Effect of different biological solutions on microbially induced carbonate precipitation and reinforcement of sand

Abstract

Sporosarcina pasteurii is widely used in the application of microbially induced carbonate precipitation (MICP) for various applications, such as ground reinforcement, erosion mitigation or stabilization of sand foreshore slopes. This study focuses on the effect of thallus resuspended by the fresh medium (RF) on urea hydrolysis, MICP, and sand reinforcement compared with untreated biological solutions (US) with high microbial concentration. The principle is investigated by tests on thallus resuspended by saline solution [NaCl (0.9%)] (RS) and supernatant (SS). The results indicate that the addition of the fresh medium is insignificant for promoting MICP and even has a slightly negative effect on urea hydrolysis and sand improvement for stationary phase bacteria. The ability of US to hydrolyze urea and MICP is derived from two sources: urease existing in the cell bodies and free urease existing in solution for lysis of partial cells, with urease in cells accounting for the majority. The preferable sand reinforcement of US is primarily due to the high amount of carbonate precipitation and formation of non-biological calcium carbonate located primarily in the pores. The results indicate that the preference of US in various engineering applications with lower cost for the realizable reinforcement.     

Theoretical considerations about the reactions of calcification in sea water

We examine the concentration variations of the different parameters X of the carbonate system in seawater when calcium carbonate precipitation occurs. Variations are expressed as ∂[X]/∂[Ca²⁺]. Four different cases are considered: spontaneous chemical precipitation; calcification combined with photosynthetic activity under a constant ΔCT/Δ[Ca²⁺] ratio; precipitation under constant p_CO2 and precipitation under constant [Ca²⁺]·[CO₃²⁻] ionic concentration product. The last condition should be maintained by an ecosystem which, thanks to the regulation of its calcifying and photosynthetic activity, would absorb 1 mol of carbon for organic tissue each time 1 mol of CaCO₃ is formed. This stoichiometric ratio would allow the activity of these biological communities to go on in practically closed systems during periods compatible with their growth or development cycles.     

The influence of particle morphology on microbially induced CaCO3 clogging in granular media

Abstract

Sporosarcina pasteurii (ATCC 11859) is a nitrogen-circulating bacterium capable of precipitating calcium carbonate given a calcium source and urea. This microbially induced carbonate precipitation (MICP) is able to infill inter-granular porosity and act as a biological clogging agent, thus having a wide potential application in strengthening coastal foundations, preventing erosion by seas and rivers and in reducing sand liquefaction potential in coastal areas. A successful MICP application requires the understanding of the primary parameters that influence the microbially mediated process to achieve its engineering goals, such as injection scheme, chemical concentrations, retention times, and injection rates. However, the granular morphology has generally been oversimplified to ideal shape without enough consideration in previous studies. The following explores the critical micro-scale influence of particle morphology on mechanisms of microbially induced clogging. Spherical, non-spherical and angular particles were used as granular aggregates in permeating column experiments with the resulting permeability and calcium carbonate content of the treated aggregates examined. Microscopic examination (SEM) defines the features of the distribution of microbially precipitated calcium carbonate and the forms of clogging. The results show: (1) given a fixed duration of treatment, the calcium carbonate content for the spherical particle aggregate is significantly higher than that for near-spherical and angular particle aggregates; (2) for identical durations of treatment, the maximum permeability reduction occurs for angular particles (rather than for spherical particles with the highest carbonate content). This suggests that the microscopic distribution of calcium carbonate is significantly influenced by particle morphology, exerting a critical control in the effectiveness of clogging. SEM images indicate that the microbial calcium carbonate precipitates encapsulate the spherical particles as a near-uniform shell and occlude the pore space only by increasing the shell thickness. In contrast, the near-spherical and angular particles are only partially coated by a calcium carbonate film with scattered crystals of vaterite and calcite further clogging the void space. The polyhedral nature of the non-spherical particles tends to result in a slot-shaped pore structure which critically defines the hydraulic conductivity of the ensemble medium. As the microbial vaterite and calcite continue to accumulate on the particle surface, these slot-shaped pore structures become increasingly more tortuous – resulting in a noticeable reduction of permeability at a lower calcium carbonate content.     

Using recycled calcium sources to solidify sandy soil through microbial induced carbonate precipitation

Abstract

The use of calcium solutions is a cost-limiting factor for bio-cement production from microbially induced carbonate precipitation (MICP). The aim of this article is to analyse the feasibility of using recycled calcium sources to solidify sand, including oyster shells, scallop shells and eggshells, by comparing the physical and mechanical properties and microstructural characteristics of solidified sand with different recycled calcium sources and chemical calcium nitrate. The results show that oyster shells have the optimal effect on MICP, with values of permeability, dry density, unconfined compressive strength and calcium carbonate precipitation of 1.12?×?10^?4 m s^?1, 2.09?g cm^?3, 1454.6?kPa and 15.28%, respectively. Strength values of bio-cemented sands made from different recycled calcium sources in this article range from 845.1 to 1454.6?kPa. According to the SEM and XRD analysis, calcium carbonates originating from the above recycled calcium sources precipitate as globular vaterite, whereas the precipitation from calcium nitrate is a cluster mixture of vaterite and calcite. Oyster shells, scallop shells and eggshells derived from kitchen waste, which is more economical and environmentally friendly than calcium nitrate, can be applied as recycled calcium solutions in MICP.     

On the variation in calcium content of the waters of Laccadives (Arabian Sea)

The concentration of calcium was determined in the samples collected from four stations in the Laccadive Sea and from two lagoons of Kavaratti and Minicoy atolls. The calcium/chlorinity ratio for the open ocean samples was found to be 0.02168 ± 0.000015 with an average calcium concentration of 424.9 mg kg^?1. A maximum in this ratio was observed at about 200 m depth, below the salinity maximum corresponding to Arabian Sea Surface Water mass. No increase in calcium concentration or in calcium/chlorinity ratio was observed down to 1500 m depth, thereby ruling out the possibility of any calcium carbonate dissolution at these depths. Samples from Kavaratti and Minicoy lagoons gave much lower values of the Ca/Cl ratio (0.02145 ± 0.000036 and 0.02142 ± 0.000046, respectively). These low values are apparently the result of calcium utilization by the coral reefs. Using the reduction in the calcium concentration inside the lagoon, in the absence of any chemical precipitation, the annual CaCO₃ production by reef flat and lagoon on Kavaratti Atoll has been estimated as 1 · 10⁷ kg. This gives an average gross production of 1.4 kg CaCO₃ per m² per yr.     

金属离子种类对珊瑚砂微生物固化影响研究

选用巴斯德芽孢杆菌,对微生物诱导钙离子、镁离子以及铁离子形成碳酸盐固化松散珊瑚砂颗粒的效果进行对比研究。试验结果表明,在相同试验方法、相同注入次数的条件下,微生物诱导形成的碳酸钙和碳酸镁能将珊瑚砂松散颗粒固化成为整体,加入铁离子的试样因为反应过程的原因没有成功。通过渗透性、干密度变化、无侧限抗压强度及微观结构等方面进行对比分析,钙离子试样相对于镁离子试样,具有固化过程平稳、干密度增量大、强度高、微观颗粒包裹更好的优点。综合试验结果得出,钙离子是现阶段微生物固化珊瑚砂较为理想的金属离子。本试验首次探讨了金属离子种类对珊瑚砂微生物固化效果的影响,为微生物固化技术提供了一定理论基础,对该技术的进一步应用具有一定借鉴意义。     

210Pb method for estimating the rate of carbonate sand sedimentation

The plot of²¹⁰Pb activity against depth in carbonate sands on the Virgin Island Bank is a negative asymmetric hyperbolic curve. As depth increases, an initial rapid decrease in²¹⁰Pb activity caused by the decay of unsupported²¹⁰Pb and²²⁶Ra is followed by increasing activity as a result of²¹⁰Pb achieving equilibrium with ingrowing²³⁰Th. As this curve is time dependent, an estimate of the relative ages in carbonate sequences and the rates of net carbonate accumulation can be made. The ease of²¹⁰Pb activity determinations makes this procedure an attractive method in obtaining carbonate sand accumulation rates.     

自动分析仪次溴酸钠氧化法测定海水中氨氮的研究

海水中氨的含量变化幅度在5—50mg-N/m~3之间,一般采用此色法测定。自1856年Nessler提出利用碱性[HgI_4]~=与氨生成黄色化合物进行其测定开始,一个多世纪来分析方法虽多并屡加改进提高,但结果仍远不能令人满意。     

Diagenetic behavior of manganese in Tokyo Bay sediment

To understand the behavior of manganese in diagenetic processes in sediments of an enclosed bay which is similar to those of an estuary, chemical analyses have been carried out on both sediment and interstitial water of a core sample collected from Tokyo Bay. The results suggest that redistribution of manganese takes place within the sediment as a result of the dissolution of buried manganese oxides and hydroxides under reducing condition, the downward diffusion of Mn²⁺ through the interstitial water toward lower layers and then the precipitation of carbonate. The carbonate formed in the sediment contains managanese carbonate probably as a solid solution between calcitic calcium carbonate and manganese carbonate.     

Low calcification rates and calcium carbonate production in Porites panamensis at its northernmost geographic distribution

Porites panamensis is a hermatypic coral present in the eastern Pacific Ocean. Skeletal growth parameters have been reported, but studies of the relationship between annual calcification rates and environmental controls are scarce. In this study, we investigated three aspects of the annual calcification rates of P. panamensis: growth parameters among three P. panamensis populations; the sea surface temperature as a calcification rate control spanning a latitudinal gradient; and calcium carbonate production among three sites. Growth parameters varied among the sites due to the colony growth form. Massive colonies in the north showed a higher calcification rate than encrusting colonies in the south (mean: 1.22–0.49 g CaCO₃ · cm^?2 · yr^?1), where variations in calcification rates were related to growth rate (0.91–0.38 cm · yr^?1) rather than to skeletal density differences (overall mean ± SD, 1.31 ± 0.04 g CaCO₃ · cm^?3). Our results showed a positive linear relationship between annual calcification rates and sea surface temperatures within these P. panamensis populations. Differences were related to distinct oceanographic environments (within and at the entrance of the Gulf of California) with different sea surface temperature regimes and other chemical properties. Different populations calcified under different environmental conditions. Calcium carbonate production was dependent upon the calcification rate and coral cover and so carbonate production was higher in the north (coral cover 12%) than in the south (coral cover 3.5). Thus, the studied sites showed low calcium carbonate production (0.25–0.43 kg CaCO₃ · m^?2 · yr^?1). Our results showed reduced calcification rates, regional temperature regime control over calcification rates, different growth forms, low coral cover and low calcium carbonate production rates in P. panamensis.     

Sediment deposition and production in SE-Asia seagrass meadows

Seagrass meadows play an important role in the trapping and binding of particles in coastal sediments. Yet seagrass may also contribute to sediment production directly, through the deposition of detritus and also the deposition of the associated mineral particles. This study aims at estimating the contribution of different seagrass species growing across an extensive range of deposition to inorganic (carbonate and non-carbonate) and organic sediment production. Total daily deposition measured with sediment traps varied from 18.8 (±2.0) g DW m⁻² d⁻¹ in Silaqui (Philippines) to 681.1 (±102) g DW m⁻² d⁻¹ in Bay Tien (Vietnam). These measurements correspond to a single sampling event and represent sedimentation conditions during the dry season in SE-Asia coastal areas. Enhalus acoroides was the most common species in the seagrass meadows visited and, together with Thalassia hemprichii, was present at sites from low to very high deposition. Halodule uninervis and Cymodocea species were present in sites from low to medium deposition. The mineral load in seagrass leaves increased with age, and was high in E. acoroides because it had the largest and long-lived leaves (up to 417 mg calcium carbonate per leaf and 507 mg non-carbonate minerals per leaf) and low in H. uninervis with short-lived leaves (4 mg calcium carbonate per leaf and 2 mg non-carbonate minerals per leaf). In SE-Asia seagrass meadows non-carbonate minerals accumulate at slower rates than the production of calcium carbonate by the epiphytic community, consequently the final loads supported by fully grown leaves were, as average, lower than calcium carbonate loads. Our results show that organic and inorganic production of the seagrasses in SE-Asia represents a small contribution (maximum of 15%) of the materials sedimented on a daily base by the water column during the sampling period. The contribution of the carbonate fraction can be locally significant (i.e. 34% in Silaqui) in areas where the depositional flux is low, but is minor (<1%) in sites were siltation is significant (i.e. Umalagan and all the visited sites in Vietnam).     

Copper accumulation by two bivalve molluscs: Salinity effect is independent of cupric ion activity

Oysters (Crassostrea virginica) and soft shell clams (Mya arenaria) were exposed to two different total copper concentrations (10 μg liter⁻¹ and 30 μg liter⁻¹) and two different cupric ion activities (10⁻¹⁰ m and 10⁻⁹ m) under high salinity and low salinity conditions. Cupric ion activities were adjusted by adding nitrilotriacetic acid (NTA) to the experimental media.Copper accumulation by both species was inversely related to salinity and positively associated with total copper and cupric ion activity. This salinity effect was proportionately greater for lower copper concentrations and activities and it was concluded that salinity would, therefore, be an important influence on metal accumulation in the natural environment. The salinity effect was still apparent when the cupric ion activity was held constant indicating that the effect is, at least in part, independent of the copper speciation in the medium.     

ON CHELATING RESINS FOR EXTRACTING URANIUM FROM SEAWATER

A number of dictating resins have been synthesized for extracting uranium from scawatcr. The feasibilities of extracting uranium directly from seawater by synthesizing chelating resins have been investigated by studying three factors:(1) the chelating ability of the resins for uranyl ion;(2) the competitive complex of calcium, magnesium and other cations with uranyl ion;(3) the competitive complex of carbonate ion with uranyl ion.It is suggested that the competitive complex of carbonate ion with uranyl ion should be the most important factor.     

The formation of whitings on the Little Bahama Bank

Whitings (patches of suspended fine-grained calcium carbonate) on the Great Bahama Bank (GBB) have been studied since the 1940s. The source and cause of these whitings have been hotly debated for a number of years. Recent studies have shown that resuspension of underlying sediments act as seed crystals for the slow precipitation of CaCO₃. Similar studies have not been conducted on the nearby more northerly Little Bahama Bank (LBB) where satellite photographs indicate the presence of extensive whitings north of the Grand Bahama Island. Research cruises were made to the LBB in July 2003 and May 2005. On board measurements were used to examine the distribution of the components of the carbonic acid system in LBB waters. The distribution of suspended calcium carbonate was also determined and samples of the suspended material and underlying sediments were collected for analyses, including ¹⁴C age determinations.The maximum residence time for waters on the LBB is a little over half (～ 144 d) that on the GBB. A ～ 20% decrease was found in the salinity-normalized titration alkalinity for inner bank waters. This yields a carbonate precipitation rate similar to waters on the GBB. However, unlike the waters in the whitings on the GBB where no changes in carbonic acid system parameters have been detected, large changes in the carbonic acid system parameters were found in the whiting waters of the LBB. These results clearly indicate that active precipitation was occurring in these waters. These observations are interpreted as indicating that there is a much slower mixing of waters associated with whitings and surrounding bank waters on the LBB than on the GBB. The more closed nature of whitings on the LBB makes them better targets for study of the processes taking place in whitings.Suspended carbonate mineralogy and geochemistry closely matched those of the fine-grained portion of the underlying sediments. These results support a close relationship between carbonates found in whitings and those in underlying sediments. This is further evidenced by a similar age for whiting carbonates (～ 700 y) and easily resuspended sediment carbonates (～ 1000 y) and is what was previously observed on the GBB.These observations indicate that the processes leading to whiting formation and associated calcium carbonate precipitation along with changes in water chemistry are quite similar in these two shallow carbonate bank environments in the Bahamas.     

Formation of chemogenic calcite in super-anoxic seawater — Framvaren, southern Norway

Framvaren, a super-anoxic fjord in southern Norway, contains 7–8 mmoll⁻¹ of sulphide and a total carbonate concentration of 18.5 mmol kg⁻¹ in the bottom water. The chemistry of calcium has been studied, considering sources, biogenic and chemical processes and sedimentary sinks. Calcium associated with the bacteria biomass at the redox interface (18m depth) appears to be the primary source of dissolved calcium in the deep, anoxic water. Excess calcium and high total carbonate cause supersaturation of calcite, which is precipitated chemogenically. Calcite (and presumably some aragonite) is identified both in sediment trap material and the bottom sediments below the depth of supersaturation.     

Low flow water chemistry in forested and pasture catchments,Mawheraiti River,Westland

Water samples taken at 19 locations in the Mawheraiti River catchment at weekly intervals during 1979–80 were analysed for sodium, magnesium, potassium, calcium, phosphate, nitrate, and ammonium ion concentrations and for electrical conductivity. Seasonal discharge effects were apparent, and lithology and land management practice also influenced solute concentrations. Solute concentrations were generally very low; nitrate and soluble phosphate were rarely greater than 0.05 mg.L^‐1 and ammonium was rarely greater than 0.01 mg.L^‐1. The 4 major cations (Na, Mg, K, and Ca) usually summed to less than 6 mg.L^‐1 much of which was supplied by precipitation. Forest management (clearfelling and slash‐burning) caused significant increases in solute concentrations, but concentrations declined rapidly during succeeding months and approached pretreatment levels after 2–3 years. The higher concentrations associated with forest management in small experimental catchments were rapidly diluted downstream; together with the low natural solute concentrations this suggests that harmful downstream effects of management practices are unlikely under low flow conditions.     

The effect of pressure on the chemical potentials of seawater components,on ionic species in seawater,and on calcite saturation levels

The activities of most of the major seawater components at 1,001 bars have been estimated, and values for the ions deduced. Equations giving the effect of pressure on the activities of ionic species in seawater ($\text{S = 35‰}$) have been developed. The species covered are: NaSO₄^?, MgSO₄⁰, CaSO₄⁰, H⁺, the free base (NH₃), the HCO₃^?/CO₃² activity ratio and the ion activity product of calcium carbonate. Comparison of the latter with the “ideal” solubility of calcite (pure solid in equilibrium with a mixed electrolyte solution) indicates a degree of saturation compatible with the trends indicated by in situ measurements.     

Diffusion of seawater ions. Part II. The role of activity coefficients and ion pairing

A theoretical evaluation of basic thermodynamic relationships reveals that variation of activity coefficients, ion pairing and electrical interactions must be considered when modelling ionic diffusion in seawater. The contributions of ion-pair formation and change in activity coefficient along the diffusion path were studied experimentally by conducting diffusion experiments in which solutions of KCl, NaCl, MgCl₂, Li₂SO₄, K₂SO₄, Na₂SO₄ and MgSO₄, at an ionic strength of 0.7, were allowed to diffuse into distilled water. The study reveals that the thermodynamic factor, required to correct for changes in the activity coefficient along the diffusion path, is significant for all the salts studied. Agreement between a simple diffusion model, which does not include ion pairing, and observed data was good for completely dissociated salts, but poor for salts which are known to form ion pairs at the concentration levels studied. The diffusion of MgSO₄, 0.425 of which is associated at I = 0.7, was successfully modelled by assuming that the diffusion coefficient of the MgSO₄⁰ ion pair is different from the diffusion coefficient of the dissociated salt. The diffusion coefficient of this ion pair is estimated to be 1.9 × 10⁻⁵ cm² s⁻¹ at 30°C, as compared to 0.49 × 10⁻⁵ cm² s⁻¹ for the dissociated salt. It is suggested that the high mobility of this ion pair could cause magnesium enrichment in pore water of sulfate depleted sediments.     

Alterations in seawater pH and CO2 affect calcification and photosynthesis in the tropical coralline alga, Hydrolithon sp. (Rhodophyta)

Calcification in the marine environment is the basis for the accretion of carbonate in structures such as coral reefs, algal ridges and carbonate sands. Among the organisms responsible for such calcification are the Corallinaceae (Rhodophyta), recognised as major contributors to the process world-wide. Hydrolithon sp. is a coralline alga that often forms rhodoliths in the Western Indian Ocean. In Zanzibar, it is commonly found in shallow lagoons, where it often grows within seagrass beds and/or surrounded by green algae such as Ulva sp. Since seagrasses in Zanzibar have recently been shown to raise the pH of the surrounding seawater during the day, and since calcification rates are sensitive to pH, which changes the saturation state of calcium carbonate, we measured the effects of pH on photosynthetic and calcification rates of this alga. It was found that pH had significant effects on both calcification and photosynthesis. While increased pH enhanced calcification rates both in the light and in the dark at pH >8.6, photosynthetic rates decreased. On the other hand, an increase in dissolved CO₂ concentration to 26 μmol kg⁻¹ (by bubbling with air containing 0.9 mbar CO₂) caused a decrease in seawater pH which resulted in 20% less calcification after 5 days of exposure, while enhancing photosynthetic rates by 13%. The ecological implications of these findings is that photosynthetically driven changes in water chemistry by surrounding plants can affect calcification rates of coralline algae, as may future ocean acidification resulting from elevated atmospheric CO₂.     

Behaviour of boron,calcium and magnesium in a polluted estuary

Behaviour of industrially added boron in the well mixed Ambika river estuary of South Gujarat, India has been studied along with that of calcium and magnesium. The ratios of Ca : Cl and Mg : Cl at varying chlorinities were always within the normal ranges found in river water at one end and seawater at the other end. B : Cl exceeded the river water end limit at the ebb tide at an upstream station. Percentage addition or removal of boron, calcium and magnesium was calculated using the concept of the theoretical dilution line. The external input raised the boron concentration by 263% in the vicinity of the industrial discharge. A correlation coefficient of ?0·82 between chlorinity and percentage addition or removal of boron supports the theory of boron incorporation in sediments in amounts proportional to salinity. Inverse relationship between percentage addition or removal of boron and suspended solids was observed. Behaviour of calcium and magnesium was in line with the replacement of Ca²⁺ ions occupying the majority of ion-exchange sites in riverine clays by Mg²⁺, Na⁺ and K⁺ during their first encounter with seawater.