Luminescence quenching of dissolved organic matter in seawater

To characterize more fully the nature of the fluorophores present in the dissolved organic matter found in seawater, steady state and time-resolved measurements of the luminescence quenching of a number of samples of marine dissolved organic matter with known quenchers, such as iodide, acrylamide and methyl viologen (MV) (1,1′-dimethyl-4,4′-bipyridinium), were compared. Quenching characteristics of these systems were analyzed using Stern-Volmer plots for both intensity and lifetime measurements. The bimolecular quenching constants, κ_q, for these quenchers were found to decrease in the order MV²⁺ (κ_q 10¹⁰M⁻¹s⁻¹) > I⁻ (κ_q 2 × 10⁹ M⁻¹ s⁻¹) >CH₂CHCONH₂ (κ_q 2 × 10⁸ M⁻¹ s⁻¹) for the samples measured. The results also show that different samples are quenched to differing extents by the quenchers studied, that ionic strength alters the quenching constants, and that both static and diffusional quenching mechanisms may operate.Such studies are appropriate to the quantification of the reactivity of the singlet states of the chromophores found within marine dissolved organic matter. Although excess energy of the singlet state may be readily transferred to another chemical species, the combination of competing physical deactivation paths and the low concentrations of efficient quenches in the oceans serves to lessen the direct chemical impact of this process.     

The fluorescence of dissolved organic matter in seawater

A total of 28 vertical profiles of seawater fluorescence was measured in the Sargasso Sea, the Straits of Florida, the Southern California Borderlands, and the central Pacific Ocean. In all cases, surface seawater fluorescence was low as a result of photochemical bleaching which occurs on the timescale of hours. Fluorescence of deep water was 2–2.5 times higher than that of surface waters, and was constant, implying a long residence time for fluorescent organic matter, possibly of the order of thousands of years. Fluorescence correlates well with nutrients (NO₃⁻, PO₄³⁻) in mid-depth waters (100–1000 m) in the Sargasso Sea and the central North Pacific, consistent with results in the central Pacific and the coastal seas of Japan. This suggests that regeneration or formation of fluorescent materials accompanies the oxidation and remineralization of settling organic particles.The various sources and sinks of fluorescent organic matter in the global oceans are assessed. The major sources are particles and in situ formation; rivers, rain, diffusion from sediments, and release from organisms are minor sources. The major sink is photochemical bleaching.     

Binding of monomeric organic compounds to marcomolecular dissolved organic matter in seawater

Several monomeric organic compounds, including amino acids, sugars, and fatty acids, were found to bind abiologically to dissolved macromolecular materials in particle-free seawater at natural substrate concentrations. The binding primarily occurred in ocean surface waters, at rates slower than in situ biological utilization rates of most of the compounds. Seasonal patterns of binding in Gulf of Maine waters may have been related to seasonal variations in macroalgal exudation of polyphenolic materials. Enhanced reactivity of relatively hydrophobic monomers implicated hydrophobic effects as potentially important in marine organic condensations. The resultant condensates showed high particle reactivity, consistent with low concentrations of dissolved condensed materials in seawater.     

Speciation of dissolved metals associated with organic matter in coastal seawaters

By combined use of chloroform extraction and Amberlite XAD-2 resin chromatography, metal-organic compounds dissolved in coastal seawaters of Harima Sound, the Seto Inland Sea, were separated into three groups: hydrophobic, hydrophilic neutral and basic, and hydrophilic acidic. The hydrophobic metal-organic compounds, which are associated with organic matter with molecular weight less than 300, accounted for only a small fraction of the metal-organic compounds; 6 % for Cu and an insignificant fraction for Fe, Mn and Zn. The hydrophilic metal-organic compounds with molecular weights between 100 and 1,500 were major components of the metal-organic compounds. The metals associated with the organic matter on average accounted for 12 % of the Fe, 11 % of the Mn, 7 % of the Zn and 23 % of the Cu of the reactive dissolved metals.     

长江口外海水中有色溶解有机物（CDOM）的光吸收特性

基于2008年5、11月2次调查数据,研究了长江口邻近海域水体有色溶解有机物（CDOM）的光吸收特性及其时空分布特征,探讨了CDOM含量、光谱斜率Sg值及其与特征波长下吸收系数a（440）的关系.结果表明,春季该海域有色溶解有机物的吸收系数a（440）的范围为2.232~8.671 m-1,平均值为4.523 m-1;秋季其吸收系数a（440）的变化范围为0.390~6.135 m-1,平均值为2.209 m-1.该水体CDOM吸收曲线基本呈指数衰减趋势.在400~440 nm波段内,春季其光谱斜率Sg值范围为0.002 0~0.014 2 nm-1,平均值为0.008 7 nm-1秋季的介于0.020 8~0.052 6 nm-1之间.平均值为0.037 5 nm-1.同时有色溶解有机物吸收系数a（440）与Sg值存在着较显著的负相关关系.     

Chromophoric dissolved organic matter and dissolved organic carbon in Chesapeake Bay

Chromophoric dissolved organic matter (CDOM) is the light absorbing fraction of dissolved organic carbon (DOC). The optical properties of CDOM potentially permit remote sensing of DOC and CDOM, and correction for CDOM absorption is essential for remote sensing of chlorophyll a (chl a) in coastal and estuarine waters. To provide data for this purpose, we report the distributions of CDOM, DOC, and chl a from seven cruises in Chesapeake Bay in 1994–1997. We observed non-conservative distributions of chl a and DOC in half of the cruises, indicating net accumulations within the estuary; however, there were no net accumulations or losses of CDOM, measured as absorption at 355 nm or as fluorescence. Freshwater end member CDOM absorption varied from 2.2 to 4.1 m⁻¹. Coastal end member CDOM absorption was considerably lower, ranging over 0.4–1.1 m⁻¹. The fluorescence/absorption ratio was similar to those reported elsewhere for estuarine and coastal waters; however, in the lower salinity/high CDOM region of the Bay, the relationship was not constant, suggestive of the mixing of two or more CDOM sources. Chl a was not correlated with the absorption for most of the cruises nor for the data set as a whole; however, CDOM and DOC were significantly correlated, with two groups evident in the data. The first group had high CDOM concentrations per unit DOC and corresponded to the conservative DOC values observed in the transects. The second group had lower CDOM concentrations per unit DOC and corresponded to the non-conservative DOC values associated with net DOC accumulation near the chl a maximum on the salinity gradient. This indicates the production of non-chromophoric DOC in the region of the chl a maximum of Chesapeake Bay. In terms of remote sensing, these data show that (1) the retrieval of the absorption coefficient of CDOM from fluorescence measurements in the Bay must consider the variability of the fluorescence/absorption relationship, and (2) estimates of DOC acquired from CDOM absorption will underestimate DOC in regions with recent, net accumulations of DOC.     

Production of bioavailable and refractory dissolved organic matter by coastal heterotrophic microbial populations

Production of dissolved organic matter (DOM) by heterotrophic microbial communities isolated from Loch Creran (Scotland) was studied in time course incubations in which cells were re-suspended in artificial seawater amended with variable proportions of glucose, ammonium and phosphate. The incubation experiments demonstrated that microheterotrophs released part of the substrate as new DOM, with a production efficiency of 11 ± 1% for DOC, 18 ± 2% for DON and 17 ± 2% for DOP. Estimating the impact of this production in Loch Creran, showed that from 3 ± 1% (DOC) to 72 ± 16% (DOP) of DOM could originate from the heterotrophic microbial community. The produced DOM (PDOM) was both bioavailable (BDOM) and refractory (RDOM). Bioavailability as assessed by the difference between the maximum and the end DOM concentration, was generally higher than found in natural systems, with DOP (73 ± 15%, average ± SD) more bioavailable than DON (70 ± 15%), and DON than DOC (34 ± 13%).The stoichiometry of PDOM was linked to both nutrient uptake and BDOM ratios. Absorption and fluorescence of DOM increased significantly during the incubation time, indicating that microheterotrophs were also a source of coloured DOM (CDOM) and that they produce both bioavailable protein-like and refractory humic-like fluorophores.     

The association of copper,mercury and lead with surface-active organic matter in coastal seawater

Significant fractions of copper (6–30%), lead (3–12%) and mercury (4–50%) were associated with surface-active dissolved or colloidal organic matter isolated from the water column of a controlled experimental ecosystem. Changes in the concentration of surface-active forms of these metals were attributed to release of surface-active metal-binding organic matter during the collapse of a phytoplankton bloom and early diagenesis of settled detritus. Naturally occurring surface-active organic matter can be expected to significantly influence the chemical speciation and transfer of metals across air-water and solid-water interfaces in the marine environment.     

Decomposition and alteration of organic compounds dissolved in seawater

The dissolved organic matter in seawater is grouped into two fractions which are defined as having greatly differing reactivities with respect to both chemical and biological decomposition. One fraction, which constitutes the bulk of the material, is extremely stable and inert and is only slowly degraded by either chemical or biological processes. The other fraction, which is composed of trace organic compounds derived from living organisms, contains components such as free amino acids which are rapidly degraded, probably by marine organisms which use these compounds as a food source. Conclusions about the cycle of organic compounds in seawater based on total organic carbon concentrations could thus be misleading, since pathways involving labile trace organic constituents would be completely obscured. Investigations of the distribution, concentration, and possible diagenetic reactions of specific organic compounds are necessary in order to elucidate the cycle of these compounds in the oceans.     

High molecular weight organic matter in seawater

The presence and nature of high molecular weight organic matter in seawater was critically reviewed and its biogeochemical cycle was discussed.Organic matter that passes through a filter of 0.5–1 μm pore size is called dissolved and that which does not pass through such a filter is defined as particulate. The size of colloidal particles ranges from 0.001 to 1 μm, and therefore, they are included in the dissolved fraction having high molecular weight.High molecular weight organic matter greater than 100,000 molecular weight was found in the seawater of Tokyo Bay. The values ranged from 0.1 to 1.5 mgC/l, and accounted for 8–45% of the total dissolved organic matter.Decomposition experiments on dissolved organic matter showed that macromolecular organic matter is refractory to bacterial attack. However, macromolecular organic materials tend to aggregate or adsorb on small particles to a sufficient size for precipitation. Organic aggregates thus formed sink to the bottom of the sea and bioelements included in them are removed from water column. High molecular weight organic materials are, therefore, considered to play an important role in transportation and distribution of matter in seawater.In order to elucidate the chemical and biological properties of macromolecular organic matter, concentration and isolation of this material are important, using methods such as adsorption on organic adsorbents or ultrafiltration.     

Variations of particulate proteins and dissolved amino acids in coastal seawater

The relationships existing between the protein-containing fraction of particulate matter and amino acids dissolved in seawater were studied in the Gulf of Marseille at different periods of the year. The concentration of particulate proteins was almost zero in February and attained maximum values during April and May, the average concentrations of dissolved amino acids (total) varied between 900 and 1200 nmole l^?1 but larger variations were encountered at the surface and in the vicinity of the sediment. The influence of meteorological conditions and the effect of the sediment on the distribution of nitrogenous substances were taken into account. Combined dissolved amino acids were more abundant than free dissolved amino acids in 90% of the cases. The concentrations of dissolved amino acids observed in a zone bordering the North Mediterranean are comparable to those found in other regions of the world.     

Assessing temporal variation of coloured dissolved organic matter in the coastal waters of South Eastern Arabian Sea

Coloured dissolved organic matter （CDOM） plays a major role in marine photochemical and biological processes and its optical properties are known to affect the underwater light penetration. This paper highlights in situ optical estimation and satellite retrieval of CDOM in deciphering its temporal variations in coastal waters of the South Eastern Arabian Sea. The study accentuated the source of CDOM as terrigenous origin during monsoon, of in situ productions during pre-monsoon and during post-monsoon of autochthonous-allocthonous origin. The matchup analysis for in situ and MODIS Aqua retrieved A_dg443 exhibited bias which decreased by incorporating the seasonal component. The study also identified degrading bloom of Noctiluca scintillans as the source for exceptionally high CDOM in the area during January and February. The study demands to incorporate seasonal components and phytoplankton abundance while assessing the performance of CDOM algorithms in optically complex coastal waters.     

Analytical fractionation of dissolved copper, lead and cadmium in coastal seawater

The speciation of dissolved Cu, Pb and Cd in twelve seawater samples from the Inner Oslofjord, Norway, has been examined by an operational scheme which involves ultrafiltration followed by determination of labile, acid soluble and total Cu, Pb and Cd by differential pulse anodic stripping voltammetry (DPASV). The techniques employed are discussed and evaluated. It was found that Cd was present entirely in low molecular weight (LMW) labile species; Pb was mainly in non-labile LMW species, with half of the total Pb probably occurring in LMW organo-metallic compounds; Cu distribution was irregular, with extensive organic and colloidal association.     

Thermogenic organic matter dissolved in the abyssal ocean

Formation and decay of thermogenic organic matter are important processes in the geological carbon cycle, but little is known about the fate of combustion-derived and petrogenic compounds in the ocean. We explored the molecular structure of marine dissolved organic matter (DOM) for thermogenic signatures in different water masses of the Southern Ocean. Ultrahigh-resolution mass spectrometry via the Fourier transform-ion cyclotron resonance technique (FT-ICR-MS) revealed the presence of polyaromatic hydrocarbons (PAHs) dissolved in the abyssal ocean. More than 200 different PAHs were discerned, most of them consisting of seven condensed rings with varying numbers of carboxyl, hydroxyl, and aliphatic functional groups. These unambiguously thermogenic compounds were homogenously distributed in the deep sea, but depleted at the sea surface. Based on the structural information alone, petrogenic and pyrogenic compounds cannot be distinguished. Surface depletion of the PAHs and first estimates for their turnover rate (> 1.2 · 10¹² mol C per year) point toward a primarily petrogenic source, possibly deep-sea hydrothermal vents, which is thus far speculative because the fluxes of combustion-derived and petrogenic matter to the ocean are not well constrained. We estimate that > 2.4% of DOM are thermogenic compounds, and their global inventory in the oceans is > 1.4 · 10¹⁵ mol C, significantly impacting global biogeochemical cycles.     

海水中溶解有机质对Fe 的迁移转化的影响

<正>Fe是海洋浮游植物生长必需的重要元素,影响浮游植物新陈代谢过程中的各个步骤,对光合作用、呼吸作用过程中电子的传递,氮的还原,叶绿素的合成,以及一些活性氧化物质的降解起到非常重要作用[1]。尽管全球接近30%的大洋表层水中氮、磷、硅营养盐含量丰富,但由于受到Fe限制,出现了高营养盐低生产力现象,这对全球碳循环和气候变化产生重大影响[2,3]。鉴于上述原因,Fe逐渐成为生物地球化学领域的研究热点。国际上对Fe的研究大致经历了三个阶     

Advanced characterization of marine dissolved organic matter by combining reversed-phase liquid chromatography and FT-ICR-MS

Marine dissolved organic matter (DOM) was separated by reversed-phase (RP) liquid chromatography method and analyzed with fluorescence/absorption detection and Fourier transform ion cyclotron mass spectrometry (FT-ICR-MS). The three key characteristics of the RP method are: (a) The C18-RP column chosen provides enhanced separation when the aqueous phase is 100% buffer-free water, and it does not degrade over time; (b) the water eluent adjusted to pH 7 significantly improves the resolution of water soluble compounds; (c) the initial flow maintained at low levels improves the separation of polar compounds. In samples, containing “fresh” DOM, specific peaks were detected, which were absent in “old” DOM samples. The combination with size exclusion chromatography (SEC) also demonstrated the relation between polarity and molecular size of DOM. FT-ICR-MS was applied to evaluate the quality of separation on a molecular scale demonstrating that physico-chemical characteristics of DOM can be related to molecular formulas. Sample extracts were separated into 4 preparative fractions, and a large suite of the identified molecular formulas only occurred in specific fractions. This is an important basis for the application of further analytical techniques in order to perform a more target-oriented analysis aiming at the determination of source and process biomarkers for DOM.     

Bioavailability and bacterial degradation rates of dissolved organic matter in a temperate coastal area during an annual cycle

The bioavailability and bacterial degradation rates of dissolved organic matter (DOM) were determined over a seasonal cycle in Loch Creran (Scotland) by measuring the decrease in dissolved organic carbon (DOC), nitrogen (DON) and phosphorous (DOP) concentrations during long-term laboratory incubations (150 days) at a constant temperature of 14 °C. The experiments showed that bioavailable DOC (BDOC) accounted for 29 ± 11% of DOC (average ± SD), bioavailable DON (BDON) for 52 ± 11% of DON and bioavailable DOP (BDOP) for 88 ± 8% of DOP. The seasonal variations in DOM concentrations were mainly due to the bioavailable fraction. BDOP was degraded at a rate of 12 ± 4% d^– 1 (average ± SD) while the degradation rates of BDOC and BDON were 7 ± 2% d^– 1 and 9 ± 2% d^– 1 respectively, indicating a preferential mineralization of DOP relative to DON and of DON relative to DOC. Positive correlations between concentration and degradation rate of DOM suggested that the higher the concentration the faster DOM would be degraded. On average, 77 ± 9% of BDOP, 62 ± 14% of BDON and 49 ± 19% of BDOC were mineralized during the residence time of water in Loch Creran, showing that this coastal area exported C-rich DOM to the adjacent Firth of Lorne. Four additional degradation experiments testing the effect of varying temperature on bioavailability and degradation rates of DOM were also conducted throughout the seasonal cycle (summer, autumn, winter and spring). Apart from the standard incubations at 14 °C, additional studies at 8 °C and 18 °C were also conducted. Bioavailability did not change with temperature, but degradation rates were stimulated by increased temperature, with a Q₁₀ of 2.6 ± 1.1 for DOC and 2.5 ± 0.7 for DON (average ± SD).     

The relationship between chromophoric dissolved organic matter and dissolved organic carbon in the European Atlantic coastal area and in the West Mediterranean Sea (Gulf of Lions)

The absorption coefficient of chromophoric dissolved organic matter (aCDOM) has been found to be correlated with fluorescence emission (excitation at 355 nm). In the coastal European Atlantic area and in the Western Mediterranean Sea (Gulf of Lions), a significant statistical dependence has been found between aCDOM and fluorescence with dissolved organic carbon (DOC) concentration. The relationship shows that, in the river plume areas (Rhine in the North Sea and Rhône in the Gulf of Lions), a consistent fraction of DOC (from 40% to 60% of the average of the DOC measured) is non-absorbing in visible light range, where the dissolved organic matter (DOM) is typically absorbent. In comparison, in the open sea, apparently not affected by the continental inputs, the entire DOC belongs to the chromophoric DOM whose specific absorption is lower (5 to 10 times) than that found in the river plume areas.     

红树林间隙水溶解态陆源有机质的光降解和生物降解行为分析

红树林输送的溶解态陆源有机质是海洋中陆源有机质的主要来源之一,对其光降解和生物降解过程的研究有助于进一步了解红树林生态系统输出的有机质在近岸的归宿以及对近岸水体生物地球化学过程的影响,因此于2010年4月在海南省清澜港红树林采集间隙水,并进行了光降解和生物降解培养实验。分析了光培养(光降解)和暗培养过程(生物降解)中溶解态有机碳(DOC)、细菌以及溶解态木质素等的变化。结果显示经历128 d的暗培养后,DOC由初始的2 216 μmol/L下降至718 μmol/L,表明红树林间隙水的生物可利用性约为70%左右;经历11 d的自然光照后,DOC下降至800 μmol/L。木质素在光降解过程中的移除速率(-0.132 d-1)远高于生物降解过程(-0.008 d-1)。光培养中,木质素的下降速率高于总体DOC。不同系列溶解态木质素的下降速率不同,随着培养的进行,紫丁香基酚类(S)与香草基酚类(V)的比值(S/V)呈下降趋势,而V系列的酸醛比值((Ad/Al)v)呈上升的趋势。对比光培养和暗培养过程中DOC和木质素的变化可以得出生物消耗是引起红树林间隙水DOC从水体中移除的主要因素;而光照则是陆源有机质从水体中移除的主要因素;光培养和暗培养过程中细菌变化的差异表明光照可以促进细菌对溶解态有机碳的利用。与其他地区比较发现,海南红树林间隙水的光降解速率与热带河流(刚果河)相近,高于温带密西西比河流,降解过程中各参数的变化[S/V和(Ad/Al)v]与其他区域接近。     

养马岛附近海域藻华期间有色溶解有机质的生物可利用性研究

本研究利用吸收光谱和荧光激发-发射矩阵光谱-平行因子分析(EEMs-PARAFAC),研究了养马岛附近海域海水中有色溶解有机质(CDOM)的浓度、组成、来源和生物可利用性,并估算了浮游植物生长繁殖对CDOM及具有生物可利用性CDOM的贡献。结果表明,表、底层海水中CDOM浓度(以吸收系数a₃₅₀计)平均值分别为1.62±0.42 m^-1和1.30±0.47 m^-1,光谱斜率(S_275-295)平均值分别为0.022±0.003 nm^-1和0.023±0.003 nm^-1。利用PARAFAC模型识别出4种荧光组分,分别为陆源类腐殖酸C1、类色氨酸C2、类酪氨酸C3和微生物源类腐殖酸C4。荧光指数(FIX)、腐殖化指数(HIX)和生物指数(BIX)显示,CDOM受陆源输入和海洋自生源的综合影响。降解实验结果显示,表、底层海水中生物可利用性CDOM百分比(%△a₃₅₀)平均值分别为(23.36%±17.94%)和(8.93%±20.30%)。C1、C2和C4组分的荧光强度在培养之后降低,而C3组分的荧光强度上升。各荧光组分生物可利用性依次递减的顺序为:%△C1(23.75%±8.96%)＞%△C4(20.83%±11.71%)＞%△C2(11.67%±38.87%)＞%△C3(-29.61%±39.90%),显示培养之后CDOM的平均分子量和腐殖化程度降低。表层海水中a₃₅₀、%△a350与Chl a之间存在显著线性相关关系,据此可以估算出浮游植物生长繁殖对CDOM的贡献为36.9%,对具有生物可利用性CDOM的贡献为85.0%。