Report on the ices international intercalibration of mercury in seawater

Results are described of an intercalibration between fourteen laboratories on mercury in seawater. Two samples were used for the intercalibration, one of acidified natural seawater of low concentration and the other acidified seawater spiked with mercuric chloride. Agreement was poor on the natural sample but better on the spiked sample.     

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.     

A STUDY ON TRANSFER RULE OF 137Cs AND 60Co IN SEAWATER AND MARINE FOOD WEB

Transfer rule of 137C3 and 60Co in seawater and an arrificial food web which made up of Platy-monas, Arca, tenaeus and Tilapia were studied.The results showed that the transfer of nuclide could be realized in a longer food chain in which seawater contained radioactivity, the transfer along food chain alone was slight, the pathway of nuclide uptaken by organism was mainly from seawater,but the pressnce of the food was helpful to the transfer of the nuclide, the transfer efficiency of 60Co by every member in the marine food chain was greater than that of 137C3.     

Interlaboratory calibration experiments using the polychaetous annelid Capitella capitata

An interlaboratory calibration experiment was conducted at three laboratories to test two sources of variation associated with bioassay experiments, variation due to the experimenter and to the natural seawater. Twenty-eight day static (with frequent media renewal) bioassays exposing the polychaete Capitella capitata to cadmium were conducted with synthetic and natural seawaters. Test results varied between the three laboratories; however, the variations are most probably explained by the shipment of the experimental animals to the participating laboratories.     

The reliability of analytical data for tributyltin (TBT) in sea water and its implications on water quality criteria

To investigate the reliability of analytical data for tributyltin (TBT) in sea water, split water samples were distributed to ten laboratories in six countries. The sub-surface samples comprised: (i) an offshore (0·5 km) water sample, (ii) the same sample but spiked with an undisclosed quantity of TBT standard compound (175 ng TBT⁺ liter⁻¹), and (iii) a sample taken from a yacht marina. The seven acceptable data sets were in good agreement for the spiked sample (178 ± 26 ng TBT⁺ liter⁻¹) but showed a greater variation in concentrations reported for the yacht marina sample (366 ± 93 ng TBT⁺ liter⁻¹). Atomic absorption and gas chromatographic-flame photometric detection techniques produced results of similar accuracy and precision. Samples acidified with 1 ml of 10% (v/v) acetic acid appeared stable for more than 2 weeks when stored refrigerated and in darkness. Analyses of the offshore seawater sample revealed TBT contamination (9 ± 7 ng TBT⁺ liter⁻¹) indicating dispersion of the compound to the shelf waters off Monaco. The spread in values reported by the laboratories demonstrates inherent difficulties in obtaining good precision below approximately 20 ng TBT⁺ liter⁻¹. This observation is discussed with respect to the setting and enforcing of water quality standards.     

A sample changer for automated seawater nutrient analysis systems

An automatic sample changer based upon a commercially available 20-port rotary valve has been developed for use in automated seawater nutrient analyses. All parts exposed to seawater are of stainless steel, Teflon®, or Kel-F®. The sampler has proven to be rugged and efficient in both shore and shipboard laboratories.     

Analysis of lead in polluted coastal seawater

The concentrations of total lead were determined in both ordinary coastal seawater and in coastal waters highly polluted with sewage. The average concentration of total lead ranged from about 25 ng/kg in surface samples of the former type to an average of 150 ng/kg in the latter type. 0.4⁻μm filtrate lead was found to be equivalent to lead extracted from untreated seawater by dithizone in chloroform. In highly polluted waters, particle lead ranged from 56 to 39% of the total lead, with the proportion increasing as the amount of sewage in the seawater increased. Virtually all of the lead in sewage is contained in the particle phase before it enters the ocean but about 11% is made freely available by cation exchange when the sewage is mixed with seawater. In ordinary coastal waters that are not highly polluted with sewage lead, particle lead ranged from 90 to > 20%, and most of this lead was associated with plankton. About one-third of total lead, or one-half of particle lead, in untreated seawater adheres to the walls of the water container within the first day. Upon prolonged standing (> 3 months) most of the remaining particle lead can be collected on the surface of algal colonies growing on the walls of the water container. The concentrations of freely available lead in seawater do not seem to be significantly affected by wall adsorption. The ²⁰⁶Pb/²⁰⁷Pb ratio of total lead in coastal surface seawater collected near Los Angeles was 1.194, and a day earlier was 1.188 near La Jolla. It is believed that this shows lack of mixing of contributions from two different sources of lead pollution: a pulse of rain-storm runoff of gasoline lead(²⁰⁶Pb/²⁰⁷Pb 1.197) from paved surfaces added to Los Angeles waters; and sewage lead (²⁰⁶Pb/²⁰⁷Pb 1.188) from San Diego added to La Jolla waters.     

Devenir des virus entériques en mer et influence des facteurs environnementaux

To improve the knowledge of the survival of enteric viruses in a marine environment, the influence of physico-chemical parameters (temperature, UV, salinity) on the survival of infectious poliovirus 1 and hepatitis A virus (HAV) in seawater was first studied, the influence of suspended solids (SS) on poliovirus adsorption and survival in seawater was then evaluated and the detection of rotavirus genome in environmental samples (shellfish, river water, treated wastewater) was finally investigated. The results show that temperature has a major impact on virus survival in seawater as the time necessary to inactivate 90 % of the virus (T₉₀) is 671 days at 4 °C and only 25 days at 25 °C. Ultraviolet light (42 mW s cm⁻²) rapidly inactivates viruses but HAV is more resistant (T₉₀ = 2.6 min) than the poliovirus 1 (T₉₀ = 1.3 min). By contrast, seawater salinity has no effect on virus survival. In presence of SS, 90 % to 99.9 % of the viruses were adsorbed. This adsorption does not provide any protection for viruses with low SS concentrations (3 and 15 mg L⁻¹) but a slight increase in virus survival was observed with a high SS concentration (500 mg L⁻¹). Finally environmental sample analysis indicated that 20 % shellfish, about 40 % river water and 40 % treated wastewater tested positive for the rotavirus genome.     

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.     

The effects of salinity on uptake and metabolism of toluene and naphthalene by Dolly Varden,Salvelinus malma

Dolly Varden (Salvelinus malma) were force-fed ¹⁴C-toluene or ¹⁴C-naphthalene and held for 12, 24 and 48 h in freshwater or seawater (30%(.)) in order to determine the effect of salinity on uptake and metabolism of aromatic hydrocarbons. Fish held in seawater had slightly more ¹⁴C removed from the gut than did fish held in freshwater. Whether held in freshwater or seawater, toluene was more readily metabolized by fish than was naphthalene: after 48 h, 2–3 times more ¹⁴C from toluene was in the metabolite fraction of liver and central nervous system tissues. Fish held in seawater metabolized significantly less toluene and naphthalene than those in freshwater. The increased toxicity of toluene and naphthalene to Dolly Varden held in seawater appears to be the result of the decreased metabolism of these compounds by the fish.     

离子色谱法测定海水中氯离子和硫酸根离子

氯离子和硫酸根离子是海水中重要的无机阴离子,在研究海洋生态变化、海洋循环作用过程与海洋全球气候变化等领域具有重要的指示意义。其测定方法较多,但缺少相应的测试方法。本文对测定海水中Cl^-,SO₄^2-的离子色谱方法进行了优化,选用IonPacAS14碳酸盐选择性离子色谱柱,以3.5 mmol/L Na₂CO₃+1 mmol/L NaHCO₃为流动相,可消除海水样品中碳酸盐及其他阴离子的干扰。该方法对Cl^-检出限为0.29 mg/L,线性相关系数r²=0.999 2,对SO₄^2-检出限为0.42 mg/L,线性相关系数r²=0.997 9。样品的加标回收率在95%~102%,Cl^-和SO₄^2-的相对标准偏差分别为1.92%和4.18%。该方法简便、迅速、灵敏、准确度高,可满足批量海水样品中Cl^-与SO₄^2-的准确测试。     

低盐度海水中重金属标准物质研制

本文介绍了低盐度海水中5种重金属元素混合溶液标准物质的研究和制备过程。以稀释的大洋海水为基体,用容量法以加标方式制备了低盐度海水中重金属标准物质。各元素统计结果表明样品的均匀性和稳定性良好。经9家具有中国计量认定(CMA)资质的实验室分别采用原子吸收分光光度法、电感耦合等离子体质谱法和阳极溶出伏安法对标准溶液进行分析定值,并用国家标准物质作量值溯源,以分析结果的总平均值作为标准值,标准值及不确定度的结果分别为铜15.2±0.7 μg/L、铅15.3±0.7 μg/L、锌98.9±4.7 μg/L、镉2.02±0.10 μg/L以及铬15.3±0.6 μg/L。该标准物质可用于近岸、河口区低盐度海水重金属分析过程的量值传递和质量控制。     

Forty years of anthropogenic radionuclides in surface seawater. Italian and Japanese data

The concentrations of man made radionuclides in surface seawater since early ′60s are here reported as measured in Italy and Japan. Most of the data refers to⁹⁰Sr and¹³⁷Cs, but occasionally the concentrations of⁸⁹Sr and¹³⁴Cs in some Italian samples are also given. The main sources of man made radionuclides were the global fallout produced by the nuclear weapon tests and the Chernobyl accident. The respective contributions to the contamination of surface seawater around both countries are discussed.     

The action of heavy metals on the gametes of the marine mussel, Mytilus edulis (L.)-II. Uptake of copper and zinc and their effect on respiration in the sperm and unfertilized egg

The addition of stock copper and zinc nitrate solutions to filtered seawater (pH 7·91) resulted in a large pH shift which was more pronounced with copper. The pH shift was minimized by increasing the buffering capacity of seawater using 10 mm Tris-Tes pH 7·91. Subsequent experimentation was carried out in both unbuffered and buffered seawater.In unbuffered seawater, both copper and zinc had a pronounced inhibitory effect on Mytilus edulis sperm respiration with 50% inhibition occurring at 0.65 mm (41·3 ppm) copper and 1.0 mm (65·4 ppm) zinc. Egg respiration was also inhibited by copper with 50% inhibition occurring at 0.9 mm (57·2 ppm) whereas zinc inhibited egg respiration by only 30% at 1·5 mM (98·1 ppm).In buffered seawater, both copper and zinc produced an inhibitory effect on sperm respiration. However, with copper the inhibition was much reduced whereas zinc had tthe same inhibitory effect as in unbuffered seawater. In contrast to unbuffered seawater, egg respiration was stimulated by copper but zinc produced a comparable respiratory inhibition. The uptake of both copper and zinc in sperm and egg in buffered seawater increased with increasing metal concentration. Metal ion uptake, when expressed as ng ions μl cell volume^?1, was approximately 3-fold greater in the sperm than in the eggs and in both cases zinc uptake exceeded copper uptake.At a seawater pH of < 7·5, in the absence of copper or zinc, the respiration of both egg and sperm was inhibited. The maximum levels of inhibition at pH 5·4 were 15% and 30% for sperm and egg, respectively.The differing actions of copper on egg respiration in buffered and unbuffered seawater appear to be due to enhanced copper uptake in unbuffered seawater.     

Kinetics of iron(II) oxidation in seawater of various pH

The rate of iron(II) oxidation in North Sea water of pH 5.5–10 in the range 10–25°C has been studied. The oxygenation rate depends linearly on the iron(II) and dissolved oxygen concentrations. The second-order dependence on [OH^?], found by several investigators for synthetic solutions, was confirmed in seawater, but only for pOH > 6.9. For pOH < 5.9 the rate appeared to be independent of the pOH. In the intermediate range, pOH 5.9–6.9, corresponding to the natural pH of seawater, a first-order dependence on the pOH is obeyed. The important discrepancy in the literature between the second-order rate constant for NaCHO₃ solutions and for seawater can be attributed predominantly to the incorrect assumption of a second-order pOH dependence in natural seawater. The results can be useful, for example, in predicting the effect of dumping acidic iron waste from the titanium-dioxide industry into the ocean.     

Arsenic in sediments of the North Atlantic Ocean and the Eastern Mediterranean Sea

Chemical extraction techniques show that the majority of the arsenic in North Atlantic deep-sea sediments is associated with an iron phase compositionally similar to that found in deep-sea ferromanganese nodules (As/Fe ～ 11 · 10^?4) and is probably of seawater origin. Some sediments also contain As associated with Fe oxides produced by continental weathering. A minority (～8%) of the arsenic is of detrital origin but is not associated with Fe or Mn oxides; it has a content (1.7 ppm) similar to the average crustal abundance. In the Eastern Mediterranean Sea, near-shore sediments contain As associated with land-derived Fe oxides (As/Fe ～ 2 · 10^?4), but As/Fe ratios increase to ～ 13 · 10^?4 in deep-sea sediments as the contribution of seawater derived arsenic becomes dominant. Arsenic is enriched in metalliferous sediments (As/Fe ～ 20?50 · 10^?4) but As/P ratios of metalliferous sediments, deep-sea ferromanganese nodules and deep-ocean water are all similar. Although a hydrothermal contribution cannot be discounted, it is likely that the arsenic is also of seawater origin, suggesting that hydrothermal iron oxyhydroxides remove As more efficiently from seawater than do iron phases (goethite) in deep-sea sediments and nodules. Arsenic accumulates in deep-sea sediments (～ 6 μg cm^?2 10^?3 yr^?1) at sediments (～ 120 μg cm^?2 10^?3 yr^?1) at rate sufficient to balance river input input (～3 · 10¹⁰ g yr^?1). These estimates give an oceanic residence time for arsenic of 1–2 · 10⁵ yr.     

The non-biological oxidative degradation of dissolved xanthopterin and 2, 4, 6-trihydroxypteridine by the pH or salt content of seawater

The degree of chemical instability of xanthopterin and related pteridines in seawater was studied with a view to assessing its role in the ecological turnover of these compounds in the marine environment. Solutions of these compounds in natural and synthetic seawater, brines containing one or more component salts of seawater, and buffers covering a wide pH range were incubated aseptically at 22–25°C in complete darkness and the chemical changes were spectrophotometrically monitored.Pterin, lumazine, and isoxanthopterin were completely stable in seawater, while the other pteridines degraded in the order dioxylumazine < leucopterin < xanthopterin <<< oxylumazine (the trivial names oxylumazine and dioxylumazine are used to denote 2, 4, 6-trihydroxy- and 2, 4, 6, 7-tetrahydroxy-pteridine, respectively). Apart from oxylumazine, the chemical instability of the other pteridines was correlated with pH corresponding to that of seawater. The high instability of oxylumazine was shown to be due to the salt content of seawater and not its pH; this pteridine required minimal concentrations of salt and traces of heavy-metal ions (such as Cu²⁺) to show significant chemical change. When the salt present was NaCl or KCl only, oxylumazine showed 1:1 oxidative conversion to dioxylumazine, but with the total salts of seawater the conversion was 2:1 with half of the oxylumazine being degraded, apparently by ring-cleavage, to unidentified non-pteridine products; this latter degradation is attributed to the total complex of ions present in seawater. In contrast to oxylumazine, xanthopterin gave evidence of 1:1 oxidative degradation via leucopterin in seawater, and this degradation appeared to be independent of trace metal ions. Chemical mechanisms are suggested for the observed degradations, and the ecological implications of the latter are discussed.     

A field study of physico-chemical states of artificial radionuclides in seawater

The physico-chemical states of artificial radionuclides,⁹⁰Sr,¹³⁷Cs and¹⁴⁴Ce in seawater were investigated by radiochemical analysis of filtered and unfiltered seawater. The difference of radionuclide concentrations between unfiltered and filtered seawaters was defined as the particulate form radioisotope and its particle ratio was discussed.Practically no particulate⁹⁰Sr, greater than 0.22 in size, was observed in both coastal and open seawaters, but some of¹³⁷Cs seemed to be insoluble in some circumstances, especially in coastal waters. A considerable amount of¹⁴⁴Ce was found to be particulate.An estimation of the radionuclides in particulate form was made for Kashima-nada seawaters collected in 1970 to 1972, and it was shown that the possible occurrence of particulate radionuclides, greater than 0.22 in size, were 1% or less for⁹⁰Sr and 6% for¹³⁷Cs. In the coastal water, 80 % of¹⁴⁴Ce were seemed to be in particulate form, but in the open seawater only a few%. The influences of suspended materials to¹³⁷Cs and¹⁴⁴Ce concentration levels in seawater were not negligible and further investigations are desirable.     

硫酸盐还原菌对热镀锌钢材氢渗透行为的影响

采用Devanathan-Stachurski 双面电解池检测氢渗透电流技术和扫描电镜分析, 研究了热镀锌钢材在灭菌海水、灭菌培养基和接种了硫酸盐还原菌(SRB)的培养基等3 种介质中的氢渗透行为。氢渗透电流检测结果表明, 培养基的部分组分对热镀锌钢材的氢渗透行为有促进作用, 试样在灭菌培养基中的氢渗透电流密度的平均值比在灭菌海水中提高了约6 倍。尽管活性SRB 代谢产生的S^2?和HS^?能够促进热镀锌钢材的氢渗透行为, 但是, 由SRB 及其代谢产物和它们所黏附的腐蚀产物所形成的致密微生物膜减少了氢的析出和试样对氢的吸收量, 导致热镀锌钢材氢渗透行为最终被抑制, 因此, 试样在接菌培养基中的氢渗透电流密度的平均值比其在灭菌培养基中降低77%。扫描电镜分析表明, 热镀锌钢材在灭菌海水中能够形成腐蚀产物膜, 而暴露于灭菌培养基中的试样表面未形成明显的腐蚀产物膜, 但在接菌培养基中试样表面能形成黏附了腐蚀产物的致密微生物膜的附着, 表明热镀锌钢材表面的微生物膜与其氢渗透行为之间存在明显的相关性。     

Investigations of iron coordination and redox reactions in seawater using Fe radiometry and ion-pair solvent extraction of amphiphilic iron complexes

Iron coordination and redox reactions in synthetic and coastal seawater were investigated at nanomolar concentrations using ⁵⁹Fe radiometry and ion-pair solvent extraction of iron chelated by sulfoxine (8-hydroxyquinoline-5-sulfonate) and BPDS (bathophenanthroline disulfonate). Using sulfoxine, we determined the rate at which the monomeric Fe(III) hydroxide species present in seawater of pH 8 are complexed by the microbial siderophore deferriferrioxamine B and the synthetic chelator EDTA (ethylenediaminetetraacetic acid). Forward rate constants of 2 × 10⁶M⁻¹s⁻¹ and 20 M⁻¹s⁻¹, respectively, were obtained. The kinetics of these reactions have not been measured previously at pH values near that of seawater. Conditional equilibrium constants measured for the Fe(III)-EDTA system are consistent with published stability constants for EDTA complexes and for Fe(III) hydrolytic equilibria minus the neutral Fe(OH)₃^o species, suggesting it is not quantitatively significant near pH 8. Commercial humic acid was found to have sufficient affinity for iron to compete with Fe(III) hydrolysis in seawater, and limited evidence was obtained for an interaction with dissolved organic matter in coastal seawater.In our investigations of redox reactions using BPDS to trap Fe(II) produced in the medium, we observed enhanced photoreduction of Fe(III) by humic acid as well as reduction induced by solutes released from phytoplankton in seawater of pH 8. Although the method is sensitive enough to work at near-oceanic levels of iron, the difficulty in distinguishing Fe(II) generated by Fe(III)-BPDS interactions from Fe(II) produced by other means limits its utility. This analytical ambiguity may be generalizable to other methods which measure ferrous iron in seawater using Fe(II)-specific ligands.