New light on a dark subject: comment

In their article, “New light on a dark subject: On the use of fluorescence data to deduce redox states of natural organic matter,” Macalady and Walton-Day (2009) subjected natural organic matter (NOM) samples to oxidation, reduction, and photochemical transformation. Fluorescence spectra were obtained on samples, which were diluted “to bring maximum uvvisible absorbance values below 1.0.” The spectra were fit to the Cory and McKnight (2005) parallel factor analysis (PARAFAC) model, and consistent variation in the redox state of quinone-like moieties was not detected. Based on these results they concluded that fitting fluorescence spectra to the Cory and McKnight (2005) PARAFAC model to obtain information about the redox state of quinone-like moieties in NOM is problematic. Recognizing that collection and correction of fluorescence spectra requires consideration of many factors, we investigated the potential for inner-filter effects to obscure the ability of fluorescence spectroscopy to quantify the redox state of quinone-like moieties. We collected fluorescence spectra on Pony Lake and Suwannee River fulvic acid standards that were diluted to cover a range of absorbance wavelengths, and fit these spectra to the Cory and McKnight (2005) PARAFAC model. Our results suggest that, in order for the commonly used inner-filter correction to effectively remove inner-filter effects, samples should be diluted such that the absorbance at 254 nm is less than 0.3 prior to the collection of fluorescence spectra. This finding indicates that inner-filter effects may have obscured changes in the redox signature of fluorescence spectra of the highly absorbing samples studied by Macalady and Walton-Day (2009).     

The Analysis of the Seasonal,Spatial, and Compositional Distribution of Humic Substances in a Subtropical Shallow Lake

The spatial and temporal distribution of humic substances in aquatic ecosystems can have important effects on ecosystem productivity, negatively impacting primary productivity while positively impacting secondary productivity. In the present investigation, a large shallow lake ecosystem was studied to determine the spatial and seasonal variation of the composition and concentration of humic substances. Concentrations of total dissolved organic matter, humic acid, and fulvic acid were found to display significant spatial distributions (1.3…13.5 mg/L, DOM; 0.1…5.4 mg/L, HA). The distribution is described by using mapping techniques and the analysis of the spatial distribution of the lake. An analysis of the seasonal variations also indicated the dependence of the occurrence of these compounds on meteorological and hydrological conditions. To identify the potential sources of these organic materials, an analysis was made of the ratio of humic and fulvic acid fractions and total DOM. It was found that areas of high DOM concentration coincided with the areas of highest HA percentage of total DOM. Furthermore using the ratio of the normalised concentrations of HA, FA, and residual DOM (< 5000 g/mol) it was found that areas dominated by each are spatially distinct. This confirms the hypothesis that in these shallow lakes, photodegradation and bacterioplankton activity will create a residence time dependent zonation of each component of the total DOM.     

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.     

Effect of pH on binding of pyrene to hydrophobic fractions of dissolved organic matter(DOM) isolated from lake water

In order to better understand the compositional and structural complexity of dissolved organic matter(DOM) macromolecules and provide mechanistic information on the binding of hydrophobic organic contaminants(HOCs) to DOM, we fractionated large amounts of lake water into three hydrophobic DOM-fractions. The variation of the partitioning coef?cients(K_(DOC)) of pyrene at different p H levels was examined by ?orescence quenching titration. Results show that, relative to the more polar acidic DOM-fractions, the hydrophobic neutral fraction exhibits a higher sorption ability to pyrene. Generally, the sorption of pyrene to the three hydrophobic fractions is strongly pH-dependent. The K_(DOC) values of pyrene generally increase with decreasing p H levels, which is especially obvious in the sorption of pyrene to the fulvic acid fractions, suggesting that the binding is controlled by hydrophobic interactions. The mechanisms underlying the binding of pyrene to the hydrophobic fractions were also discussed. Our data are bene?cial to further understanding the binding of HOCs to DOM and how it has been affected,which may result in more accurate predictions of K_(DOC).     

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%,...     

Evaluation of forest disturbance legacy effects on dissolved organic matter characteristics in streams at the Hubbard Brook Experimental Forest,New Hampshire

Dissolved organic matter (DOM) source and composition are critical drivers of its reactivity, impact microbial food webs and influence ecosystem functions. It is believed that DOM composition and abundance represent an integrated signal derived from the surrounding watershed. Recent studies have shown that land-use may have a long-term effect on DOM composition. Methods for characterizing DOM, such as those that measure the optical properties and size of the molecules, are increasingly recognized as valuable tools for assessing DOM sources, cycling, and reactivity. In this study we measured DOM optical properties and molecular weight determinations to evaluate whether the legacy of forest disturbance alters the amount and composition of stream DOM. Differences in DOM quantity and composition due to vegetation type and to a greater extent, wetland influence, were more pronounced than effects due to disturbance. Our results suggest that excitation-emission matrix fluorescence with parallel factor analysis is a more sensitive metric of disturbance than the other methods evaluated. Analyses showed that streams draining watersheds that have been clearcut had lower dissolved organic carbon (DOC) concentrations and higher microbially-derived and protein-like fluorescence features compared to reference streams. DOM optical properties in a watershed amended with calcium, were not significantly different than reference watersheds, but had higher concentrations of DOC. Collectively these results improve our understanding of how the legacy of forest disturbances and natural landscape characteristics affect the quantity and chemical composition of DOM in headwater streams, having implications for stream water quality and carbon cycling.     

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.     

新疆艾比湖流域枯、丰水期三维荧光光谱特性及其与水质的关系

以艾比湖流域主要入湖河流为研究对象,在5月（丰水期）和8月（枯水期）分别沿博尔塔拉河（博河）和精河进行采样,采用平行因子模型（PARAFAC）和三维荧光区域积分法对水体三维荧光特性进行研究并对其与水质的关系在枯、丰水期下的变化进行探讨.结果表明①河流DOM在枯水期与丰水期都含有C1（240、425 nm） UVC类腐殖质,C2（225、290 nm）紫外区内络氨酸类有机物,C3（230/280、330 nm）蛋白类有机物,C4（265、260 nm）腐殖质类共4种组分.通过对水体三维荧光进行区域积分可以看出DOM荧光成分的占比在不同时期的变化.博河在枯水期时EEM光谱中的区域Ⅲ富里酸含量低于丰水期,枯水期时区域Ⅱ芳香类蛋白质、区域Ⅳ可溶性微生物代谢物以及区域Ⅴ类腐殖质酸高于丰水期;对于精河来说,区域Ⅱ芳香类蛋白质和区域Ⅳ可溶性微生物代谢物在枯水期的含量高于丰水期,区域Ⅲ富里酸和区域Ⅴ类腐殖质酸的含量枯水期低于丰水期,这表明水体腐质化程度较高.②本研究选取了一些常规的荧光指数来描述枯、丰水期水体的荧光指数特性.经研究发现,精河的荧光指数、自生源指数和腐殖化指数在不同时期的变化幅度较小,而博河的变化幅度较大.③将荧光指数与水质参数进行相关性分析并建模,结果表明枯水期自生源指数（BIX）与化学需氧量呈显著正相关,相关系数R=0.688;丰水期时BIX与铵态氮浓度呈显著负相关,相关系数R=-0.493.通过对比分析艾比湖主要入湖河流的三维荧光光谱特性与水质在枯、丰水期时的关系进一步表明水体中DOM的特性以及在枯、丰水期下的差异,为艾比湖流域的治理改善提供一定的理论支持和参考依据.     

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.     

针铁矿对湖泊草、藻来源可溶有机质的非均质吸附

为探究富营养化湖泊中自生源可溶有机质(DOM)在泥水界面的吸附行为,以马来眼子菜(Potamogeton malaianus)和铜绿微囊藻(Microcystis aeruginosa)释放的DOM为代表,考察针铁矿对草、藻源DOM中不同组分的吸附特征.三维荧光平行因子分析表明类富里酸组分C1和类胡敏酸组分C4的含量很低,而类蛋白物质(类酪氨酸组分C2和类色氨酸组分C3)分别占草、藻源DOM荧光组成的70%和93%. 2种DOM均可被针铁矿吸附,吸附过程符合伪一级动力学.通过等温线拟合发现针铁矿吸附藻源DOM的非线性更强,饱和吸附量(23.77 mg/g)高于草源DOM(19.10 mg/g).特别地,类蛋白组分呈现非线性吸附,而类腐殖物质的吸附近似线性,且针铁矿对于DOM各荧光组分的吸附量顺序为:C3C2 C4 C1,此非均质吸附特征与DOM组分的初始含量、分子大小、芳香性及有效吸附位点有关.红外光谱证实氨基、羧基和羟基是吸附过程中的重要官能团.因此,草、藻源DOM显著改变了针铁矿表面的有机物质组成,影响湖泊沉积物的生物地球化学行为.     

洱海沉积物有色可溶性有机物(CDOM)三维荧光空间分布特性及指示意义

采用荧光光谱区域体积积分法定量研究洱海沉积物有色可溶性有机物（CDOM）三维荧光空间分布特性,结果表明,洱海沉积物CDOM中类腐殖酸组分占比最高（44.5%~74.2%）,其次为溶解性微生物代谢产物（10.7%~20.4%）和类富里酸物质（8.19%~19.7%）,而类蛋白组分占比最低,类腐殖酸占比与H/C和N/C均呈显著负相关;南部湖心平台区域沉积物类富里酸和类蛋白组分占比较高,其CDOM自生源占比较高;北部水生植物分布区溶解性微生物代谢产物占比较高,CDOM陆源性较强;中部深水区及南北湖湾区域类腐殖酸占比较高,随水深增加沉积物CDOM自生源特征增强.随沉积物深度增加类腐殖酸和溶解性微生物代谢产物占比呈下降趋势,类富里酸占比呈上升趋势,CDOM自生源特征增强,脂肪化程度增高.随湖泊富营养化程度增加沉积物CDOM受微生物代谢产物影响增强,陆源性增加,而自生源性降低,湖泊沉积物CDOM具有富营养化指示意义.     

Dissolved organic matter in surface runoff in the Loess Plateau of China: The role of rainfall events and land-use

Exploring the chemical characterization of dissolved organic matter (DOM) is important for understanding the fate of laterally transported organic matter in watersheds. We hypothesized that differences in water-extractable organic matter (WEOM) in soils of varying land uses and rainfall events may significantly affect the quality and the quantity of stream DOM. To test our hypotheses, characteristics of rainfall-runoff DOM and WEOM of source materials (topsoil from different land uses and gullies, as well as typical vegetation) were investigated at two adjacent catchments in the Loess Plateau of China, using ultraviolet–visible absorbance and excitation emission matrix fluorescence with parallel factor analysis (PARAFAC). Results indicated that land-use types may significantly affect the chemical composition of soil WEOM, including its aromaticity, molecular weight, and degree of humification. The PARAFAC analysis demonstrated that the soils and stream water were dominated by terrestrial/allochthonous humic-like substances and microbial transformable humic-like fluorophores. Shifts in the fluorescence properties of stream DOM suggested a pronounced change in the relative proportion of allochthonous versus autochthonous material under different rainfall patterns and land uses. For example, high proportions of forestland could provide more allochthonous DOM input. This study highlights the relevance of soils and hydrological dynamics on the composition and fluxes of DOM issuing from watersheds. The composition of DOM in soils was influenced by land-use type. Precipitation patterns influenced the proportion of terrestrial versus microbial origins of DOM in surface runoff. Contributions of allochthonous, terrestrially derived DOM inputs were highest from forested landscapes.     

Evaluating carbon storage on subalpine lake deltas

Mountainous regions are important contributors to the terrestrial organic carbon (OC) sink that affect global climate through the regulation of carbon‐based greenhouse gases. However, mountain OC dynamics are poorly quantified. We quantified OC storage in subalpine lake deltas in the Washington Central Cascades and Colorado Front Range with the objectives of determining the magnitude of transient carbon storage and understanding the differences in storage between the two ranges. We used field, laboratory, and GIS techniques to determine the magnitude of and controls on the subalpine lake delta OC pool in 26 subalpine lake deltas. Soil moisture, soil texture, mean basin slope, and delta valley confinement are significantly correlated with soil carbon on deltas. Average soil OC concentration on subalpine lake deltas ranges from 3 to 41%, and stocks range from 140 to 1256 Mg C/ha. Surprisingly, the carbon content of subalpine lake deltas is not significantly different between the two regions, despite stark contrasts in their climate, vegetation, and total ecosystem carbon stocks. We present a conceptual model that invokes geomorphic and biogeochemical processes to suggest that carbon is more likely to reach subalpine lake deltas from the upstream basin in the Colorado Front Range compared with the Washington Central Cascades, thus accounting for the similarity in OC storage between the two regions despite differences in total ecosystem carbon stocks and climate. This points to a complex interaction among carbon production, transport, and stability in each region, and supports the idea that geomorphic and biogeochemical processes determine the magnitude of transient OC storage more strongly than primary productivity or climate. Copyright © 2017 John Wiley & Sons, Ltd.     

Dissolved organic matter variations in coastal plain wetland watersheds: The integrated role of hydrological connectivity,land use,and seasonality

Dissolved organic matter (DOM) is integral to fluvial biogeochemical functions, and wetlands are broadly recognized as substantial sources of aromatic DOM to fluvial networks. Yet how land use change alters biogeochemical connectivity of upland wetlands to streams remains unclear. We studied depressional geographically isolated wetlands on the Delmarva Peninsula (USA) that are seasonally connected to downstream perennial waters via temporary channels. Composition and quantity of DOM from 4 forested, 4 agricultural, and 4 restored wetlands were assessed. Twenty perennial streams with watersheds containing wetlands were also sampled for DOM during times when surface connections were present versus absent. Perennial watersheds had varying amounts of forested wetland (0.4–82%) and agricultural (1–89%) cover. DOM was analysed with ultraviolet–visible spectroscopy, fluorescence spectroscopy, dissolved organic carbon (DOC) concentration, and bioassays. Forested wetlands exported more DOM that was more aromatic‐rich compared with agricultural and restored wetlands. DOM from the latter two could not be distinguished suggesting limited recovery of restored wetlands; DOM from both was more protein‐like than forested wetland DOM. Perennial streams with the highest wetland watershed cover had the highest DOC levels during all seasons; however, in fall and winter when temporary streams connect forested wetlands to perennial channels, perennial DOC concentrations peaked, and composition was linked to forested wetlands. In summer, when temporary stream connections were dry, perennial DOC concentrations were the lowest and protein‐like DOM levels the highest. Overall, DOC levels in perennial streams were linked to total wetland land cover, but the timing of peak fluxes of DOM was driven by wetland connectivity to perennial streams. Bioassays showed that DOM linked to wetlands was less available for microbial use than protein‐like DOM linked to agricultural land use. Together, this evidence indicates that geographically isolated wetlands have a significant impact on downstream water quality and ecosystem function mediated by temporary stream surface connections.