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.     

秋季胶州湾有色溶解有机物荧光特性研究及其来源分析

利用三维荧光光谱(EEMs)-平行因子分析(PARAFAC)技术研究了秋季胶州湾有色溶解有机物(CDOM)的荧光成分组成、分布特征及来源。PARAFAC模型解析出胶州湾CDOM由2类5个荧光组分组成,即类腐殖质成分C1(355nm/430nm)、C2(320nm/390nm)、C3(380nm/465nm)、C4(420(330)nm/505nm)及类蛋白质成分C5(280/325nm)。类腐殖质成分C1、C2、C3和C4的平面分布模式基本一致,呈现由近岸海域向湾中心海域逐渐减小的趋势,而类蛋白质成分C5则是由湾东北部近岸海域向西南部海域呈逐渐减小的趋势。分析表明,秋季胶州湾CDOM类腐殖质成分C1、C2、C3和C4的主要来源为陆源输入,而类蛋白质成分C5主要受城市排污的影响。系统聚类分析表明,以团岛南端和红岛西侧连线为界,所有采样站位被分为两类,分界线西部区域站位CDOM各荧光成分相对含量分别为C1:31.8%~35.5%,C2:30.3%~33.7%,C3:17.1%~20.2%,C4:4.5%~5.2%,C5:9.6%~12.5%;分界线东部区域站位CDOM各荧光成分相对含量分别为C1:30.6%~34.6%,C2:28.8%~32.7%,C3:17.0%~19.1%,C4:3.3%~4.8%,C5:12.1%~18.2%。西部区域CDOM具有较高的C4含量和较低的C5含量,大沽河等河流的陆源输入特征明显,而东部区域CDOM则具有较高的C5含量和较低的C4含量,反映该区域受城市排污影响显著。另外,秋季胶州湾CDOM的HIX范围为1.8~3.2之间,较小的腐殖化因子值反映了秋季胶州湾CDOM的腐殖化程度高较低,在环境中存在时间较短。     

THREE-WAY METHODS FOR THE CALIBRATION OF CHROMATOGRAPHIC SYSTEMS:COMPARING PARAFAC AND THREE-WAY PLS

For the calibration of chromatographic systems,different methods can be used.One class of methodsutilizes three-way approaches.The calibration problem is stated in such a way that the decompositionof a three-way array can serve for the prediction of retention on new stationary phases.Two three-way approaches are presented:the Unfold-PCA and PARAFAC models.The theory ofboth methods is presented and the differences are highlighted,the main difference being that PARAFACis a trilinear decomposition whereas Unfold-PCA is not.Both three-way methods are evaluated on asmall data set consisting of retention measurements of eight solutes at six mobile phase compositions onsix stationary phases.The differences in performance of the two models are minor,For calibration purposes,two variants of the methods are discussed:three-way PLS and an extensionof PARAFAC.Again the theory and differences between the two methods are explained.The predictiveperformance of the two methods is compared using the same data set as earlier.The differences inpredictive performance,however,are minor.Both methods are capable of predicting 98% of thevariation in the test sets.Yet,there are other considerations when comparing methods than predictiveperformance,e.g.the quality of the predictions.     

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.     

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.     

典型湖泊天然有机质与四环素的相互作用

采用荧光滴定法研究四环素(tetracycline,TC)与太湖溶解性有机质(dissolved organic matter,DOM)和玄武湖DOM的相互作用.三维荧光光谱结合平行因子分析显示,2个湖泊的DOM含有3个荧光组分:类富里酸组分C1、类色氨酸组分C2和类络氨酸组分C3.其中C2的荧光强度远高于C1和C3,是DOM的主要荧光组成.3个荧光组分与TC发生了不同程度的静态猝灭,特别当TC浓度为45.5μmol/L时,类蛋白组分的荧光强度完全被猝灭(100%),并且猝灭作用改变了DOM分子的微环境极性.同步荧光光谱联合二维相关图谱进一步表明类色氨酸组分优先和TC发生猝灭作用,其次为类络氨酸组分和类富里酸组分.Ryan-Weber方程适于拟合DOM与TC的猝灭过程,2个湖泊的DOM中3个荧光组分的络合常数lg K值范围为5.05~5.85,大小顺序为C2C3C1.因此,类蛋白组分为主的DOM对TC的络合作用大于类腐殖组分为主的DOM,影响抗生素在湖泊水体中的生物有效性和生态毒性.     

SIMPLE VALIDATORY TOOLS FOR JUDGING THE PREDICTIVE PERFORMANCE OF PARAFAC AND THREE-WAY PLS

The methods PARAFAC and three-way PLS are compared with respect to their ability to predictreversed-phase retention values.Special attention is paid to simple validatory tools,the meaning and useof which are explained.The simple validatory tools consist of percentages of explained variation in the training set and thosethat can be calculated with the use of markers.These markers are special(reference)solutes,the retentionvalues of which are used to gain information about a new object for which predictions are wanted.Different validatory tools can be calculated with the use of these marker retention values:percentagesof used variation and mean sum of squared residuals after applying the model to these marker retentionvalues.The validatory tools are evaluated on their power to estimate their test set counterparts:thepercentages of explained variation in the test set and mean sum of squared prediction errors in the test set.Two different data sets from reversed-phase chromatography are used to evaluate the validatory tools.The first data set has a high signal-to-noise ratio and is measured under the same measurementconditions.The second data set has a low signal-to-noise ratio and is measured under differentmeasurement conditions.Some of the simple validatory tools seem to have relevance to their test setcounterparts,even in the case of the second data set.     

Nitrate content and potential microbial signature of rock glacier outflow,Colorado Front Range

Here we characterize the nutrient content in the outflow of the Green Lake 5 rock glacier, located in the Green Lakes Valley of the Colorado Front Range. Dissolved organic carbon (DOC) was present in all samples with a mean concentration of 0·85 mg L^?1 . A one‐way analysis of variance test shows no statistical difference in DOC amounts among surface waters (p = 0·42). Average nitrate concentrations were 69 µmoles L^?1 in the outflow of the rock glacier, compared to 7 µmoles L^?1 in snow and 25 µmoles L^?1 in rain. Nitrate concentrations from the rock glacier generally increased with time, with maximum concentrations of 135 µmoles L^?1 in October, among the highest nitrate concentrations reported for high‐elevation surface waters. These high nitrate concentrations appear to be characteristic of rock glacier outflow in the Rocky Mountains, as a paired‐difference t‐test shows that nitrate concentrations from the outflow of 7 additional rock glaciers were significantly greater compared to their reference streams (p = 0·003). End‐member mixing analysis suggest that snow was the dominant source of nitrate in June, ‘soil’ solution was the dominant nitrate source in July, and base flow was the dominant source in September. Fluoresence index values and PARAFAC analyses of dissolved organic matter (DOM) are also consistent with a switch from terrestrial DOM in the summer time period to an increasing aquatic‐like microbial source during the autumn months. Copyright © 2006 John Wiley & Sons, Ltd.     

基于张量分解的AoT序列数据有损压缩方法

Array of Things (AoT)通过单一位置上的多传感器对城市系统进行连续动态观测。AoT观测数据量大且持续增长,使得如何利用有限的计算资源进行AoT序列数据的压缩传输成为其应用的关键瓶颈之一。本文提出了一种基于张量分解的AoT序列数据的有损压缩方法。面向其海量、高维且需在传感器端处理的需求,该方法首先将AoT序列数据组织成高维张量,利用算法复杂度较低的张量CANDECOMP/PARAFAC (CP)分解提取各维度上的特征主分量,而后利用张量重构实现特征保持的数据有损压缩。利用基于张量分解的有损压缩方法,针对美国芝加哥市区的24 h内感测的声光电磁数据进行了实验,讨论了不同压缩参数对压缩比、压缩误差、压缩精度、压缩时间、压缩过程运行内存占用和压缩结果内存占用之间的影响。实验结果表明该方法可实现AoT序列数据的有损压缩,其较小的内存占用能够支持传感器端数据压缩。并且与原始光场强度对比表明,压缩后的数据保持了原有时空分布特征。与传统矢量量化编码压缩方法相比,在相同压缩精度下,本文方法的压缩比约高27%~76%,压缩时间约节省46%~73%,压缩结果所占内存约节省17%~57%,因此本文方法具有更高的压缩比,更低的压缩时间和内存占用,可为AoT这一类数据的大规模有损压缩提供借鉴意义。     

TENSORIAL RESOLUTION:A DIRECT TRILINEAR DECOMPOSITION

Modern instrumentation in chemistry routinely generates two-dimensional(second-order)arrays of data.Considering that most analyses need to compare several samples,the analyst ends up with a three-dimensional(third-order)array which is difficult to visualize or interpret with the conventional statisticaltools.Some of these data arrays follow the so-called trilinear model,(?)These trilinear arrays of data are known to have unique factor analysis decompositions which correspondto the true physical factors that form the data,i.e.given the array (?),a unique solution can be found inmany cases for each order X,Y and Z.This is in contrast to the well-known second-order bilinear datafactor analysis,where the abstract solutions obtained are not unique and at best cannot be easilycompared with the underlying physical factors owing to a rotational ambiguity.Trilinear decompositions have had the disadvantage,however,that a non-linear optimization withmany parameters is necessary to reach a least-squares solution.This paper will introduce a method forreducing the problem to a rectangular generalized eigenvalue-eigenvector equation where the eigenbectorsare the contravariant form(pseudo-inverse)of the actual factors.It is shown that the method works wellwhen the factors are linearly independent in at least two orders(e.g.X_(jr),and Y_(jr) are full rank matrices).Finally,it is shown how trilinear decompositions relate to multicomponent calibration,curve resolutionand chemical analysis.