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.     

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.     

Assessing the spatial and temporal variability of dissolved organic matter in Liverpool Bay using excitation–emission matrix fluorescence and parallel factor analysis

The spatial and diurnal tidal variability of dissolved organic carbon (DOC) concentrations and the composition of dissolved organic matter (DOM), as evaluated by high-temperature catalytic oxidation and excitation–emission matrix combined with parallel factor analysis (EEM–PARAFAC), respectively, were determined in Liverpool Bay. EEM–PARAFAC modeling resulted in six fluorescent components characterized as terrestrial humic-like (two), microbial humic-like (two), and protein-like (two). The spatial distributions of DOC and the four humic-like components were negatively correlated with salinity in the high-salinity waters observed in this study (30.41–33.75), suggesting that terrestrial DOM was conservatively distributed. The spatial patterns of protein-like components were largely different from those of DOC, humic-like components, and chlorophyll a, suggesting that these distributions were the combined result of production and degradation in the bay in addition to river inputs. These findings suggest that the DOM dynamics in Liverpool Bay are strongly controlled by river-dominated allochthonous DOM inputs with some less significant contributions of autochthonous DOM within the bay. In addition, the temporal variations of DOM associated with the diurnal tidal cycles were determined at one inshore (31.34–32.24 salinity) and one offshore (33.64–33.75 salinity) station in the bay. Negative linear relationships between salinity and DOM characteristics, i.e., DOC, humic-like, and protein-like components, were observed at the inshore station. In contrast, no relationship was observed at the offshore station, suggesting that the export of DOM through rivers and possibly tidal flats have a noticeable influence on DOM concentration and composition up to a relatively elevated salinity of around 33 in Liverpool Bay.     

Lake metabolism scales with lake morphometry and catchment conditions

We used a comparative data set for 25 lakes in Denmark sampled during summer to explore the influence of lake morphometry, catchment conditions, light availability and nutrient input on lake metabolism. We found that (1) gross primary production (GPP) and community respiration (R) decline with lake area, water depth and drainage ratio, and increase with algal biomass (Chl), dissolved organic carbon (DOC) and total phosphorus (TP); (2) all lakes, especially small with less incident light, and forest lakes with high DOC, have negative net ecosystem production (NEP < 0); (3) daily variability of GPP decreases with lake area and water depth as a consequence of lower input of nutrients and organic matter per unit water volume; (4) the influence of benthic processes on free water metabolic measures declines with increasing lake size; and (5) with increasing lake size, lake metabolism decreases significantly per unit water volume, while depth integrated areal rates remain more constant due to a combination of increased light and nutrient limitation. Overall, these meta-parameters have as many significant but usually weaker relationships to whole-lake and benthic metabolism as have TP, Chl and DOC that are directly linked to photosynthesis and respiration. Combining water depth and Chl to predict GPP, and water depth and DOC to predict R, lead to stronger multiple regression models accounting for 57–63% of the variability of metabolism among the 25 lakes. It is therefore important to consider differences in lake morphometry and catchment conditions when comparing metabolic responses of lakes to human impacts.     

Metal binding by dissolved organic matter in hypersaline water: A size fractionation study using different isolation methods

The influence of dissolved organic matter (DOM) on mineral extraction from salt lake brines depend on DOM quality. This study contributes to our knowledge of DOM’s metal binding behavior in hypersaline environments by characterization of DOM from lakes in the Qaidam Basin, i.e., Qarhan Lake (LQDOM), Da Qaidam (DQDOM) and West Ginair Salt Lake (WGDOM). The DOM was fractionated based on solid phase extraction (SPE) and ultrafiltration (UF), and the spectral and metal binding behavior of these fractions were studied by absorption spectroscopy, Pb(II) titration techniques and fluorescence parallel factor (PARAFAC) analysis. The results showed that bulk DOM generally contained more dissolved organic carbon (DOC), lower specific UV absorbance (SUVA₂₅₄), higher fluorescence and biological indices, comparable humification index, and lower condition stability constants compared to the other nature waters. Compared with UF, SPE-derived DOM exhibited higher DOC recovery and aromaticity and lower carbohydrate yield. It appeared that the SPE procedure used affects the spectral composition of bulk DOM to a larger extent than UF. Source and molecular weight (MW)-dependent differences in abundance and quality of brine DOM was indicated by higher SUVA₂₅₄ in high MW DOM, for LQDOM and DQDOM, and humic-like fluorophores were mainly in high MW-DOM in each lake. Moreover, the high MW humic-like component exhibited higher metal binding potential than the bulk and low MW counterparts for LQDOM and DQDOM, while the inverse was observed for WGDOM. This study revealed the effects of isolation techniques on interpretation of DOM characteristics, and meanwhile highlighted the importance of origin- and MW-dependent DOM in manipulating the behavior, fate, and bioavailability of heavy metals in salt lake brine.     

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.     

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.     

Changes in the spectral and chemical properties of a water mass passing through extensive macrophyte beds in a large fluvial lake (Lake Saint-Pierre, Québec, Canada)

Large fluvial lakes, as part of river corridors, are recognized as spatially heterogeneous ecosystems. Due to their shallowness, the littoral zone of these lakes occupies a large proportion of their surface and is extensively covered by macrophytes that are known to affect their physical, chemical and biological environments in various ways. This study documents the small-scale (5 km) bio-optical variations associated with the longitudinal passage of a water mass through macrophyte beds during their maximal growth season. The utilization of a 2D hydrodynamic model allowed us to establish hydrological connectivity between stations within the beds, and thus to identify longitudinal heterogeneity along the macrophyte beds. Significant changes in the inherent properties of the water were observed along the upstream-downstream gradient. Due to their effects on hydrodynamics, macrophytes were responsible for a decrease in particles and dissolved organic carbon (DOC) resulting in an increasing penetration depth of ultraviolet (UV) and photosynthetically active radiation (PAR). Along the transect, chromophoric dissolved organic matter (CDOM) decreased more rapidly than DOC resulting in a decrease of the CDOM to DOC ratio. The observed changes in the DOC pool may be explained by the constant input of non-chromophoric DOC from macrophyte leachates and exudation within the bed and/or the photochemical and microbial degradation of CDOM. The implication of such small-scale heterogeneity on Lake Saint-Pierre productivity is discussed.     

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.     

长江中游湖泊CDOM光学特性及其空间分布对比

根据2007年秋季洪湖、东湖和梁子湖的调查结果,分析了长江中游3个典型湖泊CDOM光学特性及其空间分布差异.结果表明:(1)CDOM吸收系数在洪湖最高,梁子湖最低;(2)在洪湖,CDOM吸收系数受陆源影响较大,与悬浮泥沙浓度呈现较好正相关关系,而在梁子湖,CDOM吸收系数主要受到浮游植物降解贡献,与叶绿素浓度具有显著的正相关关系;(3)洪湖与东湖指数函数斜率S值变化不大;梁子湖CDOM吸收系数空间分布差异较大,指数函数斜率S值与400nm波段CDOM吸收系数ag(400)显著负相关.在建立梁子湖CDOM遥感反演模型时,应引入上述指数甬数斜率S值与400nm波段CDOM吸收系数之间的线性函数,对CDOM吸收系数的指数模型进行优化.     

太湖冬季有色可溶性有机物吸收荧光特性及遥感算法

基于2006年和2007年1月两次太湖采样,对50个点位的有色可溶性有机物(CDOM)光谱吸收、荧光、溶解性有机碳(DOE)浓度及遥感反射率进行测定与分析,探讨冬季太湖CDOM的吸收荧光特性及空间分布,建立CDOM吸收系数的遥感反演算法.结果表明,太湖冬季CDOM在355nm处吸收系数a(355)变化范围和均值分别为1...     

Organic matter governs N and P balance in Danube Delta lakes

The transformation of dissolved inorganic nitrogen (DIN) and soluble reactive phosphorous (SRP), and the release of dissolved organic and particulate N and P, were analyzed in two lake complexes (Uzlina–Isac and Puiu–Rosu–Rosulet) of the Danube Delta wetland during flood conditions in May and at low water level in September 2006. The Uzlina–Isac complex was hydrologically tightly-connected with the Danube River and was flushed with river-borne nutrients and organic matter. These lakes acted as effective transformers for nutrients and produced large amounts of fresh biomass, that promoted the excretion of dissolved organic N and P during active growth. Biomass breakdown created particulate matter (<0.45 μm), which was widely liberated during low flow in the fall. The Puiu–Rosu–Rosulet complex was characterized by a more distant position to the Danube and proximity to the Black Sea, and received dominantly transformed organic compounds from the flow-through water and vast vegetation cover. Due to reduced nutrient input, the internal production of organic biomass also was reduced in these more remote lakes. Total N and P export from the lake nearest to the shelf was governed by dominantly dissolved organic and particulate compounds (mean 58 and 82%, respectively). Overall, this survey found that these highly productive wetlands efficiently transform nutrients into a large pool of dissolved organic and particulate N and P. Hence, wetland lakes may behave widely as net sources of organic N and P to downstream waters and coastal marine systems.     

抚仙湖有色可溶性有机物的来源组成与时空变化

基于2017年1-12月在抚仙湖开展的逐月观测,利用紫外-可见吸收光谱和三维荧光光谱技术探讨该湖有色可溶性有机物（CDOM）的来源组成及时空变化特征.12个月CDOM吸收值a（254）的均值为3.47±0.57 m^-1,范围为1.82~5.22 m^-1,说明CDOM丰度较低.平行因子分析结果给出了2种类酪氨酸荧光组分（C1和C3）、1种类色氨酸荧光组分（C2）、1种类腐殖质荧光组分（C4）,12个月内源组分（C1+C3）对总荧光强度的平均贡献为65.81%±15.38%,外源组分（C2+C4）的平均贡献为34.19%±15.38%;荧光指数FI的均值为1.73±0.14,腐殖化指数HIX的均值为1.02±0.37,生源化指数BIX的均值为1.23±0.27,说明CDOM主要为微生物内源产生.时空变化方面,春（3-5月）、夏（6-8月）、秋（9-11月）和冬（1、2、12月）季的a（254）分别为3.20±0.47、3.76±0.64、3.67±0.50和3.23±0.38 m^-1,夏季和秋季均显著高于冬季和春季;CDOM丰度及内外源组分的空间分布具有季节异质性,可能与流域土地利用、河流输入、降雨、温度、光辐射等因素有关.     

Correlation between molecular absorption spectral slope ratios and fluorescence humification indices in characterizing CDOM

Ultraviolet–visible absorption spectral slope ratios S_R (slope in 275–295 nm divided by slope in 350–400 nm) and humification index (HIX, integrated fluorescence emission in 435–480 nm divided by that in 435–480 and 300–345 nm) were compared when characterizing chromophoric dissolved organic matter (CDOM) in three humic acids and 44 whole water samples. HIX increased with increasing pH for humic acids, while their S_R showed much more complicated dependencies on pH. There was a negative correlation between S_R and HIX. S_R increased in the order terrestrial coal/peat < terrestrial soil/river < seawater, while HIX increased in the order seawater < terrestrial soil/river < terrestrial coal/peat. The comparative study in this work indicates that terrestrially derived CDOM has higher HIX and lower S_R than marine CDOM. Investigators may potentially use these two indices to compare qualitatively the character of CDOM in different sources (e.g., terrestrial vs. marine).