Spatial and temporal variability of dissolved organic matter quantity and composition in an oligotrophic subtropical coastal wetland

Dissolved organic matter (DOM) is an essential component of the carbon cycle and a critical driver in controlling variety of biogeochemical and ecological processes in wetlands. The quality of this DOM as it relates to composition and reactivity is directly related to its sources and may vary on temporal and spatial scales. However, large scale, long-term studies of DOM dynamics in wetlands are still scarce in the literature. Here we present a multi-year DOM characterization study for monthly surface water samples collected at 14 sampling stations along two transects within the greater Everglades, a subtropical, oligotrophic, coastal freshwater wetland-mangrove-estuarine ecosystem. In an attempt to assess quantitative and qualitative variations of DOM on both spatial and temporal scales, we determined dissolved organic carbon (DOC) values and DOM optical properties, respectively. DOM quality was assessed using, excitation emission matrix (EEM) fluorescence coupled with parallel factor analysis (PARAFAC). Variations of the PARAFAC components abundance and composition were clearly observed on spatial and seasonal scales. Dry versus wet season DOC concentrations were affected by dry-down and re-wetting processes in the freshwater marshes, while DOM compositional features were controlled by soil and higher plant versus periphyton sources respectively. Peat-soil based freshwater marsh sites could be clearly differentiated from marl-soil based sites based on EEM–PARAFAC data. Freshwater marsh DOM was enriched in higher plant and soil-derived humic-like compounds, compared to estuarine sites which were more controlled by algae- and microbial-derived inputs. DOM from fringe mangrove sites could be differentiated between tidally influenced sites and sites exposed to long inundation periods. As such coastal estuarine sites were significantly controlled by hydrology, while DOM dynamics in Florida Bay were seasonally driven by both primary productivity and hydrology. This study exemplifies the application of long term optical properties monitoring as an effective technique to investigate DOM dynamics in aquatic ecosystems. The work presented here also serves as a pre-restoration condition dataset for DOM in the context of the Comprehensive Everglades Restoration Plan (CERP).     

Distribution and characteristics of molecular size fractions of freshwater-dissolved organic matter in watershed environments: its implication to degradation

Distributions of molecular size and fluorescence properties of dissolved organic matter (DOM) in the Lake Biwa and Lake Baikal watersheds were investigated using the cross-flow ultrafiltration technique and three-dimensional fluorescence measurements. From the fluorescence properties, protein-like substances were usually found in the 0.1 μm-GF/F fraction (the Durapore membrane retentate of the GF/F filtrate) of the lake DOM. The results indicated autochthonous production of protein-like organic-matters in the lake environment. Fulvic acid (FA)-like components were composed of two fractions with respect to fluorescence properties and molecular size. Two FA-like fluorescence peaks, which showed different fluorescence peak positions in the excitation-emission matrix (EEM), were partly fractionated by the molecular size of 5000 daltons (5 kDa). The FA-like fluorescence peak position of the <5-kDa fraction was observed at the shorter wavelength region compared with that of the fraction between 5 kDa and 0.1 μm (5 kDa20.1 μm fraction). A blue shift of the FA-like fluorescence peak position as well as a decrease in the molecular size of the DOM was observed in lake samples. The relative contribution of the <5 kDa fraction to the DOC concentration was high in lake waters (68%–79%) compared with river waters (44%–68%), suggesting characteristic changes in molecular size between riverine and lacustrine DOM. DOM of the 5 kDa–0.1 μm fraction was relatively higher in river waters than in lake waters. These findings coincided with in situ distributions of the fluorescence properties and molecular size of DOM found in both stream and lake environments. These results indicate that FA-like substances from forested watersheds are decomposed qualitatively and quantitatively in the river-lake environment by photochemical and biological processes.     

Application of solid surface fluorescence EEM spectroscopy for tracking organic matter quality of native halophyte and furrow-irrigated soils

Solid surface fluorescence excitation-emission matrix (EEM) is developed a potential method to characterize soil organic matter (SOM). Solid surface EEM spectroscopy with parallel factor analysis (PARAFAC) and hierarchical cluster analysis (HCA) is used to extract fluorescent components, to seek latent factors, and to investigate spatial distribution of SOM. Soil samples were collected from four native halophyte and two furrow-irrigated soil profiles, i.e. Comm. Salicornia europaea (CSE), Comm. Suaeda glauca (CSG), Comm. Kalidium cuspidatum (CKC), Comm. Sophora alopecuroides (CSA), corn fields (CFD), and wheat fields (WFD). SOM contained six fluorescent components: microbial/terrestrial fulvic-like fluorescent components (C1), tryptophan-like/lignin-derived phenol fluorescent components (C2), terrestrial humic-like fluorescent component (C3), lignin oxidative degradation by-products (C4 and C5), and amino acids (C6). The C 4 and C5 were the representative components of SOM within the CSE, CSG, CKC, CSA and CFD soil profiles, while the C2 and C6 were dominated within the WFD soil profile. The C4, C5, C1 and C2 were latent factors, and they could roughly distinguish SOM within the whole saline soil profiles except the CFD. A humification index (H/L) deduced from the fluorescent components, was very suitable to indicate humification levels of SOM. Humification levels of SOM within the halophyte soil profiles decreased with soil depth, but the opposite trends within the furrow-irrigated soil profiles. The H/L was closely correlated with exchangeable sodium percentage (ESP), and humification levels increased with the decreasing ESP. Soil surface EEM may not only indicate organic matter fractions of saline soils, but may be transferred to other types of landscape.     

Characterization of Nanming River (southwestern China) sewerage-impacted pollution using an excitation-emission matrix and PARAFAC

Nanming River, the largest urban river in Guizhou Province, southwestern China plateau, has been severely polluted for decades. This study characterizes the organic materials and their sources in the upstream and downstream waters by dissolved organic carbon (DOC), excitation emission matrix (EEM) spectroscopy, parallel factor (PARAFAC) analysis and photo-microbial experiments. DOC concentrations were low (47–120 μM C) upstream and relatively high (146–462 μM C) downstream. The PARAFAC studies on the sample EEM spectra demonstrated that the upstream dissolved organic matter (DOM) was mostly composed of one component that had a fulvic acid-like substance; downstream DOM was composed of two components with mixtures of tryptophan-like and fulvic acid-like substances. From the results of the sewerage drainage samples collected along the bank of the river, it is evident that both household detergent-like and protein-like or tryptophan-like substances are predominantly present, indicating that untreated sewerage effluents are the major sources of organic matter pollution in Nanming River. The degradation experiments conducted on river, sewerage drainage and commercial detergent samples demonstrated that the detergent-like and tryptophan-like substances are both photochemically and microbiologically more decomposable than fulvic acid-like materials under sunlight and dark incubations. These results suggest that the input of the untreated sewerage effluents along the streams is the major pollution source in Nanming River, and the fluorescent DOM was efficiently affected by both photochemical and microbial processes.     

Spectral Exploration of Calcium Accumulation in Organic Matter in Gray Desert Soil from Northwest China

Little attention has been paid to the accumulation of soil organic matter (SOM) in the fringes of the mid-latitude desert. In this paper, soil samples from a long-term field experiment conducted from 1990 to 2013 at a research station in Urumqi, China by different fertilizer treatments, were used to determine soil properties and soil dissolved organic matter (DOM) by chemical analysis, fluorescence excitation emission matrix (EEM) spectroscopy, and high resolution-transmission electron microscopy (HR-TEM). The binding features of DOM under the addition of Ca²⁺ were analyzed using a two-dimensional (2D) Fourier transform infrared (FTIR) spectrometer further to explore the response of the DOM to increasing concentrations of Ca²⁺. Long-term application of chemical fertilizers and goat manure increased soil organic carbon (SOC) by 1.34- and 1.86-fold, respectively, relative to the non-fertilized control (8.95g.kg^-1). Compared with the control, application of chemical fertilizers and manure significantly increased the concentrations of Ca, Mg, Si, humic and fulvic acid-like substances in DOM but decreased the amounts of trivalent metals (Al and Fe) and protein-like substances. Although crystalline Al/Fe nanoparticles and amorphous or short-range-order Si/Al nanoparticles existed in all DOM samples, crystalline Ca/Si nanoparticles were predominant in the samples treated with goat manure. Although organic matter and Si-O-containing nanoparticles were involved in the binding of Ca²⁺ to DOM, application of chemical fertilizers weakened Ca²⁺ association with components of the amide II group (1510 cm^-1) and Si-O linkage (1080 cm^-1), whereas application of goat manure enhanced the affinity of Ca²⁺ for Si-O linkage. Our results suggested that the enrichment of Ca in gray desert soil possibly helps accumulate SOM by forming crystalline Ca/Si nanoparticles in addition to Ca²⁺ and organic matter complexes.     

Three-dimensional fluorescence as a tool for investigating the dynamics of dissolved organic matter in the Lake Biwa watershed

Quantitative and qualitative characterizations of dissolved organic matter (DOM) were carried out at the watershed level in central Japan by measuring dissolved organic carbon (DOC) concentration and the three-dimensional excitation–emission matrix (3-D EEM). DOC concentration was low (mean 37 ± 19 µM C) in the upstream waters, whereas, in general, it increased toward the downstream areas (mean 92 ± 47 µM C). Significant variations in DOC concentration were detected among rivers and channels. DOC concentration in the epilimnion of Lake Biwa increased during the summer period and decreased during the winter period. The lake hypolimnion has lower DOC concentration (mean 87 ± 7 µM C) compared with the epilimnion (107 ± 15 µM C). Fulvic acid (FA)-like substances in the DOM were directly characterized by 3-D EEM. The fluorescence peak for upstream DOM was found in regions with longer wavelengths (excitation/emission 386 ± 6/476 ± 5 nm) compared with downstream and lake DOM (351 ± 12/446 ± 15 nm and 341 ± 6/434 ± 6 nm, respectively). The DOC concentration is correlated with fluorescence peak intensity of FA-like substances in DOM in river waters. Such a relationship was not found in lake DOM. A blueshift of the fluorescence peak from upstream to lake DOM was observed. A decrease in fluorescence intensities was also detected during the summer period. These results may suggest that the degradation of FA-like substances in DOM occurs from natural solar irradiation. Protein-like fluorescence was significantly detected in the lake epilimnion during the summer period. A linear relationship between DOC concentration and protein-like fluorescence indicated that an autochthonous input of DOM gave rise to the increase in DOC concentration in the lake epilimnion during the summer. These results may suggest that the 3-D EEM can be used as a tool for the investigation of DOM dynamics at the watershed level with concurrent measurement of DOC concentration and the fluorescence properties of fulvic acid-like and protein-like substances.     

Tracking variations in fluorescent-dissolved organic matter in an aerobic submerged membrane bioreactor using excitation–emission matrix spectra combined with parallel factor analysis

In this study, the variations in the fluorescent components of dissolved organic matter (DOM) were tracked for an aerobic submerged membrane bioreactor (MBR) at three different operation stages (cake layer formation, condensation, and after cleaning). The fluorescent DOM was characterized using excitation–emission matrix (EEM) spectroscopy combined with parallel factor analysis (PARAFAC). Non-aromatic carbon structures appear to be actively involved in the membrane fouling for the cake layer formation stage as revealed by much higher UV-absorbing DOM per organic carbon found in the effluent versus those inside the reactor. Four fluorescent components were successfully identified from the reactor and the effluent DOMs by EEM-PARAFAC modeling. Among those in the reactor, microbial humic-like fluorescence was the most abundant component at the cake layer formation stage and tryptophan-like fluorescence at the condensation stage. In contrast to the reactor, relatively similar composition of the PARAFAC components was exhibited for the effluent at all three stages. Tryptophan-like fluorescence displayed the largest difference between the reactor and the effluent, suggesting that this component could be a good tracer for membrane fouling. It appears that the fluorescent DOM was involved in membrane fouling by cake layer formation rather than by internal pore adsorption because its difference between the reactor and the effluent was the highest among all the four components, even after the membrane cleaning. Our study provided an insight into the fate and the behavior fluorescent DOM components for an MBR system, which could be an indicator of the membrane fouling.     

Pyrolysis-molecular beam mass spectrometry to characterize soil organic matter composition in chemically isolated fractions from differing land uses

Today’s questions concerning the role of soil organic matter (SOM) in soil fertility, ecosystem functioning and global change can only be addressed through knowledge of the controls on SOM stabilization and their interactions. Pyrolysis molecular beam mass spectrometry (py-MBMS) provides a powerful and rapid means of assessing the biochemical composition of SOM. However, characterization of SOM composition alone is insufficient to predict its dynamic behavior. Chemical fractionation is frequently used to isolate more homogeneous SOM components, but the composition of fractions is frequently unknown. We characterized biochemical SOM composition in two previously studied soils from the USA, under contrasting land uses: cultivated agriculture and native vegetation. Bulk soils, as well as chemically isolated SOM fractions (humic acid, humin and non-acid hydrolysable), were analyzed using py-MBMS. Principal components analysis (PCA) showed distinct differences in the SOM composition of isolated fractions. Py-MBMS spectra and PCA loadings were dominated by low molecular weight fragments associated with peptides and other N-containing compounds. The py-MBMS spectra were similar for native whole-soil samples under different vegetation, while cultivation increased heterogeneity. An approach based on previously published data on marker signals also suggests the importance of peptides in distinguishing samples. While the approach described here represents significant progress in the characterization of changing SOM composition, a truly quantitative analysis will only be achieved using multiple internal standards and by correcting for inorganic interference during py-MBMS analysis. Overall, we have provided proof of principle that py-MBMS can be a powerful tool to understand the controls on SOM dynamics, and further method development is underway.     

Fluorescence spectral characteristics of the supernatants from an anaerobic hydrogen-producing bioreactor

Microbial products formed in biological wastewater treatment systems are closely related to system performance and status, and many of them have fluorescence spectral characteristics. In this work, the fluorescence spectral characteristics of the supernatants from an anaerobic hydrogen-producing bioreactor were studied using three-dimensional excitation–emission matrix (EEM) fluorescence spectroscopy. Since the components of the microbial products are complex, the parallel factor analysis (PARAFAC) method was used to extract the real spectra from the overlapped spectra. Two principal components were identified from the EEM spectra. The peaks at excitation–emission maxima of 280/350 and 350/440 nm were, respectively, attributed to the fluorescence of proteins and NADH. Their real concentrations were quantified using the PARAFAC coupled with the second-order calibration method. Results show that the formation rate of proteins was correlated to the production rate of hydrogen and volatile fatty acids, as well as the substrate degradation rate. A close correlation between the hydrogen partial pressure and the two fluorophores was found out. This study provides a reliable and convenient approach, which could be potentially used for monitoring the wastewater treatment reactor performance through measuring the fluorescence spectra of the supernatant.     

Analysis of gene expression data using self-organizing maps.

DNA microarray technologies together with rapidly increasing genomic sequence information is leading to an explosion in available gene expression data. Currently there is a great need for efficient methods to analyze and visualize these massive data sets. A self-organizing map (SOM) is an unsupervised neural network learning algorithm which has been successfully used for the analysis and organization of large data files. We have here applied the SOM algorithm to analyze published data of yeast gene expression and show that SOM is an excellent tool for the analysis and visualization of gene expression profiles.     

冻融条件和土壤湿度对森林土壤渗漏液溶解性有机质含量与光谱结构特征的影响

土壤溶解性有机质(DOM)含量及其稳定性影响土壤碳氮循环关键过程,目前气候变化下森林土壤DOM含量及其光谱结构特征仍不明确.本研究利用长白山阔叶红松混交林和次生白桦林表层土壤进行室内冻融模拟试验,结合三维荧光光谱-平行因子分析方法,研究冻融强度和冻融循环次数及其交互作用对不同湿度温带森林土壤渗漏液DOM含量、组分和光谱结构特征的影响.结果表明: 森林土壤渗漏液DOM含量及其组分因林分类型、土壤湿度、冻融强度、冻融循环次数不同而存在差异.2种林分土壤渗漏液DOM含量均在中湿度下最低,并受高强度冻融影响显著,且随冻融循环次数增加呈现先增加后降低的趋势.可鉴别DOM的3个荧光组分:胡敏酸类DOM、富里酸类DOM和蛋白类DOM;阔叶红松混交林土壤渗漏液DOM组分以富里酸类物质为主,腐殖化程度较高;而次生白桦林土壤渗漏液DOM组分以胡敏酸类物质为主,3组分受冻融强度显著影响,稳定性较低.经冗余分析(RDA)发现,林分在很大程度上决定森林土壤DOM属性变化,次生白桦林土壤渗漏液DOM含量及其3组分荧光强度大于阔叶红松混交林;土壤湿度显著影响DOM芳香性,2种林分土壤渗漏液DOM芳香性均呈中湿度>高湿度>低湿度的趋势;随冻融强度增加,阔叶红松混交林土壤渗漏液DOM芳香性显著降低;多次冻融循环显著提高2种林分土壤渗漏液DOM腐殖化程度.因此,不同冻融作用下,低湿度温带森林土壤渗漏液DOM含量及其生物有效性呈现增加的趋势,尤其是次生白桦林土壤,可能会增加春季冻融期温带森林土壤溶解性有机质淋溶损失.这些结果可为深入研究野外冻融期温带森林土壤溶解性有机质周转机制提供参考.     

黄山松土壤可溶性有机质对氮添加的响应及其与细菌群落的关联

为探究黄山松土壤可溶性有机质(DOM)数量和质量对短期氮(N)添加的响应及其与细菌群落的关联,在福建戴云山自然保护区设置不同N添加水平(0、40和80 kg N·hm^-2·a^-1)试验,采用三维荧光与平行因子联用法,并结合高通量测序手段分别对土壤DOM和细菌群落进行分析。结果表明: 与对照相比,N添加整体降低了0～10和10～20 cm土层可溶性有机碳(DOC)含量和DOM腐殖化指数(HIX),其中,高氮(80 kg N·hm^-2·a^-1)添加下均显著降低。平行因子分析法进一步表明N添加下DOM中类腐殖质组分(C1、C2)的相对含量降低。此外,N添加减少了富营养细菌(变形菌门、酸微菌纲)的相对丰度,而增加了贫营养细菌(斯巴达杆菌纲)的相对丰度。富营养细菌的相对丰度与HIX、C1、C2呈显著正相关,与相对易分解的类富里酸组分(C3)呈显著负相关;而贫营养细菌的情况则相反。说明N添加下不同生活策略的细菌类群对DOM中难分解和易分解组分存在明显的偏好性。我们推测N沉降加剧背景下土壤微生物生活策略的转变可能有助于DOM组分的塑造。     

Reducing data acquisition for light‐sheet microscopy by extrapolation between imaged planes

Light‐sheet fluorescence microscopy (LSFM) is a powerful technique that can provide high‐resolution images of biological samples. Therefore, this technique offers significant improvement for three‐dimensional (3D) imaging of living cells. However, producing high‐resolution 3D images of a single cell or biological tissues, normally requires high acquisition rate of focal planes, which means a large amount of sample sections. Consequently, it consumes a vast amount of processing time and memory, especially when studying real‐time processes inside living cells. We describe an approach to minimize data acquisition by interpolation between planes using a phase retrieval algorithm. We demonstrate this approach on LSFM data sets and show reconstruction of intermediate sections of the sparse samples. Since this method diminishes the required amount of acquisition focal planes, it also reduces acquisition time of samples as well. Our suggested method has proven to reconstruct unacquired intermediate planes from diluted data sets up to 10× fold. The reconstructed planes were found correlated to the original preacquired samples (control group) with correlation coefficient of up to 90%. Given the findings, this procedure appears to be a powerful method for inquiring and analyzing biological samples.     

胶州湾滨海湿地土壤溶解性有机质的三维荧光特性

为了了解滨海湿地土壤中溶解性有机质的结构特征及来源,2014年1月在胶州湾采集光滩、碱蓬、芦苇和大米草湿地的土壤样品,测定土壤溶解性有机质(DOM)含量,利用三维荧光技术进行光谱分析.结果表明: 胶州湾4种湿地类型土壤溶解性有机碳(DOC)含量表现为大米草湿地＞光滩＞碱蓬湿地＞芦苇湿地,垂直剖面上随土层深度的增加DOC含量均呈减少的趋势.经光谱分析,胶州湾湿地土壤DOM的三维荧光光谱(3DEEMs)中出现了B、T、A、D和C等5种荧光峰,分别代表类酪氨酸、类色氨酸、类富里酸、类可溶性微生物副产物和类腐殖酸5种组分.利用荧光区域积分(FRI)法对5种组分进行定量分析,类色氨酸、类富里酸和类酪氨酸在DOM各组分含量中居前3位,类可溶性微生物副产物和类腐殖酸的含量次之,二者含量差异不显著.DOM的5种组分相互之间均呈显著正相关,与DOC含量呈显著正相关,与总磷、有效磷、总氮有不同程度的相关性.胶州湾4种湿地类型土壤DOM主要由生物相互作用内源产生,且腐殖化程度较低.     

Characterizing humic substances from estuarine soils and sediments by excitation-emission matrix spectroscopy and parallel factor analysis

The determination of optical properties of organic matter using spectroscopic techniques is a powerful tool for the characterization of humic substances (HS) in soils and sediments because of sensitivity, specificity and sample throughput. However, basic spectroscopic techniques have practical limitations because of the similarity in the optical properties of many HS. To improve resolution, the combination of excitation-emission matrix (EEM) fluorescence and parallel factor analysis (PARAFAC) was applied for characterizing fulvic acid (FA) and humic acid (HA) fractions from soils and sediments of two estuarine environments in Spain. Five fluorescent components were identified by EEM-PARAFAC and were found in both FA and HA fractions, consistent with the new paradigm of HS as supramolecular associations as well as the ubiquity of the HS components in the environment. Their contribution was, however, different between the FA and HA fractions. Two different, humic-like, fluorescent components were representative of FA and HA fractions, respectively. The spectral characteristics of these components were similar to previously reported PARAFAC components in dissolved organic matter (DOM) in a wide range of environments, suggesting their applicability in assessing OM quality and environmental dynamics. A microbial humic-like component was much more abundant in FA than in HA fractions. Furthermore, principal component analysis clarified that the two identified protein-like components, were enriched in sediment HA compared to soil HA, suggesting a larger contribution of refractory algaenan in sediment HA. The results of the present study demonstrate that EEM-PARAFAC is a useful technique for the biogeochemical characterization of soil and sedimentary HS.     

Erratum to: Fluorescence spectroscopy as a potential metabonomic tool for early detection of colorectal cancer

Fluorescence spectroscopy Excitation Emission Matrix (EEM) measurements were applied on human blood plasma samples from a case control study on colorectal cancer. Samples were collected before large bowel endoscopy and included patients with colorectal cancer or with adenomas, and from individuals with other non malignant findings or no findings (N = 308). The objective of the study was to explore the possibilities for applying fluorescence spectroscopy as a tool for detection of colorectal cancer. Parallel Factor Analysis (PARAFAC) was applied to decompose the fluorescence EEMs into estimates of the underlying fluorophores in the sample. Both the pooled score matrix from PARAFAC, holding the relative concentrations of the derived components, and the raw unfolded spectra were used as basis for discrimination models between cancer and the various controls. Both methods gave test set validated sensitivity and specificity values around 0.75 between cancer and controls, and poor discriminations between the various controls. The PARAFAC solution gave better options for analyzing the chemical mechanisms behind the discrimination, and revealed a blue shift in tryptophan emission in the cancer patients, a result that supports previous findings. The present findings show how fluorescence spectroscopy and chemometrics can help in cancer diagnostics, and with PARAFAC fluorescence spectroscopy can be a potential metabonomic tool.

     

Assessment of self-organizing maps to analyze sole-carbon source utilization profiles

The use of community-level physiological profiles obtained with Biolog microplates is widely employed to consider the functional diversity of bacterial communities. Biolog produces a great amount of data which analysis has been the subject of many studies. In most cases, after some transformations, these data were investigated with classical multivariate analyses. Here we provided an alternative to this method, that is the use of an artificial intelligence technique, the Self-Organizing Maps (SOM, unsupervised neural network). We used data from a microcosm study of algae-associated bacterial communities placed in various nutritive conditions. Analyses were carried out on the net absorbances at two incubation times for each substrates and on the chemical guild categorization of the total bacterial activity. Compared to Principal Components Analysis and cluster analysis, SOM appeared as a valuable tool for community classification, and to establish clear relationships between clusters of bacterial communities and sole-carbon sources utilization. Specifically, SOM offered a clear bidimensional projection of a relatively large volume of data and were easier to interpret than plots commonly obtained with multivariate analyses. They would be recommended to pattern the temporal evolution of communities' functional diversity.     

Formation of soluble microbial products (SMP) by activated sludge at various salinities

Soluble microbial products (SMP) present a significant component of effluent organic matter from biological wastewater treatment reactors, and can affect the membrane fouling and formation of disinfection by-products. Thus, SMP have attracted increasing concerns in wastewater treatment and reclamation. In this work, the formation of SMP by activated sludge at various NaCl concentrations is investigated by using fluorescence excitation–emission matrix (EEM) spectroscopy with parallel factor analysis (PARAFAC) and fluorescence regional integration (FRI). The results show that a high level of salinity decreases substrate removal efficiency and leads to an accumulation of SMP, especially proteins. Three components of SMP, one protein-like and two humic-acid-like components, are identified by PARAFAC, which exhibit different trends with the variation of NaCl concentration. FRI analysis reveals that the majority of protein fluorescence is attributed to tryptophan and tryptophan-like proteins, rather than tyrosine and tyrosine-like proteins. With an increase in NaCl concentration, the normalized volume percentages of tyrosine and tryptophan region increase, while those of humic- and fulvic-acid-like region decrease significantly. This work demonstrates that salinity affects the formation of SMP, and that EEM with PARAFAC in combination with FRI analysis is a useful tool to get insight into the formation of SMP by activated sludge.     

灞河流域溶解性有机质分子量分级表征及其与水质的相关性

溶解性有机质是水体中有机质分解与营养盐再生的核心载体之一,是碳、氮等生源要素生物地球化学循环的重要环节,也是水环境科学研究的重点内容.本研究应用液相-有机碳-有机氮检测(LC-OCD-OND)技术研究了西安市灞河流域水体中溶解性有机质(DOM)不同分子量组分特征,分析其与河水水质的相关性.结果表明: 河水DOM按照分子量分布,主要由生物大分子、腐殖质类物质、腐殖质降解产物、低分子中性物质和低分子酸组成,各组分平均浓度分别为0.15、1.75、0.48、0.36和0.002 mg·L^-1,河水中DOM总体含量水平由高到低的顺序为城市河段＞城镇河段＞源区河段.组分中分子量介于1000~20000 Da的腐殖质类物质占DOM总量的49.0%,含量及丰度从高到低依次为中游城镇段＞污水厂出口段＞污水厂下游河口段＞上游源头段;分子量＞20000 Da的生物大分子约占DOM总量的5.1%,丰度由高到低依次为污水厂出口＞污水厂下游河口＞上游源头＞中游城镇段,污水处理厂出水所产生的外生源有机质对河流DOM的贡献最大.DOM不同分子量组分与水质的相关性明显,表明基于LC-OCD-OND分级表征的DOM各分子量组分和丰度不仅可以作为水质监测的一个综合性指标,也可以用来表征河流水质的空间异质性,并能对污染物各组分进行定量化判别和来源解析.     

Controls of dissolved organic matter quality: evidence from a large‐scale boreal lake survey

Inland waters transport large amounts of dissolved organic matter (DOM) from terrestrial environments to the oceans, but DOM also reacts en route, with substantial water column losses by mineralization and sedimentation. For DOM transformations along the aquatic continuum, lakes play an important role as they retain waters in the landscape allowing for more time to alter DOM. We know DOM losses are significant at the global scale, yet little is known about how the reactivity of DOM varies across landscapes and climates. DOM reactivity is inherently linked to its chemical composition. We used fluorescence spectroscopy to explore DOM quality from 560 lakes distributed across Sweden and encompassed a wide climatic gradient typical of the boreal ecozone. Six fluorescence components were identified using parallel factor analysis (PARAFAC). The intensity and relative abundance of these components were analyzed in relation to lake chemistry, catchment, and climate characteristics. Land cover, particularly the percentage of water in the catchment, was a primary factor explaining variability in PARAFAC components. Likewise, lake water retention time influenced DOM quality. These results suggest that processes occurring in upstream water bodies, in addition to the lake itself, have a dominant influence on DOM quality. PARAFAC components with longer emission wavelengths, or red‐shifted components, were most reactive. In contrast, protein‐like components were most persistent within lakes. Generalized characteristics of PARAFAC components based on emission wavelength could ease future interpretation of fluorescence spectra. An important secondary influence on DOM quality was mean annual temperature, which ranged between ?6.2 and +7.5 °C. These results suggest that DOM reactivity depends more heavily on the duration of time taken to pass through the landscape, rather than temperature. Projected increases in runoff in the boreal region may force lake DOM toward a higher overall amount and proportion of humic‐like substances.