Relationship between the optical properties of chromophoric dissolved organic matter and total concentration of dissolved organic carbon in the southern Baltic Sea region

Absorption and fluorescence of chromophoric dissolved organic matter (CDOM) and dissolved organic carbon (DOC) measurements were performed during three oceanographic surveys in 1994 in the southern Baltic Sea (Polish area of the Baltic Proper). DOC was measured both by high-temperature catalytic oxidation (HTCO) and low-temperature oxidation (LTO) conventional persulphate methods. CDOM fluorescence was shown to be highly correlated with absorption, with the same regression parameters, despite the seasonal change in different hydrographic conditions and the fluorescence quantum yield variations (1.23 ± 0.07 in April and 0.97 ± 0.12 in September). The results show a good correlation between the optical parameters and DOC although ˜ 70% of the DOC does not display significant absorption in the UV-visible range (350–750 nm). The non-absorbing DOC measured with HTCO method appears unaffected by seasonal changes. Consequently, total DOC can be predicted by optical methods using remote sensing techniques. The non-absorbing DOC measured by LTO method varies from 62% (April) to 76% (September), which implies that there is requirement for estimates on a seasonal basis.     

Characterization of chromophoric dissolved organic matter (CDOM) in the Baltic Sea by excitation emission matrix fluorescence spectroscopy

Chromophoric dissolved organic matter (CDOM) is the major light absorber in the Baltic Sea. In this study, excitation emission matrix (EEM) fluorescence spectra and UV–visible absorption spectra of CDOM are reported as a function of salinity. Samples from different locations and over different seasons were collected during four cruises in 2002 and 2003 in the Baltic Sea in both Pomeranian Bay and the Gulf of Gdansk. Absorption by CDOM decreased with increased distance from the riverine source and reached a relatively stable absorption background in the open sea. Regression analysis showed that fluorescence intensity was linearly related to absorption by CDOM at 375 nm and a_CDOM(375) absorption coefficients were inversely related to salinity. Analysis of CDOM-EEM spectra indicated that a change in composition of CDOM occurred along the salinity gradient in the Baltic Sea. Analysis of percent contribution of respective fluorophore groups to the total intensity of EEM spectra indicated that the fluorescence peaks associated with terrestrial humic components of the CDOM and total integrated fluorescence decreased with decreasing CDOM absorption. In contrast, the protein-like fraction of CDOM decreased to a lesser degree than the others. Analysis of the percent contribution of fluorescence peak intensities to the total fluorescence along the salinity gradient showed that the contribution of protein-like fluorophores increased from 2.6% to 5.1% in the high-salinity region of the transect. Fluorescence and absorption changes observed in the Baltic Sea were similar to those observed in similar transects that have been sampled elsewhere, e.g. in European estuaries, Gulf of Mexico, Mid-Atlantic Bight and the Cape Fear River plume in the South Atlantic Bight, although the changes in the Baltic Sea occurred over a much smaller salinity gradient.     

夏季黄海不同水团溶解有机物分布特征

依据2017年8—9月对黄海海域溶解有机物(DOM)的调查,探讨了夏季黄海海水中溶解有机碳(DOC)和有色溶解有机物(CDOM)的空间分布特征。在表层海水中,受陆源影响较大的近岸海域CDOM含量相对较高,北黄海冷水团区域由于水产养殖的饵料引起DOC浓度升高,且该部分DOC以无色为主。DOC浓度随深度逐渐降低,而CDOM逐渐升高,该特征在冷水团区域更为显著,因此DOC和CDOM在冷水团区域的表底差异远大于浅水区的非冷水团区域。陆源输入和初级生产是引起表层DOC升高的主要原因,而光漂白则引起CDOM降低,同时光漂白还导致表层水体中CDOM分子量和芳香性低于底层。底层溶解氧饱和度在冷水团为80%～93%,均表现为弱不饱和状态。层化不仅阻碍了O₂向底层水体输送,还抑制了DOC和CDOM的垂向混合,这是引起冷水团区域表底层DOC和CDOM差异较大的主要原因。     

Tracing dissolved organic matter in aquatic environments using a new approach to fluorescence spectroscopy

Dissolved organic matter (DOM) is a complex and poorly understood mixture of organic polymers that plays an influential role in aquatic ecosystems. In this study we have successfully characterised the fluorescent fraction of DOM in the catchment of a Danish estuary using fluorescence excitation–emission spectroscopy and parallel factor analysis (PARAFAC). PARAFAC aids the characterisation of fluorescent DOM by decomposing the fluorescence matrices into different independent fluorescent components. The results reveal that at least five different fluorescent DOM fractions present (in significant amounts) in the catchment and that the relative composition is dependent on the source (e.g. agricultural runoff, forest soil, aquatic production). Four different allochthonous fluorescent groups and one autochthonous fluorescent group were identified. The ability to trace the different fractions of the DOM pool using this relatively cheap and fast technique represents a significant advance within the fields of aquatic ecology and chemistry, and will prove to be useful for catchment management.     

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.     

The satellite reversion of dissolved organic carbon (DOC) based on the analysis of the mixing behavior of DOC and colored dissolved organic matter: the East China Sea as an example

The retrieval of dissolved organic carbon (DOC) distribution by remote sensing is mainly based on the empirical relationship of DOC concentration and colored dissolved organic matter (CDOM) concentration in many literatures. To investigate the nature of this relationship, the distributions and mixing behaviors of DOC and CDOM are reviewed in the world’s major estuaries and bays. It is found that, generally, the CDOM concentration is well correlated with the salinity in most estuaries, while DOC usually shows a nonconservative behavior which leads to a weak correlation between the DOC concentration and the CDOM concentration. To establish a good satellite reversion of the DOC concentration, the East China Sea(ECS) was taken as an example, and the mixing behavior of DOC and CDOM as well as the influence of biogeochemical processes were analyzed except for the physical mixing process with the data from late autumn (November, 2010) and winter (December, 2009) cruises. In the two ECS cruises, the CDOM concentration was found to be tightly correlated with the salinity, influenced little by the photochemical or biological processes. The data from the winter cruise show that DOC followed a conservative mixing along the salinity gradient, while in the late autumn cruise it was significantly affected by the biological activities, resulting in a poor correlation between the DOC and the CDOM. Accordingly, an improved DOC algorithm (CSDM) was proposed: when the biological influence was significant (Chl a greater than 0.8 μg/dm3 ), DOC was retrieved by the conservative and biological model, and if the conservative mixing was dominant (Chl a less than 0.8 μg/dm3 ), the direct DOC concentration and CDOM concentration relationship was used. Based on the proposed algorithm, a reasonable DOC distribution for the ECS from satellite was obtained in this study, and the proposed method can be applied to the other large river-dominant marginal sea.     

Photochemical production of molecular hydrogen in lake water and coastal seawater

Samples of lake water and coastal seawater from Nova Scotia, Canada, were irradiated with natural or artificial sunlight to investigate the potential for photochemical hydrogen production. Hydrogen photo-production was observed in all natural water samples. Rates of hydrogen formation were highest in coloured lake water (range: 98–163 pmol L^− 1h^− 1) and lower in seawater (range: 19–45 pmol L^− 1 h ^− 1). Dilutions of the most highly coloured lake sample (Kejimkujik Lake) showed a positive linear relationship between H₂ production rates and CDOM concentration. Photo-production rates normalised to UV absorption coefficients at 350 nm indicated that the photochemical efficiency of hydrogen formation varied between samples, perhaps due to differences in the CDOM composition. Photochemical hydrogen formation was also seen in solutions of syringic acid and acetaldehyde: two low-molecular-weight carbonyl compounds found in natural waters. Photochemistry may therefore offer least a partial explanation for the persistently high levels of hydrogen observed in the low-latitude surface ocean.     

地中海黄色物质次表层极大值的季节变化观测

首次通过2008-2009年在西北地中海和东地中海海域投放的两台Bio-Argo浮标的观测数据,分析与研究了该海区黄色物质次表层极大值的季节变化规律.研究表明次表层黄色物质在夏季开始爆发,伴随着叶绿素a浓度的逐渐降低;到冬季在强烈的垂向混合作用下结束.且黄色物质极大值的深度与叶绿素a浓度极大值(DCM)的深度基本一致,说明虽然黄色物质与浮游植物之间并不存在直接联系,但浮游植物的降解是黄色物质的主要来源.文中推测,可能由于该海区浮游植物与微生物的强耦合,导致了黄色物质与叶绿素a之间存在明显的反变关系.     

Production of chromophoric dissolved organic matter by Sargasso Sea microbes

Time series of chromophoric dissolved organic matter (CDOM) light absorption coefficients indicate a local origin for a large fraction of the CDOM in the upper water column of the Sargasso Sea. In the present study, we demonstrate that CDOM is produced in bacterial culture experiments using Sargasso Sea water and naturally occurring microbial assemblages. Seawater cultures were prepared and grown at in situ temperatures in the dark for periods of weeks. Selected cultures were treated with amendments including inorganic nutrients, glucose, phytoplankton exudates, and zooplankton excretia. In all experiments, when bacterial biomass increased, CDOM increased during the first week of the experiment, followed by a decrease over a longer period of time. Cultures amended with both glucose and inorganic nitrogen and phosphorus produced more CDOM than controls or cultures amended with glucose or inorganic nutrients alone. However, when complex DOM substrates (derived from phytoplankton or zooplankton cultures) were added to seawater cultures, there was a net accumulation of CDOM over the course of the experiments. These data suggest that, in addition to microbial growth, the quality of the substrate plays an important role in net CDOM production. ‘New’ CDOM produced in culture was spectroscopically similar to CDOM appearing below the surface during summer stratification. The results of the present study support a new paradigm for CDOM in the open ocean, which allows for local origin and significant dynamics. Appreciation of CDOM dynamics will, in turn, add to our understanding of microbial productivity, photochemical rate processes, and ultraviolet radiation availability in the global ocean.     

南海北部海水中氨基酸的分布及其对溶解有机物降解行为的指示研究

于2015年6月对南海北部海区5个断面共26个站位海水中溶解态氨基酸（THAA）、溶解有机碳（DOC）和叶绿素a（Chl a）的浓度进行了科学调查。结果表明:夏季南海北部海水中THAA的浓度范围为0.40~1.95 μmol/L,平均值为（0.80±0.40） μmol/L,THAA的水平分布总体上体现出近岸高、远海低的特点,表明陆源输入对南海北部海域表层THAA分布有重要影响。THAA在断面上的垂直分布呈现出由近岸至远岸、由表层至底层逐渐降低的趋势。THAA浓度与两种D型氨基酸（D-谷氨酸:D-Glu和D-丙氨酸:D-Ala）含量之间存在显著负相关性,与天门冬氨酸/β-丙氨酸（Asp/β-Ala）和谷氨酸/γ-氨基丁酸（Glu/γ-Aba）比值之间存在显著正相关性,表明细菌的消耗是影响南海海水中THAA浓度的重要因素。D-Ala作为细菌肽聚糖中相对稳定的氨基酸,根据其占DOC的含量估算南海海水中的细菌源有机碳对DOC的贡献率为（29.32±14.32）%,其水平分布显示出近岸低、远岸高的特点;而其垂直分布则呈现出从表层至底层逐渐增加的趋势。THAA占DOC百分比（THAA-C%）的变化范围为1.02%~5.49%,平均值为（2.97±1.38）%。THAA-C%、活性因子和降解因子的高值均出现在珠江口外围区域。随着海水深度增加3种降解因子的数值均显著降低,这表明底层海水中有机物比表层海水中的有机物降解程度更大。     

Photoreactivity of chromophoric dissolved organic matter transported by the Mackenzie River to the Beaufort Sea

The photoreactivity of chromophoric dissolved organic matter (CDOM) transported to Arctic shelf environments by rivers has only recently been studied and its quantitative role in Arctic shelf biogeochemistry has received little attention. Sunlight exposure experiments were performed on CDOM collected over a three year period (2002 to 2004) from river, estuary, shelf, and gulf regions of the Western Canadian Arctic. Decreases in CDOM absorption, synchronous fluorescence (SF), and dissolved organic carbon (DOC) concentration were followed after 3 days of exposure, and in two experiments, six optical cutoff filters were used to incrementally remove ultraviolet radiation incident on the samples. Apparent quantum yields for CDOM photobleaching (AQY_ble) and for DOC photomineralization (AQY_min) were computed, as were two AQY spectra (_ble and _min) for the Mackenzie River and a sample from the Mackenzie Shelf. The photoreactivity of Mackenzie River CDOM was highest after break-up and peak discharge and lowest in late summer. The half-lives of CDOM and DOC were estimated at 3.7 days and 4.8 days, respectively, when Mackenzie River water was exposed to full sunlight. Photobleaching of Mackenzie River CDOM fluorescence after most UV-B wavelengths were removed increased the correlation between the river and offshore waters in the Beaufort Sea. When light attenuation from particle- and CDOM-rich river water was considered for the Mackenzie Shelf, our photodegradation models estimated around 10% loss of absorption and < 1% DOC loss, suggesting that sunlight exposure does not substantially degrade CDOM on Arctic shelves.     

北极孔斯峡湾表层沉积物中溶解有机质的来源与转化历史

在北极地区孔斯峡湾采集28个表层沉积物样品,测定了其中水溶性有机质(也称溶解有机质,DOM)的分子量分布、紫外/可见吸收光谱和三维荧光光谱特征,并利用平行因子分析(PARAFAC)模型对DOM的荧光组分和来源进行了解析。结果表明:孔斯峡湾表层沉积物中有色溶解有机质(CDOM)及其中的荧光溶解有机质(FDOM)含量均从内湾向外湾方向呈逐渐累积的趋势,但CDOM中的FDOM所占比例逐渐减小,与DOM趋于老龄化密切相关。沉积作用减弱以及长期的光化学降解和微生物降解作用对此起主要贡献,并导致腐殖质和小分子组分在沉积物DOM中所占的比例呈逐渐递增的趋势。沉积物DOM包含陆源类腐殖质、自生源类腐殖质和类蛋白等三个荧光组分,但是其组成比例空间差异很大。吸收光谱斜率比(S_R)随自生源所占百分比增加而减小,随DOM腐殖质组分中陆源与自生源的比值增加而增加;腐殖化指数(HIX)随类腐殖质与类蛋白质比值和水深的增加而增加,生物源指数(BIX)随自生源比例增加而增加。峡湾沉积物DOM的组成和来源存在着高度的空间差异,在冰川湾区由水体颗粒有机质(POM)的近期转化和迁移而来,而在峡湾中央及口门附近以较老的腐殖质为优势,主要源于水体DOM长期迁移和转化。研究表明,FDOM/CDOM,S_R,HIX和BIX等构成的CDOM光谱指纹信息可以作为揭露沉积物溶解有机质来源及迁移转化历史的工具,对探索海洋与冰川相互作用影响下的峡湾环境演变有着重要意义。     

Seasonal dynamics of light absorption by chromophoric dissolved organic matter (CDOM) in the NW Mediterranean Sea (BOUSSOLE site)

We analyze a two-year time-series of chromophoric dissolved organic matter (CDOM) light absorption measurements in the upper 400 m of the water column at the BOUSSOLE site in the NW Mediterranean Sea. The seasonal dynamics of the CDOM light absorption coefficients at 440 nm (a_cdom(440)) is essentially characterized by (i) subsurface maxima forming in spring and progressively reinforcing throughout summer, (ii) impoverishment in the surface layer throughout summer and (iii) vertical homogeneity in winter. Seasonal variations of the spectral dependence of CDOM absorption, as described by the exponential slope value (S_cdom), are characterized by highest values in summer and autumn at the surface and low values at the depths of a_cdom(440) subsurface maxima or just below them. Variations of a_cdom(440) are likely controlled by microbial digestion of phytoplankton cells, which leads to CDOM production, and by photochemical destruction (photobleaching), which leads to CDOM degradation. Photobleaching is also the main driver of S_cdom variations. Consistently with previous observations, a_cdom(440) for a given chlorophyll a concentration is higher than expected from Case I waters bio-optical models. The total non-water light absorption budget shows that surface waters at the BOUSSOLE site are largely dominated by CDOM during all seasons but the algal bloom in March and April. These results improve the knowledge of CDOM absorption dynamics in the Mediterranean Sea, which is scarcely documented. In addition, they open the way to improved algorithms for the retrieval of CDOM absorption from field or satellite radiometric measurements.     

Exudation and decomposition of chromophoric dissolved organic matter (CDOM) from some temperate macroalgae

The quantity of chromophoric or coloured dissolved organic matter (CDOM) released by eleven species of intertidal and sub-tidal macroalgae commonly found on UK shores was investigated. The subsequent breakdown of CDOM was also measured by exposing collected CDOM samples to light and dark conditions for over two weeks. CDOM absorption properties were compared at a fixed wavelength of 440 nm and across two integrated wave - bands; UV-A (400–315 nm) and UV-B (315–280 nm). Absorption spectra of macroalgal CDOM samples were typically characterized by peaks and shoulders in the UV bands, features which were species specific. The spectral slope, derived using the log-linear method, proved to be very specific to the species and to the effect of light. Slope measurements ranged from 0.010 to 0.027 nm⁻¹, in the range of normal seawater values. Significantly more CDOM was produced by algae which were illuminated, providing evidence for a light driven exudation mechanism. Averaged across all species, exudation in the dark accounted for 63.7% of that in the light in the UV-B band. Interspecific differences in exudation rate encompassed an order of magnitude, with the highest absorption measurements attributable to brown algae. However, some brown algae produced considerably less CDOM (e.g. Pelvetia canaliculata), which were more comparable to the green and red species. Over an exposure time of 16 days, significant photochemical degradation of CDOM was observed using a natural summer sunlight regime, showing that natural solar radiation could be an important removal mechanism for newly produced algal CDOM. Though the most obvious effect was a decrease in absorption, photo-bleaching also caused a significant increase in the spectral slope parameter of 0.004 nm⁻¹.     

舟山海域陆源溶解有机质变化及其对近岸羽状流的响应

2007年夏季在东海舟山海域河口锋区开展了陆源溶解有机质的调查研究。测定了有色溶解有机质(CDOM)在激发波长370 nm/发射波长460 nm处的荧光强度和在λ=355 nm处的吸收系数,用于代表陆源CDOM浓度,并测定了荧光指数以指示CDOM来源。结果表明,CDOM的荧光值和紫外吸收系数之间呈显著正相关性,陆源CDOM浓度大体有向海方向降低的趋势,但是纵向上存在一些"突跃"现象。在舟山海域东北角不时观测到表层水体含有高浓度的CDOM,但变异性很大,推测可能该海区受到长江口羽状流的影响。在连续观测站发现陆源CDOM浓度在低平潮时往往比高平潮时要高。河海水在混合过程中CDOM浓度与盐度呈显著的线性负相关关系。在低盐度的悬沙锋区(S<24)CDOM浓度明显低于理论稀释值,而在较高盐度的羽状锋区,CDOM浓度接近于理论稀释值。在盐度为24~31范围内,大部分水样的荧光指数在1.50上下波动,表明其中CDOM来源以陆地来源为主;在较低盐度(S<24)的水样中荧光指数在1.70至1.90以上,表明CDOM以海洋来源为主,这与其陆源组分在高浊度的低盐度区存在显著的去除过程有关。研究表明,舟山海域水质存在着显著的变异性,与近岸羽状流密切相关,陆源溶解有机质的分布特征对此有较好的响应。     

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。     

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.     

溶解有机物的光降解及其对浮游细菌和浮游植物的影响

作为海洋中最大的动态有机碳储库,溶解有机物的光降解(主要是紫外波段)对生源要素的生物地球化学循环以及海洋生态系统的结构和功能具有重要的影响。本文探讨了影响溶解有机物光降解的环境因素、其光化学过程和产物,并重点阐述了溶解有机物的光降解对浮游细菌和浮游植物的影响。溶解有机物的来源和成分复杂,其光降解在不同海区有不同的生态效应,为了能更准确地把握其生态效应,需要更全面和深入的研究。