Tracing terrigenous dissolved organic matter and its photochemical decay in the ocean by using liquid chromatography/mass spectrometry

Reversed-phase liquid chromatography/mass spectrometry (LC/MS) is introduced as a new molecular fingerprinting technique for tracing terrigenous dissolved organic matter (DOM) and its photochemical decay in the ocean. DOM along a transect from the mangrove-fringed coast in Northern Brazil to the shelf edge was compared with mangrove-derived porewater DOM exposed to natural sunlight for 2–10 days in a photodegradation experiment. DOM was isolated from all samples via solid-phase extraction (C18) for LC/MS analysis. DOM in the estuary and ocean showed a bimodal mass distribution with two distinct maxima in the lower m/z range from 400 to 1000 Da (intensity-weighted average of 895 Da). Terrigenous porewater DOM from the mangroves was characterized by a broad molecular mass distribution over the detected range from 150 to 2000 Da (intensity-weighted average of 1130 Da). Polar compounds, i.e., those that eluted early in the reversed-phase chromatography, absorbed more UV light and had on average smaller molecular masses than the more apolar compounds.     

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.     

Potential source and diagenetic signatures of oceanic dissolved and particulate organic matter as distinguished by lipid biomarker distributions

Potential biogenic sources of ultrafiltered dissolved and suspended particulate organic matter (UDOM and POM, respectively) from the Sargasso Sea (SS) and North Central Pacific (NCP) Ocean were investigated using lipid biomarker compounds. Organic carbon (OC) concentrations were ~ 20–40 times greater in UDOM than POM and decreased with depth. However, total OC-normalized lipid concentrations were 2–3 orders of magnitude higher in POM than in UDOM. Particulate total lipids decreased 3–10-fold with depth, compared to 10–20% for dissolved total lipids. Total fatty acids (FA), the most abundant lipids, showed similar patterns as total lipids, comprising ~ 62–88% of the total lipids analyzed in UDOM and ~ 57–84% in POM.FA were dominated by straight-chain saturated compounds followed by monounsaturated, polyunsaturated, and branched FA. Polyunsaturated FA were enriched in POM vs. UDOM and in surface vs. deep waters for both UDOM and POM, likely reflecting the algal origins and greater reactivity of surface-derived materials. In both UDOM and POM, sterols of planktonic origin dominated, including cholest-5-en-3β-ol (C₂₇Δ⁵), 24-methylcholesta-5,24(28)E-dien-3β-ol (C₂₈Δ^5,24(28)) and 24-ethylcholest-5-3β-ol (C₂₉Δ⁵), with varying contributions from cholesta-5,22E-3β-ol (C₂₇Δ^5,22), 24-methylcholesta-5,22E-3β-ol (C₂₈Δ^5,22) and 24-ethylcholesta-5,22E-3β-ol (C₂₉Δ^5,22).Factor analysis of lipid biomarkers showed major differences between the UDOM and POM pools and for each pool as a function of depth, but not between the SS and NCP. While UDOM and POM biomarkers were both dominated by autochthonous sources, differences between the two pools suggest potential effects from some combination of source and diagenetic factors. The lipid biomarker data are further evaluated relative to previous studies of radiocarbon (¹⁴C) and elemental (C:N:P) characteristics of UDOM and POM in the SS and NCP.     

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.     

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.     

Seasonal trends in the abundance, composition and bioavailability of particulate and dissolved organic matter in the Chukchi/Beaufort Seas and western Canada Basin

The objectives of this study were to investigate the seasonality, abundance, sources and bioreactivity of organic matter in the water column of the western Arctic Ocean. The concentrations of particulate and dissolved amino acids and amino sugars, as well as bulk properties of particulate and dissolved organic matter (DOM), were measured in shelf, slope and basin waters collected during the spring and summer of 2002. Particulate organic matter concentrations in shelf waters increased by a factor of 10 between spring and summer. Dissolved organic carbon (DOC) and nitrogen (DON) concentrations exhibited only minor seasonal variations, whereas dissolved amino acid concentrations doubled between spring and summer, and dissolved amino sugars increased by 31% in shelf waters of the Chukchi and Beaufort Seas. Concentrations of DOC did not exhibit a significant seasonal change in surface waters of the Canada Basin, but dissolved amino acid concentrations increased by 45% between spring and summer. No significant seasonal differences were detected in the concentration or composition of DOM in waters below 100 m in depth. Concentrations of particulate and dissolved amino acids and amino sugars were strongly correlated with chlorophyll-a, indicating a plankton source of freshly produced organic matter. The amino acid and amino sugar compositions of freshly produced DOM indicated that a large portion of this material is bioavailable. While freshly produced DOM was found to be relatively bioreactive, preformed DOM in the Arctic appears to be less bioreactive but similar in degradation state to average DOM in the Atlantic and Pacific. These data demonstrate substantial summer production of POM and DOM on the Chukchi and Beaufort shelves that is available for utilization in shelf waters and export to the Canada Basin.     

Photochemical production of ammonium and transformation of dissolved organic matter in the Baltic Sea

The release of ammonium from the photochemical degradation of dissolved organic matter (DOM) has been proposed by earlier studies as a potentially important remineralisation pathway for refractory organic nitrogen. In this study the photochemical production of ammonium from Baltic Sea DOM was assessed in the laboratory. Filtered samples from the Bothnian Bay, the Gulf of Finland and the Arkona Sea were exposed to UVA light at environmentally relevant levels, and the developments in ammonium concentrations, light absorption, fluorescence and molecular size distribution were followed. The exposures resulted in a decrease in DOM absorption and loss of the larger sized fraction of DOM. Analysis of the fluorescence properties of DOM using parallel factor analysis (PARAFAC) identified 6 independent components. Five components decreased in intensity as a result of the UVA exposures. One component was produced as a result of the exposures and represents labile photoproducts derived from terrestrial DOM. The characteristics of DOM in samples from the Bothnian Bay and Gulf of Finland were similar and dominated by terrestrially derived material. The DOM from the Arkona Sea was more autochthonous in character. Photoammonification differed depending on the composition of DOM. Calculated photoammonification rates in surface waters varied between 121 and 382 μmol NH₄⁺ L^− 1 d^− 1. Estimated areal daily production rates ranged between 37 and 237 μmol NH₄⁺ m^− 2 d^− 1, which are comparable to atmospheric deposition rates and suggest that photochemical remineralisation of organic nitrogen may be a significant source of bioavailable nitrogen to surface waters during summer months with high irradiance and low inorganic nitrogen concentrations.     

Vertical and horizontal distribution of fluorescent dissolved organic matter in the Southern Ocean

The vertical and horizontal distribution of fluorescent dissolved organic matter (FDOM), determined by fluorescence intensity at 320 nm excitation and 420 nm emission, were clarified in nine stations on two transects at the Southern Ocean, including a subtropical, subantarctic, polar frontal and Antarctic zone. All vertical profiles of fluorescence intensity showed that levels were lowest in the surface waters, increased with increasing the depth in mid-depth waters ( 2000 m), and then stayed within a relatively narrow range from there to the bottom. Such vertical profiles of FDOM were similar to those of nutrients, but were adverse to dissolved oxygen. In water columns below the temperature-minimum subsurface water (dichothermal waters) in the Antarctic zone and below the winter mixed layer in the other zones, we determined the relationships of fluorescence intensity to concentrations of nutrients and apparent oxygen utilization (AOU) over the entire area of the present study, and found significant linear correlations between the levels of fluorescence intensity and nutrient concentrations (r =  0.70 and 0.71 for phosphate and nitrate + nitrite, respectively) and AOU (r = 0.91). From the strong correlation coefficient between fluorescence intensity and AOU, we concluded that FDOM in the Southern Ocean is formed in situ via the biological oxidation of organic matter. The regeneration of the nutrients/consumption of the oxygen/formation of FDOM was active in mid-depth waters. However, the correlations between fluorescence intensities and nutrients and AOU were different in the mid-depth water masses, Subantarctic Mode Water (SAMW), and Antarctic Intermediate Water (AAIW), indicating that the sources of organic matter responsible for FDOM formation were different. A considerable amount of FDOM in the SAMW is thought to be produced by the remineralization of DOM in addition to sinking particulate organic matter, while DOM is less responsible for FDOM formation in the AAIW.     

Molecular characterization of dissolved organic matter (DOM) along a river to ocean transect of the lower Chesapeake Bay by ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

In this study, electrospray ionization coupled to Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) is utilized to molecularly characterize DOM as it is transported along a river to estuary to ocean transect of the lower Chesapeake Bay system. The ultrahigh resolving power (greater than 500,000) and mass accuracy of FTICR-MS allow for the resolution of the thousands of components in a single DOM sample, and can therefore elucidate the molecular-level changes that occur during DOM transformation from a terrestrial location to the marine environment. An important feature of FTICR-MS is that its sensitivity allows for direct analysis of low salinity samples without employing the traditional concentration approaches involving C₁₈ extraction or ultrafiltration. To evaluate the advantages of using direct analysis, a C₁₈ extract of riverine water is compared to its whole, unfractionated water, and it was determined that the C₁₈ extraction is selective in that it eliminates two major series of compounds. One group is aliphatic amines/amides that are not adsorbed to the C₁₈ disk because they exist as positive ions prior to extraction. The second group is tannin-like compounds with higher oxygen contents and a more polar quality that also allow them not to be adsorbed to the C₁₈ disk. This direct approach could not be used for brackish/saline waters, so the C₁₈ method is resorted to for those samples. Along the subject transect, a significant difference is observed in the molecular composition of DOM, as determined from assigned molecular formulas. The DOM tends to become more aliphatic and contain lower abundances of oxygen-rich molecules as one progresses from inshore to the offshore. A considerable amount of molecular formula overlap does exist between samples from sites along the transect. This can be explained as either the presence of refractory material that persists throughout the transect, due to its resistance to degradation, or that the assigned molecular formulas are the same but the chemical structures are different. ESI-FTICR-MS is a powerful technique for the investigation of DOM and has the ability to detect compositional variations along the river to ocean transect. Visualization tools such as two dimensional and three dimensional van Krevelen diagrams greatly assist in highlighting the shift from the more aromatic, terrestrial DOM to the more aliphatic, marine DOM.     

Complexation of mercury by dissolved organic matter in surface waters of Galveston Bay, Texas

The chemical speciation of dissolved mercury in surface waters of Galveston Bay was determined using the concentrations of mercury-complexing ligands and conditional stability constants of mercury-ligand complexes. Two classes of natural ligands associated with dissolved organic matter were determined by a competitive ligand exchange-solvent solvent extraction (CLE-SSE) method: a strong class (L_s), ranging from 19 to 93 pM with an average conditional stability constant (K_HgLs) of 10²⁸, and a weak class (L_w) ranging from 1.4 to 9.8 nM with an average K_HgLs of 10²³. The range of conditional stability constants between mercury and natural ligands suggested that sulfides and thiolates are important binding sites for dissolved mercury in estuarine waters. A positive correlation between the estuarine distribution of dissolved glutathione and that of mercury-complexing ligands supported this suggestion. Thermodynamic equilibrium modeling using stability constants for HgL, HgCl_x, Hg(OH)_x, and HgCl(OH) and concentrations of each ligand demonstrated that almost all of the dissolved mercury (> 99%) in Galveston Bay was complexed by natural ligands associated with dissolved organic matter. The importance of low concentrations of high-affinity ligands that may originate in the biological system (i.e., glutathione and phytochelatin) suggests that the greater portion of bulk dissolved organic matter may not be important for mercury complexation in estuarine surface waters.     

2011年夏季胶州湾表层溶解有机物荧光特征的时空变化

利用三维荧光光谱技术(EEMs)结合平行因子分析(PARAFAC)的方法,对2011年8月至9月胶州湾表层海水溶解有机物荧光特征的时间与空间变化进行了研究。PARAFAC模型共鉴别出四个荧光组分:类蛋白质荧光组分(C1),陆源类腐殖质荧光组分(C2,C4)和海源类腐殖质荧光组分(C3)。类蛋白组分在调查期间的荧光强度最强(0.14±0.06),其余三个组分荧光强度相近(0.07±0.02,0.09±0.02,0.05±0.02)。这四种组分在8月下旬多雨期和9月上旬受径流影响的时期荧光强度较高,在9月下旬雨季影响消退后荧光强度显著降低。研究表明各组分荧光强度总体上与叶绿素a浓度显著正相关,与盐度负相关,说明胶州湾夏季FDOM浓度主要受降雨引发的生物活动影响。     

莱州湾荧光溶解有机物的时空分布

利用三维荧光光谱-平行因子分析法(EEMs-PARAFAC)技术结合多元统计方法研究了莱州湾海域春季(2020年5月)和秋季(2020年10月)荧光溶解有机物(FDOM)的来源及时空分布特征。结果显示莱州湾海域FDOM由2类共4个荧光组分组成:C1、C4为类蛋白质组分,分别为色氨酸和酪氨酸; C2、C3为类腐殖质组分。并对各组分的来源及分布特征分析:春季FDOM分布主要受到陆源输入的影响,其中表层C1、C2、C3也受微生物活动影响。秋季表层C1、C2、C3分布受到陆源输入和浮游植物生产共同影响,秋季表层C4主要受生物现场生产影响,秋季底层C1、C2、C3主要受陆源输入影响,C4受陆源输入和浮游植物生产共同影响。各荧光组分在表层的季节性差异主要是由于春季部分FDOM经陆源输入后受偏南风作用,在莱州湾西部及南部海域扩散。FDOM在底层的季节性差异主要由于受到沉积物再悬浮的影响。HIX高值分布表明莱州湾西部和南部FDOM受陆源输入影响显著,BIX高值分布表明莱州湾远海FDOM受生物活动影响程度较高。总体上,陆源输入影响莱州湾FDOM分布的主要因素。     

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.     

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。     

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.     

中全新世以来南黄海中部沉积过程——基于岩心粒度和有机质指标

海陆交互作用下的南黄海沉积环境复杂,其沉积机制一直是古海洋研究的重点和难点。本文以取自南黄海中部泥质区的Z1岩心为载体,对196个样品的粒度和整体有机质指标(TOC、TN、TOC/TN和δ13Corg)进行了详细分析,并对5个层位进行AMS14C年龄测定,分辨率高达11 a/cm。研究结果显示,6.1 ka BP以来南黄海中部沉积过程可分为3个阶段:(1) 6.1～5.2 ka BP,沉积物粒度较粗,以残留砂和陆源粗粒物质为主,有机质含量较低且主要为陆源输入,本阶段多受东亚季风强盛的影响,动荡海洋环境下有机质保存效率低,大量陆源输入冲淡作用显著;(2) 5.2～3.9 ka BP,沉积物粒度变细且波动较大,有机质呈增加趋势且以海源为主,主要受东亚冬季风减弱的影响,海源有机质含量增加,与黄海暖流影响增强有关;(3) 3.9～0 ka BP,沉积物粒度最细且相对稳定,有机质含量继续增加,直至1.9 ka BP趋于稳定,主要受现代环流系统和东亚冬季风影响。结果表明,南黄海粒度和整体有机质指标变化过程复杂,显示中全新世以来南黄海中部泥质区沉积环境演化的复杂性。本研究获得了南黄海高分辨率的沉积环境演化记录,不仅为沉积机制研究提供更多数据支撑,还可为区域古气候和古海洋演化提供关键的指示证据。     

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.     

Seasonal variations in dissolved organic carbon concentrations and characteristics in a shallow coastal bay

Dissolved organic matter (DOM) composition and dynamics in temperate shallow coastal bays are not well described although these bays may be important as local sources of organic carbon to ocean waters and are often sites of economically-important fisheries and aquaculture. In this study surface water samples were collected on a monthly to bi-monthly basis over two years from a mid-Atlantic coastal bay (Chincoteague Bay, Virginia and Maryland, USA). Dissolved organic carbon (DOC) concentrations and light absorbance characteristics were measured on sterile-filtered water, and high-molecular weight (> 1 kDa) dissolved OM (DOM) was isolated to determine stable isotope composition and molecular-level characteristics. Our time series encompassed both a drought year (2002) and a year of above-average rainfall (2003). During the dry year, one of our sites developed a very intense bloom of the brown tide organism Aureococcus anophagefferens while during the wet year there were brown tide bloom events at both of our sampling sites. During early spring of the wet year, there were higher concentrations of > 1 kDa DOC; this fraction represented a larger proportion of overall DOC and appeared considerably more allochthonous. Based upon colored dissolved organic matter (CDOM) and high-molecular weight DOM analyses, the development of extensive phytoplankton blooms during our sampling period significantly altered the quality of the DOM. Throughout both years Chincoteague Bay had high DOC concentrations relative to values reported for the coastal ocean. This observation, in conjunction with the observed effects of phytoplankton blooms on DOM composition, indicates that Chincoteague Bay may be a significant local source of “recently-fixed” organic carbon to shelf waters. Estimating inputs of DOC from Chincoteague Bay to the Mid-Atlantic Bight suggests that shallow productive bays should be considered in studies of organic carbon on continental shelves.