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。     

海洋荧光溶解有机物研究进展

海洋荧光溶解有机物(FDOM)是海洋有色溶解有机物中可产生荧光的组分,其理化性质对于海洋上层的水色遥感、光化学以及浮游植物的生产力和生态系统结构与功能等都有重要影响。总结了FDOM的3种荧光光谱分析技术及其特点,重点对其两种主要成分(类腐殖质和类蛋白质荧光物质)的荧光特性、分布变化以及来源、分布变化及其去除等进行了全面细致的综述,阐述了研究FDOM的海洋学意义,并对今后有待深入研究的重点问题作了展望。     

厦门湾有色溶解有机物的光吸收特性研究

研究了厦门湾九龙江河口区、西海域、同安湾及东侧水道海水中有色溶解有机物(CDOM)的光吸收特性,分析了CDOM的河口行为,并讨论了CDOM光吸收特性与其荧光性质之间的关系。结果表明,厦门湾表层海水CDOM光吸收系数a(355)的水平分布表现为河口区最高、东侧水道最低、西海域和同安湾介于两者之间,底层水a(355)的分布与表层基本相似,表明陆源河流输入是厦门湾CDOM的主要来源;a(355)的垂直分布为表层高于底层,主要受水文和生物因素控制。厦门湾表层水CDOM光谱斜率S的平均值介于0.014—0.018nm-1,但河口低盐度区S值较小,反映陆源腐殖质的影响。a(355)在河口混合中呈保守行为,表明CDOM具有良好的保守性质。CDOM的吸收系数a(355)与其荧光强度之间表现为较好的相关关系,指示可以用灵敏度更高的荧光方法来研究CDOM的分布和行为。     

秋季胶州湾有色溶解有机物荧光特性研究及其来源分析

利用三维荧光光谱(EEMs)-平行因子分析(PARAFAC)技术研究了秋季胶州湾有色溶解有机物(CDOM)的荧光成分组成、分布特征及来源。PARAFAC模型解析出胶州湾CDOM由2类5个荧光组分组成,即类腐殖质成分C1(355nm/430nm)、C2(320nm/390nm)、C3(380nm/465nm)、C4(420(330)nm/505nm)及类蛋白质成分C5(280/325nm)。类腐殖质成分C1、C2、C3和C4的平面分布模式基本一致,呈现由近岸海域向湾中心海域逐渐减小的趋势,而类蛋白质成分C5则是由湾东北部近岸海域向西南部海域呈逐渐减小的趋势。分析表明,秋季胶州湾CDOM类腐殖质成分C1、C2、C3和C4的主要来源为陆源输入,而类蛋白质成分C5主要受城市排污的影响。系统聚类分析表明,以团岛南端和红岛西侧连线为界,所有采样站位被分为两类,分界线西部区域站位CDOM各荧光成分相对含量分别为C1:31.8%~35.5%,C2:30.3%~33.7%,C3:17.1%~20.2%,C4:4.5%~5.2%,C5:9.6%~12.5%;分界线东部区域站位CDOM各荧光成分相对含量分别为C1:30.6%~34.6%,C2:28.8%~32.7%,C3:17.0%~19.1%,C4:3.3%~4.8%,C5:12.1%~18.2%。西部区域CDOM具有较高的C4含量和较低的C5含量,大沽河等河流的陆源输入特征明显,而东部区域CDOM则具有较高的C5含量和较低的C4含量,反映该区域受城市排污影响显著。另外,秋季胶州湾CDOM的HIX范围为1.8~3.2之间,较小的腐殖化因子值反映了秋季胶州湾CDOM的腐殖化程度高较低,在环境中存在时间较短。     

浮游生物来源溶解有机物的三维荧光特征研究

应用三维激发-发射荧光光谱技术,研究了中肋骨条藻和采集水样中浮游植物在光照和避光条件下培养实验过程中产生的溶解有机物,分析了三维荧光光谱中荧光峰数目、位置和荧光强度的变化,探讨了浮游植物和细菌在有机物产生中的作用.结果表明,光照条件下浮游植物生长产生类蛋白和类腐殖质荧光有机物,在衰亡期2类有机物的荧光强度迅速增加;而在避光条件下,类蛋白有机物荧光强度明显降低,类腐殖质有机物的荧光强度保持不变.2类有机物的荧光峰位置和荧光强度变化与初始有机物的性质及光照环境有关.     

渤海有色溶解有机物的三维荧光光谱特征

本文采用三维荧光光谱(FEEMs)技术, 结合FEEMs特定光谱区荧光区域积分(FRI)法, 测定了2010年9月中旬渤海23个站位不同层次的有色溶解有机物(CDOM)样品, 以探讨渤海CDOM组分的水平和垂直分布特征以及控制因素。FEEMs的总累计积分和各荧光团的荧光区域积分比例可作为表征海域CDOM分布特征的一个良好指标, 且优于常规的单点荧光法。结果表明, 渤海CDOM中含有类腐殖质荧光团A、B、C, 类色氨酸荧光团M, 以及类酪氨酸荧光团N。从沿海至外海, CDOM总累计积分值不断减小。其中紫外区类腐殖质A的荧光区域积分比例无显著变化; 可见区陆源类腐殖质B的荧光区域积分比例也不断减小, 表明陆源输入为沿海区域CDOM的主要来源; 而可见区海源类腐殖质C、类蛋白质荧光团M、N的荧光区域积分比例和叶绿素浓度不断升高, 显示了生物活动的贡献。从层次来看, 沿海CDOM的总累计积分为: 表层>底层>中层; 而外海CDOM的总累计积分呈相反趋势。其中, 紫外区类腐殖质A的荧光区域积分比例在整个海域最小, 垂直分布无明显变化; 可见区陆源类腐殖质B的荧光区域积分比例与沿海CDOM总累计积分相一致; 可见区海源类腐殖质C、类蛋白质M和N的荧光区域积分比例与外海CDOM总累计积分相一致, 这反映了CDOM的垂直分布是由光化学反应、生物作用和沉积物再悬浮共同控制的特性。     

船舶压载水中荧光溶解有机物的光谱特征研究

采用三维激发-发射荧光光谱(3D-EEMs),结合平行因子分析(PARAFAC),研究了2015年12月至2020年1月停靠上海洋山港和江苏省江阴港的42艘入境船舶压载水中荧光溶解有机物(FDOM)的组成特征及其来源,并探讨了FDOM用于鉴别置换和未置换压载水的可行性。结果显示,船舶压载水中FDOM主要由3种荧光组分组成：类色氨酸荧光组分C1,λ_ex为275 nm,λ_em为332 nm;UVB类腐殖质组分C2,λ_ex为290和315 nm,λ_em为386 nm;UVA类腐殖质组分C3,λ_ex为250和360 nm,λ_em为446 nm。组分C1在船舶压载水FDOM中荧光强度百分比最高,其次为组分C3,组分C2最低。显著性分析显示,未置换压载水中组分C1显著高于置换压载水(p<0.05)的,而组分C2和C3则无显著差异(p>0.05)。荧光指数分析表明,未置换压载水FDOM受陆源输入和微生物活动的共同影响,而置换压载水由于远离近岸,水体生物活动为...     

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.     

2014年夏季长江口有色溶解有机物(CDOM)的分布、光学特性及其来源探究

通过测定有色溶解有机物(CDOM)的吸收光谱、荧光光谱、溶解有机碳(DOC)浓度,探究了2014年夏季长江口CDOM的来源及河口混合行为。结合吸收系数a(355)、光谱斜率S275-295、比紫外吸光度SUVA254与盐度的关系,结果表明南港水道受黄浦江输入影响显著,北港水道由长江径流控制呈保守性混合行为,二者CDOM的物质结构性质较为相似。DOC的浓度可通过a(275)与a(295)模拟估算:ln[DOC]=4.94–0.87ln[a(275)]+0.90ln[a(295)],a(275)8.0 m–1;ln[DOC]=4.77–6.79ln[a(275)]+8.05ln[a(295)],a(275)≥8.0 m–1。模拟结果表明,在长江口及邻近海域,CDOM对DOC具有示踪意义。利用三维荧光光谱-平行因子分析(EEMs-PARAFAC)技术,可得到夏季长江口FDOM含有3个类腐殖质组分(C2,C4和C5)和3个类蛋白质组分(C1,C3和C6)。类腐殖质组分具有相似的来源及地球化学行为,且与a(355)及盐度存在显著相关性;类蛋白质组分则与a(355)及盐度之间无显著相关性,揭示其与区域内微生物的活动有关。     

Multivariate analysis of fluorescence and source identification of dissolved organic matter in Jiaozhou Bay, China

Hierarchical clustering analysis and principal component analysis (PCA) methods were used to assess the similarities and dissimilarities of the entire Excitation-emission matrix spectroscopy (EEMs) data sets of samples collected from Jiaozhou Bay, China. The results demonstrate that multivariate analysis facilitates the complex data treatment and spectral sorting processes, and also enhances the probability to reveal otherwise hidden information concerning the chemical characteristics of the dissolved organic matter (DOM). The distribution of different water samples as revealed by multivariate results has been used to track the movement of DOM material in the study area, and the interpretation is supported by the results obtained from the numerical simulation model of substance tracing technique, which show that the substance discharged by Haibo River can be distributed in Jiaozhou Bay.     

Multivariate analysis of .uorescence and source identi. cation of dissolved organic matter in Jiaozhou Bay, China

Hierarchical clustering analysis and principal component analysis (PCA) methods were used to assess the similarities and dissimilarities of the entire Excitation-emission matrix spectroscopy (EEMs) data sets of samples collected from Jiaozhou Bay, China. The results demonstrate that multivariate analysis facilitates the complex data treatment and spectral sorting processes, and also enhances the probability to reveal otherwise hidden information concerning the chemical characteristics of the dissolved organic matter (DOM). The distribution of di.erent water samples as revealed by multivariate results has been used to track the movement of DOM material in the study area, and the interpretation is supported by the results obtained from the numerical simulation model of substance tracing technique, which show that the substance discharged by Haibo River can be distributed in Jiaozhou Bay.     

Chemical properties of colored dissolved organic matter in the sea-surface microlayer and subsurface water of Jiaozhou Bay, China in autumn and winter

The distribution and chemical properties of chromophoric dissolved organic matter (CDOM) in the Jiaozhou Bay, China were examined during four cruises in 2010-2011. The influence of freshwater and industrial and municipal sewage along the eastern coast of the bay was clearly evident as CDOM levels (defined as a 305 ), and dissolved organic carbon (DOC) concentrations were well correlated with salinity during all the cruises. Moreover, DOC concentrations were significantly correlated with chlorophyll a concentrations in the surface microlayer as well as in the subsurface water. The concentrations of DOC and CDOM displayed a gradually decreasing trend from the northwestern and eastern coast to the central bay, and the values and gradients of their concentrations on the eastern coast were generally higher than those on the western coast. In addition, CDOM and DOC levels were generally higher in the surface microlayer than in the subsurface water. In comparison with DOC, CDOM exhibited a greater extent of enrichment in the microlayer in each cruise, with average enrichment factor (E F ) values of 1.38 and 1.84, respectively. Four fluorescent components were identified from the surface microlayer and subsurface water samples and could be distinguished as peak A, peak T, peak B and peak M. For all the cruises, peak A levels were higher in the surface microlayer than in the subsurface water. This pattern of variation might be attributed to the terrestrial input.     

Spatial and temporal variability of colored dissolved organic matter absorption properties in the Taiwan Strait

Spatial and temporal variability of the absorption properties of colored dissolved organic matter (CDOM) in the Taiwan Strait was investigated in summer (July to August of 2006) and winter (from December 2006 to January of 2007) seasons. The CDOM absorption coefficient at 280 nm (a 280 ) showed a decreasing trend from nearshore to offshore areas while the spectral slope coefficient parameter calculated between wavelengths 275-295 nm (S 275 295 ) showed an increase, indicative of decreasing aromaticity and molecular weight of the CDOM. The average a 280 in winter (1.47 ± 0.50 m 1 ) was significantly higher than in summer (1.10 ± 0.41 m 1 ), while the average S 275 295 in winter (26.7 ± 5.2 μm 1 ) was significantly lower than in summer (30.6 ± 5.5 μm 1 ), demonstrating clear seasonal variation in CDOM abundance and properties in the Taiwan Strait. A three-end- member conservative mixing model showed that local terrestrial CDOM inputs from several rivers along the western coast were small (<5%). However, the distribution of CDOM in the Taiwan Strait is mainly controlled by water mass movement [i.e., the Zhe-min Coastal Current (ZCC) and the Kuroshio Branch Current (KBC) in winter and the South China Sea Water (SCSW) in summer]. Biological activity was also an important factor affecting the distribution of CDOM in the offshore region in summer months.     

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.     

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.     

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.     

A Lagrangian view of fluorescent chromophoric dissolved organic matter distributions in the Mississippi River plume

In April 2001, three instrumented surface drifters were deployed in the Mississippi River plume near the mouth of Southwest Pass. The plume was characterized by strong surface gradients of salinity, temperature, and chromophoric dissolved organic matter fluorescence (F_CDOM). The drifters initially headed west and attained peak speeds of 1 m s⁻¹ within 5 h after release. Thereafter, velocity decreased as the triad headed north in the Louisiana Bight. Linear relationships between F_CDOM and salinity identified two subsurface sources of high salinity water (salinity >35) underlying the surface plume. The platforms stalled in a surface front about 40 h after deployment, and then slowly drifted south along the eastern perimeter of the plume. Shoreward of the plume front there were patches of low-salinity, high F_CDOM ‘patches’ of surface waters that likely originated in the marshes, bayous, and other smaller distributaries of the delta.