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.     

Laboratory investigation on measuring suspended sediment by portable laser diffractometer (LISST) focusing on particle shape

This paper deals with a laboratory investigation on measuring suspended sediment volume and mass concentration (SSC) and particle size distribution (PSD) by a portable submersible laser diffractometer (LISST-100X) focusing on effects of particle shape and inversion modes on the results. Experiments were carried out in a mixing tank using suspensions of glass beads, fine quartz sand, feldspar and mica powder particles of spherical, rounded, angular and flaky shapes respectively, at various SSCs. SSCs and PSDs measured by LISST were compared to SSCs from gravimetric analysis and to PSDs obtained from image analysis of dry particles and from a non-portable laser diffractometer. Experiments using spherical and rounded particles showed that LISST with the corresponding inversion modes, i.e. spherical and ‘random shaped’, provides PSD and SSC values similar to reference methods. For angular and flaky particles, however, SSCs were found to be overestimated by factors of 1.5 and 8 respectively. Measurements in a mixture of 70% feldspar and 30% mica powders showed that the SSC overestimation factor for mixed particle-type suspensions can be predicted as the weighted sum of the SSC factors of the components and their mixing ratio. For known highly non-spherical particle types, LISST SSCs can be corrected by a gravimetrically determined or predicted overestimation factor. Moreover, correction of overestimated contributions of lower size bins, the range of measureable SSC and time averaging of LISST measurements are addressed. Further investigations are necessary to assess effects of non-spherical particles and mixtures of various particle types on LISST SSC and PSD estimates.     

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.     

Modelling the optical properties of suspended particulate matter of coral reef environments using the finite difference time domain (FDTD) method

The optical scattering properties of non-spherical calcium carbonate particles were modelled using the finite difference time domain (FDTD) method. This algorithm is computationally expensive but an implementation running on a standard computer’s graphics processing unit (GPU) provided up to 40 times speed increase and made feasible several thousand model runs for particles up to size parameter 33 (4 μm for a wavelength of 376 nm in water). The model evaluates all coefficients of the single-particle Mueller matrix and, when applied to spheres in this size range, compares closely to Mie theory. The modelled unpolarised and polarised angular irradiance scattering from elongate calcium carbonate spicules displayed many differences from that of spheres of equivalent volume. Scattering features were observed that are not immediately obvious consequences of spicule geometry. The extinction efficiency of these particles is also less than that of spheres of equivalent volume. These results suggest both potential consequences of the non-sphericity of particles on instrument calibration and radiative transfer modelling, and opportunities for information extraction by polarimetry.     

纳米碳酸钙材料的工业合成与应用

该文对目前工业上生产纳米碳酸钙的方法作了较为详细的综述。对一步碳化法、两步碳化法、多段喷雾碳化法、旋转填充床碳化反应器碳化技术制备链形、纺锤形、球形、立方形等不同形状的纳米碳酸钙材料的方法进行了比较和总结     

Effect of biogeochemical diagenesis on sediment fabric in shallow marine carbonate sediments near the Dry Tortugas, Florida

 Shallow marine carbonate sediments near the Dry Tortugas undergo extensive biogeochemical diagenesis upon deposition, resulting in postdepositional fabric comprised of micritic aggregates of clay-sized particles, a matrix of peloidal mud, and intraparticular cementation. Freshly deposited primary skeletons, mostly Halimeda fragments, yield micritic aggregates of clay-sized particles, which then form peloidal mud fabric upon compaction. The cryptocrystalline particles produced by micritization are later replaced by high magnesian calcite. Cementation is observed in the intra-particular microenvironment. However, no inter-particular, grain-binding cement was detected throughout the gravity core samples investigated.     

Carbonate dissolution in the South Atlantic Ocean: evidence from ultrastructure breakdown in Globigerina bulloides

Ultrastructure dissolution susceptibility of the planktic foraminifer Globigerina bulloides, carbonate ion content of the water column, calcium carbonate content of the sediment surface, and carbonate/carbon weight percentage ratio derived from sediment surface samples were investigated in order to reconstruct the position of the calcite saturation horizon, the sedimentary calcite lysocline, and the calcium carbonate compensation depth (CCD) in the modern South Atlantic Ocean. Carbonate ion data from the water column refer to the GEOSECS locations 48, 103, and 109 and calcium carbonate data come from 19 GeoB sediment surface samples of 4 transects into the Brazil, the Guinea, and the Cape Basins. We present a new (paleo-) oceanographic tool, namely the Globigerina bulloides dissolution index (BDX). Further, we give evidence (a) for progressive G. bulloides ultrastructural breakdown with increasing carbonate dissolution even above the lysocline; (b) for a sharp BDX increase at the sedimentary lysocline; and (c) for the total absence of this species at the CCD. BDX puts us in the position to distinguish the upper open ocean and the upwelling influenced continental margin above from the deep ocean below the sedimentary lysocline. Carbonate ion data from water column samples, calcite weight percentage data from surface sediment samples, and carbonate/carbon weight percentage ratio appear to be good proxies to confirm BDX. As shown by BDX both the calcite saturation horizon (in the water column) and the sedimentary lysocline (at the sediment–water interface) mark the boundary between the carbonate ion undersaturated and highly corrosive Antarctic Bottom Water and the carbonate ion saturated North Atlantic Deep Water (NADW) of the modern South Atlantic.     

Influence of export rain ratio changes on atmospheric CO<Subscript>2</Subscript> and sedimentary calcite preservation

The responses of atmospheric pCO₂ and sediment calcite content to changes in the export rain ratio of calcium carbonate to organic carbon are examined using a diffusion-advection ocean biogeochemical model coupled to a one-dimensional sediment geochemistry model. Our model shows that a 25% reduction in rain ratio decreases atmospheric pCO₂ by 59 ppm. This is caused by alkalinity redistribution by a weakened carbonate pump and an alkalinity increase in the whole ocean via carbonate compensation with decreasing calcite burial. The steady state responses of sedimentary calcite content and calcite preservation efficiency are rather insensitive to the deepening of the saturation horizon of 1.9 km. This insensitivity is a result of the reduced deposition flux that decreases calcite burial, counteracting the saturation horizon deepening that increases calcite burial. However, in the first 10,000 years the effect of reduced calcite deposition on the burial change is more prominent; while after 10,000 years, the effect of saturation horizon deepening is more dominant. The lowering of sediment calcite content for the first 10,000 years is effectively decoupled from the 1.9 km downward shift of the saturation horizon. Our results are in part a consequence of the more dominant role that respiration CO₂ plays in sediment calcite dissolution over bottom water chemistry in our control run and support the decoupling of calcite lysocline depth and saturation horizon shifts, as suggested originally by Archer and Maier-Reimer (1994) and Archer et al. (2000).     

Late Quaternary variations in calcium carbonate preservation of deep-sea sediments in the northern Cape Basin: results from a multiproxy approach

In this study, we test various parameters in deep-sea sediments (bulk sediment parameters and changes in microfossil abundances and preservation character) which are generally accepted as indicators of calcium carbonate dissolution. We investigate sediment material from station GeoB 1710-3 in the northern Cape Basin (eastern South Atlantic), 280 km away from the Namibian coast, well outside today’s coastal upwelling. As northern Benguela upwelling cells were displaced westward and periodically preceded the core location during the past 245 kyr (Volbers et al., submitted), GeoB 1710-3 sediments reflect these changes in upwelling productivity. Results of the most commonly used calcium carbonate dissolution proxies do not only monitor dissolution within these calcareous sediments but also reflect changes in upwelling intensity. Accordingly, these conventional proxy parameters misrepresent, to some extent, the extent of calcium carbonate dissolution. These results were verified by an independent dissolution proxy, the Globigerina bulloides dissolution index (BDX′) (Volbers and Henrich, submitted). The BDX′ is based on scanning electronic microscope ultrastructural investigation of planktonic foraminiferal tests and indicates persistent good carbonate preservation throughout the past 245 kyr, with the exception of one pronounced dissolution event at early oxygen isotopic stage (OIS) 6.

The early OIS 6 is characterized by calcium carbonate contents, sand contents, and planktonic foraminiferal concentrations all at their lowest levels for the last 245 kyr. At the same time, the ratio of radiolarian to planktonic foraminiferal abundances and the ratio of benthic to planktonic foraminiferal tests are strongly increased, as are the rain ratio, the fragmentation index, and the BDX′. The sedimentary calcite lysocline rose above the core position and GeoB 1710-3 sediments were heavily altered, as attested to by the unusual accumulation of pellets, aggregates, sponge spicules, radiolaria, benthic foraminifera, and planktonic foraminiferal assemblages.

Solely the early OIS 6 dissolution event altered the coarse fraction intensely, and is therefore reflected by all conventional calcium carbonate preservation proxies and the BDX′. We attribute the more than 1000 m rise of the sedimentary calcite lysocline to the combination of two processes: (a) a prominent change in the deep-water mass distribution within the South Atlantic and (b) intense degradation of organic material within the sediment (preserved as maximum total organic carbon content) creating microenvironments favorable for calcium carbonate dissolution.     

网纹藤壶壳板矿化结构及其碳酸钙含量测定

采用X射线衍射技术,初步研究了网纹藤壶(Balanus reticulates Utinomi)壳板矿化结构特征,并采用钙黄绿素法、钙-羧酸指示剂法和铬黑T指示剂三种方法测量了来自不同海域藤壶壳板的碳酸钙含量。实验发现,网纹藤壶壳板中的矿化组织主要由方解石构成,碳酸钙微晶体排列有一定的取向,较为复杂。海口和陵水两地藤壶壳板中碳酸钙含量没有显著差异(P<0.05),最大值为93.87%,最小值90.77%。尽管三种碳酸钙含量测量法的结果没有显著性差异(P<0.05),但进一步综合分析发现钙黄绿素法测定结果最为稳定,且简单易操作,可作为首选方法。     

Biologically mediated dissolution of calcium carbonate above the chemical lysocline?

We find a diverse but increasing amount of evidence to suggest considerable dissolution of calcium carbonate, perhaps as much as 60–80%, in the upper 500–1000 m of the ocean, well above the chemical lysocline. The same biological processes that promote the rapid settling of carbonate particles (i.e. ingestion, digestion and egestion by zooplankton) as well as biologically mediated processes within flocculates and aggregates may be responsible – directly or indirectly – for much of this dissolution. The significance of shallow-water dissolution of carbonate particles necessitates further research into both its validity and, if true, specific causal mechanisms.     

Cementation in cold-water bryozoan sand, Tasmania, Australia

Cold-water (<3–11°C) carbonate is the predominant sediment on the Tasmanian shelf. Calcitic skeletal grains (bryozoa, foraminifera, echinoderms, etc.) predominate over aragonitic (gastropods, etc.) ones. Non-skeletal grains are mostly micritic intraclasts with some pellets.

Fibrous spherulitic and rhombohedral calcite submarine cements range up to 90% in the bryozoan sand. X-ray analyses show that the bryozoan sand is characterized by a spectrum of calcites (low to high magnesian) and some aragonite.

A uniform spread of Mg concentrations from 0.06 to 2.48 wt.% indicates <3–10°C ambient water temperatures. The Mn (10–360 ppm) and Fe (176–2499 ppm) concentrations increase with increasing Mg values due to the formation of impure CaCO₃ phases. The Sr content in bryozoan sand (bryozoa = 3200 ppm Sr) decreases with increasing rhombohedral calcite cement, as low Mg-calcite precipitating from 3° C sea water would have 1350 ppm Sr. The bryozoan sand grains with fibrous spherulitic calcite cements have high Sr concentrations (4470–7000 ppm), in the same range as in aragonitic (detected only by X-ray analyses) bryozoan sand grains. The spherulitic calcite cements are either pseudomorphs after original aragonite cements or these calcite cements and aragonite were inverted from fibrous spherulitic vaterite, a predominant CaCO₃ polymorph at temperatures <10°C.     

Behavior of bromide ions during the formation of calcium carbonate

Coprecipitation of bromide ions with calcium carbonate, formed from a calcium bicarbonate solution containing bromide ions, and the influence of bromide ions in a parent solution on the crystal form of the calcium carbonate were studied experimentally. The following results were obtained: the coprecipitation is affected by the crystal form of the calcium carbonate and the concentration of sodium chloride dissolved in a parent solution. The bromide ions are more easily coprecipitated with aragonite than with calcite. The amount of bromide ions coprecipitated with aragonite decreases significantly with increasing concentration of sodium chloride in a parent solution. The presence of bromide ions in a parent solution has a slight influence on the crystal form of calcium carbonate to favor calcite formation and to inhibit aragonite formation.The role of marine carbonate sediments in the removal of bromide ions from sea water is discussed briefly.     

A literature review of the saturation state of seawater with respect to calcium carbonate and its possible significance for scale formation on OTEC heat exchangers

An investigation has been made of available data on the saturation state of seawater with respect to calcium carbonate and its possible significance for scale formation on Ocean Thermal Energy Conversion (OTEC) heat exchangers. Pertinent oceanographic data is lacking at or near potential OTEC sites for the calculation of the degree of saturation of seawater with respect to calcium carbonate. Consequently, only “extrapolated” saturation values can be used. These indicate that near surface seawater is probably supersaturated, with respect to the calcium carbonate phases calcite and aragonite, at all potential OTEC sites. The deep seawater that would be brought to the surface at the potential Atlantic Ocean sites is also likely to be supersaturated with respect to calcium carbonate. The deep seawater at the potential Pacific Ocean sites may be slightly undersaturated.The fact that OTEC heat exchangers will be operating in seawater, which is supersaturated with respect to calcium carbonate, means that if nucleation of calcite or aragonite occurs on the heat exchanger surfaces, significant growth rates of calcium carbonate scale may be expected. The potential for calcium carbonate nucleation is highest at cathodic metal surface locations, which are produced as the result of aluminum corrosion in seawater. Consequently, corrosion and scale formation may be closely related. What the possible effects of biofouling may be on this process are not known.     

Some Aspects of Fluorite and Vaterite Precipitation in Marine Environments*

Abstract. Mysid shrimps of the genus Schistornysis precipitate either fluorite (CaF₂; S. spiritus) or vaterite (CaCO3; S. assimilis) for the formation of static bodies (statoliths). In S. assirnilis, 2.44 μg calcium and 3.66 μg carbonate are precipitated for each statolith. This corresponds to 69 mg or 30 mg ambient water, respectively, using the ion content of seawater for stoichiometrical comparison. Concentmtion factors of calcium or carbonate in relation to equivalent amounts of ambient water in the statocyst cavity are 760 or 3100, respectively. In S. spiritus, 3.79 μg calcium and 3.60 μg fluoride are precipitated. This corresponds to 9.3 mg or 2788 mg ambient water, respectively. Concentration factors with respect to statocyst water mass are 610 or 183.000. respectively. Ile high fluoride accumulation for the formation of statoliths alone contributes to a fluoride content of 4500 ppm with respect to body dry weight A minimum estimate for the role of mysids in the global fluoride cycle suggests that at least 62,000 tons of fluoride are bound in mysid statoliths. Due to rapid turnover of about seven days, mysid fluorite statoliths are a crucial factor by contributing to a turnover of at most 570,000 years for overall fluoride in the oceanic system.     

The small volume particle microsampler (SVPM): a new approach to particle size distribution and composition

The characterization of trophically and geochemically important suspended particulate matter (SPM) has traditionally relied on bottle sampling and subsequent analysis with Coulter Multisizers and other instruments, which are not sufficient in preserving the in situ size, shape and composition of aggregated particles. The small volume particle microsampler (SVPM) is a sampling device that captures individual particles on filters with minimal disturbance for microscope image analysis of size distribution and composition. Sand grains, microalga (Dunaliella tertiolecta) and laboratory cultivated flocs were used to test the SVPM's ability to determine particle size. For statistical analysis of the SVPM's capabilities, sand grain and algal size distribution, calculated as equivalent spherical diameter (ESD), were compared to Multisizer data while video images provided a comparison for the flocs. Non-aggregated sand particles sampled by the SVPM showed a size distribution that was similar to that of the Multisizer. Aggregated D. tertiolecta flocs were broken up by the Multisizer, and SVPM data indicated a significantly greater mean ESD. The SVPM showed significantly smaller mean ESDs than the video images because of the higher resolution of the sampler for small particles. In terms of particle concentration, the microsampler measured values similar to those of the Multisizer and video camera. The most important feature of the SVPM is its ability to capture aggregates for the analysis of composition, by histological stains or other means. The SVPM is an alternative method of sampling that is more effective in preserving aggregates for laboratory analyses and is less complicated and expensive than in situ optical sampling techniques, especially in documenting the lower end of the particle size spectrum.     

Calcium in the Antarctic Ocean

Calcium in sea water was determined of the samples taken from the Antarctic and Indian Oceans. Surface water commonly contains less calcium relative to chlorinity than does deep water. The tendency, however, is very faint in the Antarctic Ocean. In the surface waters, the Ca/Cl ratio is lower in the tropical and subtropical waters and the ratio well correlates with phosphate. The Ca/P ratio is calculated as 37 in atomic ratio. These may indicate that calcium is uptaken by organisms to make skeletal parts from surface water which is supersaturated with respect to calcite or aragonite. On the other hand, no definite correlationship between calcium and phosphate is found in subsurface water. This fact suggests that the regeneration process of calcium from organic debris is different from that of phosphate. The increase-rate of calcium in the abyssal water is estimated to be 0.18g at./(1 yr), which is due to the dissolution of calcium carbonate. The rate is about a half of total carbonate increase in the water.     

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。     

Application of mercury injection capillary pressure to mudrocks: Conformance and compression corrections

Mercury injection capillary pressure (MICP) is a commonly-used technique for measurements of porosity, pore throat size distribution, and injection pressure vs. mercury saturation for many types of rocks. The latter two are correlated to and can be used to estimate permeability. Problems for MICP application in mudrocks are associated with two types of system errors: conformance and compression effects. These two sources of error are well-recognized, but no standard procedures to correct them exist. In this study, a new method for conformance and compression corrections was developed, and the method applied to five Eagle Ford Shale samples. Conformance correction is based on comparison of mercury injection volume vs. pressure curves between epoxy-coated and uncoated samples. Compression correction is based on calculation of compressions before and after mercury intrusion in MICP experiment. Different types of compressions are quantified and compression corrections on porosity, pore throat size distribution, and injection pressure vs. mercury saturation are performed. Porosity and permeability were calculated based on corrected MICP data. Results show that both conformance and compression corrections are important for accurate MICP porosity calculation, whereas conformance correction is more important than compression correction in permeability calculation.