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海水中铁(Ⅲ)-氨基酸盐配合物的光化学反应研究 总被引：2，自引：1，他引：1
系统研究了高压汞灯模拟日光照射下铁(Ⅲ)-氨基酸盐配合物在天然海水中的光化学反应情况,结果发现,在氨基酸盐配体的存在下,铁(Ⅲ)会发生光化学反应生成还原态的铁(Ⅱ),同时生成的铁(Ⅱ)会被容器内的氧再氧化为铁(Ⅲ).铁(Ⅲ)的光还原反应速率会受到配体浓度、pH和光强以及温度的影响.在氨基酸与铁(Ⅲ)浓度配比大于2的情况下,在铁(Ⅲ)氨基酸盐配合物的光还原反应初期铁(Ⅱ)浓度的增长符合一级动力学反应规律,100min后浓度趋于稳定.光强升高和pH降低都能加快光还原速率,而改变温度则基本上对光还原反应速率无影响,这证明铁(Ⅲ)的光还原反应为一自由基引发的电子转移过程. 相似文献
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系统研究了在高压汞灯或天然日光照射下萘在天然海水、人工海水和蒸馏水中的光降解情况。萘的光降解过程受到包括光源、溶液介质、溶解氧、重金属离子、光敏剂在内的各种因素的影响。实验证明，高压汞灯较天然日光更能有效地激发萘的光反应。开始的90min之内，萘的浓度慢慢下降，在照射90－120min后，萘的浓度迅速下降，这是整个萘光解过程中最有效的部分，一级反应速率常数为0.0075-0.0203min^-1。萘在天然海水中的光解速率大于在人工海水和蒸馏水中的光解速率，其主要原因是天然海水中存在天然光敏剂。同蒸馏水中的光反应相比，人工海水中的离子有助于提高萘的光解反应。然而，溶液中加入的重金属离子或光敏剂会改变萘的光解反应。此外，研究证明，溶解氧是必不可少的，它的存在大大加速了光反应。 相似文献
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海水中无机物的光化学反应 总被引：5，自引：0，他引：5
综述了近几十年来国内外关于海水中无机物的光化学反应的研究状况。首先，阐述了海洋光化学在海洋科学中的重要性，历年来的发展状况以及海水的光化学与其它相关领域之间的相互影响作用。其次，本文分别从阴离子的光化学反应，阳离子的光化学反应和过氧化氢的光化学反应三个方面对海水中无机物的光化学反应进行了论述，详细介绍了铁、锰、铜、汞、过氧化氢、硝酸盐和碘化物随反应介质、温度、酸碱度、有机物浓度和光照等外界因素的不同而发生的光化学反应的变化。另外，讨论了上述物质发生光化学反应的主控因素及其在反应过程中对周围环境的影响作用，并对部分物质的反应机理作了介绍。最后，本文指出了这一研究领域存在的问题和不足，并提出今后的研究建议。 相似文献
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以热带库里亚藻(Coolia tropicalis)为研究对象, 在不同锰浓度(0、1、5、10、50μmol·L -1)的人工海水培养15d, 利用叶绿素荧光动力学技术研究了其生长和光合作用对不同锰环境的响应。结果表明: 1)比生长速率(μ)和最大相对电子传递速率(rETRmax)与锰浓度均呈指数关系且对锰胁迫具有相同程度的响应; 2)锰浓度至少大于1μmol·L -1才能维持热带库里亚藻正常的光合作用活性, 当锰浓度低于该浓度时, 光合作用活性(Fv/Fm)在6d后开始下降, 而单位反应中心吸收光能(ABS/RC)和热能耗散(DI0/RC)升高; 两个反应中心之间的电子传递(φE0)及生长并未受影响, 表明此阶段锰缺乏只影响活性光反应中心数量并提高热耗散途径; 当锰缺乏延长至15d时, 胁迫作用显现(F0上升)并且电子传递(φE0)和生长受到抑制, 这阶段锰缺乏使光反应中心关闭且电子传递受阻; 3)锰缺乏的修复损伤比(r/k)并未降低, 表明锰缺乏并未影响热带库里亚藻的光保护能力。 相似文献
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用不同初始浓度的微分法测定了海水中Cu(Ⅱ)与γ-AlOOH,α-FeOOH,无定形-FeOOH,水锰矿,蒙脱石及伊利石之间的交换作用动力学数据。得t=0时上述交换作用为准一级反应,速率常数(25℃)分别为0.110,0.069,0.042,0.214,0.064,0.043(分)-1。活化能分别为12.3,5.8,4.9,<1,10.4,7.1(kcal/mol)。 根据浓度、温度和搅拌速率三者对反应速率的影响,得各反应在初始阶段均为液膜扩散控制(γ-AlOOH体系尚需进一步论证)。 相似文献
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城市污水与海水混合过程中有机污染物的转移 总被引：5，自引：2，他引：5
以３种不同混合体系模拟研究了城市污水与海水混合过程中有机污染物的转移。在“污水颗粒物－过滤海水”体系中，颗粒态有机物有一定的释放，释放率约在０．０２－０．０４ｄ－１之间。释放过程可用交换平衡动力学模式描述。在“天然海水－过滤污水”和“海水－污水”给 体系中，未发现有机污染和有明显的吸附或释放。在这３种混合体系中均发现化学耗氧量（ＣＯＤ）的降解现象，降解过程符合一级动力学方程，降解速率常数在０．０４ 相似文献
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实验研究水溶液中二甲基硫（ＤＭＳ）和Ｈ２Ｏ２进行氧化反应的动力学。结果表明ＤＭＳ被Ｈ２Ｏ２氧化的速率会受到介质、ｐＨ以及重金属离子的影响。其二级反应速率常数为２．２１×１０－２～４．９０×１０－２Ｌ·ｍｏｌ－１·Ｓ－１．Ｈｇ２＋的存在会加快反应速率，特别在人工海水条件下十分明显。ＤＭＳ易被Ｈ２Ｏ２氧化的事实说明，在海水中化学氧化过程会对ＤＭＳ的浓度和分布产生重要影响 相似文献
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Dimethylsulfide(DMS) is generally thought to be lost from the surface oceans by evasion into the atmosphere as well as consumption by microbe.However,photochemical process might be important in the removal of DMS in the oceanic photic zone.A kinetic investigation into the photochemical oxidation of DMS in seawater was performed.The photo-oxidation rates of DMS were influenced by various factors including the medium,dissolved oxygen,photosensitizers,and heavy metal ions.The photo-oxidation rates of DMS were higher in seawater than in distilled water,presumably due to the effect of salinity existing in seawater.Three usual photosensitizers(humic acid,fulvic acid and anthroquinone),especially in the presence of oxygen,were able to enhance the photo-oxidation rate of DMS,with the fastest rate observed with anthroquinone.Photo-oxidation of DMS followed first order reaction kinetics with the rate constant ranging from 2.5×10-5 to 34.3×10-5 s-1.Quantitative analysis showed that approximately 32% of the photochemically removed DMS was converted to dimethylsulfoxide.One of the important findings was that the presence of Hg2 could markedly accelerate the photo-oxidation rate of DMS in seawater.The mechanism of mercuric catalysis for DMS photolysis was suggested according to the way of CTTM(charge transfer to metal) of DMS-Hg2 complex. 相似文献
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《Marine Chemistry》2007,103(1-2):46-60
Microbial and photochemical processes affect chromophoric dissolved organic matter (CDOM) dynamics in the ocean. Some evidence suggests that dissolved nitrogen plays a role in CDOM formation, although this has received little systematic attention in marine ecosystems. Coastal seawater incubations were carried out in the presence of model dissolved organic nitrogen (DON: amino sugars and amino acids) and dissolved inorganic nitrogen (DIN) compounds to assess their role in biological and photochemical production of CDOM. For several of the dissolved N compounds, microbial processing resulted in a pulse of CDOM that was mainly labile, appearing and disappearing within 7 days. In contrast, a net loss of CDOM occurred when no N was added to the microbial incubations. The greatest net biological CDOM formation was found upon addition of amino sugars (formation of fluorescent, mostly labile CDOM) and tryptophan (formation of non-fluorescent, refractory CDOM). Photochemical formation of CDOM was only found with tryptophan, the one aromatic compound tested. This CDOM was highly fluorescent, with excitation–emission matrices (EEMs) resembling those of terrestrial, humic-like fluorophores. The heterogeneity in CDOM formation from this collection of labile N-containing compounds was surprising. These compounds are common components of biopolymers and humic substances in natural waters and likely to contribute to microbially- and photochemically-produced CDOM in coastal seawater. 相似文献
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Pentachlorophenol (PCP) and 3,4-dichloroaniline (DCA) were used as models to examine photochemical reactions in seawater.The photolysis of PCP in seawater differed in both rate and product distribution from that in distilled water; rates were slower in seawater due to the photonucleophilic interaction of PCP with chloride ions, demonstrated by the formation of 36Cl-labeled PCP in irradiated PCP solutions containing Na36Cl. DCA showed no rate change and gave identical products in both systems. Both PCP and DCA yielded greater amounts of photoreduction products in seawater than in distilled water, and tetrachloromuconic acid was isolated and identified as a new and unstable PCP photoproduct resulting from ringfission. This study demonstrates the operation of photooxidation, photonucleophilic substitution, and photoreduction reactions which differ in detail between seawater and distilled water and suggests that photochemical reactions can be a major factor in the breakdown of organic pollutants and other chemicals in the marine environment. 相似文献
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The aqueous photochemical transformation of acrylic acid 总被引：3，自引：0，他引：3
Acrylic acid in sea water is thought to occur mostly as the product of microbial cleavage of dimethylsulphoniopropionate (DMSP), but could also be a pollutant introduced by waste waters of the organic chemical industry. Solutions of acrylic acid in natural and artificial sea water, and distilled and riverine water were photolyzed using a photochemical reactor and exposure to sunlight. The transformation of acrylic acid comprises the decarboxylation of the carboxylic group and subsequent polymerization to a polyethylene type molecule. Kinetic studies showed the lowest reaction rate in distilled water and somewhat higher and very similar rates in other aqueous media. The approximately similar reaction rates in all natural waters studied suggest that inorganic ions, especially Na+, Mg2+ and halides, and dissolved organic matter (probably humics) enhance the reaction rates. On studying the influence of different concentration ranges on the reaction kinetics, an exponential increase of rates with decreasing concentration was found. The reaction rate in the sea water solution in field conditions is rather slow. In thirty days exposure about 15% of the reactant was transformed. This reaction seems to be important in the marine environment in specific conditions, especially in phycospheres and macroaggregates where higher concentrations of acrylic acid inhibit the bacterial metabolism. 相似文献
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A technique for the pH-controlled isolation and separation of dissolved copper—organic substances from large amounts of seawater is described. The method has been applied in two cruises in the Bothnian and Gotland Seas of the Baltic. In both areas the correlation between the amount of isolated dissolved organic material (DOM) and the concentration of organic copper in seawater has been found to be highly significant. Under the conditions established in our experiments, organic copper fractions detected in Baltic waters were in the range of about 5% of total copper. HPLC chromatograms and UV irradiation experiments from DOM extracts strongly indicate the existence of dissolved organic-copper compounds in Baltic waters. 相似文献
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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. 相似文献
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Results from laboratory studies indicated that low molecular weight (LMW) carbonyl compounds, especially formaldehyde, acetaldehyde, acetone and glyoxal, can be formed in seawater by photochemical processes. Once formed, these compounds appear to be readily consumed by biota. These results suggest that concentrations of LMW carbonyl compounds should undergo diurnal variations in the illuminated layer of the sea. In support of this, diurnal fluctuations of LMW carbonyl concentrations were observed in humic-rich surface waters off the west coast of Florida over a three day sampling period using a shipboard HPLC system. Fluctuations in acetaldehyde were particularly strong and reproducible, with steady night-time concentrations of 2–3 nM and day-time concentrations reaching a maximum of 20–30 nM in the early afternoon. In contrast, diurnal fluctuations in formaldehyde were less distinct, ranging from 15 to 50 nM.The laboratory and field results are discussed in terms of biotic/abiotic sources and sinks of LMW carbonyl compounds in surface seawater. It is speculated that photooxidative cleavage of biologically refractory dissolved organic matter (DOM) in seawater to yield LMW organic fragments, such as carbonyl compounds, may be important in the breakdown and geochemical cycling of DOM in the ocean. 相似文献
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Pierre Anschutz Thomas SmithAurélia Mouret Jonathan DebordeStéphane Bujan Dominique PoirierPascal Lecroart 《Estuarine, Coastal and Shelf Science》2009
Sandy sediments of continental shelves and most beaches are often thought of as geochemical deserts because they are usually poor in organic matter and other reactive substances. The present study focuses on analyses of dissolved biogenic compounds of surface seawater and pore waters of Aquitanian coastal beach sediments. To quantitatively assess the biogeochemical reactions, we collected pore waters at low tide on tidal cross-shore transects unaffected by freshwater inputs. We recorded temperature, salinity, oxygen saturation state, and nutrient concentrations. These parameters were compared to the values recorded in the seawater entering the interstitial environment during floods. Cross-shore topography and position of piezometric level at low tide were obtained from kinematics GPS records. Residence time of pore waters was estimated by a tracer approach, using dissolved silica concentration and kinetics estimate of quartz dissolution with seawater. Kinetics parameters were based on dissolved silica concentration monitoring during 20-day incubations of sediment with seawater. We found that seawater that entered the sediment during flood tides remained up to seven tidal cycles within the interstitial environment. Oxygen saturation of seawater was close to 100%, whereas it was as low as 80% in pore waters. Concentrations of dissolved nutrients were higher in pore waters than in seawater. These results suggest that aerobic respiration occurred in the sands. We propose that mineralised organic matter originated from planktonic material that infiltrated the sediment with water during flood tides. Therefore, the sandy tidal sediment of the Aquitanian coast is a biogeochemical reactor that promotes or accelerates remineralisation of coastal pelagic primary production. Mass balance calculations suggest that this single process supplies about 37 kmol of nitrate and 1.9 kmol of dissolved inorganic phosphorus (DIP) to the 250-km long Aquitanian coast during each semi-diurnal tidal cycle. It represents about 1.5% of nitrate and 5% of DIP supplied by the nearest estuary. 相似文献
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Joan D. Willey 《Marine Chemistry》1977,5(3):267-290
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. 相似文献
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海水中的一氧化碳(CO)主要由溶解有色有机物(CDOM)光降解产生,且CO的光致生成量受到环境因素的影响。采集了胶州湾及其河口表层水样,通过实验室模拟实验开展了不同的环境条件(辐射强度、光照时间、温度、pH和盐度)以及水体中CDOM的来源对CO光致生成的影响研究。结果表明胶州湾海水中CO的光致生成速率随辐射强度的增强、水温的升高和水体pH的增大而增大;随着光照时间的延长、水体盐度的增大而逐渐减小;不同来源的CDOM对水体中CO的光致生成速率产生了不同的影响。 相似文献