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).     

Identifying fluorescent pulp mill effluent in the Gulf of Maine and its watershed

Using fluorescence spectroscopy and parallel factor analysis (PARAFAC) we characterized and modeled the fluorescence properties of dissolved organic matter (DOM) in samples from the Penobscot River, Androscoggin River, Penobscot Bay, and the Gulf of Maine (GoM). We analyzed excitation-emission matrices (EEMs) using an existing PARAFAC model (Cory and McKnight, 2005) and created a system-specific model with seven components (GoM PARAFAC). The GoM PARAFAC model contained six components similar to those in other PARAFAC models and one unique component with a spectrum similar to a residual found using the Cory and McKnight (2005) model. The unique component was abundant in samples from the Androscoggin River immediately downstream of a pulp mill effluent release site. The detection of a PARAFAC component associated with an anthropogenic source of DOM, such as pulp mill effluent, demonstrates the importance for rigorously analyzing PARAFAC residuals and developing system-specific models.     

Spectroscopic investigation of humic substances in a tropical lake during a complete hydrological cycle

Fluorescence and UV‐VIS techniques were employed for the investigation of natural organic matter (NOM) of a tropical lake. The relationships of absorbance/dissolved organic carbon (A/DOC), fluorescence intensity/dissolved organic carbon (FI/DOC), fluorescence ratio (FR), and peak wavelength with the highest intensity (PW) were used to distinguish the pedogenic or aquagenic origin of NOM. The values of FR, PW and A₂₈₅/DOC of high waters (HW) or flooded period samples and of low waters (LW) period samples of the dry season, except for September 2002, confirm the predominance of pedogenic material. The spectra of water were similar to the standard fulvic acid (FA), and the spectra of FA from the lake were similar to the nearby soils, indicative of pedogenic predominance. The results confirm that the dissolved NOM of Patos Lagoon – MS (Brazil), in all sampling periods, predominantly consisted of humic substances (FA) of pedogenic origin.     

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.     

Attenuation of a Mixed Chromium and Chlorinated Etjeme Ground Wate Plume in Estuarine Influenced Glaciated Sediments

The natural attenuation behavior of a ground water contaminant plume containing chromium and chlorinated ethenes in glaciated sediments was assessed using traditional and nontraditional methods. The mixed waste is transported through and attenuated within an estuarine influenced ground water aquifer of spatially varying redox character and organic carbon content. Contaminant fate and speciation were assessed as a function of geochemical conditions. Total, speciation-based, and sequential chemical extraction analyses were performed to determine contaminant partitioning and the redox capacity of the aquifer. Chromium speciation and partitioning were correlated with the reductive capacity and redox conditions of the aquifer sediments spatially distributed within the aquifer. Reductive dechlorination and partitioning of chlorinated ethenes were correlated with the organic carbon content and redox conditions of the aquifer sediments. The data showed that sharp redox gradients existed within the aquifer. Active reduction and retardation of both chromium and chlorinated ethenes was exhibited. The aqueous hexavalent chromium concentrations decreased to near nondetect levels in the vicinity of the receptor, whereas degradation products of higher-order chlorinated ethenes increased as a fraction of the total chlorinated ethene concentrations along the length of the plume. The potential for competition for reducing power under specific cases within the aquifer was suggested by the data, highlighting the need to include contaminant interactions in natural attenuation assessments.     

Spectroscopic Investigation on Hydrophobic and Hydrophilic Fractions of Dissolved Organic Matter Extracted from Soils at Different Salinities

Organic matter can be considered one of the most important indicators of the extent of soil desertification processes. Among the causes of desertification, salinization induced by different factors is raising the greatest concern in the Mediterranean area. In the present research, hydrophilic (HI) and hydrophobic (HO) fractions of dissolved organic matter (DOM) extracted from soils at different degrees of salinization have been investigated by means of spectroscopic techniques such as tridimensional fluorescence spectroscopy in the mode of emission excitation matrix (EEM) and Fourier transform infrared spectroscopy (FT‐IR). The FT‐IR spectra were distinctive in differentiating HI from HO fractions and each DOM fraction as a function of soil salinity. The EEM spectra of HO fractions exhibited a shift toward longer emission wavelengths and higher fluorescence intensity (FI) values as compared to that of the HI fractions. These results could be ascribed to the different molecular complexities of HI and HO fractions. Further, a marked quenching effect was observed in the FI of both the DOM fractions with increasing soil salinity, which allowed to obtain immediate information on the soil salinity degree by comparing the fluorescence intensity.     

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.     

蓝藻水华暴发和衰亡对太湖有色可溶性有机物的影响

利用平行因子分析(PARAFAC)技术对藻华暴发季节太湖梅梁湾和开敞区水样中有色可溶性有机物(CDOM)的三维荧光光谱进行分析,获得代表类酪氨酸、类色氨酸和类腐殖酸等3种荧光组分,这3个组分的荧光得分值均与叶绿素a浓度呈极显著正相关,其中类腐殖酸物质荧光得分值占总分值的比例也与叶绿素a浓度极显著正相关,由此可以推测,蓝藻水华可能是太湖CDOM的一个重要来源,并极大地影响了湖泊CDOM的组成结构.为进一步探索蓝藻水华对湖泊CDOM的影响,于太湖梅梁湾湖岸进行藻华暴发和衰亡模拟试验.PARAFAC结果显示,模拟试验水样CDOM的三维荧光图谱同样含有3个组分,其中类酪氨酸和类色氨酸荧光峰位置与湖泊水样基本相同,而类腐殖酸物质荧光峰则有一定程度的蓝移,表明培养试验中有新的内源类腐殖酸物质产生.利用PARAFAC模型中的得分值计算后发现,初始叶绿素a浓度越高,类腐殖酸物质所占比例越大,而实验结束时添加了高浓度和中等浓度藻的2个处理中类腐殖酸物质对荧光的贡献率也有显著提高.因此,藻华的长期暴发可以显著改变湖泊CDOM的组成,导致类腐殖酸物质比例提高.     

Sunlight Degradation of Aquatic Humic Substances Abbau von Huminstoffen unter dem Einfluß von Sonnenlicht

Coloured bog water and an aqueous solution of fulvic acid were exposed to natural sunlight. Up to 67% reduction in colour and 32% reduction in DOC concentration were measured after 12 days exposure. Colour bleaching and reduction in ultraviolet light absorbance were independent of added preservatives. The high molecular weight fraction of dissolved organic matter was most reduced in concentration while substances with low molecular weight increased. The reduction in absorbance (λ = 254 nm) per DOC was most significant for substances with high molecular weight. The final concentration of DOC was highest in samples where microbial activity was suppressed.     

Characteristics and role of groundwater dissolved organic matter on arsenic mobilization and poisoning in Bangladesh

The fluorescence and molecular weight characteristics of dissolved organic matter (DOM) in groundwater of Bangladesh were investigated to evaluate its multiple roles on arsenic (As) mobilization and poisoning. Fluorescence properties of DOM were measured in groundwater samples collected from two As contaminated areas of Bangladesh (Faridpur at the Ganges floodplain and Sonargaon at the Meghna floodplain) from different locations and depths. The three dimensional excitation–emission matrix (3DEEM) fluorescence spectra of groundwater samples showed two characteristic peaks around Ex/Em = 335–365 nm/435–480 nm for fulvic-like peaks and peak at around Ex/Em = 275–290 nm/310–335 nm for the protein-like materials. The similarity of fluorescence spectra of groundwater and surface water of both the study areas with high intensity of fluorescence and its strong correlation with DOC reflect the in situ generation of fluorescent DOM from sedimentary organic matter (SOM) and recent recharge of terrestrial labile organic carbon into shallow aquifer. High performance size-exclusion chromatography (HPSEC) analysis of DOM shows positive correlations between fluorescence intensities (FI) of small molecular fractions (0.65 kDa) and As concentrations, with the signatures of protein-like peaks of DOM in groundwater. This result provides new evidence that small molecular weight fraction of DOM in groundwater of Bangladesh can play an important role on As mobilization and toxicity. In addition, high concentration of fluorescence materials in DOM of As contaminated groundwater of Bangladesh may pose a threat to public health.     

An isotopic model for the origin of autochthonous organic matter contained in the bottom sediments of a reservoir

Geochemical analysis of surface sediment samples collected in 2005 and 2006 was used to evaluate the potential sources of the organic matter present in sediments of southeast Poland's Solina Reservoir.Statistical analysis of sediment variables(carbon to nitrogen ratio, and the carbon 13 and nitrogen 15 isotope ratios) determined for the organic fraction indicated significant spatial variability with respect to sources of organic matter. A binary mixing model was developed from literature sources to predict the relative contributions of allochthonous and autochthonous production to sediment organic matter.Autochthonous production was shown to account for 60-75% of bulk sedimentation in the lacustrine parts of the reservoir, near the dam. In contrast, autochthonous production accounted for only 25% of sedimentation in the riverine zone receiving stream inputs. Statistical analysis identified the δ~(15)N of organic matter as the best predictor of the source of organic matter. Multiple regression analysis indicated that two water-quality variables(nitrate and dissolved silica) were significantly related to the δ~(15)N signature of organic matter. This led to a conclusion that limnetic nitrate and dissolved silica concentrations were regulating organic matter production in the Solina Reservoir.     

Fluorescence of dissolved organic matter as a natural tracer of ground water

The fluorescence properties of dissolved organic matter (DOM) in ground water in the Permian limestone of northeast England is determined from six monitoring boreholes, a private water supply well and from a natural resurgence in a flooded collapse doline in the environs of Darlington, County Durham, northeast England. Measurements of both protein and "fulvic-like" fluorescence was undertaken from January to December 1999. The wavelengths of fulvic-like fluorescence excitation and emission and of protein fluorescence emission were all determined to be sensitive fingerprints of organic matter fluxes through the ground water, with water within the till and within both gypsum and limestone strata deep inside the Magnesian Limestone being differentiated by these parameters. Previous research has suggested that proteins in waters are "young" in age, hence our seasonal variations suggest that we are sampling recently formed DOM. The rapid response of all deep borehole samples suggests relatively rapid ground water flow, probably through karstic cave systems developed in the gypsum and solution widened features in the dolomitic limestone. Our results suggest that use of both protein and fulvic-like fluorescence wavelength variations provides a DOM signature that can be used as a natural tracer.     

引黄水源水库平-丰水期有色可溶性有机物(CDOM)的来源、组成及差异分析

为探究引黄水源水库——门楼水库平水期和丰水期有色可溶性有机物(CDOM)的组成特征、来源及差异,运用紫外—可见光谱技术(UV-vis)和三维荧光光谱(EEMs)技术,结合平行因子分析法(PARAFAC)分析2022年5月(平水期)和2022年7月(丰水期)有色可溶性有机物含量及组分变化。研究结果表明:PARAFAC识别出2类荧光组分,分别是C1(Ex=355 nm,Em=476 nm,类腐殖质组分)和组分C2(Ex=225 nm,Em=320 nm,类蛋白组分);丰水期CDOM组分荧光强度显著高于平水期。CDOM光谱参数表明,门楼水库水体处于中营养状态,水体CDOM受新生内源和外源输入共同影响,以自生源为主;水库CDOM具有相对分子量小、腐殖化程度较弱的特点。丰水期水库富营养化水平和CDOM相对浓度低于平水期;丰水期CDOM疏水性组分比例和芳香化程度高于平水期。水质理化指标、CDOM组分和光谱参数相关性分析结果表明SUVA₂₆₀和SUVA₂₈₀与DOC呈显著负相关,说明紫外—可见光谱参数在一定程度上可以用来估算DOC的浓度;Chl.a浓度作为...     

Adsorbed and Bound Residues in Fulvic Acid Fractions of a Contaminated Groundwater – Isolation:, Chromatographic and Spectroscopic Characterization

Humic substances (HS) were isolated from two contaminated groundwater samples (B22 and B53) from a site of a former gas facility. The isolation yielded almost only the fulvic acid fractions (FA). For characterization spectroscopic (UV, fluorescence) and chromatographic techniques (hydrophobic interaction chromatography – HIC as well as size-exclusion chromatography – SEC) were applied. The sample designated B22 FA was collected from the contamination plume whereas the sample B53 FA was collected downstream. Distinct differences were exhibited by these samples. The UV and fluorescence spectra as well as the HIC and SEC chromatograms of the B53 FA sample resemble those of the FA fraction obtained from natural water (groundwater, bog). The HIC and SEC chromatograms reveal the presence of organic compounds in B22 FA which can be derived from coal tar contaminants or their metabolites. Some of the compounds can be extracted from the FA fraction with non-polar organic solvents indicating adsorptive forces between the contaminants and the FA fraction.     

Time-resolved Fluorescence Measurements of Aquatic Natural Organic Matter (NOM)

The fluorescence decay of aquatic natural organic matter (NOM) samples was investigated using the time-correlated single photon counting technique (TCSPC). Two different approaches for the data analysis are presented: the discrete component approach (DCA) and the exponential series method (ESM). The parameter set obtained in the DCA is discussed in terms of characterization for NOM of different origins. However, the obtained parameter set can only be interpreted as operationally defined. Using the ESM for a fluorescence decay time distribution analysis no a priori assumption about the number of fluorescing components was introduced into the data analysis. The interpretation of fluorescence decay time data for samples before and after ozonation is in good agreement with results of other analytical methods.     

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.     

太湖五里湖水体悬浮物中水溶性有机质(WSOM)的荧光光谱组分鉴别及其与氮形态的关系

采用三维荧光光谱-平行因子法(EEMs-PARAFAC)分析太湖五里湖水体悬浮物中水溶性有机质(WSOM)的荧光光谱特征,研究其组分类型、分布规律以及来源,进一步探讨悬浮物中水溶性有机氮和无机氮含量与WSOM荧光组分之间的关系.结果表明,悬浮物中WSOM荧光组分主要由2个类腐殖质(C1、C2)和1个类色氨酸类蛋白质(C3)组成.总荧光强度在57.56~200.01 R.U./g之间,平均为115.42 R.U./g,其中C1、C2、C3的相对比例分别为35.55%、34.05%和30.40%;空间上由西向东逐渐增强,东五里湖高于西五里湖,沿岸区高于湖心区.荧光指数和生物源指数变化范围分别在1.48~2.34和0.65~0.87之间,反映了悬浮物中WSOM主要来源于微生物、藻类的自生生物源.多元回归统计分析结果表明,悬浮物WSOM与氮元素的迁移转化密切相关,且有机氮与WSOM荧光组分的相关系数大于无机氮.     

Heavy metals mobility in harbour contaminated sediments: the case of Port-en-Bessin

Metallic contaminants associated with sediments showed various behaviours depending on physicochemical conditions. A contaminated sediment core from a harbour in the Bay of Seine was sampled to derive information about metal solubilization from anoxic sediment. In these anaerobic surroundings, physicochemical processes depended on the organic matter cycle, on vertical variation of redox conditions and on precipitation conditions of iron and manganese. In the studied core, anoxic conditions were developed at -15 cm depth. A three-step sequential extraction procedure, modified from the BCR method (now the SM&T), was applied to the anoxic sediment in order to evaluate the potential mobility of fixed metals. Zinc was the most labile metal, recovered in the first extraction stages, and was associated with the non-residual fraction of sediment. Lead was the least labile metal, with up to 70% associated with the residual fraction of the sediment. Copper was associated with organic matter, and its mobility was controlled by the concentration and degradation of the organic fraction. Discharge of organic-rich dredged sediments at sea results in degradation of contained organic matter and may affect the environmental impact of these metals significantly. These results therefore help to improve the waste management of such contaminated sediments.