夏季长江口水体可溶性有机质组成的空间分布特征及其控制因素

本研究通过测定有色溶解有机物(CDOM)的吸收光谱、荧光可溶性有机质(FDOM)的激发-发射-矩阵三维荧光光谱(excitation-emission-matrix spectra,EEMs)和稳定碳同位素组成(δ13C),系统探讨了长江口夏季水体可溶性有机质(DOM)的组成、来源、空间分布及河口混合行为等.研究结果表明,可溶性有机碳(DOC)浓度整体呈现由陆到海逐渐降低的趋势,表征有色溶解有机物含量水平的吸收系数a(355)与盐度呈负相关关系,指示可溶性有机质中荧光组分在河口的分布主要受稀释作用调控.利用EEMs并结合平行因子分析(PARAFAC)鉴定出代表陆源有机质的类腐殖质的荧光组分C2和C3,以及代表原地生产力的类蛋白质荧光组分C1和C4.由近岸到外海,表征海洋藻类生产力的C1组分在水体荧光有机质中所占比例增高,陆源信号则呈现逐渐降低趋势,与此相对应,外海水可溶性有机质具有高的光谱斜率S275–295/S350–400比值和重碳同位素组成.基于盐度vs.可溶性有机碳浓度、盐度vs.δ13C值的河流-海洋双端元混合模型,发现长江口最大混浊带存在可溶性有机碳的移除过程,且表现为以物理稀释作用为主的缺失性非保守混合行为.研究成果揭示了水动力条件是控制长江口-东海陆架系统可溶性有机质组成和空间分布的关键因素.     

洱海沉积物间隙水中溶解有机质的地球化学特性

对洱海沉积物间隙水中溶解有机质(DOM)含量、紫外可见吸收、荧光以及分子量等的垂直分布特征进行了研究。结果表明,DOC含量在沉积物水界面明显富集,随后急剧下降,6cm处达到最小值,随后呈上升趋势。DOC与吸光度值、荧光发射光谱强度之间具有一定的线性相关关系。DOM的E3/E4值范围在1～6之间,绝大多数在1～35之间。表征DOM中腐殖质来源的指标荧光指数值处于148～159之间,说明DOM以陆源输入为主。此外,洱海沉积物间隙水DOM分子量分布呈多峰分布模式,重均分子量(M_w)值在1462～1953Da之间,数均分子量(M_n)值在547～900Da之间,多分散性系数ρ值在202～305之间。随着沉积深度增大,M_w和M_n有略微的增大趋势,但变化不大。沉积物的氧化还原条件、微生物活动以及铁、锰氧化物等在沉积剖面的差异是控制间隙水中DOM各种地球化学特性的主要因素。     

运用3DEEMs及荧光偏振方法研究pH、离子强度及浓度效应对腐殖酸荧光光谱特性的影响

利用三维荧光激发.发射光谱(3DEEMs)及荧光偏振法研究了3例腐殖酸和1例湖泊溶解有机物(DOM)在不同腐殖酸浓度、离子强度和pH条件下的荧光光谱特性.实验结果表明,随着浓度增大,各腐殖酸样的荧光强度增大,其中垃圾渗滤液腐殖酸和Pahokee泥炭腐殖酸的荧光峰出现红移.随着浓度进一步增大,腐殖酸的荧光偏振值增大,由此推断在此浓度范围内腐殖酸由于分子间的排斥作用使其构型出现伸展.离子强度增大导致腐殖酸及阿哈湖DOM的荧光强度降低.随着氯化钾(KCI)浓度增大,Fluka腐殖酸的荧光峰A蓝移,荧光峰B的荧光偏振值出现减小,推测是由于静电中和作用使其荧光基团发生卷曲造成的.离子强度对其余腐殖酸样和阿哈湖DOM的其他荧光特性没有明显的影响.总的来说,pH值的变化对腐殖酸和湖泊DOM的荧光特征的影响是很明显的.随着pH值增大,腐殖酸和湖泊DOM的荧光强度增强.而pH值减小时,Fluka腐殖酸和Pahokee泥炭腐殖酸的荧光峰(A峰)蓝移,当pH值降到5时,Fhka腐殖酸的荧光峰突然红移到最大,随后又继续蓝移;垃圾渗滤液腐殖酸和阿哈湖DOM的荧光峰位无明显的漂移.所有样品的荧光偏振值都减小(但阿哈湖DOM的A峰变化不大),但在pHi≤5时又增大,这种现象表明随着pH值降低,腐殖酸和湖泊DOM中有机大分子发生卷曲,但在pH≤5时由于羧基的质子化又以平面伸展构型出现在溶液中.     

腐殖酸三维荧光光谱特性研究

腐殖质的荧光特性被广泛用来解析其在各种天然环境中的来源及分布.由于荧光光谱分析具有灵敏度高,选择性好,且不破坏样品结构的优点,非常适合用来研究腐殖质的结构和官能团等特征.利用三维荧光激发-发射光谱研究了 Fluka腐殖酸的荧光光谱特性,结果显示,离子强度(0～0.05 mol/L KClO4)对 Fluka腐殖酸的三维荧光光谱特性影响非常小,而腐殖酸的浓度(5～100 mg/L)和溶液 pH(2～12)对其三维荧光光谱特性影响显著.当腐殖酸浓度增大时,荧光峰出现明显红移现象.荧光强度一般随着 pH的升高而增大,当 pH大于 10后呈下降趋势,我们从垃圾渗滤液溶解有机质的实验结果中也得到相同结论;在浓度为 50 mg/L和 100 mg/L的 Fluka腐殖酸中,荧光峰 B(fulvic-like)的荧光强度却在 pH=5.0左右时达到最大值,与前人报道的土壤富里酸的行为一致,质子化常数 lgK′ HL分别为 3.57和 3.13,与二羧基化合物接近,说明荧光峰 B可能与 Fluka腐殖酸结构中的羧基有关;荧光峰 A与荧光峰 B的荧光强度比值 r(A/B)在 0.61～2.59之间,并且在 pH=2～11范围内, r(A/B)与 pH具有较好的线性相关关系,表明荧光峰 A和荧光峰 B随着 pH值的改变有着相同的变化趋势.     

贵德盆地三河流域高砷地下水中溶解性有机物三维荧光特性及其指示意义

溶解性有机物(dissolved organic matter, DOM)可以通过多种方式控制含水层中砷的迁移转化。贵德盆地承压含水层地下水砷含量显著高于潜水含水层。为查明承压水中溶解性有机物对砷浓度的影响,对研究区地表水、潜水以及承压水进行吸光度和三维荧光光谱的分析,利用平行因子分析法确定了水样中有机物成分及荧光特征。结果表明,贵德盆地水体中DOM包含陆源类腐殖质(C1)、受人为影响的腐殖质(C2)、类醌化合物(C3)和微生物来源的腐殖质(C4)4种组分。陆源类腐殖质C1可在地下水中富集,占总有机质的40%~55%。相比于地下水,C2和C3则在地表水中占据较高的比例。高砷承压水中C2、C3所占比例高于低砷潜水。其中,C1可以通过络合作用促进溶解性砷浓度的提高,C3作为电子穿梭体可以促进含砷铁氧化物或氢氧化物的还原性溶解从而释放砷。微生物降解有机质生成的HCO-3可以与砷竞争吸附,促进砷的解吸附。此外,还原性溶解产生的Fe(II)与HCO-3形成FeCO3固定一部分的砷。该研究表明,地下水中的天然有机物通过络合作用和作为电子穿梭体促进铁氧化物还原导致地下水砷的富集,为分析黄河上游地区高砷地下水的成因提供理论依据。     

沉积物不同提取态有机物特征及水文地球化学意义——以河套盆地典型研究区为例

地下水系统中有机物（OM）特征和活性对于地下水化学特征的形成和演化起着十分重要的作用。将内蒙古河套盆地表层湖相沉积物按10 cm间隔采集,并对沉积有机质的性质及来源进行重点分析。测量了不同深度上不同岩性沉积物的色度、水溶性有机物（WEOM）和盐溶性有机物（SEOM）含量及其光谱学特性。结果显示,沉积物的色度（R530-520）与TOC含量呈现相反的变化趋势:色度值较大时,TOC含量反而较小。相对于细砂层,黏土层的色度值较低,但TOC含量较高。相同的沉积物中,SEOM含量高于WEOM,但WEOM更易迁移至地下水中。有机物的光谱指数表明,WEOM以微生物来源为主,而SEOM以陆源为主。通过三维荧光光谱分析发现,荧光强度和沉积物有机碳（SOC）含量呈正相关;黏土层沉积有机物荧光强度更高;WEOM和SEOM均含类腐殖质成分和类蛋白成分,但SEOM中腐殖质成分较高;类腐殖质是所研究的沉积物中OM最主要的存在形式。     

江汉平原高砷地下水中DOM三维荧光特征及其指示意义

水体中溶解性有机质(dissolved organic matter, DOM)是含水层中砷释放的主控因素之一.江汉平原河湖众多、沟渠广布,地表水体与浅层地下水的交互作用使得DOM的组分特征及其强度有显著差异.为查明江汉平原地下水中溶解性有机质在砷迁移转化过程中的作用,对江汉平原地表水和浅层地下水进行三维荧光光谱分析,使用平行因子分析法提取水体中有机质的分子组成、功能特点和荧光特征,并分析各组分相对含量与地下水中砷与铁的关联.江汉平原水体中DOM包括3种主要组分,组分C1、C2为类腐殖质,C2是生物降解过程中产生的小分子,C3为类蛋白物质.地下水DOM以类腐殖质组分C1、C2为主,地表水以类蛋白类物质C3和小分子腐殖质C2为主.高砷地下水中DOM以陆源为主,主要通过两种途径促进As的迁移转化:(1) DOM的腐殖质组分充当微生物群落的电子运输工具,促进微生物作用下的有机质氧化和铁氧化物的还原,并伴随As的释放及大量溶解性有机碳(dissolved organic carbon, DOC)和HCO₃-的产生;(2) As以铁等金属阳离子为桥接物与腐殖质结合,通过形成As-Fe-DOM络合物,导致地下水中砷的迁移.      

黄海秋季典型站位沉降颗粒物的垂直通量

2002年9月,在海州湾外侧(E1站)、黄海冷水团(E2站)和黄、东海毗邻水域(E3站)分别放置沉积物捕获器采集沉降颗粒物,研究其垂直通量.结果显示,E1、E2和E3站底层颗粒物沉降通量分别为215.44 g/(m2·d)、165.51 g/(m2·d)、873.91 g/(m2·d),POC沉降通量分别为3.15 g/(m2·d)、2.22 g/(m2·d)、10.49 g/(m2·d).生源颗粒物是E1站位次表层POC的主要来源.E3站水体底层的大量悬浮颗粒物主要来自沉积物的再悬浮,再悬浮强烈程度及影响深度均高于E1站.通过模型计算出E2站底层颗粒物再悬浮比率平均(±SD)为95.65(±2.14)%,底表沉积物再悬浮通量占总再悬浮通量的百分比(X值)为89.53%,显示秋季底部平流对黄海冷水团区再悬浮通量影响不大,但这种影响在夏季相对较强.E2站POC净沉降通量为192 mg/(m2·d),生源颗粒物是此站位POC通量的主要贡献者.由于温跃层的长期存在,营养盐贫乏,生物生长受到抑制,导致黄海冷水团区秋季POC通量小于夏季.     

海底水一沉积物界面系统中成矿元素的组合特征与多金属结核形成的关系

利用“海洋四号”调查船HY4—871,881航次在东太平洋海盆取得的底层水、沉积物、间隙水及多金属结核样品,研究探讨了海底水—沉积物界面系统不同物质相中结核主要成矿元素间的关系,并以此为基础讨论了结核成矿元素的来源及其成矿机制。研究表明,Mn、Fc在底层水和沉积物中表现出一定的正相关关系。而在间隙水和结核中则发生了完全相反的变化。间隙水中Mn、Fc密切共生,而结核中Mn、Fc则高度离散,这表明在沉积物早期成岩阶段,Mr~Fc在间隙水中有着相同的溶出富集机制,而在结核形成过程中则有着完全不同的沉淀聚集机制。此外,Co、Ni、Cu与Mn、Fc之间组合关系的变化则反映了不同海底作用的影响。底层水与结核及间隙水与结核相应元素之间关系的变化表明结核主要成矿元素的来源不同,Mn、Ni、Cu主要来源于间隙水,Fc、Co则主要来源于底层水。     

梅梁湾、大太湖夏季和冬季CDOM特征及可能来源分析

基于2004年夏季水华暴发期和冬季在梅梁湾及大太湖各2次采样,分析了夏季、冬季CDOM的特征及其可能的来源,发现夏季CDOM吸收系数、叶绿素a浓度均明显高于冬季,DOC浓度、CDOM吸收系数a(355)的变化范围分别为5.17～12.42 mg/L、2.57～6.77 m-1,最大值均出现在冬季(12月15日)的直湖港入湖口.CDOM吸收系数与DOC浓度、定标后的荧光值一般都存在显著正相关,但夏季由于受浮游植物降解的影响,与DOC浓度和荧光的相关性明显低于冬季.表征CDOM组成和来源的参数比吸收系数、M值、S值存在显著的季节差异,夏季吸收系数a*(355)值明显要大于冬季,而S值、M值则要小于冬季.夏季水华暴发时CDOM吸收系数与叶绿素a浓度空间分布较为一致,吸收系数与叶绿素a浓度存在正相关,浮游植物降解产物可能是水体中CDOM的重要来源;相反,冬季CDOM吸收系数呈现从梁溪河入湖口、湾内往湾口递减的趋势,其来源可能主要以陆源为主,受入湖河流的影响较大.     

洱海沉积物孔隙水中溶解有机质的三维荧光光谱特征

文章应用三维荧光光谱技术对洱海沉积物孔隙水中的溶解有机质进行了研究。结果表明,所有样品均含有4个明显的荧光峰,其中A和C为类腐殖酸荧光,B和D为类蛋白荧光。荧光强度在沉积物-水界面特别强,在1cm处急剧下降,之后随着沉积深度呈上升趋势。孔隙水溶解有机质均具有强的类蛋白荧光,揭示了溶解有机质中含有大量色氨酸、酪氨酸等芳环结构的类蛋白物质,并且在早期成岩过程中随着沉积深度呈积累趋势;类蛋白荧光与类腐殖酸荧光之间具有一定的相关关系,r(A,C)值在0.94-1.79之间,随着沉积深度逐渐下降,r(D,B)值在0.9-1.75之间,与r(A,C)值极为接近,且随着沉积深度有着类似的变化趋势,说明在洱海沉积物孔隙水中,r(D,B)与r(A,C)之间具有一定的相关性。     

Comparative study of dissolved organic matter from groundwater and surface water in the Florida coastal Everglades using multi-dimensional spectrofluorometry combined with multivariate statistics

Dissolved organic matter (DOM) in groundwater and surface water samples from the Florida coastal Everglades were studied using excitation–emission matrix fluorescence modeled through parallel factor analysis (EEM-PARAFAC). DOM in both surface and groundwater from the eastern Everglades S332 basin reflected a terrestrial-derived fingerprint through dominantly higher abundances of humic-like PARAFAC components. In contrast, surface water DOM from northeastern Florida Bay featured a microbial-derived DOM signature based on the higher abundance of microbial humic-like and protein-like components consistent with its marine source. Surprisingly, groundwater DOM from northeastern Florida Bay reflected a terrestrial-derived source except for samples from central Florida Bay well, which mirrored a combination of terrestrial and marine end-member origin. Furthermore, surface water and groundwater displayed effects of different degradation pathways such as photodegradation and biodegradation as exemplified by two PARAFAC components seemingly indicative of such degradation processes. Finally, Principal Component Analysis of the EEM-PARAFAC data was able to distinguish and classify most of the samples according to DOM origins and degradation processes experienced, except for a small overlap of S332 surface water and groundwater, implying rather active surface-to-ground water interaction in some sites particularly during the rainy season. This study highlights that EEM-PARAFAC could be used successfully to trace and differentiate DOM from diverse sources across both horizontal and vertical flow profiles, and as such could be a convenient and useful tool for the better understanding of hydrological interactions and carbon biogeochemical cycling.     

Characterization of Chromophoric Dissolved Organic Matter (CDOM) in the Bohai Sea and the Yellow Sea Using Excitation-Emission Matrix Spectroscopy (EEMs) and Parallel Factor Analysis (PARAFAC)

Compositions and concentrations of chromophoric dissolved organic matter (CDOM) have been determined in the Bohai Sea (BS) and the Yellow Sea (YS) in the summer and autumn in 2013 by excitation and emission matrix spectroscopy (EEMs) and parallel factor analysis (PARAFAC). The PARAFAC model identified three humic-like components (C1, C2, and C3) and one protein-like component (C4). CDOM exhibited higher fluorescence intensities in the coastal areas in both the summer and autumn. However, its distribution patterns were different in the two seasons. Based on spatial and seasonal distributions of four components, as well as correlations with salinity, chlorophyll a (Chl-a), and apparent oxygen utilization (AOU), the following assignments were made. The C1, C2, and C3 components were mainly dominated by terrestrial inputs and influenced by the primary productivity of phytoplankton in the summer as well. C4 was assigned to terrestrial and autochthonous origins and most likely represented a biologically labile component. Terrestrial inputs were the dominant source of CDOM in the BS and YS. The humification index (HIX) and biological index (BIX) suggested that CDOM in the BS was more stable than that in the YS, which had an increase in autochthonous production, and in the summer, CDOM was less stable with a higher CDOM autochthonous production compared with that in the autumn.     

Optical characterization of CDOM in a marsh-influenced environment in the Changjiang (Yangtze River) Estuary

To elucidate the influence of tidal marshes on the amount and chemical structure of chromophoric dissolved organic matter (CDOM) in adjacent coastal waters, surface water samples were collected along three cross-marsh transects in tidal marshes within the Changjiang Estuary. In addition, three sediment cores were collected from the marshes and incubated for 10 h in the laboratory after adding overlying tidal waters. Nutrients, DOC, absorption, fluorescence excitation–emission matrix (EEM) spectroscopy, and other parameters were measured in these samples, which clearly illustrated releases by the tidal marshes of DOC, and CDOM absorbent and fluorescent molecules. To characterize the chemical nature of the marsh-derived CDOM, variations in a suite of optical indices (including molar absorptivity, absorption spectral slope, fluorescence quantum yield, and fluorescence ratios between certain excitation/emission locations) in these samples were plotted against the offshore distance of the stations as well as the incubation time. From the literature, it has been suggested that these variations are closely associated with molecular weight, aromaticity, and humic/fulvic or allochthonous/autochthonous ratios in the CDOM mixtures. This study showed that the CDOM fluorophores changed to more humic-like and were less protein-like from sea to land across the marsh gradients. Furthermore, subtractions between EEM spectra before and after laboratory incubations were applied to illustrate in greater detail the properties of the pure fluorescent compounds exchanged at the sediment–overlying water interface.     

Relationships between DOC concentration,molecular size and fluorescence properties of DOM in a stream

The patterns of dissolved organic matter (DOM) fluorescence properties were examined in a Precambrian shield stream over a seven-month field study. Unique spatial and temporal patterns of simultaneous changes were observed in dissolved organic carbon concentration (DOC), humic-like fluorescence intensity, maximum excitation and emission wavelengths and fluorescence index (the ratio of the emission intensity at a wavelength of 450 nm to that at 500 nm at an excitation wavelength of 370 nm). The spatial change indicates the alteration of DOM along the length of the stream, and temporal change corresponded to a drought event in August. In contrast to humic-like fluorescence, the protein-like fluorescence shows considerable variability, suggesting its ephemeral nature. There were strong relationships between humic-like fluorescence intensity, fluorescence index, maximum Ex/Em wavelengths, DOC concentration and molecular size of DOM. This study has significant implications to the understanding of the nature and biogeochemical cycling of DOM.     

Wave-forced resuspension of upper Chesapeake Bay muds

Moored instruments were used to make observations of near bottom currents, waves, temperature, salinity, and turbidity at shallow (3.5 m and 5.5 m depth) dredged sediment disposal sites in upper Chesapeake Bay during the winters of 1990 and 1991 to investigate time-varying characteristics of resuspension processes over extended periods. Resulting time series data show the variability of two components of the suspended sediment concentration field. Background suspended sediment concentrations varied inversely with salinity and in direct relation to Susquehanna River flow. Muddy bottom sediments were also resuspended locally by both tidal currents and wind-wave forcing, resulting in short-term increases and decreases in suspended concentration, with higher peak concentrations near the bottom. In both years, episodes of wave-forced resuspension dominated tidal resuspension on an individual event basis, exceeding most tidal resuspension peaks by a factor of 3 to 5. The winds that generated the waves responsible for the observed resuspension events were not optimal for wave generation, however. Application of a simple wind-wave model showed that much greater wave-forced resuspension than that observed might be generated under the proper conditions. The consolidated sediments investigated in 1990 were less susceptible to both tidal and wave-forced resuspension than the recently deposited sediments investigated in 1991. There was also some indication that wave-forced resuspension increased erodibility of the bottom sediments on a short-term basis. Wave-forced resuspension is implicated as an important part of sediment transport processes in much of Chesapeake Bay. Its role in deeper, narrower, and more tidally energetic estuaries is not as clear, and should be investigated on a case-by-case basis.     

Molecular characterization of dissolved organic matter in pore water of continental shelf sediments

Dissolved organic matter (DOM) in sediment pore water is a complex molecular mixture reflecting various sources and biogeochemical processes. In order to constrain those sources and processes, molecular variations of pore water DOM in surface sediments from the NW Iberian shelf were analyzed by ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and compared to river and marine water column DOM. Weighted average molecular element ratios of oxygen to carbon ((O/C)_wa) and hydrogen to carbon ((H/C)_wa) provided general information about DOM sources. DOM in local rivers was more oxygenated ((O/C)_wa 0.52) and contained less hydrogen ((H/C)_wa 1.15) than marine pore water DOM (mean (O/C)_wa 0.50, mean (H/C)_wa 1.26). The relative abundance of specific compound groups, such as highly oxygenated aromatic compounds or nitrogen-bearing compounds with low H/C ratios, correspond to a high concentration of lignin phenols (160 μg/g sediment dry weight) and a high TOC/TN ratio (13.3) in the sedimentary organic matter and were therefore assigned to terrestrial sources. The lower degree of unsaturation and a higher relative abundance of nitrogen-bearing compounds in the pore water DOM reflected microbial activity within the sediment. One sampling site on the shelf with a high sediment accumulation, and a humic-rich river sample showed a wide range of sulfur compounds in the DOM, accompanied by a higher abundance of lipid biomarkers for sulfate-reducing bacteria, probably indicating early diagenetic sulfurization of organic matter.     

Sources of Terrestrial Organic Carbon in the Mississippi Plume Region: Evidence for the Importance of Coastal Marsh Inputs

High sedimentation rates along river-dominated margins make these systems important repositories for organic carbon derived from both allochthonous and autochthonous sources. Using elemental carbon/nitrogen ratios, molecular biomarker (lignin phenol), and stable carbon isotopic (bulk and compound-specific) analyses, this study examined the sources of organic carbon to the Louisiana shelf within one of the primary dispersive pathways of the Mississippi River. Surface sediment samples were collected from stations across the inner, mid, and outer Louisiana shelf, within the Mississippi River plume region, during two cruises in the spring and fall of 2000. Lignin biomarker data showed spatial patterns in terrestrial source plant materials within the river plume, such that sediments near the mouth of the Mississippi River were comparatively less degraded and richer in C₄ plant carbon than those found at mid-depth regions of the shelf. A molecular and stable isotope-based mixing model defining riverine, marsh, and marine organic carbon suggested that the highest organic carbon inputs to the shelf in spring were from marine sources (55?C61% marine organic carbon), while riverine organic carbon was the highest (63%) in fall, likely due to lower inputs of marine organic carbon at this time compared with the spring season. This model also indicated that marsh inputs, ranging from 19 to 34% and 3?C15% of the organic carbon in spring and fall, respectively, were significantly more important sources of organic carbon on the inner Louisiana shelf than previously suggested. Finally, we propose that the decomposition of terrestrial-derived organic carbon (from the river and local wetlands sources) in mobile muds may serve as a largely unexplored additional source of oxygen-consuming organic carbon in hypoxic bottom waters of the Louisiana shelf.