Distributions and characteristics of dissolved organic matter in temperate coastal waters (Southern North Sea)

The spatial and temporal distributions of chromophoric dissolved organic matter (CDOM) and dissolved organic carbon (DOC) was studied in the East-Frisian Wadden Sea (Southern North Sea) during several cruises between 2002 and 2005. The spatial distribution of CDOM in the German Bight shows a strong gradient towards the coast. Tidal and seasonal variations of dissolved organic matter (DOM) identify freshwater discharge via flood-gates at the coastline and pore water efflux from tidal flat sediments as the most important CDOM sources within the backbarrier area of the Island of Spiekeroog. However, the amount and pattern of CDOM and DOC is strongly affected by various parameters, e.g. changes in the amount of terrestrial run-off, precipitation, evaporation, biological activity and photooxidation. A decoupling of CDOM and DOC, especially during periods of pronounced biological activity (algae blooms and microbial activity), is observed in spring and especially in summer. Mixing of the endmembers freshwater, pore water, and open sea water results in the formation of a coastal transition zone. Whilst an almost conservative behaviour during mixing is observed in winter, summer data point towards non-conservative mixing.     

Effect of organic matter source and salinity on dissolved organic matter isolation via ultrafiltration and solid phase extraction

In this study, samples were taken from three contrasting freshwater sources and amended with salt in order to determine the influence of salinity and dissolved organic matter (DOM) composition on DOM recovery via ultrafiltration and solid phase extraction (SPE) with C₁₈ disks. Salt addition caused variable recovery of DOM when using C₁₈ SPE, and ultraviolet–visible spectroscopic characterization of the extracted material showed spectral responses that varied among sample sources. In contrast, increasing sample salinity from 0 to 30 ppt consistently caused a 15–25% reduction in the amount of high molecular weight DOM isolated by ultrafiltration for both dissolved organic carbon (DOC) and chromophoric DOM (CDOM), regardless of DOM composition. We hypothesize that a change in conformation (such as coiling or disaggregation) of DOM molecules occurs in the presence of salt, allowing them to pass through the ultrafiltration membrane and thereby decreasing the DOM retained by ultrafiltration. These results are important because they demonstrate that changes in salinity can influence DOM recovery in estuaries. Interpretation of DOM characteristics along estuarine gradients needs to account for potential artifacts introduced by sample isolation techniques.     

DOM characteristics along the continuum from river to receiving basin: a comparison of freshwater and saline transects

The chemical characteristics of bulk (sterile-filtered) and high molecular-weight dissolved organic matter (HMW DOM) were analyzed for freshwater (St. Louis River, Minnesota to Lake Superior) and saline (Elizabeth River, Virginia to Chesapeake Bay) river-to-receiving basin transects. Dissolved organic carbon concentrations and UV–Visible spectroscopy of bulk DOM demonstrated a reduction in organic carbon, colored DOM and aromatic compounds downstream in both transects. The proportion of DOM recoverable via ultrafiltration as HMW material also decreased downstream in both transects, although there was an offset in recoveries between the transects that may be explained by the effects of ionic strength and/or differences in ultrafiltration technique. The analysis of HMW DOM by Fourier transform infrared spectroscopy illustrated similar trends between transects, with a general shift from aromatic/carboxylic compounds nearshore to aliphatic/carbohydrate materials offshore. The parallel changes observed along saline and freshwater transects imply that similar processes play significant roles in the down-gradient alteration of DOM and that ionic strength or pH changes cause second-order effects.     

Origin, enzymatic response and fate of dissolved organic matter during flood and non-flood conditions in a river-floodplain system of the Danube (Austria)

Spectroscopic techniques and extracellular enzyme activity measurements were combined with assessments of bacterial secondary production (BSP) to elucidate flood-pulse-linked differences in carbon (C) sources and related microbial processes in a river-floodplain system near Vienna (Austria). Surface connection with the main channel significantly influenced the quantity and quality of dissolved organic matter (DOM) in floodplain backwaters. The highest values of dissolved organic carbon (DOC) and chromophoric DOM (CDOM) were observed during the peak of the flood, when DOC increased from 1.36 to 4.37 mg l^?1 and CDOM from 2.94 to 14.32 m^?1. The flood introduced DOC which consisted of more allochthonously-derived, aromatic compounds. Bacterial enzymatic activity, as a proxy to track the response to changes in DOM, indicated elevated utilization of imported allochthonous material. Based on the enzyme measurements, new parameters were calculated: metabolic effort and enzymatic indices (EEA 1 and EEA 2). During connection, bacterial glucosidase and protease activity were dominant, whereas during disconnected phases a switch to lignin degradation (phenol oxidase) occurred. The enzymatic activity analysis revealed that flooding mobilized reactive DOM, which then supported bacterial metabolism. No significant differences in overall BSP between the two phases were detected, indicating that heterogeneous sources of C sufficiently support BSP. The study demonstrates that floods are important for delivering DOM, which, despite its allochthonous origin, is reactive and can be effectively utilized by aquatic bacteria in this river-floodplain systems. The presence of active floodplains, characterized by hydrological connectivity with the main channel, creates the opportunity to process allochthonous DOC. This has potential consequences for carbon flux, enhancing C sequestration and mineralization processes in this river-floodplain system.     

太湖有色可溶性有机物(CDOM)对COD及BOD5的指示意义

化学需氧量(COD)、五日生化需氧量(BOD_5)及溶解性有机碳(DOC)是指示湖泊水质的重要指标,然而上述指标测定通常耗费大量时间、试剂及人力物力且排放大量有害废液.有色可溶性有机物(CDOM)是溶解性有机物(DOM)中可以强烈吸收光谱中的紫外光和可见光的部分,数据测定耗时短、方便快捷,且样品处理过程环境友好,能在很大程度上反映湖泊水质.本研究基于2016年2、5和8月在太湖均匀布设的32个采样点进行样品采集,运用光谱吸收与三维荧光-平行因子分析(EEMs-PARAFAC)探究太湖CDOM的光谱吸收和荧光组分,探讨CDOM光谱指标对湖泊BOD_5、COD及DOC浓度等湖泊环境质量指标的可替代性.结果表明:(1)运用EEMs-PARAFAC方法解析出3种荧光组分:类腐殖酸C1、类酪氨酸C2和类色氨酸C3.(2) COD和BOD_5和DOC在空间上呈现出相似的分布趋势,不同水期的最高值均出现在竺山湾和梅梁湾,由西北湖区至中部敞水区、东南湖湾递减.(3)在不同水期,COD、BOD_5、DOC浓度和C1组分均表现为丰水期极显著大于枯水期和平水期,a_(254)在丰、平、枯水期间无显著性差异,最大值出现在丰水期;C2与C3组分均在枯水期和平水期极显著大于丰水期.(4)在不同水文时期,COD、BOD_5和DOC浓度均与a_(254)、类腐殖酸C1呈显著正相关,丰水期太湖COD、BOD_5和DOC浓度与CDOM光谱指标的线性相关性要优于枯水期和平水期.(5) CDOM光谱指标在不同水文时期均能很好地替代COD、BOD_5和DOC等作为反映太湖水体中有机物污染程度及湖泊水质的指标.     

不同来源有色溶解性有机物光化学/微生物降解过程

城市非点源污染向水生生态系统中输入大量的溶解有机物(DOM),对生态系统健康产生重要影响. 有色可溶性有机物(CDOM)是广泛分布于自然水体中的一类成分和结构复杂、含有多种高活性化学官能团的大分子聚合物,是DOM的重要组分,对水生生态系统健康、能量流动及生物地球化学循环有重要影响. 光化学反应和微生物代谢过程被认为是控制水体CDOM转化、降解和循环的主要影响因素. 然而,对城市化如何影响CDOM组成以及光化学和微生物如何相互作用影响城市水体CDOM动态的理解是不足的. 因此,为评估光化学过程和微生物代谢对不同城市水体CDOM降解与转化的贡献,解析不同城市水体CDOM光化学/微生物降解作用机理,本研究在英国伯明翰选择3类具有典型DOM来源的水体样本,通过实验室9 d受控培养实验,对比分析光化学以及微生物影响下CDOM来源和组成的变化. 结果表明：(1)城市河流由于接受上游污水排放及较短的水力滞留时间,含有丰富的芳香性碳,其CDOM光化学活性明显高于湖泊,光化学降解率为16.60%;(2)城市湖泊CDOM受人类活动影响,自生源类荧光成分富集,生物活性高,在微生物培养过程中CDOM增加了62.16%,而相较于城市湖泊,非城市湖泊由于接受周围景观土壤输入的大量腐殖质类CDOM,光照对其降解转化作用较为明显; (3)光化学过程促进了陆源CDOM中大分子类腐殖质物质降解成为生物活性高的小分子化合物,刺激微生物代谢生成类蛋白质类有机物; 以类蛋白质组分为主导的CDOM在光照过程中被转化为难降解状态,生物活性降低,CDOM微生物代谢过程被抑制. 研究成果为城市水体不同CDOM来源及活性差异特征研究提供了新的思路,有助于城市河流的可持续开放与管理.     

Leaching and microbial degradation of dissolved organic matter from salt marsh plants and seagrasses

Dissolved organic matter (DOM) is outwelled from highly productive salt marshes, but its sources and fates are unclear. To examine common salt marsh plants as sources of coastal DOM, two dominant salt marsh vascular plants Spartina alterniflora and Juncus roemarianus, and two major coastal seagrasses Syringodium filiforme and Halodule wrightii, were collected from a Florida salt marsh and studied using laboratory incubation experiments. We investigated the leaching dynamics of dissolved organic carbon (DOC), total dissolved nitrogen (TDN), and chromophoric dissolved organic matter (CDOM) from these plants, in conjunction with our field investigations of the sources and outwelling of DOM from Florida salt marshes. The leaching of DOM and CDOM from the plants was a rapid process, and leaching rates were 65–288 µM/g dry weight/day for DOC and 3.8–16 µM/g dry weight/day for TDN from different plants in the bacteria-inhibited incubations. DOC was proportional to TDN in the leachates, but the quantity of C and N leached was dependent on the species and growth stage of the plants. At the end of the 25-day experiments, 5.4–23 % and 10–45 % of solid phase C and N were released into DOC and TDN pools, respectively. Bacteria played an important role during the leaching process. The majority of DOC and TDN leached from marsh plants and seagrasses was labile and highly biodegradable with 56–90 % of the leached DOC and 44–72 % of the leached TDN being decomposed at the end of the experiments. The fluorescence measurements of CDOM indicate that organic matter leached from marsh plants and seagrasses contained mainly protein-like DOM which was degraded rapidly by bacteria. Our study suggests that leaching of DOM from salt marsh plants and seagrasses provide not only major sources of DOC, TDN, and CDOM that affect many biogeochemical processes, but also as important food sources to microbial communities in the marsh and adjacent coastal waters.     

Photochemical degradation of dissolved organic matter from streams in the western Lake Superior watershed

The input and fate of dissolved organic matter (DOM) can have important consequences for coastal zone productivity in large lakes and oceans. Chromophoric DOM (CDOM) is often delivered to coastal zones from rivers and streams and affects light penetration in a water column. CDOM can protect biota from damaging ultraviolet (UV) light by acting as sunscreen, resulting in increased ecosystem productivity. Alternatively, CDOM can decrease ecosystem productivity by absorbing light needed for photosynthesis and forming photoreaction products that are harmful to coastal zone biota. Increased urbanization of watersheds and seasonal differences in weather patterns change the delivery pathways, reactivity, input, and energy flow of DOM (and its CDOM component) into aquatic systems. This study investigated the effects of watershed and season on the concentrations and potential photodegradation of stream-derived DOM in Lake Superior tributaries, chosen to be geographically and geologically similar but differing in land use. Organic carbon analysis, UV–Visible spectrophotometry, and terrestrial (land use) analysis were used to investigate differences among samples and sample treatments. The major differences in DOM concentration and photochemical response appeared seasonal rather than site specific, with snow-melt samples showing stronger and more consistent changes in UV–Visible parameters while base-flow samples showed stronger and more consistent losses in DOC.     

Distribution,characteristics and potential impacts of chromophoric dissolved organic matter (CDOM) in Hudson Strait and Hudson Bay,Canada

The characteristics of chromophoric dissolved organic matter (CDOM) were studied in Hudson Bay and Hudson Strait in the Canadian Arctic. Hudson Bay receives a disproportionately large influx of river runoff. With high dissolved organic matter (DOM) concentrations in Arctic rivers the influence of CDOM on coastal and ocean systems can be significant, yet the distribution, characteristics and potential consequences of CDOM in these waters remain unknown. We collected 470 discrete water samples in offshore, coastal, estuarine and river waters in the region during September and October 2005. Mixing of CDOM appeared conservative with salinity, although regional differences exist due to variable DOM composition in the rivers discharging to the Bay and the presence of sea-ice melt, which has low CDOM concentrations and low salinity. There were higher concentrations of CDOM in Hudson Bay, especially in coastal waters with salinities <28$<28$, due to river runoff. Using CDOM composition of water masses as a tracer for the freshwater components revealed that river runoff is largely constrained to nearshore waters in Hudson Bay, while sea-ice melt is distributed more evenly in the Bay. Strong inshore–offshore gradients in the bio-optical properties of the surface waters in the Hudson Bay cause large variation in penetration of ultraviolet radiation and the photic depth within the bay, potentially controlling the vertical distribution of biomass and occurrence of deep chlorophyll maxima which are prevalent only in the more transparent offshore waters of the bay. The CDOM distribution and associated photoprocesses may influence the thermodynamics and stratification of the coastal waters, through trapping of radiant heating within the top few meters of the water column. Photoproduction of biologically labile substrates from CDOM could potentially stimulate the growth of biomass in Hudson Bay coastal waters. Further studies are needed to investigate the importance of terrestrial DOM in the Hudson Bay region, and the impact of hydroelectric development and climate change on these processes.     

Hydroclimatic controls on dissolved organic matter (DOM) characteristics and implications for trace metal transport in Hwangryong River Watershed,Korea, during a summer monsoon period

Frequent heavy rainfalls during the East Asian summer monsoon drastically increase water flow and chemical loadings to surface waters. A solid understanding of hydroclimatic controls on watershed biogeochemical processes is crucial for water quality control during the monsoon period. We investigated spatio‐temporal variations in the concentrations and spectroscopic properties of dissolved organic matter (DOM) and the concentrations of trace metals in Hwangryong River, Korea, during a summer period from the relatively dry month of June through the following months with heavy rainfall. DOM and its spectroscopic properties differed spatially along the river, and also depended on storm and flow characteristics around each sampling time. At a headwater stream draining a forested watershed, the concentrations (measured as dissolved organic carbon (DOC)), aromaticity (measured as specific UV absorbance at 254 nm), and fulvic acid‐ and protein‐like fluorescence of DOM were higher in stormflow than in baseflow waters. DOC concentrations and fluorescence intensities increased along the downstream rural and urban sites, in which DOC and fluorescence were not higher in stormflow waters, except for the ‘first flush’ at the urban site. The response of DOM in reservoir waters to monsoon rainfalls differed from that of stream and river waters, as illustrated by storm‐induced increases in DOM aromaticity and fulvic‐like fluorescence, and no significant changes in protein‐like fluorescence. The results suggest that surface water DOM and its spectroscopic properties differentially respond to changes in hydroclimatic conditions, depending on watershed characteristics and the influence of anthropogenic organic matter loadings. DOC concentrations and intensities of spectroscopic parameters were positively correlated with some of the measured trace metals (As, Co, and Fe). Further research will be needed to obtain a better understanding of climate effects on the interaction between DOM and trace metals. Copyright © 2006 John Wiley & Sons, Ltd.     

Distribution and photoreactivity of chromophoric dissolved organic matter in northern Gulf of Mexico shelf waters

The distribution and photoreactivity of chromophoric dissolved organic matter (CDOM) in the northern Gulf of Mexico along the Louisiana coastal shelf were examined during three cruises in summer 2007, fall 2007, and summer 2008. The influence of the Mississippi River plume was clearly evident as CDOM levels (defined as a₃₀₅) and dissolved organic carbon (DOC) concentrations were well-correlated with salinity during all cruises. Elevated CDOM and CDOM:DOC ratios of surface samples collected offshore of Atchafalaya Bay and the Breton-Chandeleur Sound complex indicated emanations of organic-rich waters from coastal wetlands are also an important source to nearshore shelf waters. Generally, CDOM and DOC levels were highest in surface waters and decreased with depth, but during summer 2007 and summer 2008, CDOM levels in near-bottom samples were occasionally higher than at mid-depths without concomitant increases in DOC. CDOM photobleaching was measured during 24 irradiations using a SunTest XLS+ solar simulator with photobleaching rate coefficients (k₃₀₅) ranging from 0.011 to 0.32 h⁻¹. For fall 2007 and summer 2008, higher k₃₀₅ values were generally observed in samples with higher initial CDOM levels. However, samples collected during summer 2007 did not exhibit a similar pattern nor were there differences in photobleaching rates between surface and bottom samples. Spectral slope coefficients (S_275-295 or S_350-400) and DOC levels were largely unchanged after 24 h irradiations. Modeled CDOM photobleaching for northern Gulf of Mexico mid-shelf waters predicts that during the summer when solar irradiance is high and the water column becomes stratified, nearly 90% of the CDOM in the upper 1 m may be lost to photobleaching, with losses up to 20% possible even at 10 m depth.     

The optical and molecular signatures of DOM under the eutrophication status in a shallow,semi-enclosed coastal bay in southeast China

We applied stable carbon isotopes, ultraviolet-visible absorption(UV-Vis), fluorescence excitation-emission matrices spectroscopy(EEMs), and Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR-MS) to investigate the chemical composition and sources of the dissolved organic matter(DOM) in both the water column and pore water in Xiangshan Bay, a representative semi-enclosed and eutrophic bay in Zhejiang Province, China. One protein-like fluorescent component(C1) and two humic-like fluorescent components(C2 and C3) were identified by PARAFAC modeling. The concentration of dissolved organic carbon(DOC), the relative intensities of C2, C3, and black carbon-like compounds are all negatively correlated with salinity, indicating that there is a dilution effect of terrestrial signals by seawater in Xiangshan Bay. The differences in light penetration ability of Xiangshan Bay cause different degrees of photo-degradation, which may play an important role in the transformation of organic matter in Xiangshan Bay. The weak correlation between the C1 fluorescent component and salinity indicates that autochthonous sources cannot dominate the protein-like FDOM in the Xiangshan Bay drainage area. Multiple sources(such as anthropogenic inputs and release of pore water) also affect the distribution of the protein-like fluorescent component under eutrophication conditions. The relative proportion of the protein-like fluorescent component in Xiangshan Bay is on a medium level in China and anthropogenic inputs may be a significant source of DOM in coastal bays.