Combined effects of water pH and alkalinity on the accumulation of lead, cadmium and chromium to Labeo rohita (Hamilton)

Influence of pH (5.5, 7.0 and 8.5) and alkalinity (40 to 200 mg/L as CaCO₃) on the accumulation of Pb (NO₃)₂ CdCl₂, H₂O and K₂Cr₂O₇ to Labeo rohita (Hamilton) was investigated in the laboratory. Highest accumulation of Pb and Cr in whole fish occurred at pH 5.5 and at alkalinity level of 40 to 46 mg/L as CaCO₃ compared to 7.0 and 8.5. In case of Cd maximum accumulation occurred at pH 7.0 and at alkalinity of 100 mg/L as CaCO₃ than that of pH 5.5 and 8.5 and alkalinity 42 and 156 mg/L as CaCO₃. Maximum accumulation of lead and chromium occurred at total alkalinity level of 40 and 46 mg/L as CaCO₃, respectively while maximum accumulation of cadmium occurred at an alkalinity level of 200 mg/L as CaCO₃. A significant (p<0.05) linear relationship was demonstrated between increasing pH/ alkalinity and decreasing accumulation in Pb and Cr treatment at all exposure period while for Cd there was no significant linear relationship established.     

Analytical Model for the Palaeoenvironmental Evolution of the Nihewan Beds

In this paper, the evolutional characteristics of palaeoclimate and oxidation-reduction conditions as well asacidity-alkalinity environment are discussed by means of the step-regression, cluster, optimal partitioning andcorrelation analyses of CaCO_3, C / P_2O_5, Fe~(2+) / Fe~(3+), pH and Eh values, taking the Xiaodukou section in theNihewan basin as an example. The CaCO_3, C / P_2O_5 and pH were calculated respectively using the optimalpartitioning method. Thus five cold zones and six warm zones as well as five reduction and six oxidation zoneswere distinguished. Then the inductive method was used to produce four numerical groups: 8.10, 8.3-8.4,8.6-8.7 and 8.9-8,97. The above-mentioned results are respectively based on CaCO_3 content, C/P_2O_5 andpH values. From Fig. 3, Tables 1 and 2 it can be seen that the Nihewan Beds were formed mainly under a re-duction and slightly alkaline environment of cold climate, with pH values of 8.3-8.4. Fig. 3 shows that bed 35is approximately near the boundary between the Brunhes and Matuyama polarity epochs, 0.73 Ma in age; bed26 is roughly near the Jaramillo event (base), 0.97 Ma in age; bed 18 coincides roughly with themagnetostratigraphic boundary of 2.00 Ma (?). Bed 13 may be the Pleistocene-Pliocene boundary, 2.48 Ma inage. Thus geochemical zones Ⅰ, Ⅱ, Ⅲ and Ⅳ include respectively cold zones 1; 2 and 3; 4; and 5.     

Limestone drains to increase pH and remove dissolved metals from acidic mine drainage

Despite encrustation by Fe and Al hydroxides, limestone can be effective for remediation of acidic mine drainage (AMD). Samples of water and limestone (CaCO₃) were collected periodically for 1 a at 3 identical limestone-filled drains in Pennsylvania to evaluate the attenuation of dissolved metals and the effects of pH and Fe- and Al-hydrolysis products on the rate of CaCO₃ dissolution. The influent was acidic and relatively dilute (pH<4; acidity <90 mg) but contained 1–4 mg·L⁻¹ of O₂, Fe³⁺, Al³⁺ and Mn²⁺. The total retention time in the oxic limestone drains (OLDs) ranged from 1.0 to 3.1 hr. Effluent remained oxic (O₂>1 mg·L⁻¹) but was near neutral (pH=6.2–7.0); Fe and Al decreased to less than 5% of influent concentrations. As pH increased near the inflow, hydrous Fe and Al oxides precipitated in the OLDs. The hydrous oxides, nominally Fe(OH)₃ and Al(OH)₃, were visible as loosely bound, orange-yellow coatings on limestone near the inflow. As time elapsed, Fe(OH)₃ and Al(OH)₃ particles were transported downflow. The accumulation of hydrous oxides and elevated pH (>5) in the downflow part of the OLDs promoted sorption and coprecipitation of dissolved Mn, Cu, Co, Ni and Zn as indicated by decreased UK concentrations of the metals in effluent and their enrichment relative to Fe in hydrous-oxide particles and coatings on limestone. Despite thick (∼1 mm) hydrous-oxide coatings on limestone near the inflow, CaCO₃ dissolution was more rapid near the inflow than at downflow points within and the OLD where the limestone was not coated. The high rates of CaCO₃ dissolution and Fe(OH₃) precipitation were associated with the relatively low pH and high Fe³⁺ concentration near the inflow. The rate of CaCO₃ dissolution decreased with increased pH and concentrations of Ca²⁺ and HCO₃⁻ and decreased Pco₂. Because overall efficiency is increased by combining neutralization and hydrolysis reactions, an OLD followed by a settling pond requires less land area than needed for a two-stage treatment system consisting of an anoxic limestone drain an oxidation-settling pond or wetland. To facilitate removal of hydrous-oxide sludge, a perforated-pipe subdrain can be installed within an OLD.     

Evaluating locally available organic substrates for vertical flow passive treatment cells at Cerro Rico de Potosí, Bolivia

Vertical flow cells (VFCs) are key components of passive acid mine drainage (AMD) treatment systems and require organic substrates that create anaerobic conditions and encourage bacterial sulfate reduction. In the high elevation desert of Potosí, Bolivia, the low productivity landscape limits the availability of sustainable and economical organic substrates. Locally available brewery waste, llama manure, and cow manure were evaluated as potential VFC substrates in a preliminary laboratory fed-batch study to assist in passive treatment system design. Two abandoned AMD discharges were collected from Cerro Rico de Potosí. Discharge A had an initial pH of 2.96, specific conductance of 3.31 mS/cm, and acidity of 1,350 mg/L as CaCO₃ equivalent. Discharge B had an initial pH of 3.85, specific conductance of 1.87 mS/cm, and acidity of 1,000 mg/L as CaCO₃ equivalent. Triplicate fed-batch reactors were set up in 1-L cubitainers with each potential substrate exposed to each AMD, yielding a total of 18 reactors exposed for 9 days and sampled two times for anions and dissolved metals. Cow manure reactors exhibited the greatest pH and alkalinity increases. Cd, Co, Fe, Mn, Ni, Pb, and Zn decreased in all reactors. SO₄ concentrations only decreased in brewery waste reactors. However, SO₄ reducing bacteria was higher for cow manure reactors. Results suggest that llama and cow manure are the more labile substrates, with llama manure being the most affordable. Brewery waste could be a suitable less-labile long-term substrate amendment. However, longer-term studies are needed to determine the optimum VFC substrate mixture in this unique circumstance.     

Oxygen and sulfur isotope systematics of sulfate produced by bacterial and abiotic oxidation of pyrite

To better understand reaction pathways of pyrite oxidation and biogeochemical controls on δ¹⁸O and δ³⁴S values of the generated sulfate in acid mine drainage (AMD) and other natural environments, we conducted a series of pyrite oxidation experiments in the laboratory. Our biological and abiotic experiments were conducted under aerobic conditions by using O₂ as an oxidizing agent and under anaerobic conditions by using dissolved Fe(III)_aq as an oxidant with varying δ¹⁸O_H2O values in the presence and absence of Acidithiobacillus ferrooxidans. In addition, aerobic biological experiments were designed as short- and long-term experiments where the final pH was controlled at ∼2.7 and 2.2, respectively. Due to the slower kinetics of abiotic sulfide oxidation, the aerobic abiotic experiments were only conducted as long term with a final pH of ∼2.7. The δ³⁴S_SO4 values from both the biological and abiotic anaerobic experiments indicated a small but significant sulfur isotope fractionation (∼−0.7‰) in contrast to no significant fractionation observed from any of the aerobic experiments. Relative percentages of the incorporation of water-derived oxygen and dissolved oxygen (O₂) to sulfate were estimated, in addition to the oxygen isotope fractionation between sulfate and water, and dissolved oxygen. As expected, during the biological and abiotic anaerobic experiments all of the sulfate oxygen was derived from water. The percentage incorporation of water-derived oxygen into sulfate during the oxidation experiments by O₂ varied with longer incubation and lower pH, but not due to the presence or absence of bacteria. These percentages were estimated as 85%, 92% and 87% from the short-term biological, long-term biological and abiotic control experiments, respectively. An oxygen isotope fractionation effect between sulfate and water (ε¹⁸O_SO4-H2O) of ∼3.5‰ was determined for the anaerobic (biological and abiotic) experiments. This measured value was then used to estimate the oxygen isotope fractionation effects between sulfate and dissolved oxygen in the aerobic experiments which were −10.0‰, −10.8‰, and −9.8‰ for the short-term biological, long-term biological and abiotic control experiments, respectively. Based on the similarity between δ¹⁸O_SO4 values in the biological and abiotic experiments, it is suggested that δ¹⁸O_SO4 values cannot be used to distinguish biological and abiotic mechanisms of pyrite oxidation. The results presented here suggest that Fe(III)_aq is the primary oxidant for pyrite at pH < 3, even in the presence of dissolved oxygen, and that the main oxygen source of sulfate is water-oxygen under both aerobic and anaerobic conditions.     

Clues from Current High CO2 Environments on the Effects of Ocean Acidification on CaCO3 Preservation

Acidification of surface seawater owing to anthropogenic activities has raised serious concerns on its consequences for marine calcifying organisms and ecosystems. To acquire knowledge concerning the future consequences of ocean acidification (OA), researchers have relied on incubation experiments with organisms exposed to future seawater conditions, numerical models, evidence from the geological record, and recently, observations from aquatic environments exposed to naturally high CO₂ and low pH, e.g., owing to volcanic CO₂ vents, upwelling, and groundwater input. In the present study, we briefly evaluate the distribution of dissolved CO₂–carbonic acid parameters at (1) two locations in the Pacific and the Atlantic Ocean as a function of depth, (2) a mangrove environment in Bermuda, (3) a seasonally stratified body of water in a semi-enclosed sound in Bermuda, and (4) in temporarily isolated tide pools in Southern California. We demonstrate that current in situ conditions of seawater pCO₂, pH, and CaCO₃ saturation state (Ω) in these environments are similar or even exceed the anticipated changes to these parameters in the open ocean over the next century as a result of OA. The observed differences between the Pacific and Atlantic Oceans with respect to seawater CO₂–carbonic acid chemistry, preservation of CaCO₃ minerals, and the occurrence and distribution of deep-sea marine calcifiers, support the hypothesized negative effects of OA on the production and preservation of CaCO₃ in surface seawater. Clues provided from shallow near-shore environments in Bermuda and Southern California support these predictions, but also highlight that many marine calcifiers already experience relatively high seawater pCO₂ and low pH conditions.     

A geochemical model for evaluating theories on the genesis of Florida''s sedimentary phosphate deposits

Present ionic concentrations of Ca ⁺⁺,HCO ₃ ^- ,and HPO ₄ ⁼ in surface and groundwater runoff in Florida indicate that phosphorus is being concentrated in rock through dissolution and reprecipitation, with calcium phosphate increasing at the expense of calcium carbonate. Analog computer simulation of a systems model of this process suggests that significant enrichment can occur in 20 million years. The degree of enrichment depends on the supply of new phosphorus to Florida through rain and oceanic exchange processes. If the calcium phosphate content of original rock is 0.5 to 1.0 percent (0.52 to 1.05 percent P ₂ O ₅),a formation with 10 to 20 percent calcium phosphate (CaPO ₄ or 10.5 to 21.0 percent P ₂ O ₅)as in the Hawthorn Formation (Miocene)may result. Nutrient upwelling along the continental slope coupled with transport to the estuaries by lateral eddy diffusion can supply an additional 400 mg P|m ² |yr which, if deposited, would result in a sediment with a 4.3 percent CaPO ₄ (4.5 percent P ₂ O ₅)content. If this is enriched later by resolution, 40 percent CaPO ₄ (42 percent P ₂ O ₅)results. Through geologic time, the ocean may be considered as a source of phosphorus to the land through rain or estuarine sediment.     

A geochemical model for evaluating theories on the genesis of Florida's sedimentary phosphate deposits

Present ionic concentrations of Ca ⁺⁺,HCO ₃ ^- ,and HPO ₄ ⁼ in surface and groundwater runoff in Florida indicate that phosphorus is being concentrated in rock through dissolution and reprecipitation, with calcium phosphate increasing at the expense of calcium carbonate. Analog computer simulation of a systems model of this process suggests that significant enrichment can occur in 20 million years. The degree of enrichment depends on the supply of new phosphorus to Florida through rain and oceanic exchange processes. If the calcium phosphate content of original rock is 0.5 to 1.0 percent (0.52 to 1.05 percent P ₂ O ₅),a formation with 10 to 20 percent calcium phosphate (CaPO ₄ or 10.5 to 21.0 percent P ₂ O ₅)as in the Hawthorn Formation (Miocene)may result. Nutrient upwelling along the continental slope coupled with transport to the estuaries by lateral eddy diffusion can supply an additional 400 mg P|m ² |yr which, if deposited, would result in a sediment with a 4.3 percent CaPO ₄ (4.5 percent P ₂ O ₅)content. If this is enriched later by resolution, 40 percent CaPO ₄ (42 percent P ₂ O ₅)results. Through geologic time, the ocean may be considered as a source of phosphorus to the land through rain or estuarine sediment.     

新疆吐鲁番盆地古近纪气候事件的研究

吐鲁番盆地是天山山脉中的一个山间盆地,古近系保存完好,是研究中国西北地区古近纪气候变迁的良好地区。通过对吐鲁番盆地连木沁剖面古近系多种气候代用指标（Fe₂O₃、FeO、CaCO₃、有机碳、有机碳同位素）的研究,探讨了吐鲁番盆地古近纪的气候变迁和重要气候事件。利用Fe3+/Fe2+值,恢复了吐鲁番盆地古近纪的气温：古新世的年均气温为22.35℃,始新世为21.82℃,渐新世为15.69℃,并且在渐新世的早期和晚期发生较大幅度的降温事件。对地层中CaCO3（碳酸钙）含量的研究表明,古新统和始新统碳酸钙平均含量分别为468％和666％,指示该沉积时期气候相对比较湿润,而渐新统达15.01％,指示渐新世气候明显干旱化,并且渐新世的早期和晚期气候更为干旱。有机碳同位素（δ¹³Corg）值分布于C3植物的范围内,表明其受C3植物的影响。对地层中的δ¹³Corg值研究显示,该值与地层中碳酸钙含量呈负相关,与气温呈正相关,即该值偏负时,地层中碳酸钙含量增加,气温降低。各种气候指标指示吐鲁番盆地古新世和始新世气候比较温暖湿润,而渐新世气候干旱温凉。     

Calcium carbonate dissolution in deep sea sediments: reconciling microelectrode, pore water and benthic flux chamber results

We report the benthic fluxes of O₂, titration alkalinity (TA), Ca²⁺, NO₃⁻, PO₄³⁻, and Si(OH)₄ from in situ benthic flux chamber incubations on the Ceara Rise and Cape Verde Plateau and compare them to previously published results. We find within analytical uncertainty that the TA flux is twice the calcium flux, suggesting that dissolution/precipitation of CaCO₃ is the principal mechanism controlling benthic TA and Ca²⁺ fluxes. At sites where the sediments contain significant (>35%) CaCO₃ and the overlying waters are supersaturated with respect to CaCO₃, the ratios of the total dissolution rate to the remineralization rate are significantly less than at all other study sites. We propose that these observations can be explained by precipitation of fresh CaCO₃ at the supersaturated sediment surface followed by redissolution deeper in the sediments because of metabolically-produced CO₂. A numerical simulation is presented to demonstrate the feasibility of this explanation. In addition, surface exchange reactions in high-CaCO₃ sediments coupled with high rates of particle mixing may also impact rates of metabolic dissolution and depress chamber-derived estimates of carbonate alkalinity and calcium benthic fluxes. These results suggest that at supersaturated, high CaCO₃ locations, previous models of sediment diagenesis may have overestimated the impact of metabolic dissolution on the preservation of CaCO₃ deposited on the sea floor.     

The Paleoclimatic Variation Records of Carbonate and Iron Oxides in the Weinan Loess Section

The contents and distributions of CaCO3,Fe2O3.FeO and free Fe2O3 in the Weinan loess section of Shaanxi Province of China were investigated through dense sampling.The results show that the contents of CaCO3 and the ration of Fe2O3/FeO may be chosen as proxy in dices for the precipitation and temperature changes in the formation time of the strata,respectively.According to these geochemical indices,six stages of plaeoclimate evolution are proposed in this region since 142 ka B.P.,and secondary climate changes are discussed as well based on the curves of geochemical indices.     

Influence of microbial photosynthesis on tufa stromatolite formation and ambient water chemistry, SW Japan

Photosynthetic influences on tufa stromatolite formation and ambient water chemistry were investigated at two well-studied streams depositing tufa in Southwestern Japan (Shirokawa and Shimokuraida). The tufa stromatolites in both streams are composed of fine-grained calcite crystals showing annual lamination, and colonized by a number of filamentous cyanobacteria as well as non-phototrophic bacteria. Microelectrode measurements of pH, O₂, and Ca²⁺ near the stromatolite surface (the diffusive boundary layer; DBL) revealed that the investigated tufa stromatolites are formed by photosynthesis-induced CaCO₃ precipitation (PCP): cyanobacterial photosynthesis induces calcite precipitation under light conditions, while respiration of cyanobacteria and non-phototrophic bacteria inhibits precipitation in the dark. The bulk water chemistry at the lower sites of the investigated streams showed the daytime decreases of Ca²⁺ concentration and alkalinity that was expected for significant influence of PCP, while the other expected change, increased pH, was not observed. In order to examine this discrepancy, a novel approach using semi-in situ microelectrode measurements was applied to perform precise quantitative calculations. The calculation results demonstrated that the observed Ca²⁺ concentration and alkalinity decreases were caused by PCP, and that the concomitant pH increase was expected to be under the detection level of a conventional pH meter. Although the amount of PCP is supposed to be significantly affected by light intensity, observations in Shimokuraida revealed that the amount of PCP on cloudy day nonetheless accounted for about 80% of that on sunny day. Despite the significant role of PCP for tufa stromatolite formation, PCP accounted for only about 10% of the precipitated calcite in the investigated streams, which indicates that tufa stromatolites, the characteristic deposits in the streams, are responsible for only a small portion of calcite precipitation, and the rest is considered to precipitate inorganically at biofilm-free substrates.     

The calcium carbonate saturation state in cyanobacterial mats throughout Earth’s history

Through early lithification, cyanobacterial mats produced vast amounts of CaCO₃ on Precambrian carbonate platforms (before 540 Myr ago). The superposition of lithified cyanobacterial mats forms internally laminated, macroscopic structures known as stromatolites. Similar structures can be important constituents of Phanerozoic carbonate platforms (540 Myr to present). Early lithification in modern marine cyanobacterial mats is thought to be driven by a metabolically-induced increase of the CaCO₃ saturation state (Ω_CaCO3) in the mat. However, it is uncertain which microbial processes produce the Ω_CaCO3 increase and to which extent similar Ω_CaCO3 shifts were possible in Precambrian oceans whose chemistry differed from that of the modern ocean. I developed a numerical model that calculates Ω_CaCO3 in cyanobacterial mats and used it to tackle these questions. The model is first applied to simulate Ω_CaCO3 in modern calcifying cyanobacterial mats forming at Highborne Cay (Bahamas); it shows that while cyanobacterial photosynthesis increases Ω_CaCO3 considerably, sulphate reduction has a small and opposite effect on mat Ω_CaCO3 because it is coupled to H₂S oxidation with O₂ which produces acidity. Numerical experiments show that the magnitude of the Ω_CaCO3 increase is proportional to DIC in DIC-limited waters (DIC < 3-10 mM), is proportional to pH when ambient water DIC is not limiting and always proportional to the concentration of Ca²⁺ in ambient waters. With oceanic Ca²⁺ concentrations greater than a few millimolar, an appreciable increase in Ω_CaCO3 occurs in mats under a wide range of environmental conditions, including those supposed to exist in the oceans of the past 2.8 Gyr. The likely lithological expression is the formation of the microsparitic stromatolite microtexture—indicative of CaCO₃ precipitation within the mats under the control of microbial activity—which is found in carbonate rocks spanning from the Precambrian to recent. The model highlights the potential for an increase in the magnitude of the Ω_CaCO3 shift in cyanobacterial mats throughout Earth’s history produced by a decrease in salinity and temperature of the ocean, a decrease in atmospheric pCO₂ and an increase in solar irradiance. Such a trend would explain how the formation of the microsparitic stromatolite microtexture was possible as the Ω_CaCO3 of the ocean decreased from the Paleoproterozoic to the Phanerozoic.     

Calcite dissolution driven by benthic mineralization in the deep-sea: in situ measurements of Ca2+, pH,pCO2 and O2

In situ measured microprofiles of Ca²⁺, pCO₂, pH and O₂ were performed to quantify the CaCO₃ dissolution and organic matter mineralization in marine sediments in the eastern South Atlantic. A numerical model simulating the organic matter decay with oxygen was used to estimate the calcite dissolution rate. From the oxygen microprofiles measured at four stations along a 1300-m isobath of the eastern African margin and one in front of the river Niger at a water depth of 2200 m the diffusive oxygen uptake (DOU) and oxygen penetration depth (OPD) was calculated. DOU rates were in the range of 0.3 to 3 mmol m⁻² d⁻¹ and showed a decrease with increasing water depth, corresponding to an increase in OPD. The calculated amount of degradated organic matter is in the range of 1 to 8.5 gC m⁻² a⁻¹. The metabolic CO₂, released from mineralization of the organic matter drives calcite dissolution in these sediments overlain by calcite-supersaturated water. Fluxes across the sediment water interface calculated from the in situ Ca²⁺ microprofiles were 0.6 mmol m⁻² d⁻¹ for two stations at a water depth of 1300 m. The ratio of calcite dissolution flux and organic C degradation is 0.53 and 0.97, respectively. The microprofiles indicate that CO₂ produced within the upper oxic sediment layer dissolves up to 85% of the calcite rain to the seafloor. Modeling our O₂, pH and Ca²⁺ profiles from one station predicted a calcite dissolution rate constant for this calcite-poor site of 1000 mol kgw⁻¹ a⁻¹ (mol per kg water and year), which equals 95% d⁻¹. This rate constant is at the upper end of reported in situ values.     

Methane‐related microbial gypsum calcitization in stromatolites of a marine evaporative setting (Münder Formation,Upper Jurassic,Hils Syncline,north Germany)

Fossil stromatolites may reveal information about their hydrochemical palaeoenvironment, provided that assignment to a specific microbial community and a corresponding biogeochemical mechanism of formation can be made. Tithonian stromatolites of the Münder Formation at Thüste, north Germany, have traditionally been considered as formed by intertidal cyanobacterial communities. However, thin sections of the stromatolites show elongated angular traces of former gypsum crystals in a dense arrangement, but no algal or cyanobacterial filament traces. Moreover, high Fe²⁺ and Mn²⁺ contents, oxygen‐isotope and sulphur‐isotope ratios of carbonate‐bound sulphates, and sulphurized hydrocarbon biomarkers of the stromatolitic carbonate indicate that CaCO₃ precipitation occurred near the oxic–anoxic interface as a result of intensive bacterial sulphur cycling rather than photosynthetic activity. Furthermore, anaerobic oxidation of methane by Archaea may have driven CaCO₃ precipitation in deeper parts of the biofilm community, as reflected by high concentrations of squalane with a strongly negative δ¹³C in conjunction with evaporite pseudomorphs showing extremely low δ¹³C_Carb ratios. Consequently, the Thüste stromatolites are now interpreted as having initially formed by gypsum impregnation of biofilms. Subsequently, early Mg‐calcitic calcitization within the biofilms occurred because of combined bacterial iron, manganese and sulphate reduction, with an increasing contribution of anaerobic oxidation of methane with depth. This model plausibly explains the prominent preservation of signals derived from oxygen‐independent metabolic pathways, whereas virtually no geochemical record exists for an aerobic community that may, nevertheless, have prevailed at the stromatolite surface. Photic‐zone stromatolites with a prominent signal of anaerobic oxidation of methane may be common in, and indicative of, oxygen‐depleted sulphate‐bearing environments with high rates of methane production, conditions that possibly were fulfilled at the Archaean to Proterozoic transition.     

Inhibiting effects of lanthanum ion on calcite formation from CaCL2-NaHCO3 solutions at 25°C

The influence of La³⁺ on calcite formation was studied using CaCl₂-NaHCO₃ solutions. We adopted a closed system, where the pH change of the solutions was monitored in a closed vessel. The closed system reduces a number of thermodynamic variables of the solution, thus enabling us to calculate the amount of CaCO₃ precipitate only from pH with the assumption of equilibria among dissolved components in solution. After the analytical inspection of the calculation and assumption on which the calculation is based on, it was applied to experiments of the calcite formation in a Teflon vessel. The mole concentration of lanthanum added in the experiments was smaller than 1/3000 of that of calcium ion in the solutions. The addition of lanthanum oxide, chloride, and nitrate caused the difference in the pH change of the solution. The decrease of pH was smaller when lanthanum reagents were added, indicating that the amount of CaCO₃ precipitate decreased. The smallest decrease was observed when lanthanum chloride or nitrate salt was added. The X-ray diffraction study showed that the CaCO₃ precipitated in any solutions were calcite. If an equilibrium is assumed, which is considered to be likely from the pH change, the ion activity product (IAP) calculated in this study increased about 6 times when lanthanum ion, whose concentration is only 1/14 000 mole of calcium ion, was present.     

Carbonate saturation and the effect of pressure on the alkalinity of interstitial waters from the Guatemala Basin

Interstitial water samples were collected from the Guatemala Basin using an in situ sampler and by centrifuging box core sediment samples. Results from these two sampling methods for Mn, Si, PO₄ agree well. There is a systematic difference in the alkalinity values, however, which suggests that CaCO₃ (s) precipitates from the box core samples when they are brought from in situ pressure at 1 atm. Thus the alkalinity on box core samples is less than that on samples collected in situ. The magnitude of the alkalinity decrease can be calculated using basic thermodynamic principles and the observed and predicted differences agree well.Both sampling methods show a sharp drop in pH just below the sediment water interface which can be explained by the oxidation of organic matter by O₂ in the absence of CaCO₃. Alkalinity increases during the reduction of MnO₂(s) and release of Mn²⁺ to the interstitial water. The result is that interstitial waters become undersaturated with CaCO₃ immediately below the sediment/water interface and then return to or nearly to saturation at depth.     

Buffering from secondary minerals as a migration limiting factor in lead polluted soils at historical smelting sites

Examination of calcareous slags from several historical smelting sites has indicated that the specific soil environment, in particular the soil pH, may have a very significant effect on the rate of weathering and metal release. A series of acid titration experiments were used to investigate whether the weathering of the calcareous slags could be increasing the buffering effect of the soils through accumulating CaCO₃ in the slag-rich horizons. Such a buffering mechanism would maintain high pH levels and so limit the migration of Pb through the soil profile. Three sites were chosen; one with high levels of Ca in the soil, one with relatively low Ca levels and one with intermediate Ca levels. Analysis of metal concentrations was determined using ICP-AES. The results support the hypothesis that, while the soil pH remains between 8 and 5, the CaCO₃ provides an effective buffer against the mobilisation of Pb. Between soil pH 5 and 4 it is suggested that both CaCO₃ and PbCO₃ participate in the buffering reaction, which slows down with a further drop in pH. However, this reaction ultimately releases Pb into the soil solution, although at a much slower rate than would be the case in an unbuffered soil. An important implication of these findings is that migration rates of metals in soils cannot be assumed to be constant over time, if such buffering mechanisms are operational.