The influence of organics on the adsorption of copper (II) on γ-Al2O3 in seawater,model studies with EDTA

The natural “complexing capacity” of aquatic systems was determined using titration with cupric ions. It was compared with “complexing capacity” determined in the presence of both EDTA, used as a model for organic substances, and of EDTA and γ-Al₂O₃. The γ-Al₂O₃ was used as a model for solid particles of hydrous oxide in natural waters. The adsorption isotherm of copper in seawater on γ-Al₂O₃ particles was determined with and without EDTA.For EDTA alone and for the Cu—EDTA complex, it was found that they are not adsorbed on γ-Al₂O₃ in the natural seawater. However, by adsorption on solid particles, the labile ionic Cu-complex can be removed from the seawater.     

Fugacity analysis of polycyclic aromatic hydrocarbons between microplastics and seawater

Recently, the accumulation of plastic debris in the marine environment has become a great concern worldwide. Although plastics are biologically and chemically inert, plastic debris has been suspected of causing adverse effects on ecosystems due to the increase in reactivity by size reduction and/or micropollutants associated with plastics. Because of the high sorption capacity of microplastics toward organic micropollutants, it is suspected that microplastics may play roles in the distribution and fate of micropollutants. In order to quantitatively evaluate the “net flow” of environmental contaminants in water-plastic-organism systems, a fugacity analysis was conducted using concentrations of polycyclic aromatic hydrocarbons (PAHs) in open oceans and in polyethylene as a representative material of plastic debris. Ratio of fugacity in polyethylene to that in seawater showed a decreasing trend with increasing partition coefficient between polyethylene and seawater (K_PE/sw). This indicates that phase equilibrium between polyethylene and seawater is not attained for higher molecular weight PAHs. Disequilibrium of high molecular weight PAHs suggests that transfer from seawater to plastic debris is thermodynamically driven and the role of plastic debris as a vector to transfer them to living organisms would be minimal. However, additives may slowly migrate from plastics into the environment causing potentially serious effects on ecosystems.     

Coprecipitation of zinc with silica in seawater and in distilled water

Dissolved silica can coprecipitate with zinc from seawater or distilled water that has been enriched with both elements. More than 2 ppm Si are necessary for the reaction to begin. The coprecipitation shows pH dependence. The addition of pulverized illite or natural sediment as suspended particulate material does not enhance the reaction in seawater. The organic material present in the nearshore seawater samples decreases the rate and extent of reaction, as indicated by comparisons of results of experiments using natural seawater with results obtained using UV-irradiated seawater. In unbuffered distilled water the reaction must compete with hydrolysis of zinc; however, reaction does occur, which indicates that the seawater matrix is not essential for the reaction. The coprecipitation can limit the concentration of zinc in seawater to less than the solubility concentration assumed for ZnCO₃ or Zn(OH)₂. The results suggest that a zinc silicate can precipitate directly from seawater or interstitial water as an authigenic mineral.     

文登区浅层地下水化学演化与海水入侵研究

作者采用水化学演化图（hydrochemical facies evolution diagram,HFE-D）和海水入侵地下水质量指数（GQI_SWI）对山东威海文登区地下水的化学演化和海水入侵情况进行了分析。Piper图的结果表明文登区从北到南地下水的化学组成分别是Ca-HCO₃、Ca-Mg-Cl、Na-Cl。HFE-D表明沿海地区的含水层中海水占主导地位,并且地下淡水补给不足,无明显淡化趋势;内陆地区含水层中的淡水多数处于海水侵入期,有咸化趋势。运用GQI_SWI、地理信息系统和空间插值法结合,得到了文登区浅层海水入侵现状图。另外,作者考虑渗透系数对离子浓度的影响,运用反距离加权插值算法并结合渗透系数分析了文登区浅层地下水海水入侵程度。结果表明文登沿海地区已经发生了极其严重的海水入侵现象,结合HFED可知咸水有向内陆继续扩散的趋势。研究结果对文登区地下水资源的利用和海水入侵的防治具有重要意义。另外本文是HFE-D和GQI_SWI在国内文献中的首次应用,为国内其他地区的海水入侵评价提供了参考。     

海水冷冻预淡化系统的试验研究

本文提出了一种基于冷冻脱盐的海水双级冷冻预淡化系统。该系统利用蒸发结晶器对海水进行冷冻,并通过振动分离与洗涤实现冰晶与卤水的分离,以此实现海水的初步脱盐,可作为反渗透淡化的预处理系统。同时,海水冷冻淡化过程中消耗的冷量可重新回收用于空调制冷,淡化成本得以有效降低。本文建立了海水双级冷冻预淡化系统的数学模型,获得了试验系统的关键设计参数,以此搭建了试验平台并完成了试验测试,并对海水双级冷冻预淡化系统进行了经济性分析。试验结果表明:经过海水冷冻预淡化系统,预淡化海水产量可维持在21~27 L/h之间;预淡化海水盐度可从35降低到约11;预淡化过程可回收总冷量7.91 kW;反渗透淡化总成本可降低约33%。     

海水ORP对3C钢腐蚀行为的影响

研究了氧化还原电位(Oxidation Reduction Potential, ORP)对海水中碳钢腐蚀电化学特征的影响,应用动电位极化曲线法探讨了 ORP 与碳钢腐蚀行为之间的关系。结果表明,海水的 ORP 参数对碳钢腐蚀行为具有较大的影响,其中 O2/OH?电对的作用占主导,其他电对如 Fe3+/Fe2+也有一定的影响。随着海水 ORP 的增大,其氧化能力越强,碳钢腐蚀电流增大,腐蚀速度加快。水质相对稳定的开放性大洋海水中,可以考虑海水氧化还原电位在碳钢腐蚀速度预测评估中的应用。     

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.     

Simultaneous Measurement of Hydrogen Peroxide and Fe Species (Fe(II) and Fe<Subscript>(tot)</Subscript>) in Okinawa Island Seawater: Impacts of Red Soil Pollution

The northern part of Okinawa Island suffers from red soil pollution—runoff of red soil into coastal seawater—which damages coastal ecosystems and scenery. To elucidate the impacts of red soil pollution on the oxidizing power of seawater, hydrogen peroxide (HOOH) and iron species including Fe(II) and total iron (Fe_(tot), defined as the sum of Fe(II) and Fe(III)) were measured simultaneously in seawater from Taira Bay (red-soil-polluted sea) and Sesoko Island (unpolluted sea), off the northern part of Okinawa Island, Japan. We performed simultaneous measurements of HOOH and Fe(II) because the reaction between HOOH and Fe(II) forms hydroxyl radical (•OH), the most potent environmental oxidant. Gas-phase HOOH concentrations were also measured to better understand the sources of HOOH in seawater. Both HOOH and Fe(II) in seawater showed a clear diurnal variation, i.e. higher in the daytime and lower at night, while Fe_(tot) concentrations were relatively constant throughout the sampling period. Fe(II) and Fe_(tot) concentrations were approximately 58% and 19% higher in red-soil-polluted seawater than in unpolluted seawater. Gas-phase HOOH and seawater HOOH concentrations were comparable at both sampling sites, ranging from 1.4 to 5.4 ppbv in air and 30 to 160 nM in seawater. Since Fe(II) concentrations were higher in red-soil-polluted seawater while concentrations of HOOH were similar, •OH would form faster in red-soil-polluted seawater than in unpolluted seawater. Since the major scavenger of •OH, Br⁻, is expected to have similar concentrations at both sites, red-soil-polluted seawater is expected to have higher steady-state •OH concentrations.     

钢渣在海洋中无机固碳行为及其应用

钢渣是钢铁生产过程中的副产物,是一种放错的资源。钢渣投放在水体中可显著提升水体pH值,并能吸收大量的CO₂。为了解钢渣投放在海洋中可能引起的pH变化及其无机固碳能力,本研究考察了不同粒径、钢渣含量、初始pH及是否扰动等条件下钢渣/海水的pH变化特征和固碳能力。结果表明,不同条件下的钢渣/海水体系,随着浸泡时间的延长,浸出液pH初期都快速升高,后期趋于平缓,且钢渣粒径越小、投入钢渣含量越多及外加振荡作用,都可使浸出液pH提升;同时,浸出液能维持的pH水平对钢渣/海水体系固碳效率影响较大,而钢渣粒径的大小是钢渣固碳能力的最直接影响因素。本工作结果还表明,在实海环境中投放一定量的钢渣有助于预防局部水体酸化,并起到固碳减排的目的。     

Evaluation of the chemical forms of plutonium in seawater

Thermodynamic considerations based on existing data from various laboratory studies of plutonium species in aqueous solution are used to predict the speciation of this radioactive pollutant in seawater. Oxidation-reduction data for plutonium suggest that Pu(VI) should be very dominant in seawater solution compared to Pu(IV), and that Pu(III) and Pu(V) should be absent. The disproportionation reactions and the alpha reduction mechanism are probably of no consequence to the oxidation state in seawater. However, the irreversible hydrolysis of Pu⁴⁺ and the associated formation of polymeric Pu(OH)₄ colloids are important mechanisms of speciation control and plutonium removal to sediments, by adsorption onto suspended matter. Stability constants for plutonium complexation with inorganic ligands in seawater suggest that Pu(VI) dissolved in seawater will be dominantly PuO₂CO₃OH⁻.The theoretical predictions of plutonium speciation and behaviour in seawater are compared to the only available data on plutonium speciation in seawater (Nelson and Lovett, 1978). Good agreement between the predictions and field observations was obtained, within the limitations imposed by the scarcity of data on this subject.     

光照和盐度对海水介质中磷化氢转化的影响

通过室内模拟实验,研究了光照和盐度对海水介质中磷化氢转化的影响。结果表明,不同光照条件下磷化氢转化率有明显差异,按对磷化氢转化促进作用由大到小排列依次为：UVC〉UVB〉日光〉UVA〉避光条件,单位辐照强度的UVC比UVB更能促进磷化氢的转化。在实验体系中加入臭氧、过碳酸钠的实验进一步验证自由基反应对磷化氢转化有促进作...     

Copper complexing capacity of phytoplanktonic cell exudates

Copper complexing capacity of cell exudates of Dunaliella salina in natural seawater culture medium was investigated in order to evaluate the influence of this organism on speciation of trace metals in seawater.Seawater samples were collected at 200 m and 2 miles off the coast and immediately filtered. Copper complexing capacity (CC_Cu) and stability constants (K′) of related cupric complexes were then measured. They were, respectively, 27.1 × 10⁻⁸ mol l⁻¹ and 0.56 × 10⁷ l mol⁻¹ for the samples collected at 200 m and 12.8 × 10⁻⁸ mol l⁻¹ and 6.10 × 10⁷ l mol⁻¹ for those collected 2 miles off the coast. A stock culture (20 ml, 10⁶ cells ml⁻¹) in log-phase was inoculated in 2 l of each sample of filtered natural seawater. The trend of cell influence was estimated on filtered culture medium by measuring CC_Cu and K′ after 1 h, 3 and 7 days. From the results it appears that CC_Cu increased with respect to time and this was related to the growth rate, indicating a certain relationship with cell metabolic activity.It can be concluded that a comparison between the culture referring to 200 m and 2 miles, respectively, shows that the former presents a CC_Cu two times higher than the latter while the K′ is ten times higher at 2 miles than that at 200 m.     

Quantitative adsorption of organic matter from seawater on solid matrices

The influence of several operational parameters, including pH, flow rate, total volume of water passed, and choice of eluants, upon the efficiency of extraction of organic matter from seawater by two forms of commercially-available resin, XAD-2 and XAD-8, is considered. The overall efficiency of adsorption is at best 40%. The main factor determining the adsorption efficiency of XAD resin for natural organic matter is pH. The efficiency at normal seawater pH is only half that at pH 2.0. Although the efficiency decreases with increasing flow rate, the decrease is not great up to 3 bed vol./min. With increasing volume of water passed, the adsorption capacity of the resin initially drops, but reaches an approximately constant level after 1000 bed volumes. Alkaline solutions, either NH₄OH or NaOH, followed by methanol, completely recover adsorbed organic material from the resin. There is no significant advantage of XAD-8 over XAD-2 for seawater extractions, and the materials adsorbed by the two forms of resin are not substantially different.A new separation method combining XAD-2 resin and activated carbon as adsorbents in series in a column has been developed. Efficiencies of up to 90% were obtained in the extraction of acidified seawater. When the volume of water passed was less than 500 bed volumes, the adsorption as measured by UV-oxidation was quantitative. Elution of 90–100% of the adsorbed organic carbon was possible when ammonium hydroxide (7 M), methanol and an ammonium hydroxide—methanol mixture were used sequentially.     

Measurements of carbon dioxide in the Seto Inland Sea of Japan

The carbon dioxide in seawater (pCO₂) was measured in the Seto Inland Sea of Japan using newly developed equilibrator instrument designed to be free from the correction for addition or extraction of the carbon dioxide from carrier gas. The temperature dependence of pCO₂ was about 4.5%pCO₂/°C for a single seawater sample which was processed as free from biological activity and change in total carbon dioxide content during an experiment. The decrease in pCO₂ during daylight hours due to the photosynthetic fixation was about 30% of the daily mean of pCO₂ during warm months and about 15% during cold months. The effect of carbon dioxide exchange between air and seawater on pCO₂ was about 0.6 ppm in August and about 0.1 ppm in March. This is negligible small compared with the daily oscillation of carbon dioxide in seawater.     

Origin of high H2S concentrations in the Upper Permian Changxing reservoirs of the Northeast Sichuan Basin,China

Intense thermochemical sulfate reduction (TSR) and up to 18% H₂S are found in the Upper Permian Changxing Formation (P₃ch) in the northeast (NE) Sichuan Basin, China, despite that rare gypsum or anhydrite was found in this formation. Here, we present new concentration data of carbonate-associated sulfate (CAS) from carbonate host rocks, C, O, and Sr isotope data for TSR-related calcites, and S isotope data for sulfur compounds obtained during this study. These data along with spatial-temporal changes in palaeogeopressure conditions, hydraulic conductivity and the physical capacity indicate that the H₂S was generated locally from TSR within the P₃ch reservoirs. We propose that the reactive sulfates were derived from CAS released during dolomitization and recrystallization of earlier dolomite within the P₃ch Fm. and from the cross-formational migration of evaporative brines from the Lower Triassic Feixianguan Formation (T₁f) to P₃ch Fm. Our calculation shows that the two sources could provide enough SO₄²⁻ for the generation of H₂S within the P₃ch reservoirs. Early downward migration of sulfate-rich evaporative brines from the T₁f formation occurred in near-surface and shallow burial diagenetic settings (mainly <1000 m). The evaporative brines seeped into porous grainstones and displaced preexisting seawater, causing pervasive dolomitization within the P₃ch Fm. Subsequently, TSR calcites precipitated from the pore water have high Sr concentrations (up to 7767 ppm), close to the T₁f TSR calcites, and ⁸⁷Sr/⁸⁶Sr ratios mainly from 0.7074 to 0.7078, which are significantly higher than those of Late Permian seawater but within the range of early Triassic seawater.     

A catalytic oxidation method for the determination of total nitrogen dissolved in seawater

A detailed examination of a high-temperature catalytic oxidation method for liquid samples in the analysis of total nitrogen dissolved in seawater is reported. The nitrogenous compounds in liquid samples are oxidized on a platinum catalyzer at 680°C under oxygen atmosphere and the generated NO₂ is absorbed into a chromogenic reagent, followed by a spectrophotometric determination. The results of this method are much higher than those of wet oxidation methods. Molecular size dependency of the results clearly indicates that the above discrepancy is caused by the low oxidation capacity of the wet oxidation method against high-polymer organic matter dissolved in seawater. The results revealed that the concentration of total nitrogen in seawater is nearly constant from surface to bottom, ranging from 30 to 40 μM 1^?1, which organic nitrogen concentration higher in the surface layer, and a rapid decrease with depth. An examination of molecular size distribution indicates that the concentration of high-polymer organic nitrogen decreases rapidly from surface to deeper layers, with molecular sizes ranging from 5 × 10³ to 3 × 10⁴. Because of the well-defined principle of the oxidation process, its reliability, ease of sample handling and of analytical procedure on board or in the land laboratory, the present method is much more suitable for the marine analytical chemistry of total and organic nitrogen than the other previous methods.     

Hydrogen ion exchange on amorphous silica in seawater

The amount of hydrogen ion exchange on the surface of amorphous silica in seawater was measured as a function of pH at 2 and 25°C. Hydrogen ion exchange with the cations present in seawater is pH dependent and at 25°C the fraction of the surface in the cation form increases from 9% at pH 7 to 22% at pH 8. The exchange is temperature dependent and at 2°C and pH 8, 14% of the exchange sites are occupied by cations, as opposed to 22% of the exchange sites at 25°C. These results were used to calculate the buffer capacity of a model sediment consisting of pore water and amorphous silica. For a sediment of 70% porosity, pH 7.7, and 25°C, the buffer capacity of sediment plus pore water is 67 times the buffer capacity of pure seawater.     

沙海蜇(Nemopilema nomurai)代谢及分解过程对水环境理化因子及浮游植物影响的研究

从上行控制角度,通过野外采样和围隔培养实验,研究了水母的代谢及分解过程对水体环境中pH、溶解氧、营养盐组成的影响,以及该过程中浮游植物的变化。实验结果表明,沙海蜇在代谢过程中短时间内会大量消耗水体中的溶解氧（dissolved oxygen,DO）,使水体出现低氧和轻度酸化。代谢过程释放出大量营养盐,使水体中的溶解无机氮（dissolved inorganic nitrogen,DIN）浓度在24h内增加为原来的12倍,溶解无机磷（dissolved inorganic phosphorus,DIP）浓度增加了40多倍,进而引起水体中叶绿素a（chlorophyll a,chl a）浓度的增加。沙海蜇的分解过程使水体表现出明显的低氧（缺氧）和酸化现象。沙海蜇生物量越大,分解时间越长,对水体的改变程度越明显,此外,还释放出大量的营养盐并改变原有的营养盐结构,可以刺激甲藻和绿藻的生长,甚至可能引发藻华。     

An ion-exchange technique for concentrating ammonia from small volumes of seawater

An ion-exchange technique was used to concentrate ammonia from seawater. Precipitation of bivalent cations, prior to concentration, reduced the variability of ammonia recovery from the ion-exchange column and lengthened column life. Analysis of the eluate was by the phenolhypochlorite reaction. The method was designed for use with small seawater samples (>10ml) and has the advantage that it can be adapted for use with small volumes of seawater with no loss in sensitivity. In a 10 ml seawater example NH₃-N concentrations of 10–150 μg l^?1 were accurately determined.     

Voltammetric study of adsorption of cu(II) species on solid particles added to seawater

The adsorption on solid particles of natural organic ligand in seawater of Cu(II) ions, and of the inert Cu(II) complexes has been studied. Model solids, γ-Al₂O₃, Na⁺-0.392-γ-Al₂O₃, ‘Aerosil 200’, chrysotile, northupite and CaCO₃ were added to seawater. It was observed that at pH 8 natural organic matter was strongly adsorbed on chrysotile and was not adsorbed on Na⁺ -0.392-γ-Al₂O₃; it was also adsorbed on γ-Al₂O₃ over the range of 3 < pH < 7. In this pH range, the complexing capacity and adsorption of Cu is at a minimum because Cu(II) is not adsorbed on γ-Al₂O₃ and natural organic matter is adsorbed. Inert CuL complexes were adsorbed at pH 8.0 on γ-Al₂O₃, ‘Aerosil 200’, CaCO₃, and chrysotile but they were not adsorbed on northupite. The voltammetric method can be recommended for use in natural waters for distinguishing between metal ionic and metal inert complex species which are adsorbed from solution onto various solid particles.