School of Biological Sciences, The University of Western Australia, 35 Stirling Highway, Crawley, Western Australia, 6009, Australia.
School of Social Sciences, The University of Western Australia, 35 Stirling Highway, Crawley, Western Australia, 6009, Australia.
Geobiology. 2023 Sep;21(5):644-670. doi: 10.1111/gbi.12555. Epub 2023 Mar 27.
Dolomite (CaMg(CO ) ) precipitation is kinetically inhibited at surface temperatures and pressures. Experimental studies have demonstrated that microbial extracellular polymeric substances (EPS) as well as certain clay minerals may catalyse dolomite precipitation. However, the combined association of EPS with clay minerals and dolomite and their occurrence in the natural environment are not well documented. We investigated the mineral and textural associations within groundwater dolocrete profiles from arid northwest Australia. Microbial EPS is a site of nucleation for both dolomite and authigenic clay minerals in this Late Miocene to Pliocene dolocrete. Dolomite crystals are commonly encased in EPS alveolar structures, which have been mineralised by various clay minerals, including montmorillonite, trioctahedral smectite and palygorskite-sepiolite. Observations of microbial microstructures and their association with minerals resemble textures documented in various lacustrine and marine microbialites, indicating that similar mineralisation processes may have occurred to form these dolocretes. EPS may attract and bind cations that concentrate to form the initial particles for mineral nucleation. The dolomite developed as nanocrystals, likely via a disordered precursor, which coalesced to form larger micritic crystal aggregates and rhombic crystals. Spheroidal dolomite textures, commonly with hollow cores, are also present and may reflect the mineralisation of a biofilm surrounding coccoid bacterial cells. Dolomite formation within an Mg-clay matrix is also observed, more commonly within a shallow pedogenic horizon. The ability of the negatively charged surfaces of clay and EPS to bind and dewater Mg , as well as the slow diffusion of ions through a viscous clay or EPS matrix, may promote the incorporation of Mg into the mineral and overcome the kinetic effects to allow disordered dolomite nucleation and its later growth. The results of this study show that the precipitation of clay and carbonate minerals in alkaline environments may be closely associated and can develop from the same initial amorphous Ca-Mg-Si-rich matrix within EPS. The abundance of EPS preserved within the profiles is evidence of past microbial activity. Local fluctuations in chemistry, such as small increases in alkalinity, associated with the degradation of EPS or microbial activity, were likely important for both clay and dolomite formation. Groundwater environments may be important and hitherto understudied settings for microbially influenced mineralisation and for low-temperature dolomite precipitation.
白云石(CaMg(CO3)2)的沉淀在地表温度和压力下受到动力学抑制。实验研究表明,微生物胞外聚合物(EPS)以及某些粘土矿物可能催化白云石的沉淀。然而,EPS 与粘土矿物以及白云石的联合作用及其在自然环境中的存在情况还没有得到很好的记录。我们研究了澳大利亚西北部干旱地区地下水中白云石化胶结物剖面中的矿物和结构组合。在这个中新世到上新世的白云石化胶结物中,微生物 EPS 是白云石和自生粘土矿物成核的场所。白云石晶体通常被 EPS 肺泡结构包裹,这些结构被各种粘土矿物,包括蒙脱石、三八面体蒙脱石和坡缕石-海泡石所矿化。微生物微观结构及其与矿物的组合的观察结果与各种湖泊和海洋微生物岩中记录的纹理相似,表明可能发生了类似的矿化过程来形成这些白云石化胶结物。EPS 可能会吸引和结合阳离子,这些阳离子浓缩形成矿物成核的初始颗粒。白云石是通过无序前体形成纳米晶体,然后聚结形成更大的泥晶晶体聚集体和菱形晶体。也存在球形白云石纹理,通常具有空心核心,这可能反映了围绕球形细菌细胞的生物膜的矿化。在 Mg-粘土基质内也观察到白云石的形成,更常见于浅层成壤层。粘土和 EPS 的带负电荷表面结合和脱水 Mg 的能力,以及离子通过粘性粘土或 EPS 基质的缓慢扩散,可能促进 Mg 掺入矿物并克服动力学效应,从而允许无序白云石成核及其随后的生长。本研究的结果表明,在碱性环境中粘土和碳酸盐矿物的沉淀可能密切相关,并可从 EPS 中的同一初始无定形 Ca-Mg-Si 富基质中发育而来。剖面中保存的 EPS 的丰度是过去微生物活动的证据。与 EPS 降解或微生物活动相关的化学性质的局部波动,如碱度的微小增加,可能对粘土和白云石的形成都很重要。地下水环境可能是微生物影响的矿化和低温白云石沉淀的重要且迄今研究不足的环境。