Microbial influence on dolomite and authigenic clay mineralisation in dolocrete profiles of NW Australia.

Dolomite (CaMg(CO3 )2 ) 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 Mg2+ , as well as the slow diffusion of ions through a viscous clay or EPS matrix, may promote the incorporation of Mg2+ 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.

Partitioning and potential mobilization of aluminum, arsenic, iron, and heavy metals in tropical active and post-active acid sulfate soils: Influence of long-term paddy rice cultivation.

Drainage of potential acid sulfate soils (PASS) for paddy rice cultivation results in the formation of active acid sulfate soils (AASS) and subsequently post-active acid sulfate soils (PAASS). The drainage of PASS causes severe environmental problems including acidification and metal contamination of soil and water resources. This study examined the vertical distribution and partitioning of Al, As, Co, Cu, Fe, Mn, Ni, Pb, and Zn in six tropical acid sulfate soils representing AASS and PAASS under long-term paddy rice cultivation (>145 years). The bulk soil samples were analyzed for total concentrations of Al, As, Co, Cu, Fe, Mn, Ni, Pb, and Zn. The partitioning of these elements was examined by a sequential extraction procedure. Labile Al is higher in ASS which is associated with low soil pH. During drainage, mobilization of As, Cu, and Pb is limited by coprecipitation with (poorly) crystalline Fe oxides minerals in the topsoil and partly oxidized layer of both soil types. These elements are associated with iron (mono) sulfides in unoxidized layer. When PASS are exposed to air, Co, Mn, Ni, and Zn are leached from the soils and are dominantly associated with iron sulfides in the unoxidized sediments. Labile Mn, Ni, and Zn are elevated in the unoxidized layer of PAASS because these elements are leached from the partly oxidized layers and adsorbed onto soil constituents. Cobalt is probably precipitated or adsorbed onto (poorly) crystalline minerals.

Relationship between heavy metals and minerals extracted from soil clay by standard and novel acid extraction procedures.

Strong acid digestions are commonly used to determine heavy metal (HM) contents in soils. In order to understand more fully the acid digestion processes, a logical step is to determine the extent of dissolution of mineral phases. The aims of this study were to compare the efficiency of extraction of HM by different acid digestions and to monitor the associated dissolution of the clay fraction. The context of the study was to develop a milder chemical extraction method (microwave-assisted 1 mol L-1 HNO3 closed system (NACS)), which recovers more reactive HM and with little dissolution of minerals. The different acid digestion methods dissolved different amounts of minerals from the clay fraction. Both aqua regia (AR) and EPA 3051 dissolved all of the Fe and Al oxides, and the dissolution of kaolin was limited to thinner particles (c dimension), smaller particles in a and b dimensions and grains with lower crystallinity. The lower recovery of HM for AR compared with EPA 3051 was related to the large amount of short-range order phases formed during the AR extraction as these phases have the capacity to re-adsorb HM. The new method (NACS) has the potential to replace other methods of determining bioavailable forms of HM, such as AR and EPA 3051. The contents of Pb, As, Co, Zn, and Cu determined by EPA 3051 and EPA 3052 were quite close.