Determination of dissolved organic matter in streamwater using visible spectrophotometry: A reply

A reply to Finlayson (1986) suggesting that the priority should be for more widespread measurement of dissolved organic matter, without the need for special equipment. The use of chemical oxygen demand is also clarified.     

Determination of dissolved organic matter in streamwater using visible spectrophotometry

Absorbance at 360 nm was measured on 44 filtered streamwater samples of different dissolved organic matter (DOM) contents. A regression equation of DOM on absorbance predicted DOM with a standard error of estimate of 1.26 mgl^?1, Use of a published equation relating dissolved organic carbon (DOC) to absorbance gave DOC values for the samples which were consistent with measured DOM. The method offers considerable potential for rapid quantification of dissolved organic matter concentrations in streamwater.     

Patterns of dissolved organic matter in subarctic peatlands

Samples of water from poor to very rich fens in the Schefferville region of subarctic Quebec revealed strong spatial and temporal variations in dissolved organic carbon (DOC), ranging from 2 to 40 mg 1^?1. Concentrations of DOC tend to increase during the summer and decrease in the autumn, at most sites, which probably reflects increased plant tissue decomposition and higher rates of evapotranspiration. Principal components analysis revealed that DOC is strongly associated with Fe, NO^?₃-N and NO^?₂-N, but essentially independent of other chemical properties of the peat water, such as pH, Ca, Mg, K, P, and NH⁺₄-N. Based on observed concentrations of DOC and estimates of summer runoff (June to September), export of DOC from four peatlands ranges from 1·1 to 4·9 gCm^?2, with the lowest values for peatlands underlain by dolomite. Molecular weight fractionation of four samples revealed significant differences in the dissolved organic matter (DOM), with the largest fractions (GF/C to 10 000 nmw) being dominant in the more acid samples. The ratio of absorbance at 400 and 600 nm wavelengths (E₄:E₆) has been used as a simple indicator of differences in DOM type, ranging from 3 to 15. There is a strong seasonal pattern of increasing E₄:E₆ ratio during the summer at many sites, though this ratio is essentially independent of other chemical properties of peat waters.     

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.     

溶解性有机质与水生生物的直接相互作用研究进展

溶解性有机质广泛存在于天然水体中,具有重要的生态与环境意义.然而在环境科学领域内,天然水体中的溶解性有机质长期以来仅仅被作为惰性的吸附剂对待,其自身的与生物的直接作用却一直被忽视.近年来,越来越多的研究证据表明溶解性有机质自身即具有生物效应.它能在生物表面吸附.并影响细胞膜的电化学性质与膜渗透性,能被生物吸收,进而诱导...     

Relationships among dissolved organic matter,iron, and discharge in a moorland stream

Dissolved organic matter (DOM) and iron in a moorland stream were determined at 8-hour intervals over a 6-month period to examine relationships with streamflow. Regression of both solutes on discharge were positive and explained 50–70 per cent of the variance in the solute data, but better predictions were obtained in both cases when a covariate reflecting temporal variation in the relationships was introduced (explained variance 80–90 per cent). Variations in the regression of Fe on DOM were also identified, indicating differences in the complexing power of DOM for Fe and possible variations in the chemical composition of the DOM.     

草源型可溶性有机物降解过程中活性氧物种产生过程

活性氧物种(ROS)参与天然水体系统中的光化学反应、氧化还原反应,是影响水体中有机污染物的迁移、转化、环境归宿及生态效应的重要因素.然而目前对草源型可溶性有机物(DOM)分解过程中ROS的产生过程并不清楚.本文通过室内模拟实验首先构建了室内测定3种ROS(³CDOM^*、¹O₂、·OH)的方法,进而分析草源植物——苔草(Carex tristachya)残体浸出液中DOM光降解过程中ROS的产生过程.结果表明:ROS累积含量的产生随着DOM的降解逐渐升高在3种自由基含量中,³CDOM*的产生含量最多,·OH产生含量低于另外2种ROS两个数量级.CDOM含量与³CDOM^*、¹O2、·OH浓度呈现正相关关系,尤其与³CDOM^*和¹O₂浓度的显著性水平最高,·OH次之.ROS浓度与水质指标呈现出不同的线性相关关系,与硝态氮浓度呈负相关...     

三峡库区土地利用对河流溶解性有机质的多时空尺度影响

三峡库区拥有目前世界上规模最大的水利枢纽工程,自投入使用以来,为长江流域提供了丰富的水源及电力,促进了经济的发展,但同时也对该区域的生态环境造成了严重的冲击。澎溪河流域作为三峡库区长江流域干流的典型回水区和消落带,是众多学者研究三峡库区生态环境变化的重点区域。为探究不同时空尺度下土地利用对河流溶解性有机质（DOM）的影响,以澎溪河流域为研究对象,基于紫外-可见光谱分析和三维荧光光谱矩阵-平行因子分析,结合河段缓冲区、河岸带缓冲区及子流域3种空间尺度的二级土地利用类型,解析了旱雨季水体DOM的组成及来源特征,并采用相关分析和冗余分析方法探讨了3种空间尺度下土地利用方式对旱雨季水体DOM的多时空尺度影响。结果表明：（1）旱季水体DOM荧光组分以陆源类腐殖质所占比例更大,雨季水体DOM荧光组分以富里酸贡献为主。（2）流域内陆源输入和内源产生对水体DOM丰度均有贡献,雨季较旱季水体DOM的陆源性更强,自生源特征较弱。（3）土地利用在雨季和子流域尺度下对水体DOM的影响更显著,其中,雨季子流域尺度下,土地利用指数对水体DOM参数的解释率为90.35%。（4）不同土地利用方式对水体DOM产生的影响...     

Compositions and constituents of freshwater dissolved organic matter isolated by reverse osmosis

Dissolved organic matter (DOM) from riverine and lacustrine water was isolated using a reverse osmosis (RO) system. Solid-state ¹³C nuclear magnetic resonance (¹³C NMR) was used to quantitatively evaluate the compositions and constituents of DOM, which are compared with previous investigations on marine DOM. Results indicated that concentration factor (CF) was a key metric controlling yield and sorption of DOM on the RO system. The sorption was likely non-selective, based on the ¹³C NMR and δ¹³C analyses. Carbohydrates and lipids accounted for 25.0–41.5% and 30.2–46.3% of the identifiable DOM, followed by proteins (18.2–19.8%) and lignin (7.17–12.8%). The freshwater DOM contained much higher alkyl and aromatic C but lower alkoxyl and carboxyl C than marine DOM. The structural difference was not completely accounted for by using structure of high molecular weight (HMW) DOM, suggesting a size change involved in transformations of DOM during the transport from rivers to oceans.     

周村水库汛期暴雨中溶解有机物(DOM)的光谱特征及来源解析

运用三维荧光光谱（EEMs）技术结合平行因子分析法（PARAFAC）,对周村水库夏季两场暴雨不同降雨历时以及分子量的溶解有机物光谱特征和来源进行分析.结果表明：周村水库不同暴雨荧光光谱中出现了5种组分,分别为类腐殖质（C1、C2）、可见区富里酸（C3）和类蛋白（C4、C5）;相关性分析显示C1与C2、C3、C4以及C5具有显著的相关性,C2与C3具有显著的相关性,C3与C4以及C5具有显著的相关性;同一分子量下的雨水有机质总荧光强度以及各组分荧光强度随着降雨历时的增加均呈下降趋势,并且在各个历时和分子量间差异明显;同一降雨历时下,第一场暴雨总荧光强度随着分子量的减少而增加,第二场暴雨总荧光强度随着分子量的减少而减少;两场暴雨都呈现自生源的特征,其中第一场暴雨具有以陆源输入为主的特征;组分C1和C3与水质参数硝态氮、氨氮、总氮以及有机碳呈显著相关性.通过对暴雨在不同降雨历时以及分子量DOM光谱特征研究,可以进一步分析水库外源输入的天然有机质特征,为水库水质管理提供技术支持.     

Seasonal changes in iron transport and nature of dissolved organic matter in a humic river in northern Finland

Changes in the concentration of iron and dissolved organic matter (DOM), and in the colour and fluorescence properties in the River Kiiminkijoki were investigated as functions of the seasonal flow regime over a two-year period. The iron concentration in filtrates and the ratio of Fe to DOC in the river increased under low flow conditions and decreased during the flood periods. The colour of the dissolved organic matter increased with increasing iron content, the effect being more pronounced during the warm period of the year than in winter. The ratio of fluorescence to DOC increased during the warm period of the year but not in winter, and decreased rapidly with discharge at the beginning of the flood period in autumn. The results give indications of the origin, formation, nature, and fate of the DOM in the river water. Temperature-dependent microbiological processes in the formation and sedimentation of iron-organic colloids seem to be important. Estimates are given for the amounts and transport rates of iron discharged into the Gulf of Bothnia by the river.     

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:C3>C2> 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.     

On the use of UV spectrophotometry to assess dissolved organic carbon origin variations in the Upper Rhône River

To detect temporal changes and the origin of the refractory dissolved organic matter in the Upper Rhône River, UV light absorbance (A) at 285 nm and quantitative dissolved organic carbon (DOC) measurements were carried out. Data from 63 visits to the main channel over a period of two years and from visits to different waterbodies in the alluvial plain before and after a flood are presented. There was a good correlation between A (0.019–0.160) and the DOC content (1.40–9.81 mg/L) for the waterbodies, but not for the river axis with lower A (0.013–0.044) and DOC content (1.13–2.20 mg/L). Due to this good correlation, the DOC content could be quantified for the waterbodies by absorbance measurements only. For the river water this indirect determination of the DOC content was not possible. However, the A/DOC ratio showed changes in the composition of DOC of river water and provided indications about the origin of the dissolved organic matter in the Upper Rhône River.     

Short term fluctuations in dissolved organic matter concentrations in streamflow draining a forested watershed and their relation to the catchment budget

Dissolved organic matter (DOM) concentrations in throughfall, throughflow, and runoff were recorded in a small (95 ha) woodland catchment in North Warwickshire for a period of eight weeks following a prolonged dry spell. DOM is shown to be positively related to stream discharge over the sampling period, although distinctive flushing effects were identified. The net contribution of DOM to total dissolved solids load carried in the river was only 2.4 per cent, and represented significantly less than published carbon losses by mineralization of soil organic matter. Throughfall inputs were some 100 times higher than streamflow outputs from the catchment.     

Optical signatures of dissolved organic matter in the watershed of a globally large river (Yangtze River,China)

Parallel factor analysis of fluorescence excitation emission matrices of surface water samples of a globally large river (Yangtze River, China) watershed identified three classes of fluorescent dissolved organic matter (FDOM) that had ex/em = 280/330 nm, 305/385 nm and 350/450 nm respectively, resembling “peak T”, “peak M” and “peak C” commonly identified in natural water, respectively. Peak T (a tyrosine/tryptophan-like FDOM) did not show correlations to peak M or C which were humic-like substances, while a positive correlation (r = 0.935, p < 0.001) was present between the natural log-transformed maximum fluorescence intensity (F_max) of peaks T and M indicating a tight link during their production and processing. F_max values (in Raman unit nm^?1) normalized to dissolved organic carbon (DOC) concentration were low, varying in ranges 15.93–85.95, 29.83–83.54 and 19.73–51.05 × 10^?5 nm^?1 (μmol/L)^?1 for peaks T, M and C, respectively, in line with the history of strong photobleaching of the water samples as indicated by fairly high absorption spectral slope ratios (0.75–1.53 with a mean 1.03). Intermediate fluorescence index (FI) (1.46–1.83 with a mean 1.61) and small specific absorption at 254 nm (0.64–1.93 with a mean 1.15 m^?1 mg^?1 L) of the water samples, indicated the presence of both aquatic microbial DOM (e.g. peak T) and soil DOM (e.g. peak C). Peak C could be substantially removed by UV-A (320–400 nm) irradiation, while peak M was slightly increased when a microbe-containing water was exposed to the same UV-A irradiation. Taken together, peak C was attributed to diffuse soil source while peak M was likely attributed to joint effects of microbial activities and solar irradiation on the chromophores in the sample.     

Changes in dissolved organic matter (DOM) amount and composition along nested headwater stream locations during baseflow and stormflow

Amount and composition of dissolved organic matter (DOM) were evaluated for multiple, nested stream locations in a forested watershed to investigate the role of hydrologic flow paths, wetlands and drainage scale. Sampling was performed over a 4‐year period (2008–2011) for five locations with drainage areas of 0.62, 3.5, 4.5, 12 and 79 ha. Hydrologic flow paths were characterized using an end‐member mixing model. DOM composition was determined using a suite of spectrofluorometric indices and a site‐specific parallel factor analysis model. Dissolved organic carbon (DOC), humic‐like DOM and fluorescence index were most sensitive to changes with drainage scale, whereas dissolved organic nitrogen, specific UV absorbance, Sr and protein‐like DOM were least sensitive. DOM concentrations and humic‐like DOM constituents were highest during both baseflow and stormflow for a 3.5‐ha catchment with a wetland near the catchment outlet. Whereas storm‐event concentrations of DOC and humic DOM constituents declined, the mass exports of DOC increased with increasing catchment scale. A pronounced dilution in storm‐event DOC concentration was observed at peak stream discharge for the 12‐ha drainage location, which was not as apparent at the 79‐ha scale, suggesting key differences in supply and transport of DOM. Our observations indicate that hydrologic flow paths, especially during storms, and the location and extent of wetlands in the catchment are key determinants of DOM concentration and composition. This study furthers our understanding of changes in DOM with drainage scale and the controls on DOM in headwater, forested catchments. Copyright © 2014 John Wiley & Sons, Ltd.     

Spectrophotometric discrimination of river dissolved organic matter

There is a need to be able to differentiate the dissolved organic matter (DOM) fraction in river waters. Research in the 1970s and 1980s has attempted to utilize both absorbance and fluorescence to distinguish between DOM fractions in river waters, but both were limited by the available technology. Total organic carbon content has, therefore, been widely used as a standard method of measuring DOM concentration, although it has little power to differentiate DOM fractions. Recent advances in fluorescence spectrophotometry enable rapid and optically precise analysis of DOM. Here, we show how a combination of both fluorescence and absorbance can be used to discriminate statistically between spatial variations of DOM in tributaries in a small catchment of the Ouseburn, NE England. The results of the discriminant analysis suggest that about 70% of the samples can be correctly classified to its tributary. Discriminant function 1 explains 60·8% of the variance in the data and the fulvic‐like fluorescence intensity has the largest absolute correlation within this function; discriminant function 2 explains a further 21·5% of the variance and the fulvic‐like fluorescence emission wavelength has the largest absolute correlation within this function. The discriminant analysis does not correctly classify all tributaries every time, and successfully discriminates between the different tributaries 70% of the time. Occasions when the tributary waters are less well discriminated are due to either episodic pollution events (at two sites) or due to tributaries that have strong seasonal trends in spectrophotometric parameters, which allows the sites to be misclassified. Results suggest that spectrophotometric techniques have considerable potential in the discrimination of DOM in rivers. Copyright © 2002 John Wiley & Sons, Ltd.