Incorporation of lead into calcium carbonate granules secreted by earthworms living in lead contaminated soils

The influence of soil organisms on metal mobility and bioavailability in soils is not currently fully understood. We conducted experiments to determine whether calcium carbonate granules secreted by the earthworm Lumbricus terrestris could incorporate and immobilise lead in lead- and calcium-amended artificial soils. Soil lead concentrations were up to 2000 mg kg⁻¹ and lead:calcium ratios by mass were 0.5-8. Average granule production rates of 0.39 ± 0.04 mg_calcite earthworm⁻¹ day⁻¹ did not vary with soil lead concentration. The lead:calcium ratio in granules increased significantly with that of the soil (r² = 0.81, p = 0.015) with lead concentrations in granules reaching 1577 mg kg⁻¹. X-ray diffraction detected calcite and aragonite in the granules with indications that lead was incorporated into the calcite at the surface of the granules. In addition to the presence of calcite and aragonite X-ray absorption spectroscopy indicated that lead was present in the granules mainly as complexes sorbed to the surface but with traces of lead-bearing calcite and cerussite. The impact that lead-incorporation into earthworm calcite granules has on lead mobility at lead-contaminated sites will depend on the fraction of total soil lead that would be otherwise mobile.     

Simultaneous production of magnesium carbonate and calcium carbonate from dolomites and dolomitic limestones

By use of a recarbonation process, it is possible to separate magnesium carbonate and calcium carbonate from dolomites/dolomitic limestones. Magnesium carbonate can be used for manufacturing basic refractories and magnesium chemicals; the portion rich in calcium carbonate can be used for cement manufacture if the MgO content is below 3%. In this paper the process developed for the purpose and the results of bench scale tests are reported. The results indicate that, under optimum conditions, both objectives can be fulfilled by the recarbonation process.     

生物膜脂参与的非晶碳酸钙形成和稳定

非晶碳酸钙(amorphous calcium carbonate,ACC)是碳酸钙矿物体系中极不稳定的矿物相。但由海鞘类动物的研究表明,ACC可作为碳酸钙晶体矿物的前驱体在生物体内稳定存在,并且这些生物成因的ACC常常是由膜包裹着的。文中选用生物膜的主要成分卵磷脂(PC)为主要矿化调节剂,通过调控与碳酸钙矿化过程密切相关的无机离子Mg2+的浓度,模拟生物膜表面碳酸钙矿化作用过程。在空气/水界面处的膜脂调控下合成出可在溶液中稳定存在数天的非晶碳酸钙。该结果有力地证明了在生物矿化过程中,除了受生物体中可溶性有机大分子调控外,生物膜可能对ACC的形成和稳定也有显著的调控作用。     

Variation in production,input and preservation of metastable calcium carbonate off Somalia during the last 90,000 years

To improve our understanding of the Late Pleistocene and Holocene carbonate system of the western Arabian Sea a high-resolution sedimentary record off Somalia has been analysed. The 15.26-m-long piston core 905 comprises a complete record of the last 90,000 years. We have measured concentrations of carbonate minerals, i.e., aragonite, calcite, Mg-calcite, and element ratios (Sr/Ca) together with pteropod counts and an estimation of the preservation state of pteropod shells to trace temporal changes in carbonate production and preservation.The Sr/Ca ratio shows strong similarities to the aragonite percentage and the δ¹⁸O record of the planktic foraminifer Neogloboquadrina dutertrei. High Sr/Ca ratios together with fragments of corals found in the coarse fraction indicate that most of the aragonite is of shallow water origin (high-Sr aragonite) and pteropods contribute much less than expected. High resuspensional input of shallow-marine aragonite occurs during sea-level highstands (interglacials) and low input during lowstands (glacials).The Mg-calcite concentration record resembles the whole pteropod abundance and pteropod shell preservation records confirming the use of Mg-calcite in combination with pteropod preservation proxies to reconstruct past fluctuations in carbonate dissolution. Preservation of aragonite and Mg-calcite increases during stadials, H-equivalents, YD and late Marine Isotope Stage (MIS) 3. During late MIS 5/early MIS 4 and in the Late Holocene absence of few pteropods as well as low Mg-calcite weight percentages point to strong dissolution of aragonite and Mg-calcite.     

Oxygen isotope fractionation during the dolomitization of calcium carbonate

The oxygen isotope fractionation accompanying the hydrothermal dolomitization of CaCO₃ between 252 and 295°C has been investigated. Dolomitization (which occurs via the crystallization of one or more intermediate magnesian calcite phases) is characterised by a progressive lowering in δ⁸O, which smoothly correlates with the change in the Mg/(Mg + Ca) and the $\text{Sr}\text{(Mg + Ca)}$ ratios and with the sequential phase formation. The data support the proposals of Katz and Matthews (1977) that (a) all reaction occurs by solution and reprecipitation, (b) intermediate phases and dolomite form sequentially and (c) the intermediate phases form within limited solution zones surrounding the dissolving precursor. Calculated volumes of the solution zone for the aragonite → low magnesian calcite transformation are within the range 3.7–6.7 × 10^?5 liters (out of 5 × 10^?3 liters, the volume of the bulk solution used in the present study), and agree well with those calculated from strontium and magnesium partitioning data. Dolomite precipitates in apparent isotopic equilibrium with the bulk solution. The temperature dependence of the fractionation is defined by the equation 1000 Inα_D-H2O = 3.06 × 10⁶T^?2 ? 3.24 Dolomite-water fractionations from this equation are significantly lower than those obtained by extrapolation of the Northrop And Clayton (1966) calibration. The reaction zone model can be applied to explain near zero dolomite-calcite oxygen isotope fractionations reported by Epsteinet al. (1964).     

Interaction between dissolved silica and calcium carbonate: 1. Spontaneous precipitation of calcium carbonate in the presence of dissolved silica

The kinetics of spontaneous precipitation of CaCO₃ from aqueous solution in the presence of dissolved silica was investigated by recording pH as a function of time. The presence of dissolved silica, at concentrations below saturation with respect to the amorphous phase, decreases induction time for CaCO₃ nucleation, but does not affect CaCO₃ polymorphism. For a “pure” system without silica, the surface free energy, σ, determined from classical nucleation theory is 42 mJ m⁻². This agrees well with values reported in the literature for vaterite and indicates some degree of heterogeneous nucleation, which can occur because of the relatively low degree of supersaturation used for the experiments. In the presence of 1 and 2 mM silica, σ is 37 and 34 mJ m⁻², indicating an increasing degree of heterogeneous nucleation as the amount of polymeric silica increases. The ratio of Ca²⁺ to CO₃²⁻ activity was a governing parameter for determining which CaCO₃ polymorph precipitated. At high Ca²⁺ to CO₃²⁻ activity ratios, almost all initial solid was vaterite, whereas at low ratios, a mixture of vaterite and calcite was observed. In solutions with low Ca²⁺ to CO₃²⁻ activity ratios, the presence of silica at concentrations above saturation with respect to amorphous silica led to formation of only calcite and strongly influenced the crystalline structure and morphology of the precipitates. At high Ca²⁺ to CO₃²⁻ ratios, system behaviour did not differ from that without silica.     

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。     

酶诱导碳酸钙沉淀加固遗址土动力特性试验研究

中国西北地区地震频发,土遗址长期受到地震活动的不利影响。为了研究酶诱导碳酸钙沉淀技术（EICP）加固遗址土的动力特性,对1.55、1.65、1.75 g/cm³这3种初始干密度的遗址土进行EICP处理,并设置未经EICP处理的对照组。开展了不同围压、振动频率下的动三轴试验。结果表明：在相同动应力作用下,相比对照组,试验组的动应变更小,耗散的能量更少,阻尼比更小;在EICP加固后,随着干密度、围压、振动频率增大,可以降低动应变的产生,但这种效果依次减弱。动本构关系符合Hardin模型,干密度、围压、振动频率对模型参数a（动弹性模量）的影响程度逐渐减小;微观分析发现,EICP加固后,碳酸钙沉淀在土颗粒表面附着,填充孔隙,并与土颗粒相互胶结成致密结构,土体结构强度增强。     

Was Phanerozoic reef history controlled by the distribution of non-enzymatically secreted reef carbonates (microbial carbonate and biologically induced cement)?

Throughout most of the Phanerozoic, reef rigidity resulted as much, or more, from early lithification by microbial carbonates and biologically induced cements (non-enzymatic carbonates) than from biological encrustation of, or by, large, enzymatically secreted metazoan skeletons. Reef framework is divided into four categories: (1) skeletal metazoan; (2) non-skeletal microbialite (stromatolite and thrombolite); (3) calcimicrobe; and (4) biocementstone, in which small or delicate organisms serve as scaffolds for rigid cement crusts. The last three categories are dominated by non-enzymatic carbonates. Skeletal framework and non-skeletal microbialite framework were the most abundant framework types through the Phanerozoic. The composition and abundance of skeletal framework was controlled largely by mass extinction events, but most reefs consisted of both microbialite and skeletal organisms in a mutually beneficial relationship. Microbialite framework was abundant throughout the Palaeozoic and early Mesozoic, but declined after the Jurassic. Calcimicrobe framework was important during the Cambrian-Early Ordovician and Devonian and biocementstone framework was important from the late Mississippian to the Late Triassic. The Phanerozoic history of reefs does not correlate well with the stratigraphic distribution of large, skeletal ‘reef builders’, or with a variety of physicochemical parameters, including sea-level history, Wilson Cycle or global climate cycles. Because non-enzymatic carbonates result from induction by non-obligate calcifiers, and not enzymatic precipitation by obligate calcifiers, the distribution of these carbonates was controlled to a larger extent by temporal changes in physicochemical parameters affecting the saturation state of sea water with respect to carbonate minerals. Changes in pCO₂, Ca/Mg ratios, cation concentrations and temperature may have affected the abundance of non-enzymatic carbonates and, hence, reefs, independently from the effects of these same parameters and mass extinction events on skeletal reef biota. The decline in abundance of reefal microbialite and absence of calcimicrobe and biocementstone reef framework after the Jurassic may be a result of relatively low saturation states of sea water owing to increased removal and sequestration of finite marine carbonate resources by calcareous plankton since the Jurassic. Reef history is difficult to correlate with temporal changes in specific global parameters because these parameters affect skeletal biota and biologically induced carbonate precipitation independently. Hence, reef history was regulated not just by skeletal reef biota, but by parameters governing non-enzymatic carbonates.     

The significance of Chara vegetation in the precipitation of lacustrine calcium carbonate

A significant portion of calcium carbonate is deposited in lake sediments as a result of biological processes related to the photosynthetic activity of phytoplankton in the pelagic realm and, in addition, macrophytes in the littoral zone. Lake Wigry, one of the largest lakes in Poland (north‐east Poland), is characterized by: (i) carbonate sediments with a CaCO₃ content exceeding 80% within the littoral zone; and (ii) large areas of submerged vegetation dominated by charophytes (macroscopic green algae, Characeae family). It is claimed that charophytes are highly effective in utilizing HCO₃^? and forming thick CaCO₃ encrustations. Thus, this study was aimed at evaluating the CaCO₃ production by dense Chara stands overgrowing the lake bottom reaching a depth of 4 m. In late July 2009, the fresh and dry mass of plants, the percentage contribution of calcium carbonate and the production of CaCO₃ per 1 m² were investigated along three transects at three depths (1 m, 2 m and 3 m, with each sample area equal to 0·0625 m²) per transect. The composition and structure of phytoplankton and the physico‐chemical properties of the water analysed in both the littoral and pelagic zones served as the environmental background and demonstrated moderately low fertility in the lake. The greatest dry plant mass exceeded 1000 g m^?2 and CaCO₃ encrustations constituted from 59% to over 76% of the charophyte dry weight. Thus, the maximum and average values of carbonates precipitated by charophytes were 685·5 and 438 g m^?2, respectively, which exceeded previously reported results. A correlation of carbonate production with the depth of Chara stands was detected, and intermediate depths offered the most favourable conditions for carbonate precipitation (589 g m^?2 on average). As precipitated carbonates are ultimately stored in bottom deposits, the results highlight the significance of charophytes in lacustrine CaCO₃ sedimentation.     

The determination of calcium and magnesium in carbonate rocks by atomic-absorption spectrophotometry after acetic-acid decomposition

An atomic-absorption spectrophotometric method is described for the determination of Ca and Mg in carbonate rocks after an acetic-acid decomposition. KCl is used as a releasing agent instead of the more commonly used LaCl₃. Results obtained using both releasing agents compare favourably in accuracy and precision, KCl having the advantage that it is much less expensive.     

Oceannographic Chemistry of Calcium Carbonate in the Sea Area at the Pearl River Mouth

Based on the analytical results for 101 samples from 50 survey spots,this paper describes the changes in rations of various components in calcium carbonate from the sea area at the Pearl River mouth with pH.Relations of ∑CO2 with salinity,and Ca concentration with salinity in different parts of the river mouth have been established.The annual throughput of Ca from the Pearl River and the saturation degrees of calcite and aragonite have been calculated.     

单生卵囊藻对DIC的利用及其对CaCO_3沉积影响的研究

以生长在钙华池中的单生卵囊藻（Oocystis solitaria Wittr）为研究对象,利用pH漂移方法,探讨了封闭系统中单生卵囊藻在岩溶水和非岩溶水环境下对溶解无机碳（DIC）利用及其对水体Ca^2＋沉积影响的差异。结果表明,单生卵囊藻在低CO2浓度时,通过胞外碳酸酐酶的催化,以HCO3^-作为无机碳源进行光合作用。在岩溶水环境下单生卵囊藻DIC利用能力要高于非岩溶水环境（4．78倍）,而在此过程中对水体中Ca^2＋沉积的影响也更高（2．13倍）。在岩溶水（非岩溶水）环境下,有42．6％（8．9％）的Ca^2＋通过物理化学效应以CaCO3形式沉积,其余Ca^2＋可能被藻体生长而吸收利用．．     

黄龙嗜冷细菌两种胞外单糖对碳酸钙矿化影响

为了探究黄龙水体中嗜冷细菌的胞外代谢产物对钙华沉积速率及沉积产物的影响,本文从黄龙钙华水体中分离到优势土著嗜冷细菌,并以其标志性胞外代谢产物D-葡萄糖和D-核糖作为研究对象,研究了两种单糖组分在低温环境下对钙华沉积的影响,并通过X射线衍射(XRD)、扫描电子显微镜(SEM)、红外吸收光谱(FT-IR)等分析手段对碳酸钙晶型、形貌以及结构组成进行了表征。实验表明:D-葡萄糖在低温条件下能促进方解石型碳酸钙的沉积,并加快沉积速率。低浓度下(20 mg/L和40 mg/L)的沉积产物均为方解石型碳酸钙并对其形貌有一定的影响;高浓度下(80 mg/L和160 mg/L)能诱导少量的文石型碳酸钙的合成。D-核糖在低温条件下能促进碳酸钙的沉积,加快沉积速率。与D-葡萄糖不同,D-核糖仅能合成方解石型碳酸钙,但对方解石晶面的生长表现为抑制作用,且随浓度增大抑制作用益明显。此结果可为黄龙钙华生物成因的探究提供一定的理论研究基础。     

Bio-mediated calcium carbonate precipitation and its effect on the shear behaviour of calcareous sand

Calcareous sands have abundant intraparticle pores and are prone to particle breakage. This often leads to poor engineering properties, which poses a challenge to coastal infrastructure construction. A study using bio-cementation to improve the engineering properties of calcareous sand is presented in this paper. The macro- and microscopic properties of bio-cemented calcareous sand were characterized by drained triaxial tests and scanning electron microscopy observations. Experimental results show that the precipitated calcium carbonate can effectively fill the intra- and interparticle pores and bond adjacent particles, thus enhancing the shear strength of calcareous sand. The special structures (e.g. abundant intraparticle pores and rough surface) and mineral components (i.e. calcium carbonate) of calcareous sand are beneficial for improving bacterial retention in soil, which leads to a relatively uniform and dense calcium carbonate distribution on the sand particle surface, exhibiting a layer-by-layer growth pattern. This growth pattern and the abundant interparticle pores would result in less effective calcium carbonate. The strength enhancement of bio-cemented calcareous sand is significantly lower than that of bio-cemented silica sand at the same calcium carbonate content, which may be caused by the differences in the following: (a) soil skeleton strength; (b) the amount of effective calcium carbonate; and (c) interparticle pore-filling of calcium carbonate.

     

萃取富集-火焰原子吸收法测定碳酸钙中铅和镉

将碳酸钙试样用盐酸溶解后,在0.6mol/L的盐酸介质中,用KI-MIBK萃取试样中微量的铅和镉,有机相用原子吸收分光光度法测定。该方法测定铅的相对标准偏差为2.38%-6.31%,回收率为96.5%-97.0%;测定镉的相对标准偏差为4.50%-5.52%,回收率为96%-102.8%。结果可靠,具有灵敏、准确、快速、选择性好等优点。适用于碳酸钙中铅、镉的测定。     

Theoretical study of the dimerization of calcium carbonate in aqueous solution under natural water conditions

First principles calculations have been used to investigate the condensation reactions of hydrated calcium bicarbonate monomers in a simulated aqueous environment. The reaction pathway for the calcium bicarbonate dimerization process has been computed at the density functional theory-PBE level with the COSMO dielectric continuum model to simulate the hydrated environment. The results indicate that calcium bicarbonate dimers form via an associative mechanism: the first step involves a sevenfold calcium bicarbonate intermediate followed by the loss of one water molecule from the first coordination shell of calcium. Both steps are characterised by a low energy barrier of approximately 2 kcal mol⁻¹, suggesting that the dimerization process is not kinetically hindered in aqueous solution. However, the Gibbs free energies for the condensation reactions to form the calcium bicarbonate dimers and the species Ca(HCO₃)₂(H₂O)₄, Ca(HCO₃)₃(H₂O)₃⁻ and Ca₂(HCO₃)(H₂O)₁₀³⁺, computed using the PBE and mPW1B95 density functional theory levels for the gas-phase component and the UAHF-CPCM solvation model for the hydration contribution, are all positive, which indicates that the formation of these early calcium bicarbonate clusters is thermodynamically unfavourable in aqueous solutions. Our calculations therefore suggest that the oligomerization of calcium carbonate is not spontaneous in water, at the conditions considered in our simulations, i.e. T = 298 K and neutral pH, which indicates that the nucleation of calcium carbonate cannot occur through a homogeneous process when calcium-bicarbonate ion pairs are the major source of CaCO₃ in the aqueous environment.     

Influence of lysozyme on the precipitation of calcium carbonate: a kinetic and morphologic study

Several mechanisms have been proposed to explain the interactions between proteins and mineral surfaces, among them a combination of electrostatic, stereochemical interactions and molecular recognition between the protein and the crystal surface. To identify the mechanisms of interaction in the lysozyme-calcium carbonate model system, the effect of this protein on the precipitation kinetics and morphology of calcite crystals was examined. The solution chemistry and morphology of the solid were monitored over time in a set of time-series free-drift experiments in which CaCO₃ was precipitated from solution in a closed system at 25°C and 1 atm total pressure, in the presence and absence of lysozyme. The precipitation of calcite was preceded by the precipitation of a metastable phase that later dissolved and gave rise to calcite as the sole phase. With increasing lysozyme concentration, the nucleation of both the metastable phase and calcite occurred at lower Ω_calcite, indicating that lysozyme favored the nucleation of both phases. Calcite growth rate was not affected by the presence of lysozyme, at least at protein concentrations ranging from 0 mg/mL to 10 mg/mL.Lysozyme modified the habit of calcite crystals. The degree of habit modification changed with protein concentration. At lower concentrations of lysozyme, the typical rhombohedral habit of calcite crystals was modified by the expression of {110} faces, which resulted from the preferential adsorption of protein on these faces. With increasing lysozyme concentration, the growth of {110}, {100}, and finally {001} faces was sequentially inhibited. This adsorption sequence may be explained by an electrostatic interaction between lysozyme and calcite, in which the inhibition of the growth of {110}, {100}, and {001} faces could be explained by a combined effect of the density of carbonate groups in the calcite face and the specific orientation (perpendicular) of these carbonate groups with respect to the calcite surface. Overgrowth of calcite in the presence of lysozyme demonstrated that the protein favored and controlled the nucleation on the calcite substrate. Overgrowth crystals nucleated epitaxially in lines which run diagonal to rhombohedral {104} faces.     

基于钙均衡估算黄龙钙华沉积速率的探讨

从黄龙钙华的成因研究出发,结合地质历史分析及长观资料对核心景区景观水系统的相对稳定性作出了评价。通过对景观水中钙离子及其它组分含量在时间及空间上变化特征的分析研究,揭示了钙离子含量在时间上的相对稳定以及在空间上自上游而下逐渐降低的规律,这为采用钙均衡模式来研究钙华堆积区内的年沉积量提供了重要保证。在此基础上,进一步通过同位素测年、物探、测绘等综合手段对钙华堆积区内的历史与现代的平均沉积速率进行系统研究,并与前人的研究成果对比,验证了钙均衡模型的可行性和可靠性。计算结果表明,黄龙核心景区钙华的平均沉积速率为1～ 4. 86mm /a。      

土壤pH值实验室测定过程中影响因素的探讨

土壤pH值是土壤酸碱强度的指标,是土壤的基本性质之一,由于土壤成分复杂且内部处于不断交换的过程,其pH值的准确测定较为困难,因此展开影响因素的逐一研究对其pH值的准确测定有着重要意义。本文就实验室玻璃电极法测定土壤pH值过程中的几个重要影响因素展开实验并研究讨论。结果表明,陈化时间对实验室测定土壤pH值影响较大,20天以上的陈化能使土壤pH值稳定;不同方式处理实验用水浸提所测得的土壤pH值基本无差别;浸提时间对样品的测定有很大的影响,应尽量选择浸提时间在30～60 min;液土比过小则浸提液少,过大则稀释效应显著,均不利于pH值的准确测定,通常选择选择液土比为2. 5∶1。