近海养殖水体溶解性有机质的荧光特征及环境指示意义

为探究近海养殖水体溶解性有机质(dissolved organic matter,DOM)的荧光特征及环境指示意义,以山东省东营市凡纳滨对虾池塘为研究对象,利用三维荧光光谱-平行因子分析(EEMs-PARAFAC)技术对2020年9月14日至10月17日凡纳滨对虾池塘养殖水体中DOM的荧光特征进行了分析,以期揭示其来源及环境指示意义。结果表明,养殖池水体DOM有4种荧光组分,包括1种类蛋白质物质(C4)和3种类腐殖酸物质(C1、C2与C3),前者作为养殖池水体DOM特有组分,且其荧光强度高于对照池各组分。养殖池水体DOM总荧光强度、总有机碳和溶解有机碳含量于采样时期均明显高于对照池。综合3种荧光指数(FI、BIX、HIX),对照池和养殖池水体DOM以内源输入为主,自生源特征明显。对照池和养殖池水体DOM组分与营养盐(氮、磷营养盐为主)具有显著相关性,表明DOM组分的产生与利用和营养盐的消耗与生成过程相耦合。养殖池DOM组分C1和C4与chl a呈显著正相关性,表明浮游藻类是养殖水体DOM类蛋白质和类腐殖酸物质的重要来源。该研究揭示了养殖水体有机质高度积累,对养殖环境的富营养化带来潜在威胁,同时为进一步揭示养殖水体DOM的光化学性质提供了科学依据。     

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。     

云贵高原湖泊沉积物─水界面碱度扩散通量研究

于1991-1995年间5次在云贵高原泸沽湖、洱海湖和贵州阿哈湖、百花湖的湖心采集沉积物柱芯、界面水和湖水样品，通过其pH值和HCO-3浓度剖面及界面碱度扩散通量的研究，首次定量评估高原湖泊界面扩散作用上覆水体碱度的影响程度。研究结果表明，云贵高原某些湖水寄宿时间相对较长、湖水深度相对小的湖泊，界面扩散作用是水体碱度的重要来源之一;湖水寄宿时间较短、深度较小的湖泊，界面扩散对上覆水体的影响可以忽略不计。     

西太平洋秋季130°E断面有色溶解有机物的分布特征及光降解行为研究

对2018年秋季西太平洋130°E断面上层水体有色溶解有机物(CDOM)的光学特性及光降解行为进行了研究。结果表明,西太平洋上层水体CDOM的吸收系数a(320)变化范围为0.025～0.64 m?1,平均值为(0.20±0.08) m?1;a(320)在表层相对较低,主要与表层CDOM的光漂白去除有关;在100～200 m水层较高,主要与次表层的生物活动有关。利用三维荧光光谱?平行因子分析技术,识别出两种荧光组分:类酪氨酸组分C1和海洋类腐殖质组分C2。C1主要源于棉兰老冷涡?上升流所带来的营养物质对浮游植物生产活动和微生物活动的促进作用;C2主要源于黑潮所带来的海洋类腐殖的输入。光化学降解实验发现,CDOM吸收值的损失主要发生在紫外波段;光照60 h后,类酪氨酸组分相较于海洋类腐殖质组分更易发生光降解;且光降解是西太平洋海域CDOM的重要去除途径。     

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。     

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。     

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。     

固相萃取法提取典型海水溶解有机质及其红外光谱和固态13C核磁共振表征

由于海水盐度大、有机质含量低,从海水中提取和纯化克级溶解性有机质(dissolved organic matter,DOM)一直十分困难。基于Bond Elut PPL固相萃取小柱法进行海水DOM固体样品提取的放大试验,建立DOM自动化调酸、PPL树脂吸附技术,最后形成提纯、冷冻干燥PPL-DOM(通过PPL树脂提取的DOM)完整工艺。采用元素分析、三维荧光光谱、红外光谱和固态¹³C核磁共振(NMR)波谱法进行样品表征。结果表明:(1)该方法对近海表层海水DOM回收率稳定在50%以上,搭建的提取装置DOM日吸附量可达230mg;(2)鳌山湾四个季节批次PPL-DOM整体分析结果表明,样品的元素组成和光谱特征相似,表明方法适用性和稳定性较好;(3)三种水生态环境的PPL-DOM¹³C NMR谱图显示样品的基本特征相似,以烷基碳、碳水化合物碳、芳香碳和羧基碳/酰胺碳为主,其中偶极去相(dipolar dephasing)谱显示了DOM前体化合物来源的差异。多种结果表明放大后的PPL固相萃取法可稳定提取克级DOM样品。     

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。     

2022年6月珠江流域洪水对下游溶解有机物浓度和组成的影响

当前极端气候事件频发,引起了人们广泛的关注。然而,气候变化对中国典型河流溶解有机物(DOM)的影响尚且未得到充分的认识。2021年11月至2022年10月,每月于珠江下游广州段采集河水样品,并分析其中溶解有机碳(DOC)、发色溶解有机物(CDOM)和荧光溶解有机物(FDOM)的浓度和组成。采样期间, 2022年6月珠江流域遭遇百年一遇的洪水。结果显示,洪水大幅度降低了河水中的DOC和CDOM浓度,并提高了DOM的芳香化程度。尽管洪水对DOM浓度产生了明显的稀释效应,但通过分析FDOM组成,进一步发现FDOM中不同组分对洪水的响应存在较大差异。FDOM短激发波长(230～235nm)处的类蛋白质组分峰值在洪水期间出现高值;与此同时,长激发波长(280～285nm)的类蛋白质组分和激发波长在345nm处的类腐殖质组分峰值在洪水期间出现最低值。此外,与长江下游相比,珠江下游水体中往往具有较高的DOC和CDOM浓度、DOM芳香化程度以及CDOM分子量。研究将有助于进一步了解珠江等世界大河DOM浓度和组成的变化规律和控制机制,以及揭示极端洪水对大河DOM动态变化产生的影响。     

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.     

云贵高原湖泊沉积物─水界面碱度扩散通量研究

于１９９１－１９９５年间５次在云贵高原泸沽湖，洱海湖和贵州阿哈湖，百花湖的湖心采集沉积物柱芯，界面水和湖水样品，通过其ｐＨ值和ＨＣＯ３浓度剖面及界面碱度扩散通量的研究，首次定量评估高原湖泊界面扩散作用上不体碱度的影响程度，研究结果表明，云贵高原某些湖水寄宿时间对较长，湖水深度相对小的湖泊，界面扩散作用是水体碱度的重要来源之一，湖水寄宿时间较短，深度较小的湖泊，界面扩散对上覆水体的影响可以忽略不地。     

Stocks and dynamics of dissolved and particulate organic matter in the southern Ross Sea, Antarctica

Dissolved and particulate organic matter was measured during six cruises to the southern Ross Sea. The cruises were conducted during late austral winter to autumn from 1994 to 1997 and included coverage of various stages of the seasonal phytoplankton bloom. The data from the various years are compiled into a representative seasonal cycle in order to assess general patterns of dissolved organic matter (DOM) and particulate organic matter (POM) dynamics in the southern Ross Sea. Dissolved organic carbon (DOC) and particulate organic carbon (POC) were at background concentrations of approximately 42 and 3 μM C, respectively, during the late winter conditions in October. As the spring phytoplankton bloom progressed, organic matter increased, and by January DOC and POC reached as high as 30 and 107 μM C, respectively, in excess of initial wintertime conditions. Stocks and concentrations of DOC and POC returned to near background values by autumn (April). Approximately 90% of the accumulated organic matter was partitioned into POM, with modest net accumulation of DOM stocks despite large net organic matter production and the dominance of Phaeocystis antarctica. Changes in NO₃ concentration from wintertime values were used to calculate the equivalent biological drawdown of dissolved inorganic carbon (DIC_equiv). The fraction of DIC_equiv drawdown resulting in net DOC production was relatively constant (ca. 11%), despite large temporal and spatial variability in DIC_equiv drawdown. The C : N (molar ratio) of the seasonally produced DOM had a geometric mean of 6.2 and was nitrogen-rich compared to background DOM. The DOM stocks that accumulate in excess of deep refractory background stocks are often referred to as “semi-labile” DOM. The “semi-labile” pool in the Ross Sea turns over on timescales of about 6 months. As a result of the modest net DOM production and its lability, the role DOM plays in export to the deep sea is small in this region.     

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.     

Spring distribution of dissolved organic matter in a system encompassing the Northeast Water Polynya: Implications for early-season sources and sinks

This study addresses sources and diagenetic state of early-season dissolved organic matter (DOM) in the Northeast Water Polynya (NEWP) area northeast of Greenland from distributions of humic substance fluorescence (HSfl), dissolved organic carbon (DOC), and dissolved organic nitrogen (DON) in the water column inside and outside the NEWP area. The water masses of the polynya area had acquired their spring/summer temperature–salinity characteristics at the time of sampling, and also had individual, different DOM signatures. DOC concentrations were variable within and among water masses in the polynya area, indicating patchy local sources and sinks of DOC. PySW and polynya intermediate water (PyIW) had higher average DON concentrations and average lower C:N ratios than polynya bottom water (PyBW), indicating a larger fraction of fresh DOM in PySW and PyIW than in PyBW. Ice-covered, polynya area surface waters (PySW) had higher DOC concentrations (113±14 μM, n=68) than surface water (SW) outside the polynya area (96±18 μM, n=6). The DOM C:N ratios in a low-salinity, ice-melt subgroup of PySW samples indicate labile material, and these low-salinity surface waters appeared to have a local DOC and DON source. In contrast, HSfl was significantly lower inside than outside the NEWP area. Despite the lower HSfl values within the NEWP area, the PySW values were high when compared to open-ocean water. There were no local terrestrial sources for HSfl to the NEWP area and the East Greenland Current is therefore proposed as a likely source of allochtonous HSfl. When HSfl was used as a conservative tracer, up to 70% of the water in PySW and PyIW was found to be derived from SW, which contains a high fraction of water from the East Greenland Current. Similarly, a mixing model based on HSfl indicated that 80% of early-season DOC and 90–100% of early-season DON in PySW and PyIW were derived from SW, indicating a potentially high fraction of terrestrially-derived, relatively refractory DOM in the early-season NEWP area.     

锯缘青蟹碱性磷酸酶分离纯化及部分理化性质研究

于１９９５年２月在厦门海域采集锯缘青蟹,取其内脏经正丁醇抽提,硫酸铵分级分离ＤＥＡＥ－５２离子交换柱层析及ＳｅｐｈａｄｅｘＧ－２００凝胶过滤柱层析纯化,获得碱性磷酸酶 制剂,以快速 蛋白液相色谱及聚丙烯酰胺凝胶电泳检验萁 纯度,获得单一蛋白纯的酶 制剂。     

海湾扇贝控温育苗采卵时间的预报方法

于１９８８年３月－１９９３年５月，在威海崮山渔业公司和文登市海水养殖一场，采集海湾扇贝，运用二点法、最小二乘法和电动计数式积温仪测积温３种方法，进行海湾扇贝生物临界温度和控温育苗采卵时间预报方法的研究。结果表明：在升温促熟中，用３种方法求出的海湾扇贝的生物学临界温度分别为Ｔ０１＝９．００℃，Ｔ０２＝６．５４℃，Ｔ０３℃＝７．１１℃；这些结果是实验条件精度差异的反映，Ｔ０３精度较高。亲贝入池温度与促     

Analysis of marine DOC using a dry combustion method

As part of a continuing effort to verify and improve measurements of marine dissolved organic carbon (DOC), we combusted dried sea salts + adhered organic matter to assay DOC concentrations in representative samples from the Atlantic and Pacific oceans. Combustions were performed overnight at 580 °C in sealed tubes, and oxidation of organic materials occurred via a novel mechanism, thermal sulfate reduction: 2H₂SO₄ + CH₂O → 2SO₂ + 3H₂O + CO₂Measured DOC concentrations ranged from 43 to 114 μM C, with highest values observed in inshore surface samples from Woods Hole Harbor, and lowest values observed in twelve deep offshore Atlantic and Pacific waters. Stable carbon isotope values determined for all samples were near − 22%., consistent with a predominantly marine phytoplankton origin for DOC. A seasonal study in Woods Hole Harbor showed no significant temporal trend in nearshore DOC concentrations. Problems associated with sample storage and contamination during drying steps prevented highly precise (± 1 μM) DOC concentration determinations; however, an improved drying and measurement system is outlined (Appendix A) for possible future dry-combustion studies of DOC concentrations.     

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.