Influence of Salinity on pH and Aluminum Concentration on the Interaction of Acidic Red Soil with Seawater

Contamination of acidic red soil in the coastal areas of Okinawa Islands is a serious environmental problem. This study was conducted to examine the effects of the salinity on pH and aluminum concentration when the acidic red soil interacts with seawater. Acidic red soil from Gushikawa recreation center was fractionated into bulk soil, coarse sand and silt + clay. Different weights of each fraction were equilibrated with seawater solutions. The pH and concentrations of Al³⁺, Na⁺, K⁺, Ca²⁺ and Mg²⁺ were then analyzed in the extracts. The results showed a decreasing trend of pH with increasing soil to solution ratio while the extracted Al³⁺ revealed an increasing trend. The lowest pH values were 3.85, 4.06, 4.41, 4.66 and their corresponding highest Al³⁺ concentrations were 2.50, 1.01, 0.062 and 0.036 mmolL⁻¹ in the seawater extracts, one-tenth seawater extracts, one-hundredth seawater extracts and one-thousandth seawater solution extracts, respectively. Mostly, the concentrations of Na⁺, Ca²⁺, Mg²⁺ and especially K⁺ decreased with increasing soil weight in the high salinities but showed the opposite trend in the low salinity samples. Potassium concentration decreased by 39%, 53% and 40% in the seawater extracts, one-tenth and one-hundredth seawater extracts but increased by 200% in one-thousandth seawater extracts. The coincidence of the increase in Al³⁺ and H⁺ concentrations, and the decrease of Na⁺, K⁺, Ca²⁺ and Mg²⁺ concentrations in the solutions suggests ion exchange/adsorption, while the increased patterns, particularly at low salinity could be attributed to the dissolution of the species from the soils.     

吸附法制取低硼海水镁砂的研究

海水氧化镁(烧结后亦称海水镁砂)具有纯度高、成份稳定,既可制得高质量产品,生产中又易于配料等优点,因而是炼钢炉碱性耐火材料的优良原料。 当用石灰乳以海水沉淀镁时,因Mg(OH)_2胶体带正电荷,海水中硼呈B(OH)_4-负离子,由于静电吸引,将硼一起吸附下来;若海水中硼全部被Mg(OH)_2胶体吸附,可使MgO中的硼含量达到0.7％(以B_2O_3计)。Byrne和Kestor指出,海水中B(OH)_4-负离子有部分与Na~+,Mg~(2+),Ca~(2+)等形成络合物NaB(OH)_4,MgB(OH)_4~+,CaB(OH)~+,它们不带电荷或     

A study of fluoride,calcium and magnesium in the Northern Indian Ocean

Estimation of fluoride in the Northern Indian Ocean gives an average concentration of 1.31 ± 0.01 mg/l and a F/Cl ratio of (6.84 ± 0.01) · 10^?5. The Ca/Cl ratio in the area is 0.02229 ± 0.000005 with an average calcium concentration of 432 ± 5 mg/l. In the Bay of Bengal this ratio is influenced by river runoff while in the Arabian Sea the outflow from the Red Sea increases the ratio. The Mg/Cl ratio is observed to be 0.06631 ± 0.00003 with an average magnesium concentration of 1281 ± 14 mg/l. Neither the river runoff nor the Red Sea outflow has any influence on this ratio. Similarities or differences of these values spatially and with reference to literature data are discussed.     

Colorimetric determination of nanomolar concentrations of ammonium in seawater using solvent extraction

A solvent extraction method for measuring nanomolar concentrations of ammonium in seawater is described. The procedure is based on formation of indophenol in alkaline solution by reaction of phenol, hypochlorite and ammonia using sodium aquopentacyanoferrate as a coupling agent. Indophenol is then concentrated by extraction into n-hexanol at low pH and re-extraction into aqueous alkaline buffer. The concentration of indophenol blue is determined colorimetrically. The molar absorbance is 2.08 × 10⁵ absorbance units per molar NH₄⁺ in seawater with a precision of ± 1.9 nM NH₄⁺ (95% Cl) for concentrations ≤ 50 nanomolar. This represents a 12-fold improvement in sensitivity and a 26-fold improvement in precision over standard aqueous analyses. Calibration curves are linear to at least 2 μM NH₄⁺. Sensitivity in seawater is 97% of that found in deionized distilled water due to a slight salt effect.     

保存液中Ca2+、Mg2+、K+对中华绒螯蟹（Eriocheir sinensis）精子体外保存存活率的影响

提要以伊红染色法检测样品精子存活率为依据,研究了4℃下5种保存液及Ca2 、Mg2 离子对中华绒螯蟹精子体外保存效果的影响。5种保存液分别为人工海水(ASW)、2倍钙离子人工海水(2×Ca2 -ASW)、无镁离子人工海水(Mg2 -FASW)、无钾离子人工海水(K -FASW)、无钙离子人工海水(Ca2 -FASW),经4天保存后,各保存液中精子样品的存活率和精子密度均出现明显差异,K -FASW、ASW及2×Ca2 -ASW三种保存液中的精子因发生顶体反应而大量死亡,而Mg2 -FASW、Ca2 -FASW的保存效果较好。在此基础上,进一步探讨了不同Mg2 和Ca2 浓度对精子存活率的影响,结果发现,经24h保存后各实验组精子存活率均随着两种离子浓度的增加而明显下降。上述结果表明:K -FASW、ASW及2×Ca2 -ASW不适合精子保存,而Mg2 -FASW和Ca2 -FASW均可作为该蟹精子的保存液;Ca2 因可引起精子顶体反应而造成保存液中精子的大量死亡,其浓度与存活率呈明显的负相关;无K 的保存液中,Ca2 、Mg2 的存在与否对精子的保存效果起关键作用;无Mg2 人工海水之所以具有较好的保存效果,可能与Mg2 的缺乏而导致Ca2 逆浓度差转运受阻,避免了因Ca2 进入而诱发顶体反应有关。     

A theoretical study of the kinetics of the boric acid–borate equilibrium in seawater

Dissolved boron in seawater occurs mainly in the form of boric acid (B(OH)₃) and borate (B(OH)₄⁻). While the equilibrium properties of the dissociation of boric acid have been studied in detail, very little work has focused on the kinetics of the boric acid–borate equilibrium in seawater. Here, we present a theoretical study of the relaxation of the seawater borate–carbonate system towards equilibrium using the experimental data of Mallo et al. [Nouv. J. Chim. 8 (1984) 373] and Waton et al. [J. Phys. Chem. 88 (1984) 3301]. The reaction rate constants are two to four orders of magnitude smaller than typical rate constants of diffusion-controlled reactions of other acid–base equilibria. This is presumably due to the substantial structural change that is involved in the conversion from planar B(OH)₃ to tetrahedral B(OH)₄. The time required to establish the boric acid–borate equilibrium in seawater is calculated to be ∼95μs at temperature T=25°C and salinity S=35. Considering stable boron isotopes ¹¹B and ¹⁰B, the isotopic equilibration time is ∼125 μs. As a result, kinetic isotope effects during coprecipitation of boron in calcium carbonate are unlikely and therefore do not affect the use of stable boron isotopes as a paleo-pH recorder.     

Diffusion coefficients of major ions in seawater

Self-diffusion coefficients of five major ions have been determined by a radioactive tracer method (capillary tube method) in seawater of salinity 34.86 at 25°C. Data are presented for Na⁺, Ca²⁺, Cl⁻, SO₄², and HCO₃⁻, which constitute about 95% by weight of sea salt. The influence of temperature and salinity on these coefficients has been studied for Na⁺ and Cl⁻ which are the major components of sea salt: self-diffusion coefficients of these two ions have been measured in seawater, at different temperatures for a salinity of 34.86 and at different salinities for a temperature of 25°C. Diffusion coefficients of the same ions have been determined at 25°C by using another radioactive tracer method (quasi-steady cell method). In this experiment, seawater ions were allowed to diffuse from natural seawater into dilute seawater. Data have been obtained at 25°C for Na⁺, Ca ²⁺, Cl⁻, SO₄²⁻ and HCO₃⁻, corresponding to different salinity gradients.     

Interstitial water chemistry of the inner continental shelf sediments off the gironde estuary

The interstitial water composition ( , alkalinity, Ca²⁺, Mg²⁺, Sr²⁺, Na⁺, K⁺) and the cation exchange capacity (CEC) were determined for the muddy sediments of the continental shelf off the Gironde Estuary (France), in the area where the sediment represents the deposit of the muddy suspension of the river. In comparison with seawater concentrations, the pore waters below 10 cm depth, show depletions of and Ca²⁺ and below a 30 cm depth show depletions of Mg²⁺. Inversely, the upper 10 cm an enrichment of Ca²⁺ concentration, and an increase of K⁺ concentration to a 40 cm depth. High values of are observed at the top 4 cm. Alkalinity enrichment is observed along the length of the core. Applying the alkalinity models for the sediment below a 10 cm depth demonstrates generally that calculated alkalinities are higher than the measured ones. Ca²⁺ dissolution occurs at the first 10 cm and authigenic carbonate precipitation starts beneath that level. Mg²⁺ depletion is accompanied by bicarbonate loss. This proves that Mg²⁺ depletion is due to a Mg-silicate reaction. The result of the CEC does not confirm the Mg²⁺ uptake by clay minerals in exchangeable site, under reducing conditions. Diffusion and bioturbation play an important role in the pore water concentration at the top of the core.     

Study of magnesium precipitation based on biocementation

Abstract

Magnesium carbonate has a cementing character like calcium carbonate, and the addition of magnesium ion enables the microbe cementitious material to have the denser microstructure with the lower porosity. The effects of various factors, such as the concentration of Ca²⁺ and Mg²⁺, on the urease activity were studied. Comparison of the productive rates for calcium carbonate and magnesium carbonate were carried out, as well as productive rates for magnesium carbonate with adding different amount of urea to medium. Calcium acetate and magnesium acetate were, respectively, used for sands solidification. Results showed that the increase in urea concentration and magnesium ion enhanced urease activity, while calcium ion significantly impaired urease activity. Sodium chloride and acetate ion had little influence on it. Productive rates for magnesium carbonate were dramatically smaller than its calcium counterpart. However, adding urea to medium allowed for more magnesium precipitation, and the higher the urea concentration, the more the magnesium precipitation. The sand columns with adding urea to medium can have a high strength despite using magnesium acetate. Therefore, the method could solve the problem of insufficient magnesium precipitation. The results will act as a guide for the application of biocementation technology with magnesium carbonate.     

Effect of changes in water salinity on ammonium, calcium, dissolved inorganic carbon and influence on water/sediment dynamics

The effect of a sudden increase in salinity from 10 to 37 in porewater concentration and the benthic fluxes of ammonium, calcium and dissolved inorganic carbon were studied in sediments of a small coastal lagoon, the Albufera d'Es Grau (Minorca Island, Spain). The temporal effects of the changes in salinity were examined over 17 days using a single diffusion-reaction model and a mass-balance approach. After the salinity change, NH₄⁺-flux to the water and Ca-flux toward sediments increased (NH₄⁺-flux: 5000–3000 μmol m⁻² d⁻¹ in seawater and 600/250 μmol m⁻² d⁻¹ in brackish water; Ca-flux: −40/−76 meq m⁻² d⁻¹ at S=37 and −13/−10 meq m⁻² d⁻¹ at S=10); however, later NH₄⁺-flux decreased in seawater, reaching values lower than in brackish water. In contrast, Ca-flux presented similar values in both conditions. The fluxes of dissolved inorganic carbon, which were constant at S=10 (55/45 mmol m⁻² d⁻¹), increased during the experiment at S=37 (from 30 mmol m⁻² d⁻¹ immediately after salinity increase to 60 mmol m⁻² d⁻¹ after 17 days).In brackish conditions, NH₄⁺ and Ca²⁺ fluxes were consistent with a single diffusion-reaction model that assumes a zero-order reaction for NH₄⁺ production and a first-order reaction for Ca²⁺ production. In seawater, this model explained the Ca-flux observed, but did not account for the high initial flux of NH₄⁺.The mass balance for 17 days indicated a higher retention of NH₄⁺ in porewater in the littoral station in seawater conditions (9.5 mmol m⁻² at S=37 and 1.6 mmol m⁻² at S=10) and a significant reduction in the water consumption at both sites (5 mmol m⁻² at S=37; 35/23 mmol m⁻² at S=10). In contrast, accumulation of dissolved inorganic carbon in porewater was lower in seawater incubations (−10/−1 meq m⁻² at S=37; 50/90 meq m⁻² at S=10) and was linked to a higher efflux of CO₂ to the atmosphere, because of calcium carbonate precipitation in water (675/500 meq m⁻²). These results indicate that increased salinity in shallow coastal waters could play a major role in the global carbon cycle.     

Boron isotopic fractionation during seawater evaporation

Laboratory experiments were undertaken to investigate the behaviour of boron at the seawater–air interface during seawater evaporation. Seawaters adjusted to different pH values were heated to 27, 33 and 40 °C inside a quartz evaporator. The vapor was collected with a quartz condenser using a cold trap. A natural seawater–vapor process in quiet air conditions and excluding the sea-spray component was realized using this arrangement. The results indicate an enrichment of ¹¹B in the condensate. This implies that in the natural environment, rainfall with δ¹¹B values lower than that of seawater has been affected either by continental boron sources or by the boron extracted from seawater under airflow conditions. While the net flux of boron carried away from the ocean by air masses due to seawater evaporation is significant compared to other fractionation-associated processes removing boron from the ocean, the effect of isotopic fractionation as boron enters the vapor phase on the isotopic composition of boron in the ocean over time is small.     

翡翠贻贝幼体附着和变态的离子控制

于１９９３年５－１２月在厦门大学海滨实验场,以人工培养的悲翠贻贝幼体作为实验材料,在人工海水中添加３－１５ｍｍｏｌ／Ｌ     

The interaction of manganese(II) with the surface of calcite in dilute solutions and seawater

The interaction of Mn²⁺ with the surface of calcite in aqueous solutions is complex. In dilute solutions the Mn²⁺ is rapidly absorbed, MnCO3₃ nucleates on the calcite surface and then grows by a first order reaction with respect to the initial Mn²⁺ concentration. At higher ionic strengths in NaCl solutions, the rate of these processes is slower, but the same general pattern persists. In solutions containing Mg²⁺, at the concentration of seawater and in seawater, the nucleation phase of the uptake process does not appear to occur. The long-term uptake rate of Mn²⁺ on the surface of calcite in seawater is first order with respect to the dissolved Mn²⁺ concentration. The rate constant is over three orders of magnitude smaller than that found in dilute Mg²⁺-free solutions. A probable explanation for the slower growth rate in seawater is that MnCO₃ is not nucleated on the calcite surface due to the presence of high Mg²⁺ concentrations. The Mg²⁺, through site competition, prevents enough Mn²⁺ from being adsorbed to reach a critical concentration for MnCO₃ nucleation. This behavior is similar to that found for orthophosphate with calcite surfaces in dilute solutions and seawater. It indicates that rhodochrosite cannot nucleate in carbonate-rich recent sediments unless the Mg²⁺ concentration is lowered below that of seawater.Measurements of the solubility of rhodochrosite in seawater gave results from an undersaturation approach to equilibrium in excellent agreement with those found in previous studies in dilute solutions. When equilibrium was approached from supersaturation, approximately fifty times more calcium was precipitated than Mn²⁺. The measured solubility was over twice that determined from undersaturation. It is possible that a Mn—calcite containing 25 to 30 mol% MnCO₃ formed on the rhodochrosite from the supersaturated solutions. Consequently, it is doubtful that pure rhodochrosite controls the concentration of Mn²⁺ even in calcium carbonate-poor marine environments.     

Solubility of hydrous ferric oxide and iron speciation in seawater

Iron solubility equilibria were investigated in seawater at 36.22‰ salinity and 25°C using several filtration and dialysis techniques. In simple filtration experiments with 0.05 μm filters and Millipore ultra-filters, ferric chlorides fluorides, sulfates, and FeOH²⁺ species were found to be insignificant relative to Fe(OH)₂⁺ at p[H⁺] = ?log [H⁺] greater than 6.0. Hydrous ferric oxide freshly precipitated from seawater yielded a solubility product of ${}^1\text{K}{}_{\mathrm{<mtext>so</mtext>}}\text{=}\text{[Fe}{}^{\mathrm{3+}}\text{][H}{}^{\mathrm{+}}\text{]}{}^{\mathrm{?3}}\text{= 4.7 · 10}{}^5$. Solubility studies based on the rates of dialysis of various seawater solutions and on the filtration of acidified seawater solutions indicated the existence of the Fe(OH)₃⁰ species. The formation constant for this species can be calculated as ${}^1\text{β}{}_3\text{=}\text{[Fe(OH)}{}_3{}^0\text{] [H}{}^{\mathrm{+}}\text{]}{}^3\text{/[Fe}{}^{\mathrm{3+}}\text{] = 2.4 · 10}{}^{\mathrm{?14}}$. The Fe(OH)₄^? species is present at concentrations which are negligible compared to Fe(OH)₂⁺ and Fe(OH)₃⁰ in the normal pH range of seawater. However, there is at least one other significant ferric complex in seawater above p[H⁺] = 8.0 (possibly with bicarbonate, carbonate, or borate ions) in addition to the Fe(OH)₂⁺ and Fe(OH)₃⁰ species.     

海南省海岸带典型区域海水入侵现状评价

基于海南省东部和南部海岸带地区地下水现场监测数据和室内水化学测定数据,研究了各水化学指标间的相关性,分析了区域海水入侵现状。研究结果表明地下水中Cl~–与Na~+的变异系数较高,与矿化度(TDS)具有强的相关性;以m(Cl~–)(m表示质量浓度)和TDS分别作为评价因子开展了海水入侵现状评价,结果表明研究区域内地下水未受到海水入侵的影响;m(Na~+)/m(Cl~–)、 m(Cl~–)/m(HCO_3~–)、m(Cl~–)/m(SO_4~(2–))、m(Ca~(2+))/m(Na~+)、m(Ca~(2+))/m(Mg~(2+))、钠吸附比(SAR)与m(Cl~–)的相关性分析结果表明m(Na~+)/m(Cl~–)、m(Ca~(2+))/m(Na~+)、m(Ca~(2+))/m(Mg~(2+))以及SAR4个参数可以作为海南省海水入侵判定的评价因子。研究结果对建设海南省"国际旅游岛"战略目标,指导当地合理利用地下水具有参考价值。     

Study of fluoride in polluted and unpolluted estuarine environments

Mindhola River estuary, which receives industrial waste containing high concentrations of fluoride, and Purna River estuary, which is free from fluoride contamination, have been investigated. While fluoride behaved conservatively in Purna River estuary, significant deviation from the theoretical dilution line (TDL) in the chlorinity range 0·5–8‰ was observed in Mindhola River estuary due to the externally added fluoride which largely remained in solution. The excess of fluroide over the theoretically calculated value was at a maximum around a chlorinity of 3‰. High natural fluoride content of the river waters resulted in F/Cl ratios exceeding 300 × 10⁻⁵ at low chlorinities. The ratio decreased rapidly with increasing chlorinity and the value near to that of seawater was observed at chlorinities above 14‰.     

利用孔隙水Br/Cl、I/Cl比和氯同位素组成来示踪南海北部东沙海域浅层流体来源

The Dongsha area is one of the most promising target areas for gas hydrate exploration in the South China Sea(SCS).The study of pore water geochemistry has played a key role in Chinese gas hydrate exploration.Br/Cl,I/Cl and δ37Cl in pore water were applied here in tracing gas hydrate occurrence,chemical evolution of pore fluids and water/rock interactions in low temperature sediment environments.The samples were collected from Sites HD255 PC and HD309 PC in the Dongsha area in 2004.At Site HD255 PC,we found the elevated Br/Cl,I/Cl and decreased SO_4/Cl at the depth of 4–5 m,suggestive of a laterally migrated fluid probably generated from the gas hydrate occurrence.The range of δ37Cl is –0.54‰ to +0.96‰,and positive δ~(37)Cl at 4–5 m interval should be related with different diffusion rates between ~(35)Cl and ~(37)Cl.At Site HD309 PC,a laterally migrated fluid was also found at the depth of 3–4 m,with the Br/Cl two times to that of the seawater and decreased I/Cl,indicating the fluid has no relationship with the gas hydrate.In this site,the chlorine isotopic composition varies from –0.7‰ to+1.9‰.Extra high Br/Cl might relate with the deep generated fluid.At higher temperature and pressure,the Br/Cl of the fluid is elevated during the hydrous silicate formation,while positive δ37Cl is also associated with the same mechanism.     

Dissociation of hydrogen sulphide in seawater and comparison of pH scales

The protonization constant of HS^? (K₁₂) has been determined potentiometrically (glass electrode) at atmospheric pressure in synthetic seawater in the salinity range 2.5–40‰ at 5 and 25°C and in NaCl solutions in the formal ionic strength of 0.1–0.8 M at 5 and 25°C. The difference between synthetic seawater and an NaCl solution with the same formal ionic strength can be explained in terms of the complexation of H⁺ by sulphate in seawater. These results can be used to compare the pH scales suggested by Hansson (1973c) and Bates (1975). Furthermore, comparison between the present values of K₁₂ and those of Goldhaber and Kaplan (1975) makes it possible to compare the conventional pH scale with Hansson's titration pH scale. The conditional protonization constant of HS^? in seawater of different salinities can be used to modify the Gran plots (Hansson and Jagner, 1973) for alkalinity measurements in anoxic seawater. Ion-pair formation between HS^? and Mg²⁺ or Ca²⁺ seems to be very weak.     

Disruption of magnesium regulation in the crab Cancer productus exposed to chlorinated seawater

Exposure of the crab Cancer productus to chlorinated seawater resulted in alterations in haemolymph sodium and magnesium concentrations. At the highest chlorination levels, which approached the 96-h LC₅₀, regulation of both ions was essentially abolished. Reciprocal changes in the sodium and magnesium levels suggested an effect on the activity of the bladder wall, which has been implicated in the regulation of haemolymph magnesium in crustaceans.Additionally, exposure to 1·19 μg/ml applied Cl (0·68 μg/ml TRO) for 96 h resulted in a fourfold increase in the ammonia excretion rate. Crabs also contributed considerable chlorine demand to the exposure seawater. Measurements of TRO in the inhalant seawater and water exiting the crabs' branchial chambers indicated a reduction in TRO equivalent to 57% of that initially present in the inhalant water (0·51 μg/ml TRO).Measurements of ammonia concentrations in the exposure water indicated that ammonia in seawater was consumed in reactions with oxidants. This was especially evident at higher levels of chlorination. At 0·58 μg/ml applied Cl and above, chlorination resulted in near disappearance of ammonia from the water.     

Complexation of dimethylsulfide with mercuric ion in aqueous solutions

The tendency of dimethylsulfide (DMS) to form complexes with heavy metal ions in aqueous solutions and the factors that influence it have been investigated. Among five heavy metal ions examined (Cu²⁺, Cd²⁺, Zn²⁺, Pb²⁺ and Hg²⁺), only Hg²⁺ bound significantly with DMS in aqueous solutions in which Hg²⁺ concentration was increased to much higher levels than that of natural seawater. The complexation capacity of Hg²⁺ for DMS was influenced by pH and media. The affinity of Hg²⁺ for DMS was generally lower at high than at low pH, presumably due to the competition of hydroxide ion to form hydroxomercury species. In different solutions, the affinity of Hg²⁺ for DMS followed the following sequence: ultra-purified water > 35‰ NaCl solution > seawater. It seems apparent that chloride had a negative impact on the complexation of DMS by Hg²⁺, owing to the competition of chloride with DMS for complexing Hg²⁺. In addition, the affinity of Hg²⁺ for DMS in the bulk seawater appeared to be higher than that in the surface microlayer seawater. The tendency of Hg²⁺ to form complexes with DMS in aqueous solution can be reduced by the presence of 2 mM amino-acid such as glycine, alanine, serine and cysteine, as these ligands give stable mercury complexes. However, the presence of 2 mM acetate in experimental solutions had no significant effect on the complexation of Hg²⁺ with DMS, even though this ligand has a relatively strong complexing capacity for Hg²⁺. Although mercury ions appeared to have a strong affinity for DMS, the concentration of mercury in seawater is too low to produce a great effect on the distribution of DMS in oceans.