位素比值(0.70721-0.70861)之间.基于锶同位素组成的端元模式计算结果表明:在真菌培养前期,黑曲霉优先选择方解石进行风化,而青霉则优先风化磷灰石;随着培养时间的延长,青霉对方解石风化能力逐渐增强.应用Sr同位素方法可示踪识别微生物对不同矿物风化作用的差异性.     

鄂尔多斯盆地东南部奥陶系马五段去白云石化过程的地球化学示踪

高Ca/Mg值流体与白云石反应的去白云石化作用在较多地层中可见,但对其形成过程的探讨甚少。本文运用碳、氧、锶同位素及锶元素的示踪原理,对鄂尔多斯盆地东南部奥陶系马五段去白云石化作用的两类不同颜色的次生方解石形成过程进行示踪,结果显示:红色次生方解石具低Sr元素含量、高87Sr/86Sr值及负偏的δ13C特征;白色次生方解石呈现出高Sr元素含量、低87Sr/86Sr值及明显负偏的δ18O特征。结合去白云石化次生方解石岩石学特征,推测去白云石化作用可能有两个阶段:近地表时期,受大气淡水淋滤发生去白云石化作用,形成不彻底灰化的棕红色、红色次生方解石;中-深埋藏期,受温度、压力及海源性流体影响与叠加进一步发生去白云石化作用,形成白色次生方解石。      

多组分有机质作用下碳酸钙的矿化现象

采用SEM、XRD、FT-IR等手段对氨基酸、多糖以及有机酸混合体系中形成的碳酸钙晶体进行了表征,进而比较了多组分有机质作用下碳酸钙的矿化现象。结果表明,氨基酸-单糖体系(A-M)促进了碳酸钙的沉积,其钙化速率相较于对照组提高了36%;有机酸则抑制了碳酸钙的沉积,单糖-有机酸体系(M-O)、氨基酸-有机酸体系(A-O)和氨基酸-有机酸-单糖体系(A-O-M)的钙化速率分别下降了33%、29%、17%。其次,A-M体系合成的晶体以方解石为主,包含少量的球霰石,M-O、A-O和A-O-M体系则在柠檬酸的调控下合成了方解石。最后,A-M体系合成了块状晶体(粒径为10μm)及中空的环状晶体(粒径为5μm),而A-O和M-O体系合成了棒状晶体(长轴径5～15μm,短轴径3～5μm)。A-O-M体系存在含量最高的有机质,导致成核速率高于生长速率,因此合成的晶体呈粒状(粒径1～3μm)且发育不完整。研究揭示了多组分共存体系中的生物矿化现象,阐明了柠檬酸在多组分体系中对晶体成核及生长的主导调控作用,对研究黄龙高寒环境下的生物矿化机制具有重要意义。     

自发极化电气石对CaCO3结晶过程和晶体形貌的影响

电气石是一种天然的硅酸盐矿物,具有自发极化效应,晶体表面存在静电场,在水处理领域具有广阔的应用前景。本研究利用碳酸钙沉积法考察电气石颗粒的阻垢性能,对投加不同粒径电气石颗粒后产生的碳酸钙钙垢的结构和微观形貌进行分析,探讨电气石颗粒对碳酸钙水溶液结晶性能的影响。实验结果表明,电气石颗粒具有一定的表面阻垢效果,能够降低碳酸钙在水溶液中的溶解度,促使溶液中碳酸钙形成并黏附在电气石颗粒表面,从而抑制碳酸钙钙垢黏附在换热固体表面,且电气石颗粒粒径越小,抑制效果越明显。XRD和SEM分析表明,电气石颗粒能够影响碳酸钙晶体的成核过程,改变碳酸钙的晶体形貌,形成附着性较差的文石型碳酸钙,达到阻垢效果。     

闽西行洛坑钨矿流体演化过程与成矿机制:白钨矿原位微量元素、Sr同位素的制约

行洛坑钨矿位于武夷山成矿带中部,是该带目前规模最大的钨矿床。钨矿体主要产于强烈蚀变的似斑状黑云母花岗岩岩株顶部,发育细脉浸染状、网脉状及大脉状多种矿化类型,黑钨矿与白钨矿含量近1∶1。关于矿床的流体演化过程与成矿机制目前仍不清楚,成因存在较大争议。本文在详细成矿阶段划分的基础上,对不同阶段产出的不同世代白钨矿开展了系统的原位LA-ICP-MS微量元素和Sr同位素、以及流体包裹体和H-O同位素的研究工作。行洛坑钨矿由早至晚可以划分为3个成矿阶段:细脉浸染状白钨矿-辉钼矿阶段(阶段Ⅰ)、钾长石-白钨矿-黑钨矿-绿柱石阶段(阶段Ⅱ)及硫化物-黑钨矿-白钨矿-碳酸盐阶段(阶段Ⅲ)。流体包裹体研究显示成矿流体为中高温、低盐度的Na Cl-H_2O-CO_2体系。H-O与Sr同位素表明成矿流体主要为岩浆流体,仅成矿晚期阶段有少量的大气降水加入。阶段I白钨矿相对富REE、Mo、Na和Nb,贫Sr;而随着流体演化,白钨矿REE、Mo、Na、Nb含量逐渐降低,Sr含量显著升高。阶段I白钨矿呈自形-半自形粒状,CL图像显示细密的、均匀的震荡环带,稀土元素主要与Na和Nb结合进入白钨矿晶格;阶段Ⅱ、阶段Ⅲ白钨矿呈半自形-他形,不发育或仅发育宽缓的、不规则震荡环带,稀土元素与Ca(Ca的离子空位)结合置换白钨矿中的Ca。结合蚀变与矿化特征,认为阶段I白钨矿形成于低水岩比环境,由初始岩浆流体沿微小裂隙渗透交代而形成;而阶段Ⅱ、Ⅲ白钨矿形成于高水岩比环境,CO_2的不混溶作用伴随强烈的水岩反应导致了钨的富集沉淀。结合矿床地质特征,认为行洛坑钨矿属于广义的斑岩型钨矿,细脉浸染状矿化构成了钨成矿的基础,而网脉状、大脉状矿化的叠加是钨进一步富集的关键。     

基于微生物诱导矿化的钙质砂加固影响因素

基于微生物诱导矿化技术,分别以钙源、营养液浓度及颗粒粒径为变量开展了钙质砂微生物注浆试验。通过无侧限抗压强度测试结合扫描电镜测试综合研究了固化试样碳酸钙产率、无侧限抗压强度与各因素间关系,探究了不同因素对固化效果的影响及固化机理。结果表明:钙源是影响钙质砂固化效果的关键,氯化钙作为钙源时的固化效果优于乙酸钙;低浓度营养液较高浓度营养液更有利于钙质砂胶结成型,高浓度营养液易造成大量碳酸钙晶体阻塞管口部位并影响脲酶活性;小粒径钙质砂微生物固化效果较好,微生物诱导生成的碳酸钙晶体更易将小粒径钙质砂粒间孔隙充填。     

酸雨对桂林枯水期岩溶地下水δ13CDIC及碳汇效应的影响

定量评价硫酸对岩溶碳汇效应的影响有助于提高岩石风化碳汇通量估算精度, 对当前全球气候变化研究意义重大.选取受酸雨影响的桂林岩溶区为研究对象, 在枯水期对研究区14个岩溶大泉和15条地下河水化学成分和碳同位素进行了测试分析, 结果表明: 岩溶大泉和地下河中阳离子以Mg2+和Ca2+为主, 阴离子以HCO₃-为主, 分别占阳离子和阴离子组成的90%以上, SO₄2-含量较低, 其含量范围为0.004~0.213mmol/L; 所占阴离子组成比例为0.12%~6.11%;δ13C_DIC、[Ca2++Mg2+]/[HCO₃-]更偏向于碳酸溶解端元, 离硫酸溶解端元距离远, 证实硫酸参与碳酸盐岩的溶解对地下水无机碳(dissolved inorganic carbon, 简称DIC)及δ13C_DIC的影响有限; 与Sr2+/Ca2+值一样, δ13C_DIC主要受径流条件控制, 其大小可以反映地下水径流条件的强弱.利用化学计量关系计算出由硫酸溶蚀碳酸盐岩的平均比例为22.64%, 产生的DIC(HCO₃-_H2SO4)占总DIC的平均比例为13.04%, 碳酸产生的DIC(HCO₃-_H2CO3)占地下水总DIC的比例为86.96%, 其中来源于土壤大气中的HCO₃-比例为43.48%.因此, 扣除硫酸对地下水中DIC的贡献后, 岩溶碳汇效应将减少13.04%.      

Seasonal dripwater Mg/Ca and Sr/Ca variations driven by cave ventilation: Implications for and modeling of speleothem paleoclimate records

A 4-year study in a central Texas cave quantifies multiple mechanisms that control dripwater composition and how these mechanisms vary at different drip sites. We monitored cave-air compositions, in situ calcite growth, dripwater composition and drip rate every 4-6 weeks. Three groups of drip sites are delineated (Groups 1-3) based on geochemical variations in dripwater composition. Quantitative modeling of mineral-solution reactions within the host carbonate rock and cave environments is used to identify mechanisms that can account for variations in dripwater compositions. The covariation of Mg/Ca (and Sr/Ca) and Sr isotopes is key in delineating whether Mg/Ca and Sr/Ca variations are dictated by water-rock interaction (i.e., calcite or dolomite recrystallization) or prior calcite precipitation (PCP). Group 1 dripwater compositions reflects a narrow range of the extent of water-rock interaction followed by varying amounts of prior calcite precipitation (PCP). Group 2 dripwater compositions are controlled by varying amounts of water-rock interaction with little to no PCP influence. Group 3 dripwater compositions are dictated by variable extents of both water-rock interaction and PCP. Group 1 drip sites show seasonal variations in dripwater Mg/Ca and Sr/Ca, whereas the other drip sites do not. In contrast to the findings of most previous dripwater Mg/Ca-Sr/Ca studies, these seasonal variations (at Group 1 drip sites) are independent of changes in water flux (i.e., rainfall and/or drip rate), and instead significantly correlate with changes in cave-air CO₂ concentrations. These results are consistent with lower cave-air CO₂, related to cool season ventilation of the cave atmosphere, enhancing calcite precipitation and leading to dripwater geochemical evolution via PCP. Group 1 dripwater Mg/Ca and Sr/Ca seasonality and evidence for PCP as a mechanism that can account for that seasonality, have two implications for many other regions where seasonal ventilation of caves is likely: (1) speleothem trace-element records may provide seasonal signals, and (2) such records may be biased toward recording climate conditions during the season when calcite is depositing. Additionally, we use our results to construct a forward model that illustrates the types of speleothem Mg/Ca and Sr/Ca variations that would result from varying controls on dripwater compositions. The model provides a basis for interpreting paleo-dripwater controls from high frequency Mg/Ca and Sr/Ca variations for speleothems from caves at which long term monitoring studies are not feasible.     

Sequestration of Sr(II) by calcium oxalate—A batch uptake study and EXAFS analysis of model compounds and reaction products

Calcium oxalate monohydrate (CaC₂O₄·H₂O—abbreviated as CaOx) is produced by two-thirds of all plant families, comprising up to 80 wt.% of the plant tissue and found in many surface environments. It is unclear, however, how CaOx in plants and soils interacts with metal ions and possibly sequesters them. This study examines the speciation of Sr(II)_aq following its reaction with CaOx. Batch uptake experiments were conducted over the pH range 4-10, with initial Sr solution concentrations, [Sr]_aq, ranging from 1 × 10⁻⁴ to 1 × 10⁻³ M and ionic strengths ranging of 0.001-0.1 M, using NaCl as the background electrolyte. Experimental results indicate that Sr uptake is independent of pH and ionic strength over these ranges. After exposure of CaOx to Sr_aq for two days, the solution Ca concentration, [Ca]_aq, increased for all samples relative to the control CaOx suspension (with no Sr added). The amount of Sr_aq removed from solution was nearly equal to the total [Ca]_aq after exposure of CaOx to Sr. These results suggest that nearly 90% of the Sr is removed from solution to a solid phase as Ca is released into solution. We suggest that the other 10% is sequestered through surface adsorption on a solid phase, although we have no direct evidence for this. Extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the molecular-level speciation of Sr in the reaction products. Deconvolutions of the Sr K-edge EXAFS spectra were performed to identify multi-electron excitation (MEE) features. MEE effects were found to give rise to low-frequency peaks in the Fourier transform before the first shell of oxygen atoms and do not affect EXAFS fitting results. Because of potential problems caused by asymmetric distributions of Sr-O distances when fitting Sr K-edge EXAFS data using the standard harmonic model, we also employed a cumulant expansion model and an asymmetric analytical model to account for anharmonic effects in the EXAFS data. For Sr-bearing phases with low to moderate first-shell (Sr-O pair correlation) anharmonicity, the cumulant expansion model is sufficient for EXAFS fitting; however, for higher degrees of anharmonicity, an analytical model is required. Based on batch uptake results and EXAFS analyses of reaction products, we conclude that Sr is dominantly sequestered by a solid phase at the CaOx surface, likely the result of a dissolution-reprecipitation mechanism, to form SrC₂O₄ of mixed hydration state (i.e. SrOx·nH₂O, where n = 0, 1, or 2). Surprisingly, no spectroscopic or XRD evidence was found for a (Sr,Ca)Ox solid solution or for a separate SrCO₃ phase. In addition, we found no evidence for Sr(II) inner-sphere sorption complexes on CaOx surfaces based on lack of Sr-Ca second-neighbor pair correlations in the EXAFS spectra, although some type of Sr(II) surface complex (perhaps a type B Sr-oxalate ternary complex or an outer-sphere Sr(II) complex) or some as yet undetected Sr-bearing solid phases are needed to account for approximately 10% of Sr uptake by CaOx. The formation of a hydrated SrOx phase in environments under conditions similar to those of our experiments should retard Sr mobility and could be a significant factor in the biogeochemical cycling of Sr in soils and sediments or in plants and plant litter where CaOx is present.     

贵阳市区地表/地下水化学与锶同位素研究

贵阳市及邻近地区地表和地下水的化学与Sr同位素组成变化反映了典型喀斯特地区地表/地下水文系统的水-岩反应和城市污染特征:水体中的化学溶解物质主要来源于碳酸盐岩(石灰岩和白云岩)的风化作用和膏岩层的溶解,其次为人为污染物的输入;污染物以K⁺,Na⁺,Cl^-,SO^2-₄,NO^-₃为主,枯水期因大气降水补给小而受人为活动影响较大;丰水期和枯水期地表/地下水的化学组成变化说明地表/地下水交换活跃,地下水环境容易受到人为活动影响。     

Effects of seawater carbonate ion concentration and temperature on shell U, Mg, and Sr in cultured planktonic foraminifera

We investigate the sensitivity of U/Ca, Mg/Ca, and Sr/Ca to changes in seawater [CO₃²⁻] and temperature in calcite produced by the two planktonic foraminifera species, Orbulina universa and Globigerina bulloides, in laboratory culture experiments. Our results demonstrate that at constant temperature, U/Ca in O. universa decreases by 25 ± 7% per 100 μmol [CO₃²⁻] kg⁻¹, as seawater [CO₃²⁻] increases from 110 to 470 μmol kg⁻¹. Results from G. bulloides suggest a similar relationship, but U/Ca is consistently offset by ∼+40% at the same environmental [CO₃²⁻]. In O. universa, U/Ca is insensitive to temperature between 15°C and 25°C. Applying the O. universa relationship to three U/Ca records from a related species, Globigerinoides sacculifer, we estimate that Caribbean and tropical Atlantic [CO₃²⁻] was 110 ± 70 μmol kg⁻¹ and 80 ± 40 μmol kg⁻¹ higher, respectively, during the last glacial period relative to the Holocene. This result is consistent with estimates of the glacial-interglacial change in surface water [CO₃²⁻] based on both modeling and on boron isotope pH estimates. In settings where the addition of U by diagenetic processes is not a factor, down-core records of foraminiferal U/Ca have potential to provide information about changes in the ocean’s carbonate concentration.Below ambient pH (pH < 8.2), Mg/Ca decreased by 7 ± 5% (O. universa) to 16 ± 6% (G. bulloides) per 0.1 unit increase in pH. Above ambient pH, the change in Mg/Ca was not significant for either species. This result suggests that Mg/Ca-based paleotemperature estimates for the Quaternary, during which surface-ocean pH has been at or above modern levels, have not been biased by variations in surface-water pH. Sr/Ca increased linearly by 1.6 ± 0.4% per 0.1 unit increase in pH. Shell Mg/Ca increased exponentially with temperature in O. universa, where Mg/Ca = 0.85 exp (0.096*T), whereas the change in Sr/Ca with temperature was within the reproducibility of replicate measurements.     

An Isotope Dilution ICP‐MS Method for the Determination of Mg/Ca and Sr/Ca Ratios in Calcium Carbonate

Mg/Ca and Sr/Ca ratios in calcium carbonate are important components of many palaeoclimate studies. We present an isotope dilution method relying on a single mixed spike containing ²⁵Mg, ⁴³Ca and ⁸⁷Sr. Dozens of samples per day, as small as 10 μg of carbonate, could be dissolved, spiked and run in an ICP‐MS with a precision of 0.8% (2 RSD). Two instruments types, a sector field and a quadrupole ICP‐MS, were compared. The best long term precision found was 0.4% (2 RSD), although this increased by up to a factor of two when samples of very different Mg or Sr content were run together in the same sequence. Long term averages for the two instruments concurred. No matrix effects were detected for a range of Ca concentrations between 0.2 and 2 mmol l^‐1. Accuracy, tested by measuring synthetic standard solutions, was 0.8% with some systematic trends. We demonstrate the strength of this isotope dilution method for (a) obtaining accurate results for sample sets that present a broad Mg and Sr range and (b) testing solid carbonates as candidate reference materials for interlaboratory consistency. Mg/Ca and Sr/Ca results for reference materials were in good agreement with values from the literature.     

Improving SST reconstructions from coral Sr/Ca records: multiple corals from Tahiti (French Polynesia)

We reconstruct SST from coral Sr/Ca ratios measured at three coral cores taken from the lagoon of Tahiti (French Polynesia). Two coral cores were drilled from the same coral colony (one horizontally and one vertically), and a third core was drilled vertically from another coral growing at a different site. We evaluate several Sr/Ca records as proxies for regional SST variations: (1) the three single-core records from Tahiti, (2) an average Sr/Ca record computed from the two cores drilled from the same coral colony, (3) an average Sr/Ca record computed from all three Tahiti cores, and (4) an average Sr/Ca record computed from the three Tahiti cores and a fourth core taken from a different island (Rarotonga). On a monthly scale, the average Sr/Ca record including the four coral cores from Tahiti and Rarotonga shows the best correlation with regional SST. The variance of the SST reconstruction is very realistic and the residual SST is low. This suggests that reconstructing SST from average proxy records gives a better representation of regional SST variations. Of the three Tahiti cores, the one that was drilled horizontally shows the best correlation with grid-SST on an annual mean scale. All three Tahiti corals show much larger interannual SST variations than that indicated by grid-SST.     

δB, Sr, Mg and B in a modern Porites coral: the relationship between calcification site pH and skeletal chemistry

Sr/Ca, B/Ca, Mg/Ca and δ¹¹B were determined at high spatial resolution across ∼1 year of a modern Hawaiian Porites lobata coral by secondary ion mass spectrometry (SIMS). We observe significant variations in B/Ca, Mg/Ca, Sr/Ca and δ¹¹B over short skeletal distances (nominally equivalent to periods of <20 days). This heterogeneity probably reflects variations in the composition of the extracellular calcifying fluid (ECF) from which the skeleton precipitates. Calcification site pH (total scale) was estimated from skeletal δ¹¹B and ranged from 8.3 to 8.8 (± ∼0.1) with a mean of ∼8.6. Sr/Ca and B/Ca heterogeneity is not simply correlated with calcification site pH, as might be expected if Ca-ATPase activity increases the pH and decreases the Sr/Ca and B(OH)₄⁻/CO₃²⁻ ratios of the ECF. We produced a simple model of the ECF composition and the skeleton deposited from it, over a range of calcium transport and carbonate scenarios, which can account for these observed geochemical variations. The relationship between the pH and Sr/Ca of the ECF is dependent on the concentration of DIC at the calcification site. At higher DIC concentrations the ECF has a high capacity to buffer the [H⁺] changes induced by Ca-ATPase pumping. Conversely, at low DIC concentrations, this buffering capacity is reduced and ECF pH changes more rapidly in response to Ca-ATPase pumping. The absence of a simple correlation between ECF pH and skeletal Sr/Ca implies that calcification occurred under a range of DIC concentrations, reflecting variations in the respiration and photosynthesis of the coral and symbiotic zooxanthellate in the overlying coral tissues. Our observations have important implications for the use of coral skeletons as indicators of palaeo-ocean pH.     

Controls on Sr/Ca and Mg/Ca in scleractinian corals: The effects of Ca-ATPase and transcellular Ca channels on skeletal chemistry

The Sr/Ca of aragonitic coral skeletons is a commonly used palaeothermometer. However skeletal Sr/Ca is typically dominated by weekly-monthly oscillations which do not reflect temperature or seawater composition and the origins of which are currently unknown. To test the impact of transcellular Ca²⁺ transport processes on skeletal Sr/Ca, colonies of the branching coral, Pocillopora damicornis, were cultured in the presence of inhibitors of Ca-ATPase (ruthenium red) and Ca channels (verapamil hydrochloride). The photosynthesis, respiration and calcification rates of the colonies were monitored throughout the experiment. The skeleton deposited in the presence of the inhibitors was identified (by ⁴²Ca spike) and analysed for Sr/Ca and Mg/Ca by secondary ion mass spectrometry. The Sr/Ca of the aragonite deposited in the presence of either of the inhibitors was not significantly different from that of the solvent (dimethyl sulfoxide) control, although the coral calcification rate was reduced by up to 66% and 73% in the ruthenium red and verapamil treatments, respectively. The typical precision (95% confidence limits) of mean Sr/Ca determinations within any treatment was <±1% and differences in skeletal Sr/Ca between treatments were correspondingly small. Either Ca-ATPase and Ca channels transport Sr²⁺ and Ca²⁺ in virtually the same ratio in which they are present in seawater or transcellular processes contribute little Ca²⁺ to the skeleton and most Ca is derived from seawater transported directly to the calcification site. Variations in the activities of Ca-ATPase and Ca-channels are not responsible for the weekly-monthly Sr/Ca oscillations observed in skeletal chronologies, assuming that the specificities of Ca transcellular transport processes are similar between coral genera.