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。     

On the sensitized photo-oxidation of alkylbenzenes in seawater

Several homologous monoalkylated benzenes were photo-oxidized as surface films on and dissolved in pure water and purified natural seawater by solar and equivalent artificial UV irradiation in the presence of anthraquinone as photo-sensitizer. The main reaction products were the 1-phenylalkanones, the corresponding secondary alcohols, benzaldehyde and, when the side chain contained four or more carbon atoms, the products of what appears to be a Norrish type II photo-degradation. The detection among the reaction products of an aldehyde with one carbon atom less than the olefin produced by the Norrish type II photo-degradation suggests a photolytic decomposition of 1-alkenes, resulting in the formation of highly reactive compounds capable of abiotic reactions in the electronic ground state with a variety of organic compounds occurring in seawater.     

Impact of halides on the photobleaching of dissolved organic matter

Understanding absorbance photobleaching of marine dissolved organic matter (DOM) is important because DOM chromophores impact oceanic primary productivity by affecting the depth of the photic zone, absorb UV radiation and affect ocean color used in remote sensing. However, the fundamental mechanisms which account for this bleaching are largely unknown. Controlled laboratory studies demonstrated that the presence of seawater concentrations of chloride and bromide ions enhanced absorbance photobleaching reaction rates by ~ 40%, regardless of DOM source or the presence or absence of carbonate ions. In contrast, halide ions generally did not affect fluorescence bleaching rates. Variations in ionic strength did not alter the enhancement in absorbance photobleaching by halide ions. Accordingly, the enhancement in absorbance photobleaching was specific to halide ions, rather than a generalized salinity effect. We confirmed the formation of hydroxyl radical (HO^•) in illuminated samples, and its significant scavenging in the presence of halide salts. Gamma-radiolysis experiments and associated modeling indicated that a small component (~ 12%) of the photobleaching enhancement by halides was consistent with the hypothesis that halide scavenging of HO^• will form reactive halogen radicals that target electron-rich chromophores within DOM more selectively than HO^•. The mechanism responsible for the major component of absorbance photobleaching rate enhancement by halides remains unresolved.     

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.     

Nitrate photolysis in seawater by sunlight

The photolysis of nitrate in seawater by sunlight has been re-examined using abiotic seawater and naturally occurring concentrations. Photochemical formation of nitrite from nitrate was observed. First-order nitrate photolysis rate coefficients calculated from nitrite appearance (corrected for concomitant nitrite photolysis) ranged from 0 to 2.3 yr^?1, median 0.7 yr^?1. The coefficients did not correlate well with water chemistry, but decreased with increasing light dose. A first-order rate coefficient of 0.4 yr^?1 was calculated for the primary photochemical process $\text{NO}{}_3{}^{\mathrm{?}}\text{+}\text{h}\text{υ =}\text{NO}{}_2{}^{\mathrm{?}}\text{+ O(}{}^3\text{P)}$ under sea surface equatorial insolation and cloudiness conditions. However, no significant nitrate concentration decreases could be detected, suggesting an upper limit for the net first-order nitrate loss rate coefficient of 0.3 yr^?1. The data thus imply some conversion in the reverse sense: NO₂^? + hυ →→ NO₃^?.If our median rate estimate applies to surface oceanic conditions, nitrate photolysis proceeds at roughly 0.02–0.5% of the rate of N incorporation during primary production. It is thus not a significant NO₃-N sink. Since such reactive species as oxygen atoms, nitrogen dioxide, and hydroxyl radicals are produced, the reaction may have significant consequences in seawater. However, nitrite photolysis is almost certainly a more significant process.The results show internal inconsistencies and our rates are markedly different from those calculated using data from other studies. Nitrate photolysis rates are theoretically concentration- and light dose-dependent. Whether these dependencies explain the apparent discrepancies is unclear, as methodological effects may also be involved. The system requires further study.     

海水腐植质的基本化学组成研究

于１９９２－１９９３年用＾１Ｈ－ＮＭＲ，＾１３Ｃ－ＮＭＲ和ＩＲ等分析技术对甲基化前后的海水腐植质（１９９２年从青岛近岸海水中吸附提取）的基本化学组成和结构特征进行研究，并与风化煤和海洋沉积物中的腐植质作比较。结果表明，ＩＲ和＾１Ｈ－ＮＭＲ谱图显示，海水腐植质主要由脂肪链化合物组成，含有一定量的肽类和多糖，芳香结构较少。采用ＮＮＥ技术的＾１３Ｃ－ＮＭＲ谱图中各类碳的相对含量为：脂肪族碳，３３．２％；     

Photochemical decomposition rates of pteridines and flavins in seawater exposed to surface solar radiation

Rates of photochemical decomposition of pteridines and flavins, known to occur in reef waters of the Central Great Barrier Reef, Australia, were determined by reverse-phase liquid chromatography with fluorometric detection. The fluorescent transformation products of photodecomposition were identified. First-order photochemical rates were determined for pteridines and flavins exposed to surface solar radiation under aseptic conditions at ambient seawater temperature. Kinetic rates were determined in seawater and compared to photochemical rates determined in distilled water or distilled water with added divalent metal ions (Cu²⁺, Fe²⁺ Mn²⁺ and Mg²⁺).All pteridines were more stable in seawater than distilled water when exposed to solar radiation. With the exception of folic acid, addition of Cu²⁺ enhanced the stability of these pteridines, suggesting that natural concentrations of divalent metal ions may be responsible for diminished photochemical decomposition rates in seawater.Riboflavin and riboflavin-5′-phosphate in seawater solution were extremely sensitive to sunlight. The products of riboflavin photochemical decomposition, lumiflavin and lumichrome, proved relatively refractory to solar irradiation.     

Nitrite photolysis in seawater by sunlight

Nitrite is chemically stable but photochemically unstable in seawater. The net disappearance rate in abiotic low-nitrate seawater exposed to sunlight is ～ 10% per day. The primary products are the free radicals NO and OH. Quantitative aspects of the kinetics and secondary product formation are discussed in terms of a fourteen-step reaction scheme. Possible pathways explaining the results are suggested but not unequivocally identified.The rate of reaction in various marine environments is estimated from cruise data and extrapolations to vary between 0.2–60·10^?3 moles m^?2yr^?1, with a suggested global average for comparison purposes of 1–10·10³ moles m^?2yr^?1.These results confirm and quantify our previous suggestion that nitrite photolysis represents a source of OH radical in seawater. The reaction rate is large enough that significant impacts on the geochemical cycles of dissolved organic carbon and nitrogen and heavy metals may plausibly result. Effects on marine biota and atmospheric trace gas composition are also possible. However, specific reactions coupling the nitrite system to other processes have not yet been identified or demonstrated empirically.     

Silicate correction in the colorimetric determination of phosphate in seawater

An improved Strickland and Parsons' method, in which silicate correction is made, is described for the colorimetric determination of phosphate in seawater. Silicate correction is made by subtracting the value of 0.025 (C/100)², whereC is silicate concentration (µg atoms 1^?1), from the observed phosphate concentration. The relative standard deviations are 2 % at the 1 µg atom PO ₄ ^3? ?Pl^?1 level and less than 1 % at the 3 µg atoms PO ₄ ^3? ?Pl^?1 level in seawater.     

Dynamics of dissolved organic carbon in the northwestern Indian Ocean

We report here the non-conservative behaviour of DOC in the northwestern Indian Ocean by studying this parameter together with other carbon and nitrogen components. This contrasts with earlier reports of conservative behaviour. Concentrations of DOC, 3–4 times higher than those reported earlier, were found to decrease northward from the equator. Total carbon dioxide (TCO₂) increases in proportion of the oxygen utilized, thus revealing the dominant biological role in the carbon turnover. The CO₂ added through dissolution of biogenic debris is found to decrease southward, in general. Decomposition of organic material contributes at least 64% to the CO₂ addition that increases southward, the rest being from dissolution of skeletal material. Evidence is provided for the utilization of oxygen and nitrate for DOC oxidative decomposition. Accumulation of DOC without its complete oxidation to CO₂ could be the main reason for the TCO₂ decrease in southern Arabian Sea. Relationships of DOC with nitrification and denitrification processes show that the microbial population plays a major role in regulating the DOC contents in the seawater of this region. Consumption/decomposition by denitrifying bacteria and other micro-organisms responsible for nitrogen cycling in the sea are found to be intimately related to the DOC dynamics and are responsible for decreased DOC concentrations in the north. DOC accumulation in the southern Arabian Sea seems to facilitate bacterio-particulate aggregate formation and consequent nitrification, which results in excess nitrate. Application of a one-dimensional advection-diffusion model to the present data set provides evidence for the non-conservative nature of DOC in the Arabian Sea.     

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.     

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     

On the feasibility of some photochemical reactions of iodide in seawater

Aerated solutions of potassium iodide in de-ionised water, of between 5–20% (w/v), were exposed to ambient spring sunlight to estimate the rate of photochemical production of molecular iodine from iodide and oxygen in seawater. This rate cannot be measured directly as other reactions, for example the reduction of molecular iodine by organic matter, interfere. Also, a parallel photo-oxidation, initiated by organic matter in real seawater, may also occur. The experiments yield a half-life for iodide in tropical surface waters of about 29 months suggesting that the reaction is insignificant. At this rate it will not compete effectively against the reduction of molecular iodine by organic matter, and hence molecular iodine should not appear. The experiments also consider the photo-oxidation by nitrate, and iodate, a combination of nitrite and oxygen, and eliminate significant interference by chloride, bromide and the phosphate buffer. The rate of photo-oxidation with each of the first three oxidations is found to be first order with respect to oxidant concentration. The variation of photo-oxidation rate with pH is also studied, with a brief investigation without conventional oxidant, where electron cage complexes still promote photo-oxidation. The photochemical action spectrum for these reactions in sunlight is shown to extend between 300 and 425 nm. The photo-oxidation of iodide by iodate is more interesting to marine chemistry as the photo-reduction of iodate. Nevertheless, the reduction-rate is judged to be several orders too low to be significant in seawater. The mechanism of the reactions are discussed and lessons drawn on the stability of potassium iodide solutions used in iodate analysis. The KI actinometer is recommended to those studying other photochemical systems activated by UV-A light as it is linear and very simple and reliable.     

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...     

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.     

The effect of ionic interaction on the rates of oxidation in natural waters

The effect of ionic interactions on the kinetics of disproportionation of HO₂, and the oxidation of Fe(II) and Cu(I) has been examined. The interactions of O₂ with Mg²⁺ and Ca²⁺ ions in seawater increases the lifetime by 3–5 times compared to water. The effect of OH⁻ on the oxidation of Fe(II) in water and seawater shows a second degree dependence from 5 to 45°C. The effect of salinity on the oxidation of Fe(II) was found to be independent of temperature, while the effect of temperature was found to be independent of salinity. The energy of activation for the overall rate constant was found to be 7 ± 0.5 kcal mol⁻¹.The effect of pH, temperature, salinity and ionic composition on the oxidation of Cu(I) has also been examined. In NaCl solutions from 0.5 to 6 M, the log k for the oxidation was a linear function of pH (6–8) with a slope of 0.2 ± 0.05. The reaction was strongly dependent on the Cl⁻ concentration with variation of from 0.3 to 340 min from 0.5 to 6 M Cl⁻. The rates of oxidation of Cu⁺ and CuCl⁰ responsible for these effects are dependent upon ionic strength. The energy of activation for the reaction was 8.5–9.9 kcal mol⁻¹ from 0.5 to 6 M. Studies of the oxidation in various NaX salts (X = I⁻, Br⁻ and Cl⁻) give rates in the order Cl⁻ > Br⁻ > I⁻ as expected, due to complex formation of Cu⁺ with X⁻.     

Influence of the Mediterranean intermediate waters on oxygen distribution in the Atlantic Ocean

The fine structure of oxygen in some regions of the north-eastern Atlantic has been studied. A discrete-continuous inflow of the Mediterranean intermediate water has a strong effect on the O₂ distribution in the layer of the main minimum of oxygen concentration. In general, this layer tends to increase and become more oxygenated when the mean vertical gradients of the oxygen concentration become smaller. Lenses of intrusion and inversion of the seawater with a high O₂ content are observed in the layer. Passage of the lens in the layer of the main minimum of oxygen concentration induces vertical advection of waters and a decrease of the oxygen concentration above and below the lens within 500–700 m. Translated by V. Puchkin.     

Hypoxia by degrees: Establishing definitions for a changing ocean

The marked increase in occurrences of low oxygen events on continental shelves coupled with observed expansion of low oxygen regions of the ocean has drawn significant scientific and public attention. With this has come the need for the establishment of better definitions for widely used terms such as “hypoxia” and “dead zones”. Ocean chemists and physicists use concentration units such as ??molO₂/kg for reporting since these units are independent of temperature, salinity and pressure and are required for mass balances and for numerical models of ocean transport. Much of the reporting of dead zone occurrences is in volumetric concentration units of mlO₂/l or mgO₂/l for historical reasons. And direct measurements of the physiological state of marine animals require reporting of the partial pressure of oxygen (pO₂) in matm or kPa since this provides the thermodynamic driving force for molecular transfer through tissue. This necessarily incorporates temperature and salinity terms and thus accommodates changes driven by climate warming and the influence of the very large temperature range around the world where oxygen limiting values are reported. Here we examine the various definitions used and boundaries set and place them within a common framework. We examine the large scale ocean pO₂ fields required for pairing with pCO₂ data for examination of the combined impacts of ocean acidification and global warming. The term “dead zones”, which recently has received considerable attention in both the scientific literature and the press, usually describes shallow, coastal regions of low oxygen caused either by coastal eutrophication and organic matter decomposition or by upwelling of low oxygen waters. While we make clear that bathyal low oxygen waters should not be confused with shallow-water “dead zones”, as deep water species are well adapted, we show that those waters represent a global vast reservoir of low oxygen water which can readily be entrained in upwelling waters and contribute to coastal hypoxia around the world and may be characterized identically. We examine the potential for expansion of those water masses onto continental shelves worldwide, thereby crossing limits set for many not adapted species.     

(Na,K)-phillipsite: Its stability conditions and geochemical role in the deep sea

Phillipsite occurs in the deep sea in areas of very slow sedimentation and as the final alteration product of basalt, suggesting that it is thermodynamically stable. The thermodynamic data for gibbsite, kaolinite, K-feldspar, Na-feldspar, analcime and H₄ SiO₄ (aq), as well as the activities of seawater constituents are reasonably well known. These values and estimated entropies for Na- and K-phillipsites permit an estimate of the free energy of formation (at 25°C) for Na-phillipsite (5337.6 ± 6.7 kcal/mole) and for K-phillipsite (5382.4 ± 1.9 kcal/mole). The decomposition of phillipsite to analcime at 250°C yields the same result, suggesting that phillipsite is indeed a stable mineral.Phillipsite does not regulate the concentration of Na⁺ and K⁺ in seawater, but probably affects the pH of bottom waters and the composition of interstitial waters. No indications exist of “frozen in” equilibria from hydrothermal reactions at 100–200°C as could be expected by submarine volcanism.     

The analysis of wax esters,very long mid-chain ketones and sterol ethers isolated from walvis bay diatomaceous ooze

Wax esters (ranging from C₃₂ to C₄₄), very long mid-chain ketones (ranging from C₃₁ to C₄₃) and sterol ethers were isolated from Walvis Bay diatomaceous ooze and identified by glass capillary gas chromatography/mass spectrometry and direct probe high-resolution mass spectrometry.The wax ester compositions of co-eluting wax esters with the same molecular weight were determined from fragment ions characteristic for the alcohol and fatty acid moieties. Dominant wax esters are the C₃(16F-20A), C₃₆(18F-18A), C₃₈(16F-22A), C₃₈(18F-20A), C₄₀(18F-22A), C₄₀(20F-20A) and C₄₀(24F-16A).The presence of isoprenoid wax esters and the chain length distributions of alcohol and fatty acid moieties point to an origin from zooplankton. The position of the ketogroup in the mid-chain ketones is determined from characteristic fragment ions. Major ketones are the C₃₈(C₁₈H₃₇-CO-C₁₉H₃₉) and C₄₀(C₁₈H₃₇-CO-C₂₁H₄₃).The sterol ethers have C₈ and C₉ ether moieties and C₂₇, C₂₈, and C₂₉ steroid moieties. The origin and significance of the ketones and the sterol ethers is obscure.