镉和汞两种重金属离子对四角蛤蜊的急性毒性

采用毒理学实验方法,比较研究了Cd~(2+)和Hg~(2+)对四角蛤蜊(Mactra veneriformis Reeve)急性毒性效应的差异,以期为进一步评价重金属离子对四角蛤蜊的毒性效应和作用机理等提供理论依据.死亡概率单位和实验液浓度对数的线性回归分析表明,Cd~(2+)对四角蛤蜊在24、48和96 h的半致死浓度(LC_(50))分别为15.961、5.149和2.383 mg/L,Hg~(2+)的LC_(50)分别为3.714、0.607和0.207 mg/L;Cd~(2+) 和Hg~(2+) 对四角蛤蜊的安全质量浓度分别为0.023 8 mg/L和0.002 1 mg/L,分别是我国渔业水质标准(GB11607-89)限定量的4.76倍和4.02倍.     

可口革囊星虫(Phascolosoma esculenta)重组铁蛋白富集Pb2+等重金属特性和功能研究

利用可口革囊星虫重组铁蛋白富集Pb²⁺、Fe³⁺、Cd²⁺、Cr³⁺、Cu²⁺、Mn²⁺、Sn²⁺和Zn²⁺等8 种重金属离子后, 通过透射显微镜和傅里叶红外光谱测定蛋白的超微结构变化和内部基团特性。以 天然的马脾铁蛋白为对照, 观察重组铁蛋白与天然铁蛋白的差别。结果显示, 重组铁蛋白富集Pb²⁺ 和其它7 种重金属离子后蛋白体积大小与重金属离子种类直接相关。重组铁蛋白相对天然铁蛋白来 说在富集不同种类重金属离子后, 除了非特异性酰胺特征峰和蛋白特征峰外, 还出现一些专门富集 某些重金属离子的特异基团, 如:-CH₃、-CH₂-、-CH-、-NH-、-SO₃-、-COOH、-S=S-和-C-S-C 等。 通过细胞实验进一步验证了铁结合蛋白能够通过富集重金属离子Pb²⁺来保护小鼠成骨前体细胞 MRC3T3-E1, 使细胞的死亡率明显降低(P<0.05).     

Cd2+和Cu2+对泥蚶的急性毒性和联合毒性试验

为了解重金属Cd2+和Cu2+对泥蚶的毒害程度和泥蚶对重金属Cd2+和Cu2+的解毒能力,用毒理学实验方法研究了Cd2+和Cu2+对泥蚶(Tegillarca granosa)的急性毒性和联合毒性效应。结果表明:Cd2+、Cu2+对泥蚶的96 h半致死质量浓度分别为6.189、0.460 mg/L;安全质量浓度分别为0.062、0.005 mg/L;相对毒性Cu2+Cd2+。在1︰1毒性单位的联合作用下,Cd2+和Cu2+对泥蚶96 h的半致死质量浓度分别为1.984、0.147 mg/L;安全质量浓度分别为0.020、0.001 mg/L。2种重金属离子的联合毒性大于任一重金属离子的毒性,联合毒性表现为协同作用。     

Ion association of chloride and sulphate with sodium,potassium, magnesium and calcium in seawater at 25°C

Stoichiometric association constants, which have been measured for the ion pairs of Cl^? and SO₄^?2 with Na⁺, K⁺, Mg²⁺, and Ca²⁺, were used to determine the speciation in an artificial sea water containing only these ions. The resulting distribution is quite different to that found in earlier models in which chloride ion association was ignored. The concentrations of chloride ion pairs with the cations are 4 to 5 times larger than the concentrations of the sulphate ion pairs with the same cations. The total activity coefficients of the neutral salts in sea water calculated from the model are in good agreement with the experimentally measured values. The concentration of MgSO₄⁰ calculated to be present agrees with the amount determined from ultrasonic absorption data. The calculated solubility of gypsum is also in good agreement with the measured values.     

Stability constants of NaSO4−, MgSO4, MgF+, MgCl+ ion pairs at the ionic strength of seawater by potentiometry

The stability of the ion pair NaSO₄ was determined by measuring the change in sodium activity with medium composition at constant ionic strength, using a sodium-sensitive glass electrode. The stability constants of MgSO₄ and MgCl⁺ were determined indirectly from measurements of the stability of MgF⁺ in different media. All measurements were performed at 1 atm pressure, 25 ± 0.1 °C and 0.7 M formal ionic strength. The stability constants for NaSO₄^?, MgSO₄, MgF⁺ and MgCl⁺ are 1.8 ± 0.1, 6.3 ± 0.1, 22.9 ± 0.1 and 0.34 ± 0.02 M^?1, respectively.     

Stability of ion pairs from gypsum solubility degree of ion pair formation between the major constituents of seawater

The stability constants of the ion pairs NaSO₄^?, KSO₄^?, MgSO₄^?, CaSO₄, MgCl⁺ and CaCl⁺ were determined at 25°C and 0.7 M formal ionic strength, by measuring the solubility of gypsum (CaSO₄ · 2H₂O) in different media. The media used contained one or two of the following electrolytes: NaCl, KCl, MgCl₂, NaClO₄, Mg(ClO₄)₂, Na₂SO₄. Values for the stability constants are 1.22, 1.84, 12.3, 30.6, 0.48 and 1.20 M^?1, respectively, and the solubility product for gypsum is 2.87 · 10^?4M². The distribution of the main constituents of seawater was calculated using these results and the values of the carbonate and bicarbonate constants given by Dyrssen and Hansson (1972–1973). The solubility of gypsum in seawater as calculated and determined experimentally was 21.43 mM and 21.10 mM, respectively.     

Cu2+对青蛤的胁迫效应

为研究青蛤(Cyclina sinensis)对重金属Cu~(2+)的蓄积作用及免疫机能的影响,开展了Cu~(2+)对青蛤的急性毒性实验,观察青蛤在96 h Cu~(2+)半致死浓度和安全浓度胁迫下,不同组织的蓄积趋势,及血淋巴液中SOD、CAT和ACP活性的变化。结果显示:Cu~(2+)的半致死浓度为0.807 mg/L,安全浓度为0.00807 mg/L。鳃和内脏团组织中蓄积的Cu~(2+)浓度与处理时间呈正相关;在半致死和安全浓度胁迫下,鳃组织中Cu~(2+)蓄积速度均快于内脏团;在半致死浓度胁迫下血淋巴液中SOD、CAT和ACP活性呈现先诱导再抑制的趋势,安全浓度下无明显变化,但均高于对照组水平。     

Stability constants of phosphoric acid in seawater of 5–40‰ salinity and temperatures of 5–25°C

The stability constants K₁ and K₁₂ of phosphoric acid were determined for artificial seawater of six different salinities (5, 10, 20, 30, 35, 40‰) and in 0.2, 0.4 and 0.7 M NaCl at three temperatures (5, 15, 25°C). The results are compared with those of Kester and Pytkowicz (1967), Atlas et al. (1976) and Dickson and Riley (1979). The ionic product of water, K_w, was determined in sodium chloride media at 5, 15 and 25°C. Complex formation among Ca²⁺, Mg²⁺, HPO₄^2? and PO₄^3? is discussed.     

Equilibrium and structural studies of silicon(IV) and aluminium(III) in aqueous solution. II. Formation constants for the monosilicate ions SiO(OH)3− and SiO2(OH)22−. A precision study at 25°C in a simplified seawater medium

The hydrolysis of silicic acid, Si(OH)₄, was studied in a simplified seawater medium (0.6 M Na(Cl)) at 25°C. The measurements were performed as potentiometric titrations (hydrogen electrode) in which OH^? was generated coulometrically. The total concentration of Si(OH)₄, B, and log[H⁺] were varied within the limits 0.00075 ? B ? 0.008 M and 2.5 ? -log[H⁺] ? 11.7, respectively. Within these ranges the formation of SiO(OH)₃^? and SiO₂(OH)₂^2? with formation constants log β_?11(Si(OH)₄ ? SiO(OH)₃^? + H⁺) = ?9.472 ±0.002 and log β_?21(Si(OH)₄ ? SiO₂(OH)₂^2? + 2H⁺) = ?22.07 ± 0.01 was established. With B > 0.003 M polysilicate complexes are formed, however, with $\text{-}\text{log[H}{}^{\mathrm{+}}\text{] ? 10.7}$ their formation does not significantly affect the evaluated formation constants. Data were analyzed with the least squares computer program LETAGROPVRID.     

Ca2+、Mg2+及盐度对凡纳滨对虾体内代谢酶的影响

为探讨Ca2+、Mg2+、盐度对凡纳滨对虾体内代谢酶的相对独立作用和相互影响,进而为提高凡纳滨对虾生长力和免疫力提供理论依据,本实验采取L49(78)安排7水平Ca2+、Mg2+、盐度,L8(27)安排2水平Ca2+、Mg2+、盐度,开展60 d凡纳滨对虾(Litopenaeus vannamei)养殖试验,通过比较对虾体内消化酶、ATP酶及免疫类酶的活性以分析Ca2+、Mg2+、盐度对凡纳滨对虾生长力和免疫力的影响。结果表明:水体中Ca2+、Mg2+、盐度对消化酶具有显著影响(P<0.05),其中与对虾消化吸收联系最紧密的蛋白酶中,盐度对胃蛋白酶影响显著,盐度为10时酶活最高,Ca2+、盐度对类胰蛋白酶影响显著,Ca2+为200 mg/L,盐度为20时,酶活最高;Ca2+、Mg2+、盐度对ATP酶具有显著影响(P<0.05),其中对Na+-K+-ATP酶都有显著影响,Ca2+为300 mg/L,Mg2+为500 mg/L,盐度为30时酶活最高,Ca2+、Mg2+对Mg2+-ATP酶具有显著影响,Ca2+为200 mg/L,Mg2+为500 mg/L时酶活最高,Ca2+对Ca2+-ATP酶具有显著影响,Ca2+为200、300 mg/L时酶活最高;Ca2+、Mg2+、盐度对凡纳滨对虾体内免疫酶具有显著影响(P<0.05),Ca2+、Mg2+、盐度对ACP都有显著影响,Ca2+为100 mg/L,Mg2+为150 mg/L,盐度为30时酶活最高,Mg2+对AKP具有显著影响,在150 mg/L时酶活最高,Ca2+、盐度对SOD酶活具有显著影响,Ca2+为100 mg/L,盐度为35时酶活最高;Ca2+、Mg2+、盐度间的交互作用对体内代谢酶也有一定影响。     

Cd~(2+)对青蛤(Cyclina sinensis)的毒性及蓄积过程研究

利用水生动物急性毒性实验方法,在6个浓度下Cd2+对青蛤的急性毒性进行测定,经回归分析后,得到Cd2+对青蛤96h半致死浓度为20.09mg/L,安全浓度为0.201mg/L。分别对半致死浓度和安全浓度下Cd2+在青蛤体内不同组织的蓄积情况进行了分析。结果表明,在半致死浓度条件下,168h青蛤各组织Cd2+的含量依次为肌肉内脏团鳃;而在安全浓度下,其结果为内脏团鳃肌肉,内脏团对于Cd2+富集能力远高于肌肉。讨论了青蛤的养殖环境及产品检验等问题。     

A potentiometric study of ferric ion complexes in synthetic media and seawater

An investigation of ferric ion complexing has been conducted in synthetic media and seawater at 25°C. Formation constants were potentiometrically determined for the species FeCl²⁺, FeCl₂⁺, FeOH²⁺, and Fe(OH)₂⁺ at an ionic strength of 0.68 m. Formation constants for the ferric chloride complexes were determined as _Clβ₁ = 2.76 and _Clβ₂ = 0.44. In a study of the reaction Fe³⁺ + nH₂O ? Fe(OH)_n^(3?n)+ + nH⁺ in NaClO₄, NaNO₃ and NaCl the formation constants ${}^1\text{β}{}_1\text{and}{}^1\text{β}{}_2$ were shown to be relatively independent of medium when the effects of nitrate and chloride complexing were taken into account. The average values obtained for these constants are ${}^1\text{β}{}_1\text{= 1.93 · 10}{}^{\mathrm{?3}}\text{and}{}^1\text{β}{}_2\text{= 8.6 · 10}{}^{\mathrm{?8}}$. Reasonable agreement with these values was obtained when these constants were determined in seawater by accounting for the effects of chloride, fluoride and sulfate complexing.     

Sulphate complexation in seawater: A relation between the stability constants of sodium sulphate and magnesium sulphate in seawater from a determination of the stability constant of hydrogen sulphate and a calculation of the single ion activity coefficient of sulphate

The conditional stability constant of HSO₄^? has been determined at 25°C, 1 atm and a formal ionic strength of 0.7 M in solutions containing sodium, magnesium, chloride and sulphate. This was done spectrophotometrically (UV), using diphenylamine as indicator. The value obtained was 17.0 ± 0.1 (molar scale). Single ion activity coefficients for Na₂SO₄, K₂SO₄ and MgSO₄ have been calculated according to the Bates et al. (1970) model, assuming that the sulphate ion is not hydrated. It was found that the single ion activity coefficient of sulphate changes very little between Na₂SO₄, K₂SO₄ and MgSO₄ when the formal ionic strength is kept constant.These results have been used to obtain relations between the stability constants of NaSO₄^? and MgSO₄ valid for seawater.     

Calorimetric study of the thermodynamics of formation of MgSO4 and NaSO4− ion pairs at the ionic strength of seawater

The formation of the ion pairs MgSO₄ and NaSO₄^? was investigated calorimetrically at 0.75 M ionic strength, 25°C, 1 atm. Simultaneous determinations of enthalpy changes, ΔH₁⁰, and stability constants, K₁, were not possible, and values of K₁ determined independently had to be introduced for the calculation of ΔH₁⁰. The values of ΔH₁⁰ obtained were 1–3 kJ mol^?1 for MgSO₄ and 0 kJ mol^?1 for NaSO₄^?.     

极大螺旋藻富积重金属机理的研究

于1993年5月由南京大学藻类培养室提供极大螺旋藻藻种,用Zarrouk培养基培养后,用活藻体和甲醛杀死的藻体分别进行吸附实验;过滤出的藻体置于6×10－3g／L左右浓度的Co2+,Ni2+,Cu2+,Zn2+离子混合液中。结果显示,死、活藻体都具有相似的吸附能力,对Co2+,Ni2+,Zn2+的富积大于203倍,对Cu2+的富积大于185倍;用热水提取、DEAE-纤维素D-23柱和SephadexG－200柱纯化后,获得了纯细胞外壁多糖,其分子量为52kD。将该糖溶液盛在透析袋内,并置于4种离子混合液中进行吸附实验,结果显示,核糖对Co2+,Ni2+,Cu2+,Zn2+的富积倍数分别达1744,1644,1340,1750。藻体和多糖对Co2+,Ni2+,Zn2+的吸附都高于对Cu2+的吸附。比较藻体与多糖对4种离子的吸附结果可见,藻体对离子的吸附主要是多糖的作用;多糖的红外光谱显示,金属离子改变OH和CO－NH的吸收峰,表明这两种基团与金属离子发生了络合作用;对Cu2+的络合滴定测定表明,Cu2+与多糖的结合度为0．40。     

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。     

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

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

Distribution of some ions and minor gaseous components by concentrations in the atmospheric surface layer of some regions in Eastern Siberia and the Far East

We consider the resemblance between the ion composition of the fraction of soluble aerosols and gaseous admixtures in the atmospheric surface layer at the high-level Mondy station (East Sayan), those in the Listvyanka settlement south of Lake Baikal, in the city of Irkutsk, and at the Primorskaya station near the city of Ussuriysk (Primorskii krai). We use measurement data on the concentrations of the following ions: HCO ₃ ^? , SO ₄ ^2? , NO ₃ ^? , Cl^?, H⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺ in the soluble fraction of aerosols and gases HNO₃, HCl, NH₃, and SO₂ in air samples over a 10-year period conducted in the mode of online monitoring. We found the lognormal form of distributions of concentrations of each of the abovementioned components according to the number of samples. A versatile scheme of the distribution of mean geometric concentrations of atmospheric components was proposed for all four groups.     

Formation and stability of mixed Mg/Ca/phytate species in synthetic seawater media: Consequences on ligand speciation

The results of a potentiometric investigation (by ISE-H⁺, glass electrode) on the speciation of phytate ion (Phy¹²⁻) in an ionic medium simulating the major components (Na⁺, K⁺, Ca²⁺, Mg²⁺, Cl⁻ and SO₄²⁻) of natural seawater, at different salinities and t = 25 °C, are reported. The work was particularly aimed at determining the possible formation of mixed Ca²⁺–Mg²⁺–phytate ion pairs, and to establish how including the formation of these mixed species would affect the speciation modeling in seawater media. After testing various speciation models, that considering the formation of the MgCaH₃Phy⁵⁻, MgCaH₄Phy⁴⁻, Mg₂CaH₃Phy³⁻ and Mg₂CaH₄Phy²⁻ species was accepted, and corresponding stability constants were determined at two salinities (S = 5, 10). A discussion is reported both on the choice of the experimental conditions and on the possibility to extend these results to those typical of real seawater. A detailed procedure is also described to demonstrate that the stability of these species is higher than that statistically predicted. As reported in literature, a parameter, namely log X, has been determined in order to quantify this extra stability for the formation of each mixed species at various salinities. For example, at S = 10, log X₁₁₃ = 2.67 and log X₁₁₄ = 1.37 for MgCaH₃Phy⁵⁻ and MgCaH₄Phy⁴⁻ (statistical value is log X_stat = 0.60), and log X₂₁₃ = 6.11 and log X₂₁₄ = 2.15 for Mg₂CaH₃Phy³⁻ and Mg₂CaH₄Phy²⁻ (log X_stat = 1.43), respectively. Results obtained also showed that the formation of these species may occur even in conditions of low salinity (i.e. low concentration of alkaline earth cations) and low pH (i.e., more protonated ligand).     

The speciation of Fe(II) and Fe(III) in natural waters

The interactions of Fe(II) and Fe(III) with the inorganic anions of natural waters have been examined using the specific interaction and ion pairing models. The specific interaction model as formulated by Pitzer is used to examine the interactions of the major components (Na⁺, Mg²⁺, Ca²⁺, K⁺, Sr²⁺, Cl⁻, SO₄⁻, HCO₃⁻, Br⁻, CO₃²⁻, B(OH)₄⁻, B(OH)₃ and CO₂) of seawater and the ion pairing model is used to account for the strong interaction of Fe(II) and Fe(III) with major and minor ligands (Cl⁻, SO₄²⁻, OH⁻, HCO₃⁻, CO₃²⁻ and HS⁻) in the waters. The model can be used to estimate the activity and speciation of iron in natural waters as a function of composition (major sea salts) and ionic strength (0 to 3 M). The measured stability constants (K_FeX^*) of Fe(II) and Fe(III) have been used to estimate the thermodynamic constants (K_FeX) and the activity coefficient of iron complexes (γ_FeX) with a number of inorganic ligands in NaClO₄ medium at various ionic strengths: In(K_FeX/γ_Feγ_X) = InK_FeX − In(γ_FeX) The activity coefficients for free ions (γ_Fe, γ_x) needed for this extrapolation have been estimated from the Pitzer equations. The activity coefficients of the ion pairs have been used to determine Pitzer parameters (B_FeX, B_FeX⁰, C_FeX^φ) for the iron complexes. These results make it possible to estimate the stability constants for the formation of Fe(II) and Fe(III) complexes over a wide range of ionic strengths and in different media. The model has been used to determine the solubility of Fe(III) in seawater as a function of pH. The results are in good agreement with the measurements of Byrne and Kester and Kuma et al. When the formation of Fe organic complexes is considered, the solubility of Fe(III) in seawater is increased by about 25%.