Adsorption of uranyl complex ions on hydrous titanium oxide (HTO)——Ⅱ. Infrared spectrum investigation

-The i. r. spectra of Na4 [UO2 (CO3)3], Na [UO2 (OH)3] and the surface species of uranium on HTO underthe condition of flowing natural seawater and concentrated seawater (NaCl-NaHCO3-U) were recorded, with the bands of urany! of surface species obtained and the finding that iigands of surface species besides HTO are mainly water and OH, and there are some CO32- groups under the condition of natural seawater. Some relations between the complex properties and the j. r. spectroscopic characters for uranyl complexes were studied, and the transferred change quantity of surface complex was calculated.Structure models for surface species of adsorption are herein presented and the mechanism for uranium adsorption is deduced.     

Fibrous adsorbent containing amidoxime and carboxyl groups and adsorption of uranium

Through introducing amidoxime and carboxyl groups into polyacrylonitrile fiber, a fibrous adsorbent with high capacity and fast adsorption rate was obtained, which could adsorb 4.6 mg uranium/g in 10 days from natural seawater. The influence of the functional group content on equilibrium adsorption capacity Xm and adsorption rate constant K of the adsorbent was studied, thus indicating that the contents of amidoxime and carboxyl groups correlated with Xm and K respectively. It is concluded that the amidoxime group is of reactive adsorption, while the carboxyl group is of promotion in the adsorption of uranium. In this paper, the mechanism of uranium adsorption on the fibrous adsorbent is deduced and the chelating structure of adsorption species is discussed with molecule orbit theory.     

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。     

铀、钍在碳酸钙-海水界面的附着行为研究

运用实验模拟的手段,对铀(U)、钍(Th)在碳酸钙-海水界面的附着行为进行了初步研究,通过测定相关的分异系数(D)定量评估了文石和方解石两种碳酸钙矿物对U和Th的捕集作用。实验结果显示,不仅U和Th之间存在显著差异,而且两种碳酸钙矿物之间也存在明显不同。U介于碳酸钙和海水之间的分异系数(DU)分别在1.5~3.5(文石)和0.04~0.19(方解石)区间内变化,分异行为非常微弱但其分异系数随着碳酸钙沉淀速率的增加而逐渐上升。这表明U元素主要是以共沉淀的方式进入到文石或方解石沉淀中,但由于其在海水溶液中主要以2 22 3UO(CO)nn的形式存在,因而只能以占据晶格缺陷的方式进入碳酸钙。与之相反的是,文石和方解石都对Th表现出极强的捕集能力,所测定的分异系数(DTh)分别在240~6 330(文石)和430~6 160(方解石)范围内变化,但DTh与碳酸钙沉淀速率之间无明显关联。Th在碳酸钙表面的附着行为可界定为单纯的吸附作用,这一行为应与Th主要以Th(OH)4的形式赋存于溶液中有关。     

海水中微量元素无机离子交换动力学研究 Ⅳ.海水中铀(Ⅵ)与水合氧化钛离子交换反应的级数和活化能的测定

关于海水中铀(Ⅵ)与水合氧化钛的作用、国内外已有许多报导,内容包括水合氧化钛制备方法的不同对交换铀量的影响,水合氧化钛和海水中铀的基本物理—化学性质的研究及它们在反应过程中物理—化学性质变化规律的研究,海水中铀与水合氧化钛作用机理的研究等等。但对这一反应的动力学研究文献上报导极少,除了在本研究Ⅰ、Ⅱ和Ⅲ中报导的反应机理的研究[1,2]证明反应过程的速率由液膜扩散所控制之外,关于这一离子交换过程的反应级数和活化能的研究却至今未见有文献报导。     

Solvent extraction of copper acetylacetonate in studies of copper(II) speciation in seawater

A liquid-liquid partition, ligand exchange procedure involving the formation of copper(II) complexes with acetylacetone is presented for the determination of stability constants and concentrations of copper chelators in seawater. Acetylacetone competes with natural ligands for copper, and the equilibrium concentration of the copper acetylacetonate complex is used in speciation calculations. The concentration of the complex is calculated by partitioning a fraction of it into an organic phase and determining the total Cu concentration in that phase by back extracting with acid, and analyzing by flameless atomic absorption spectroscopy. The concentration of Cu acetylacetonate in seawater in equilibrium with the organic phase is calculated from the partition coefficient. The simple, thermodynamically well characterized procedure offers several advantages over previous techniques. Studies using organic free seawater and model ligands show good agreement between experimental and calculated conditional stability constants. Studies from seawater in Biscayne Bay, Florida, indicate two ligand types are present; type 1, K₁ = 1.2 × 10¹², C_L1 = 5.1 × 10⁻⁹ M; type 2, K₂ = 2.8 × 10¹⁰, C_L2 = 1.1 × 10⁻⁷ M. Speciation is dominated by ligand type 1. Depth profiles of [Cu(II)]_free/[Cu(II)]_total measured with the procedure at ambient copper concentrations show an increase from < 5 × 10⁻⁵ at 50–60 m to > 1 × 10⁻³ at the surface at two stations off the Florida coast.     

The influence of surfactants on the measurements of copper and cadmium speciation in model seawater by differential pulse anodic stripping voltammetry

Model systems consisting of a heavy metal ion (Cu²⁺ or Cd²⁺), complexing ligand (EDTA or NTA), a surfactant (9,12-octadecadienoic acid, C₁₈H₃₂O₂, i.e., linoleic acid), and a surfactant which is at the same time a complexing ligand (tert-octylphenol etoxylate, C₈H₁₇(C₆H₄)(OC₂H₄)_9–10OH, i.e., Triton-X-100) in seawater and NaCl solution were used in order to investigate the influence of the surfactant adsorption (on the electrode surface) on the heavy metal speciation measurements. The samples were titrated with either the metal, complexing ligand or surfactant and were measured by differential pulse anodic stripping voltammetry. It was shown that the surfactant adsorption exerts a strong influence upon the overall metal redox process and, thus, changes considerably both the apparent complexing capacity and the conditional stability constant of the system. Considering the presence of high concentrations of surfactants in polluted seawaters, the danger of measuring the apparent complexing capacity with the anodic stripping voltammetry method, without a detailed knowledge of surfactant properties and influence upon the system, is discussed.     

Adsorption of lead and cadmium ions on calcite in the Krka estuary

The adsorption of Pb²⁺ and of Cd²⁺ ions from calcareous Krka river water of various salinities (3, 14, 20 and 38 psu) on calcite (CaCO₃, Merck p.a.) was investigated. Simultaneous adsorption of Pb²⁺ and Cd²⁺ ions was studied as well. The results suggest that the two ions are adsorbed at different calcite surface sites; Pb²⁺ remained firmly bound to calcite at all salinities, whereas Cd²⁺ was firmly bound at low salinities and released at high salinities. Dissolved natural organic ligands at the freshwater-seawater interface (FSI; at 14 psu) promoted and below the FSI (at 20 psu) decreased the adsorption of Cd²⁺. The experiments were performed at metal concentrations of 8 × 10⁻⁸ mol l⁻¹ and at natural pH values around pH 8. Adsorbed amounts of trace metal ions were determined in filtered samples by differential pulse anodic stripping voltammetry (DPASV) with a three-electrode system, after 24 h of equilibration with calcite. Several adsorption models were tested, such as Freundlich's, Langmuir's and Schindler-Stumm's surface coordination model. Adsorption isotherms belong to S-1 class of empirical adsorption isotherms. None gave reasonable values of adsorption constants. The fractional partitioning of adsorbent to the solid phase when normalized to the quantity of adsorbent present (K_d) declined as solid concentration increased. It was found that the surface charge is not responsible for the observed effect. Instead, aggregate size increased, which effected a loss in surface area. This is a reasonable explanation for the observed S-shaped adsorption isotherms curves.     

Study of apparent complexing capacities of trace heavy-metals in the Huanghe River Estuary

-By the electroanalysis method combining the complexation titrating technique with the investigation of ip-Ea* characteristic curves, this paper measures apparent complexing capacities of trace heavy-metals in water samples from the Huanghe River Estuary. The results show that the order of apparent complexing capacities of trace heavy-metals in the samples isCu>Cd>Pb,and that apparent complexing capacities of near shore sample are higher than those far from shore. The effect of ultraviolet irradiation on the dissociation of organic ligands and the adsorption effect of cell walls (cells being treated with acid and seawater respectively) are investigated. The reduction (on electrodes) mechanism of species of trace heavy-metals in seawater is approached by ip-Ea* characteristic curves.     

考洲洋牡蛎养殖海域海-气界面CO2交换通量的时空变化

根据2018年7月、11月和2019年1月、4月对广东考洲洋牡蛎养殖海域进行4个季节调查获得的pH、溶解无机碳(DIC)、水温、盐度、溶解氧(DO)及叶绿素a(Chla)等数据,估算该区域表层海水溶解无机碳体系各分量的浓度、初级生产力(P_P)、表层海水CO₂分压[p(CO₂)]和海-气界面CO₂交换通量(F_CO2),分析牡蛎养殖活动对养殖区碳循环的影响。结果表明:牡蛎养殖区表层海水中Chla、DIC、HCO₃^–和P_P显著低于非养殖区;养殖淡季表层海水中pH、DO、DIC、HCO₃^–、和CO₃^2–显著大于养殖旺季,养殖旺季的p(CO₂)和F_CO2显著大于养殖淡季。牡蛎养殖区表层海水夏季、秋季、冬季和春季的海-气界面CO₂交换通量F_CO2平均值分别是(42.04±9.56)、(276.14±52.55)、(–11.59±18.15)和(–13.02±6.71)mmol/(m²·d),冬季各站位F_CO2值离散度较大,其中位数是–10.73mmol/(m²·d)。在全年尺度,表层海水p(CO₂)及F_CO2与水温呈显著正相关,与盐度呈显著负相关。在非养殖区,浮游植物光合作用可能对影响表层海水p(CO₂)及F_CO2起主导作用。养殖牡蛎钙化、呼吸作用等生理因素释放的CO₂对表层海水p(CO₂)及F_CO2未产生显著影响。考洲洋养殖海域养殖旺季为CO₂的源,养殖淡季整体为CO₂的弱汇。     

On the sulphur chemistry of a super-anoxic fjord, Framvaren, South Norway

The concentrations of total carbonate (C_t), sulphate, sulphide, thiols and oxygen, the ratio between the stable sulphur isotopes ³⁴S and ³²S in sulphate and sulphide, and the density (used to calculate salinity) were determined on samples from the water column of Framvaren, a superanoxic fjord in southern Norway. From a depth of 18m (the oxic-anoxic boundary) the initial sulphate concentration, ([SO₄]_init), as calculated from salinity, is significantly higher than the sum of the measured sulphur species. This is attributed to a loss of sulphur from the water column. The amount of total carbonate produced, corrected for the initial concentration (C_t - 2.4 Sal/35) is found to be proportional to the amount of sulphate consumed, ([SO₄]_init - [SO₄]), according to the following relation C_t- 2.4 Sal/35 = 1.84 ([SO₄]_init - [SO₄]). Isotopic fractionation caused by bacterial sulphate reduction in the anoxic part of the water column produces sulphide with a δ³⁴S 40‰ lower than the δ³⁴S for sulphate at corresponding depths. The isotopic fractionation also results in δ³⁴S value for the remaining sulphate at depths below 80 m being considerably higher than the mean value for ocean water, which is close to + 20‰. The δ³⁴S values for sulphate at depths between 10 and 50 m were lower than + 20‰ which indicates oxidation of sulphide, which follows upon diffusion of sulphide from deeper parts of the water column and inflow of oxygenated seawater over the sill into the anoxic water of the fjord. A conclusive scenario of the Framvaren sulphur chemistry is presented.     

Postdepositional injections of uranium-rich solutions into East Pacific Rise sediments

An 8.5 m long apparently undisturbed core from a hilltop on the crest of the East Pacific Rise has uranium and thorium isotope distributions that are very unusual. The core is very poor in ²³²Th, and very rich in U, particularly at the 500-cm level, where a value of about 150 ppm is reached. At the same depth the ²³⁰Th_xs reaches very large negative values. These facts could be accounted for if one assumes that solutions rich in U and poor in Th had been postdepositionally injected into the sediments about 90,000–110,000 years ago. The top of the sediment received much of its U from seawater, judging from the ${}^{234}\text{U}{}^{238}\text{U}$ ratio. Possibly carbonate rich solutions were the carriers of the injected uranium.     

Determining confidence intervals in analyzing climatic series

In the context of the problem of global warming, the question of how much the observed increase in the mean air temperature over the last decades is likely due only to natural variability is studied. It is assumed that an observed temperature-data series of length N is a segment of a stationary random sequence with a spectrum known on an interval that does not include the lowest frequencies. The variance σ²(N) of the sample mean m* and the standard deviation σ(N), which determines the width of the confidence interval of m*, are calculated for different continuations of the spectrum to the low-frequency region. For a continuation of the spectrum that boundlessly increases, as does ω^−2α (0 < α < 1/2) when the frequency ω tends to zero (red-noise spectrum), it is shown that, the closer the parameter α is to 1/2, the more slowly σ(N) tends to zero at N → ∞. Using an empirical spectrum of a global mean annual temperature series as an example, it is shown that the standard deviation significantly depends on the form of the spectrum in the lowest frequency region. An attempt has been made to assess the measure of standard-deviation uncertainty due to a lack of exact information on the spectrum in the low-frequency region. Important series characteristics—the equivalent number of independent observations N _eq(N) and the time scale of correlation T ₁(N) which are determined through the variance σ²(N) of m*—also depend on the form of the spectrum in the low-frequency region. For the red-noise spectrum, N _eq(N) increases with an increase in N proportionally to N ^1–2α (but not proportionally to N as in the case of bounded spectrum); the correlation scale T ₁(N) is no longer constant (as in the case of bounded spectrum) and increases with an increase in N proportionally to N ^2α.     

Consumption,absorption efficiency,respiration and excretion in the South African abalone Haliotis midae

Feeding periodicity, consumption rate, absorption efficiency, respiration rate and ammonia excretion were measured as functions of wet body mass in abalone collected from the western and southern Cape coasts. A well developed diel feeding rhythm was evident, consumption being restricted to the period 16h00–08h00. Food intake averaged 8,1 per cent of wet flesh mass·d^?1 at 14°C and 11,4 percent at 19°C. The daily consumption rate was related to body mass by the relationships C(g) = 0,54 W(g)^0,67 at 14°C and C(g) = 0,35 W(g)^0,77 at 19°C. Absorption efficiency averaged 37 per cent and was independent of body size. Equations relating respiration rate to wet body mass were R(m? O₂·h^?1) = 0,03 W(g)^0,83 at 14°C and R = 0,03 W(g)^0,94 at 19°C. No significant differences were detected between day and night rates or between fed and starved individuals. The rate of ammonia excretion (μmole·h^?1) was related to wet body mass (g) by the equations U = 0,22 W^0,43 at 14°C and U = 0,03 W^0,85 at 19°C.     

Estimation of phytoplankton pigments,total suspended matter and the concentration of its components by Secchi depth in Guinea's coastal zone

Relationships between the surface concentrations of phytoplankton pigments (C _ph), total suspended matter (C _sm), particulate organic carbon (C _poc), and total suspended phosphorus (C _sp), on the one hand, and the relative water transparency determined through the Secchi disc depth (z _d), on the other, are analysed using the data compiled in the Guinean coastal waters (Tabunsu and Tonkima river estuaries) during November–December 1990. The functions ofC _ph,C _sm=f(z _d) are matched up with the experimentally derived data, as well as with the model bio-optical state of seawater. The general regression equation has been calculated using the data characteristic of various types of water.Translated by Vladimir A. Puchkin.     

海水中铀与碱式碳酸锌的反应级数及活化能

目前国外对碱式碳酸锌吸附海水中铀的报导较少,对其吸附海水中铀的反应级数及活化能测定的报导尚未见到。本文试图用三颈瓶反应器及分光光度法,测定海水中铀与碱式碳酸锌的反应级数及活化能,并获得较满意的实验结果。     

DETERMINATION FO URANIUM IN SEAWATER

This article deals with a new method of analysing in seawater, i. e. the uranium is concentrated with an aqueous suspension of basic zinc carbonate, subsequently isolated and determined by extraction-photometric method. In concentrating uranium such factors as stirring time, amount of adsorbent used, acidity of seawater were studied and conditions suitable for analysis were found. This method is simple, accurate and good in reproducibility. It is not necessary to adjust the pH of seawater before analysis. This technique can also be applied to determination of uranium in river or lake.     

Kinetic and equilibrium studies of copper-dissolved organic matter complexation in water column of the stratified Krka River estuary (Croatia)

An interaction of dissolved natural organic matter (DNOM) with copper ions in the water column of the stratified Krka River estuary (Croatia) was studied. The experimental methodology was based on the differential pulse anodic stripping voltammetric (DPASV) determination of labile copper species by titrating the sample using increments of copper additions uniformly distributed on the logarithmic scale. A classical at-equilibrium approach (determination of copper complexing capacity, CuCC) and a kinetic approach (tracing of equilibrium reconstitution) of copper complexation were considered and compared. A model of discrete distribution of organic ligands forming inert copper complexes was applied. For both approaches, a home-written fitting program was used for the determination of apparent stability constants (K_i^equ), total ligands concentration (L_iT) and association/dissociation rate constants (k_i¹,k_i^- 1).A non-conservative behaviour of dissolved organic matter (DOC) and total copper concentration in a water column was registered. An enhanced biological activity at the freshwater–seawater interface (FSI) triggered an increase of total copper concentration and total ligand concentration in this water layer. The copper complexation in fresh water of Krka River was characterised by one type of binding ligands, while in most of the estuarine and marine samples two classes of ligands were identified. The distribution of apparent stability constants (log K₁^equ: 11.2–13.0, log K₂^equ:8.8–10.0) showed increasing trend towards higher salinities, indicating stronger copper complexation by autochthonous seawater organic matter.Copper complexation parameters (ligand concentrations and apparent stability constants) obtained by at-equilibrium model are in very good accordance with those of kinetic model. Calculated association rate constants (k₁¹:6.1–20 × 10³ (M s)^− 1, k₂¹: 1.3–6.3 × 10³ (M s)^− 1) indicate that copper complexation by DNOM takes place relatively slowly. The time needed to achieve a new pseudo-equilibrium induced by an increase of copper concentration (which is common for Krka River estuary during summer period due to the nautical traffic), is estimated to be from 2 to 4 h.It is found that in such oligotrophic environment (dissolved organic carbon content under 83 µM_C, i.e. 1 mg_CL^− 1) an increase of the total copper concentration above 12 nM could enhance a free copper concentration exceeding the level considered as potentially toxic for microorganisms (10 pM).     

The proportions and variations of the light absorption coefficients of major ocean color components in the East China Sea

The East China Sea (ECS),one of the largest continental seas,has dynamic hydrology and complex optical characteristics that make ocean color remote-sensing retrieval difficult.The distributions and proportions of the light absorption coefficients of major ocean color components based on two large-scale investigations in the ECS are presented,showing these features in typical summer and winter seasons.The absorption coefficient a CDOM,a NAP and a phy of colored dissolved organic matter,non-algal particle,and pigment of phytoplankton show a decreasing trend from the coast to the outer shelf.According to the a CDOM distribution at 440 nm,the Changjiang River plume shows an abnormal southeastward transport.An extremely high a NAP value patch at 440 nm is present in the middle coast.The chlorophyll-a-specific phytoplankton pigment absorption (a phy) is much higher in winter than in summer,which may cause serious underestimated results when applying the averaged a phy into remote-sensing algorithms for chlorophyll concentration retrieval.The importance of phytoplankton size was evident in outer shelf waters.The absorption of a CDOM (440) is a dominant component accounting for over half of the total seawater absorption in summer.The a NAP (440) accounts for 64% of the absorption of the ECS coastal area in winter.     

Mechanisms of enrichment of the rarer elements in marine manganese nodules

The rare-earth distribution has been determined in five manganese nodules from a range of marine environments. Manganese nodules from Loch Fyne, Scotland, and the Gulf of Aden are characterized by a low absolute abundance of the rare-earth elements and a low Ce/La ratio compared with deep-sea nodules. This difference is interpreted in terms of the diagenetic remobilization of manganese in the high sedimentation regimes leading to the effective fractionation of manganese from the rare-earth elements and the resultant depletion of the rare earths in nodules from these environments. The mechanism of incorporation of the rare-earth elements into manganese nodules is thought to be either the direct adsorption of these elements from seawater or the scavenging of the elements by colloidal iron oxide prior to their incorporation into the authigenic phase of nodules. There appears to be no evidence for the surface transfer of these elements from inorganic detritus into the authigenic phase of nodules as suggested by previous authors. The distribution of U and Th in the nodules is controlled by factors similar to those controlling the rare-earth abundance in nodules. The higher U/Th ratios in nodules from Loch Fyne and the Gulf of Aden is considered to be due to the preferential reduction of UO₂(CO₃)₃^4? to some lower-valency uranium species such as U₃O₈ in nodules from less oxidizing environments.