Characterization of dissolved organic matter fluorescence in the South Atlantic Bight with use of PARAFAC model: Relationships between fluorescence and its components,absorption coefficients and organic carbon concentrations

In this study, the CDOM absorption coefficient at 350 nm [a_CDOM(350)] and CDOM excitation emission matrix (EEM) fluorescence were used to estimate annual fluxes of dissolved organic carbon (DOC) from the Cape Fear River to Long Bay in the South Atlantic Bight. Water samples were collected during a 3.5 year period, from October 2001 through March 2005, in the vicinity of the Cape Fear River (CFR) outlet and adjacent Onslow Bay (OB). Parallel factor analysis (PARAFAC) of CDOM EEM spectra identified six components: three terrestrial humic-like, one marine humic-like and two protein-like. Empirical relationships were derived from the PARAFAC model between DOC concentration and a_CDOM(350), total fluorescence intensity and the intensities of respective EEM components. DOC concentration and CDOM optical parameters were very well correlated and R² values ranged from 0.77 to 0.90. Regression analyses revealed that the non-absorbing DOC fraction, in DOC concentration estimated from CDOM optical parameters, varied with the qualitative composition of the CDOM. DOC concentration and intensity of the humic-like CDOM components characterized by excitation maxima at longer wavelengths have significantly higher estimated non-absorbing DOC compared to the analogous relationships between DOC and intensity of the humic-like CDOM components characterized by excitation maxima at shorter wavelengths. The relationships between DOC concentration and intensity of one of the protein-like components resulted in significantly reduced non-absorbing DOC fraction in DOC concentration estimation. Results of regression analyses between fluorescence intensities of specific EEM components and CDOM-specific absorption coefficients suggest that the relative proportion of humic-like CDOM components (characterized by excitation maximum at longer wavelengths) and the main protein-like component have the most impact on the values of a?_CDOM(350). Based on the relationships between a_CDOM(350), Cape Fear River flow, and DOC concentrations, DOC fluxes were estimated for 2002, 2003 and 2004. DOC fluxes varied from 1.5 to 6.2 × 10¹⁰ g C yr^? 1, depending on river flow.     

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。     

Variation of dissolved organic matter and fluorescence characteristics before,during and after phytoplankton bloom

The variation of dissolved organic matter (DOM) and fluorescence characteristics during the phytoplankton bloom were investigated in Yashima Bay, at the eastern part of the Seto Inland Sea, Japan. We found significant accumulations of dissolved organic carbon (DOC), dissolved organic nitrogen (DON), chromophoric dissolved organic matter (CDOM) fluorescence, and UV₂₆₀ during the phytoplankton bloom period in 2005, although lower accumulations of DOC and DON and only increases of CDOM fluorescence were observed during the bloom period in 2006. Little or no correlation between DOM and phytoplankton abundance might be due to the composition of DOM, which is a complex mixture of organic materials. The 3D-EEM results revealed that the DOM produced around the phytoplankton bloom period contained tyrosine, tryptophan, and humic-like substances. Our results showed that the occurrence of phytoplankton bloom contributed to the production of DOM in coastal water but the DOM accumulation depended on the type of phytoplankton bloom, the phytoplankton species in particular. From our results, we concluded that phytoplankton have a great role in the dynamics of DOM as a producer in a coastal environment.     

Fluorescence characteristics of dissolved organic matter in the deep waters of the Okhotsk Sea and the northwestern North Pacific Ocean

Fluorescent dissolved organic matter (DOM), a fraction of chromophoric DOM, is known to be produced in the deep ocean and is considered to be bio-refractory. However, the factors controlling fluorescence properties of DOM in the deep ocean are still not well understood. In this study, we determined the fluorescence properties of DOM in the deep waters of the Okhotsk Sea and the northwestern North Pacific Ocean using excitation-emission matrix (EEM) fluorescence and parallel factor analysis (PARAFAC). One protein-like, two humic-like components, and one uncertain component, which might be derived from a fluorometer artifact, were identified by EEM-PARAFAC. Fluorescence intensity levels of the protein-like component were highest in the surface waters, decreased with depth, but did not change systematically in the bathypelagic layer (1000 m - bottom). Fluorescence characteristics of the two humic-like components were similar to those traditionally defined as marine and terrestrial humic-like fluorophores. The fluorescence intensity levels of the two humic-like components were lowest in the surface waters, increased with depth in the mesopelagic layer (200 - 1000 m), and then slightly decreased with depth in the bathypelagic layer. The ratio of the two humic-like components remained in a relatively narrow range in the bathypelagic layer compared to that in the surface layer, suggesting a similar composition of humic-like fluorophores in the bathypelagic layer. In addition, the fluorescence intensities of the two humic-like components were linearly correlated to apparent oxygen utilization (AOU) in the bathypelagic layer, suggesting that both humic-like components are produced in situ as organic matter is oxidized biologically. These findings imply that optical characteristics of humic-like fluorophores once formed might not be altered further biologically or geochemically in the deep ocean. On the other hand, relationships of fluorescence intensities with AOU and Fe(III) solubility were different between the two humic-like components in the mesopelagic layer, suggesting different environmental dynamics and biogeochemical roles for the two humic-like components.     

珠江口磨刀门溶解有机物CDOM 三维荧光光谱特征

采用三维荧光对珠江口磨刀门夏秋季有色溶解有机物(CDOM)时空变化进行研究,分析其组成及荧光强度。结果表明, CDOM 三维荧光峰谱包括 UV 类腐殖质 A、陆源 Vis 类腐殖质 C 和海源 Vis类腐殖质M,以及类蛋白质T。在入海过程中,其组成未发生变化,但其荧光强度随盐度增加逐渐减小,反映了CDOM主要来源是陆源,并且主要受海水物理稀释控制,是一种典型的保守混合行为。在定点站位涨落潮周期中, CDOM的荧光强度不仅受到海水稀释的作用,表层水体CDOM受到紫外线的光降解作用,同时中层水体CDOM受到浮游植物的影响,反映了盐度、紫外线强度、生物活动对CDOM具有的共同影响。     

用三维荧光光谱-平行因子分析法研究长江口南部有色溶解有机物荧光的季节变化

The southern Changjiang River Estuary has attracted considerable attention from marine scientists because it is a highly biologically active area and is biogeochemically significant.Moreover,land-ocean interactions strongly impact the estuary,and harmful algal blooms(HABs) frequently occur in the area.In October 2010 and May 2011,water samples of chromophoric dissolved organic matter(CDOM) were collected from the southern Changjiang River Estuary.Parallel factor analysis(PARAFAC) was used to assess the samples' CDOM composition using excitation-emission matrix(EEM) spectroscopy.Four components were identified:three were humic-like(C1,C2 and C3) and one was protein-like(C4).Analysis based on spatial and seasonal distributions,as well as relationships with salinity,Chl a and apparent oxygen utilization(AOU),revealed that terrestrial inputs had the most significant effect on the three humic-like Components C1,C2 and C3 in autumn.In spring,microbial processes and phytoplankton blooms were also important factors that impacted the three components.The protein-like Component C4 had autochthonous and allochthonous origins and likely represented a biologically labile component.CDOM in the southern Changjiang River Estuary was mostly affected by terrestrial inputs.Microbial processes and phytoplankton blooms were also important sources of CDOM,especially in spring.The fluorescence intensities of the four components were significantly higher in spring than in autumn.On average,C1,C2,C3,C4 and the total fluorescence intensity(TFI) in the surface,middle and bottom layers increased by123%–242%,105%–195%,167%–665%,483%–567% and 184%–245% in spring than in autumn,respectively.This finding corresponded with a Chl a concentration that was 16–20 times higher in spring than in autumn and an AOU that was two to four times lower in spring than in autumn.The humification index(HIX) was lower in spring that in autumn,and the fluorescence index(FI) was higher in spring than in autumn.This result indicated that the CDOM was labile and the biological activity was intense in spring.     

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.     

The role of nitrogen in chromophoric and fluorescent dissolved organic matter formation

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.     

Optical properties of estuarine dissolved organic matter isolated using cross-flow ultrafiltration

Dissolved organic matter(DOM) from freshwater, mid-salinity, and seawater endmember samples in the Jiulong River Estuary, China were fractionated using cross-flow ultrafiltration with a 10-kDa membrane. The colloidal organic matter(COM; 10 kDa–0.22 μm) retentate, low molecular weight(LMW) DOM(10 kDa) permeate, and bulk samples were analyzed using absorption spectroscopy and three-dimensional fluorescence excitation-emission-matrix spectroscopy. The UV-visible spectra of COM were very similar to those obtained for permeate and bulk samples, decreasing monotonically with increasing wavelength. Most of the chromophoric DOM(CDOM, expressed as the absorption coefficient a355) occurred in the LMW fraction, while the percentage of CDOM in the colloidal fraction was substantially higher in the freshwater endmember(13.4% of the total) than in the seawater endmember(6.8%). The bulk CDOM showed a conservative mixing behavior in the estuary, while there was removal of the COM fraction and a concurrent addition of the permeate fraction in the mid-salinity sample, implying that part of the colloidal CDOM was transformed into LMW CDOM. Two humic-like components(C1: 250, 325/402 nm; and C2: 265, 360/458 nm) and one protein-like component(C3: 275/334 nm) were identified using parallel factor analysis. The contributions of the C1, C2, and C3 components of the COM fraction to the bulk sample were 2.5%–8.7%, 4.8%–12.6%, and 7.4%–14.7%, respectively, revealing that fluorescent DOM occurred mainly in the LMW fraction in the Jiulong River Estuary. The C1 and C2 components in the retentate and permeate samples showed conservative mixing behavior, but the intensity ratio of C2/C1 was higher in the retentate than in the permeate fractions for all salinity samples, showing that the humic component was more enriched in the COM than the fulvic component. The intensity ratio of C3/(C1+C2) was much higher in the retentate than in the permeate fraction for mid-salinity and seawater samples, revealing that the protein-like component was relatively more enriched in COM than the humic-like component. The contribution of the protein-like component(C3) to the total fluorescence in the retentate increased from 14% in the freshwater endmember to 72% for the seawater endmember samples, clearly indicating the variation of dominance by the humic-like component compared to the protein-like component during the estuarine mixing process of COM.     

长江口及邻近海域有色溶解有机物的分布及河口混合行为的季节变化研究

于2019年3月、7月和10月对长江口及邻近海域有色溶解有机物(CDOM)的分布及河口混合行为进行分析研究。通过对盐度、吸收光谱斜率S_275～295、吸收系数a_CDOM(355)以及叶绿素a的分析发现,在河口内低盐度区,7月淡水流量大,陆源输入量最大,a_CDOM(355)值最高,3月CDOM来源主要受陆源输入和浮游植物生产活动的影响,a_CDOM(355)值较10月高;在口外高盐度区,3月和7月的a_CDOM(355)值相近,均低于10月,CDOM分布主要受浮游植物生产活动的影响。利用三维荧光光谱?平行因子分析方法共鉴定出4个荧光组分:类蛋白质组分C1(280/330 nm)、类腐殖质组分C2(300/350 nm)、类腐殖质组分C3(260/465 nm)和类腐殖质组分C4(320/410 nm)。在3月、7月及10月,4个荧光组分强度由长江口内到口外呈递减趋势,受陆源输入和浮游植物生产活动的影响,平均荧光强度的季节变化总体上来说,由大到小依次为7月、10月、3月。3个季节CDOM荧光组分均存在偏离理论稀释线的现象,说明CDOM的来源(陆源输入、沉积物再悬浮和现场生物活动)和去除(被颗粒物吸附、光降解和细菌降解)机制复杂多变,揭示了长江口区域CDOM在不同时空下的不保守混合行为。     

西太平洋冬季上层水体有色溶解有机物的分布和转化特征

为深入解析西太平洋溶解有机碳的生物地球化学过程，本研究于2015年12月至2016年1月，开展了西太平洋上层水体有色溶解有机物（CDOM）吸收光谱和荧光光谱特征研究。研究结果表明，西太平洋上层水体CDOM吸收系数a（320）变化范围为0.01~1.07 m-1，平均值为0.18 m-1；其较高值位于100~200 m水层，表层的海水相对含量较低，主要以有机物的光化学分解为主。采用PARAFAC分析CDOM三维荧光光谱特征，得到1种类腐殖质组分C2（252（310 nm）/405 nm）及2种类蛋白组分C1（224（276 nm）/335 nm）和C3（224（260 nm）/300 nm），其中类腐殖质荧光组分占总荧光强度的11%~22%，蛋白质荧光组分占总荧光强度的78%~89%，蛋白质荧光中类色氨酸和类络氨酸组分对荧光强度的贡献相当。洋流在大尺度上控制西太平洋CDOM的分布特征，两流交界处和环流形成区域的CDOM相对含量较高，荧光信号较强。西太上层水体CDOM相对含量和荧光信息，与温度、盐度、DO和营养盐等理化因素之间的相关分析结果表明，CDOM主要成分类蛋白质的产生主要受上层水体初级生产过程控制。     

Release of dissolved organic matter during oxic and anoxic decomposition of salt marsh cordgrass

Chromophoric dissolved organic matter (CDOM), as the light absorbing fraction of bulk dissolved organic matter (DOM), plays a number of important roles in the global and local biogeochemical cycling of dissolved organic carbon (DOC) and in controlling the optical properties of estuarine and coastal waters. Intertidal areas such as salt marshes can contribute significant amounts of the CDOM that is exported to the ocean, but the processes controlling this CDOM source are not well understood. In this study, we investigate the production of DOM and CDOM from the decomposition of two salt marsh cordgrasses, Spartina patens, a C₄ grass, and Typha latifolia, a C₃ grass, in well-controlled laboratory experiments. During the seven-week incubation period of the salt marsh grasses in oxic and anoxic seawater, changes in dissolved organic carbon (DOC) concentrations, dissolved nitrogen (DN) concentrations, stable carbon isotopic composition of DOC (DOC-δ¹³C), and CDOM fluorescence demonstrate a significant contribution of DOC and CDOM to estuarine waters from salt marsh plants, such as Spartina and Typha species. In the natural environment, however, the release processes of CDOM from different cordgrass species could be controlled largely by the in situ oxic and anoxic conditions present during degradation which affects both the production and decomposition of DOC and CDOM, as well as the optical properties of CDOM in estuarine and coastal waters.     

Characterization of dissolved organic matter across the Subtropical Convergence off the South Island,New Zealand

Dissolved organic matter (DOM) was investigated along a gradient across the Subtropical Convergence (STC) off the South Island, New Zealand. Ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), excitation emission matrix fluorescence (EEM) spectroscopy, and molecular lignin analysis techniques were used to study this DOM. The analysis revealed a group of compounds found only in the coastal DOM samples, which were also characterized by an elevated terrestrial DOM fluorescence pattern and elevated lignin content if compared to the offshore samples. This group exhibited a high degree of carbon unsaturation, as evident from high double bond equivalence minus oxygen values (DBE-O > 9) and maximum fluorescence intensity. Sulfur-containing molecular formulae for summer DOM samples were much more abundant across the entire transect of the STC compared to winter and exhibited distinctly different hydrogen:carbon and oxygen:carbon elemental ratios, suggesting a possible correlation between biological activity and sulfur compounds. The molecular formulae common to all STC samples were compared with those calculated for DOM extracted from freshwater collected from a stream discharging into Doubtful Sound (West Coast, New Zealand). ESI-FT-ICR-MS measurements undertaken in negative electrospray ionization (ESI?) mode indicated that 30% of the molecular formulae were present in both types of DOM, while in positive ESI mode (ESI+) over 90% of the formulae were present in all samples. Hence, a significant portion of the molecular formulae assigned to the solid-phase extractable DOM pool (SPE-DOM) appear to be identical in oceanic and freshwater samples.     

长江口溶解有机物光漂白和光矿化表观量子产率

溶解有机物(DOM)经太阳光照射导致其吸光度(光漂白)和溶解有机碳(光矿化)损失,从而影响水体生态系统光学特性及碳循环。本文通过测定冬季长江口及其邻近海域DOM光降解表观量子产率(AQY),初步探讨了DOM光反应活性在河口及陆架海的变化特征。DOM光降解AQY由口内至口外逐渐递减,且有色溶解有机物(CDOM)光漂白速率是溶解有机碳(DOC)光矿化速率的10倍。Φ_ble(CDOM光漂白表观量子产率)和Φ_min(DOC光矿化平均量子产率)在最大浑浊带以东海域与盐度和SUVA₂₅₄分别呈显著的线性负相关与正相关,表明DOM光反应活性在长江口外受物理混合影响为主,且陆源DOM光反应活性比海源高。此外,最大浑浊带下游DOM光降解AQY显著低于上游。DOM光降解速率随波长的变化呈现非高斯分布,且峰值出现在330 nm,积分结果表明UVA是DOM光降解的主要贡献者。本研究结果将为完善我国东海碳通量模型提供帮助。     

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.     

Tracing of dissolved organic matter from the Sepetiba Bay (Brazil) by PARAFAC analysis of total luminescence matrices

Fluorescent excitation-emission matrices (FEEM) of the fluorescent dissolved organic matter (FDOM) are widely used for DOM characterization and tracing. In this work, a set of FEEM from sampling campaigns in the Sepetiba Bay (Brazil) was decomposed into independent components using the parallel factor analysis (PARAFAC) algorithm. Four independent components were extracted describing the total fluorescence of the FDOM. The well described peaks A, C, M, B and T were found, and a new peak, A', linked to the C peak, was detected. Relative contribution of each of four components to the total fluorescence confirms that the coastal water has DOM of terrestrial origin, except for the 275Ex/400-500Em range (nm), which primarily occurs in marine waters.     

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。     

长江口盐度梯度下有色溶解有机物的分布、来源与季节变化

通过测定有色溶解有机物（CDOM）的吸收光谱和荧光光谱研究了2015年3月和7月长江口盐度梯度下CDOM的分布、组成、来源及河口混合行为等。利用激发发射矩阵荧光光谱（EEMs）并结合平行因子分析（PARAFAC）,研究了CDOM的荧光组分特征,共识别出两类4个荧光组分组成,即类腐殖质荧光组分C1（260,375/490 nm）、C2（365/440 nm）、C3（330/400 nm）及类蛋白质荧光组分C4（295/345 nm）。结果表明,3月和7月,4种荧光组分的分布模式与总荧光强度都基本一致:从口内到口外,先升高后降低,且4种组分都在河口呈现不保守混合行为,在最大浑浊带处存在添加过程,达到峰值,在口外有去除过程。3月腐殖化指数HIX范围在1.12~7.19,而7月HIX的范围在0.87~6.71;生物指数BIX在3月范围在0.76~1.11,7月为0.62~1.15,表明3月CDOM的腐殖化程度较7月高,而自生贡献比例较7月略低。3月吸收系数α（355）的平均值为0.55 m-1 ,7月的略高,为0.61 m-1,表明7月长江口CDOM的含量略高。光谱斜率比值S_R的季节性变化不大,都是近岸低,远岸高,表明CDOM的平均分子质量从口内到口外在逐渐增加。     

Spatial and temporal distribution of chromophoric dissolved organic matter (CDOM) fluorescence and its contribution to light attenuation in UK waterbodies

Vertical attenuation of light through the water column (K_d) is attributable to the optically active components of phytoplankton, suspended particulate material (SPM) and chromophoric dissolved organic matter (CDOM). Of these, CDOM is not routinely monitored and was the main focus of this study. Concentrations and spatio-temporal patterns of CDOM fluorescence were investigated between August 2004 and March 2006, to quantify the correlation coefficient between CDOM and salinity and to better characterise the contribution of CDOM to K_d. Sampling was conducted at a broad range of UK and Republic of Ireland locations; these included more than 15 estuaries, 30 coastal and 70 offshore sites in the southern North Sea, Irish Sea, Liverpool Bay, Western Approaches and the English Channel.An instrument package was used; a logger with multi-sensor array was deployed vertically through the water column and concurrent water samples were taken to determine salinity, CDOM fluorescence and SPM. Surface CDOM fluorescence values ranged between 0.05 and 16.80 S.Fl.U. (standardised fluorescence units). A strong, negative correlation coefficient of CDOM to salinity (r² = 0.81) was found. CDOM absorption (aCDOM_λ) was derived from fluorescence measurements and was in the range 0.02–2.2 m⁻¹ with mean 0.15 m⁻¹. These results were comparable with direct measurements of aCDOM_λ in the same geographic regions, as published by other workers.Spatial differences in CDOM fluorescence were generally explicable by variation in salinity, in local conditions or catchment areas; e.g. CDOM at the freshwater end was 3.54–11.30 S.Fl.U., reflecting the variety of rivers sampled and their different catchments. Temporal changes in CDOM fluorescence were related to salinity. A significant and positive correlation was found between CDOM and K_d, and although CDOM was found to be less influential than SPM on K_d, it was still of significance particularly in coastal and offshore waters of lower turbidity.     

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.