Fluorescence spectroscopy of aromatic species produced in rich premixed ethylene flames

The fluorescence spectra of the condensed species (CS) collected in the soot inception region of a rich premixed laminar ethylene/oxygen flame have been measured by excitation in the UV at 266 and 355 nm excitation wavelength. The contribution of the most abundant polycyclic aromatic hydrocarbons (PAH) to the CS fluorescence has been evaluated in order to attribute the CS fluorescence at different emission wavelengths to specific aromatic structures. The fluorescence peaks detected in the UV region of the CS fluorescence spectrum was found to be mainly due to a typical PAH like fluorene, that is, the most fluorescent one among the PAH analyzed in the CS by chromatographic analysis. The CS exhibited the larger emission in the visible where the PAH contribution has been shown to be negligible and other fluorescing aromatic species, not identified by chromatographic analysis of the CS, have to be considered responsible for the visible fluorescence. Laser induced fluorescence (LIF) flame measurements excited at 266 nm and detected at two selected wavelengths (310 and 410 nm) have been performed along the flame axis and compared with the CS fluorescence intensity. The LIF and CS fluorescence signals show quite similar axial trends demonstrating that the LIF signals are related to CS fluorescence. In particular, the LIF fluorescence signals detected in the UV could be attributed to the PAH fluorescence whereas the unidentified species contained in the CS can be followed by LIF detection in the visible region.     

Analysis of extinction in ultraviolet and visible spectra of water bodies of the Paraguay and Brazil wetlands

The extinction spectra in ultraviolet and visible radiation were analyzed using filtered and unfiltered water samples obtained in 11 open water bodies in the Neembucù (Paraguay) and Pantanal (Brazil) wetlands. The role of dissolved and suspended matter in the total extinction was analyzed between 260 nm and 700 nm. The chromophoric dissolved organic matter (CDOM) was the major component in extinction of considered ultraviolet radiation (260-400 nm). The differences in CDOM concentrations explained the main pattern of extinction of the ultraviolet radiation in the samples. Nevertheless, differences between the studied water bodies were found also to depend on the rate of photodegradation and photobleaching. The methodology developed in the present study was to distinguish "humic optic waters" according to quantity and quality of dissolved and suspended matter present. In the "humic optic water", the penetration of 10% of incident UV radiation and the photoactive layer are estimated. The influence of particulate matter increases in the total extinction of the wavelengths higher than 400 nm. The integral of the extinction curve of suspended matter in the visible wavelengths (400-700 nm) was found to relate with the total suspended solids and chlorophyll concentrations.     

Fluorescence of sediment humic substance and its effect on the sorption of selected endocrine disruptors

Humic substances (HS) have a critical influence on the sorption of organic contaminants by soils and sediments. This paper describes investigations into the sorption behavior of three representative endocrine disruptors, bisphenol A (BPA), 17beta-estradiol (E2), and 17alpha-ethynylestradiol (EE2), onto sediments and HS extracted sediments using a batch technique. The organic carbon-normalized partition coefficients (K(oc)) for the extracted HS (K(oc)(hs)) were calculated, and the fluorescence spectra of the HS extraced from different sediment samples were gained using excitation/emission matrix (EEM). Particular attention was paid to the correlations between the fluorescence characteristics of HS and the log K(oc)(hs) of selected endocrine disruptors. The results show that the log K(oc)(hs) values range from 3.14 to 4.09 for BPA, from 3.47 to 4.33 for E2, and from 3.65 to 4.32 for EE2. Two characteristic excitation-emission peaks were observed for HS samples extracted from sediments. They are located at Ex/Em=250-260 nm/400-450 nm (peak alpha') and Ex/Em=310-330 nm/390-400 nm (peak alpha) respectively. The alpha' and alpha peak relative intensities I(alpha')/I(alpha) vary from 0.46 to 1.64 for different extracted HS samples. The similarity between fulvic acids (FA) Ex/Em pairs and those observed for HS indicates that FA is the predominant fraction of HS extracted from sediments. Moreover, the log K(oc)(hs) values of BPA, E2, and EE2 have a negative linear correlation to I(alpha')/I(alpha) values. Peak alpha is often attributed to relatively stable and high molecular weight aromatic fulvic-like matter. Therefore, the result presented here reveals that the abundance of aromatic rings in HS molecular structure plays a critical role in the sorption of selected endocrine disruptors.     

Monitoring of fuel consumption and aromatics formation in a kerosene spray flame as characterized by fluorescence spectroscopy

The large presence of aromatic compounds in distillate fossil fuels should allow, in line of principle, to follow the fuel consumption and/or the presence of unburned fuel in a high temperature environment like a burner or the exhaust of combustion systems by exploiting the high fluorescence emission of aromatic fuel components. To this aim an UV-excited fluorescence source has to be used since the aromatic fuel components are strongly fluorescing in the UV region of the emission spectrum.

In this work UV-excited laser induced fluorescence (LIF) diagnostics was applied to spray flames of kerosene in order to follow the fuel consumption and the formation of aromatic species. A strong UV signal was detected in the spray region of the flame that presented a shape similar to that found in the LIF spectra preliminary measured on the cold spray and in the room-temperature fluorescence of fuel solutions.

The decrease of UV signal along the spray flame region was associated to the consumption of the fuel, but more difficult seems to be the attribution of a broad visible emission, that is present downstream of the flame.

The visible emission feature could be assigned to flame-formed PAH species contained in the high molecular weight species, hypothesizing that their fluorescence spectra are shifted toward the visible for effect of the high temperature flame environment.     

Alkaline hydrolysis of humic substances--spectroscopic and chromatographic investigations.

To find out more on the structure of humic substances (HS), isolated dissolved organic carbon (DOC) samples from a brown water lake and a wastewater effluent were fractionated and subjected to alkaline hydrolysis. UV/Vis and fluorescence spectroscopy, as well as size-exclusion chromatography with on-line detection of UV absorption, fluorescence and DOC concentration were used to investigate the structural changes caused by the hydrolysis reaction. Following hydrolysis, the fluorescence intensity increased considerably despite a decrease in the UV absorption. The UV absorption and the DOC data from the SEC experiments revealed a strong shift to smaller molecular sizes after hydrolysis. The spectra of the hydrolysed samples, as well as the size-exclusion chromatograms, were compared to spectra of hydroxybenzoic acids and hydroxycinnamic acids. From this comparison, it can be concluded that the hydrolysis products have a structure similar to these organic acids.     

城市生活垃圾填埋初期有机质演化规律研究

为阐明生活垃圾填埋初期有机质演化规律,于填埋场打井采集填埋1～3年3个不同时期垃圾样品,用水浸提制备水溶性有机物(DOM)。采用红外光谱、同步荧光光谱及紫外光谱,对浸提液中DOM的结构和演化特征进行了研究。结果显示,生活垃圾中含有脂肪类、蛋白类、糖类及木质素类物质,在填埋初期,有机质中的脂肪类、蛋白质类、糖类及木质素类物质均发生了降解,羧基、氨类及水溶性芳香结构物质减少,DOM分子量降低。研究结果表明,垃圾填埋初期有机质以降解为主。     

乌梁素海沉积物孔隙水中溶解有机质的荧光及紫外光谱研究

运用紫外可见光吸收光谱与荧光光谱研究乌梁素海沉积物孔隙水中溶解有机质的来源、结构及腐殖化程度。r_(A，C)、HIX、SUVA₂₈₀和SUVA₂₅₄等被用于表征DOM的腐殖化程度和芳香构化程度及结构，f_450/500用于指示DOM的来源。研究结果表明：腐殖化程度最高的点为湖泊东部的W4样点，腐殖化程度最低的为总排干影响区域的W1样点。E_253/203表明湖泊入口处沉积物孔隙水中有机质主要为不可取代的芳香环结构。荧光指数f_450/500为1.57～1.82之间。总体而言，f_450/500的值更接近于1.6，处于2个端源中间，说明乌梁素海DOM中的腐殖质主要来源于陆源输入。相关分析的结果表明， DOM的不同来源对其腐殖化程度产生影响。随着腐殖化值的增大，DOM的来源由生物源向陆源过渡。     

Fluorescence fingerprint of fulvic and humic acids from varied origins as viewed by single-scan and excitation/emission matrix techniques

Excitation/emission matrix (EEM), single-scan excitation and synchronous fluorescence spectra of a series of FA and HA from distinct environments are presented. The EEM plots show at least four spectral features whose corresponding Ex/Em pairs relate to the alpha', alpha, beta and gamma (or delta) fluorophores previously found in natural waters spectra. The alpha' and alpha peaks, which identify typical humic-like components, are present in all samples, independently of the organic matter (OM) source. In FA, their Ex/Em pairs are approximately 260 nm/460 nm and approximately 310 nm/440 nm, respectively. In HA their excitation and emission maxima are red-shifted, the corresponding Ex/Em pairs being located at approximately 265 nm/525 nm and approximately 360 nm/520 nm, respectively. The appearance of beta and gamma (or delta) peaks is dependent both on the OM origin and on HS aging. The former (Ex/Em approximately 320 nm/430 nm), that has been associated with the incidence of marine humic-like material, is present only in a few marine and estuarine HA. It emerges as a shoulder on the alpha peak and its detection is dependent on a balance between its magnitude and the magnitude and emission maxima location of the alpha peak. The gamma (or delta) peak (Ex/Em approximately 275 nm/315 nm in FA, and approximately 275 nm/330 nm in HA), on the other hand, is better visualized in FA than in HA diagrams. It has typical protein-, mainly tryptophan-like, fluorescence properties and appears with varied significance in a few marine and estuarine samples being hardly detected in samples from exclusively terrestrial environments. It is also shown in this study that with selected lambda(ex), lambda(em) and (delta)(lambda) values, regular emission, excitation and synchronous spectra can, together, provide a good picture of the OM sources and aging for extracted HS.     

Comparison of photochemical behavior of various humic substances in water: III. Spectroscopic properties of humic substances

Spectral absorption coefficients and fluorescence quantum efficiencies were determined for humic substances from a variety of sources. Specific absorption coefficients k_h, for humic substances at wavelengths λ from 300 to 500 nm can be closely described by the relation Ae^B(450-λ), where A and B are constants. When the k_h values are in units of liter (mg organic carbon)^?1meter^?1 and wavelength λ is in nanometers, mean values of A and B for aquatic humus in the 12 water bodies studied were 0.6±0.3 and 0.014±0.001, respectively. Spectral absorption coefficients of dissolved organic matter in blackwater rivers, of the “yellow substance” in the sea, and of fulvic acids extracted from soils are very similar. Fluorescence quantum yields of humic substances were low and more variable than the absorption coefficients, ranging from 0.0005 to 0.012 with excitation at 350 nm (average of 0.0045±0.0038 for 6 waters). Fluorescence spectra for the humic substances were remarkably similar with maximum emission at 430 to 470 nm. Results of this study can be used to compute photolysis rates of pollutants as a function of depth in natural water bodies.     

Relating dissolved organic matter fluorescence and functional properties

The fluorescence excitation–emission matrix properties of 25 dissolved organic matter samples from three rivers and one lake are analysed. All sites are sampled in duplicate, and the 25 samples include ten taken from the lake site, and nine from one of the rivers, to cover variations in dissolved organic matter composition due to season and river flow. Fluorescence properties are compared to the functional properties of the dissolved organic matter; the functional assays provide quantitative information on photochemical fading, buffering capacity, copper binding, benzo[a]pyrene binding, hydrophilicity and adsorption to alumina. Optical (absorbance and fluorescence) characterization of the dissolved organic matter samples demonstrates that (1) peak C (excitation 300–350 nm; emission 400–460 nm) fluorescence emission wavelength; (2) the ratio of peak T (excitation 220–235 nm; emission 330–370 nm) to peak C fluorescence intensity; and (3) the peak C fluorescence intensity: absorbance at 340 nm ratio have strong correlations with many of the functional assays. Strongest correlations are with benzo[a]pyrene binding, alumina adsorption, hydrophilicity and buffering capacity, and in many cases linear regression equations with a correlation coefficient >0.8 are obtained. These optical properties are independent of freshwater dissolved organic carbon concentration (for concentrations <10 mg L⁻¹) and therefore hold the potential for laboratory, field and on-line monitoring and prediction of organic matter functional properties.     

Organic matter source discrimination by humic acid characterization: Synchronous scan fluorescence spectroscopy and Ferrate(VI)

In this study, seven soil and sedimentary humic acid samples were analyzed by synchronous scan fluorescence (SSF) spectroscopy. The spectra of these humic acids were compared to each other and characterized, based on three major SSF peaks centered at approximately 281, 367 and 470 nm. Intensity ratios were calculated based on these peaks that were used to numerically assist in source discrimination. All humic acid samples were then reacted with Ferrate(VI) and were again analyzed with SSF. Upon the addition of Ferrate(VI) SSF spectra were obtained which more readily differentiated humic acid source. This method will assist geochemists and water management districts in tracing sources of organic matter to receiving water bodies and may aid in the elucidation of the chemical nature of humic acids.     

Tracking the spectroscopic and chromatographic changes of algal derived organic matter in a microbial fuel cell

Changes in the characteristics of algae-derived organic matter (AOM) were examined upon the operation of a microbial fuel cell (MFC) using multiple analytical methods. Temporal variations in the UV absorption and fluorescence excitation–emission matrix of the AOM revealed that less condensed humic-like components and large-sized protein-like fluorescent compounds were preferentially decomposed over the period of electricity generation. They also showed that low UV-absorbing extracellular organic matters (EOM) were produced at the end of the operation. SEC chromatograms demonstrated that smaller-sized UV-absorbing components were initially decomposed, followed by the net production of EOM with an intermediate molecular weight. Fourier transform infrared (FT-IR) spectra showed that proteins and polysaccharides were the two most dominant structures of the AOM in the MFC. Two-dimensional correlation spectroscopy combined with FT-IR provided additional valuable information on the sequential changes of the AOM, which occurred in the order of proteins → acidic functional groups → polysaccharides → amino acids/proteins.     

Extractability of water-soluble soil organic matter as monitored by spectroscopic and chromatographic analyses

Purpose

Cold and hot water processes have been intensively used to recover soil organic matter, but the effect of extraction conditions on the composition of the extracts were not well investigated. Our objective was to optimize the extraction conditions (time and temperature) to increase the extracted carbon efficiency while minimizing the possible alteration of water extractable organic matter of soil (WEOM).

Method

WEOM were extracted at 20°C, 60°C, or 80°C for 24?h, 10?C60?min, and 20?min, respectively. The different processes were compared in terms of pH of suspensions, yield of organic carbon, spectroscopic properties (ultraviolet?Cvisible absorption and fluorescence), and by chromatographic analyses.

Results

For extraction at 60°C, the time 30?min was optimal in terms of yield of organic carbon extracted and concentration of absorbing and fluorescent species. The comparison of WEOM 20°C, 24?h; 60°C, 30?min; and 80°C, 20?min highlighted significant differences. The content of total organic carbon, the value of specific ultraviolet absorbance (SUVA₂₅₄), the absorbance ratio at 254 and 365?nm (E ₂/E ₃), and the humification index varied in the order: WEOM (20°C, 24?h)?Conclusions For the soil chosen, extraction at 60°C for 30?min is the best procedure for enrichment in organic chemicals and minimal alteration of the organic matter.     

Amorphous and condensed organic matter domains: the effect of persulfate oxidation on the composition of soil/sediment organic matter

The composition of amorphous and condensed soil/sediment organic matter (SOM) domains was investigated for one soil sample and four sediment samples. These samples were oxidized with persulfate to remove amorphous SOM, before and after which the composition of SOM was studied by thermogravimetric analysis, pyrolysis-GC/MS, and cross polarization magic angle spinning 13C-NMR. Comparison of the SOM composition before and after oxidation showed that condensed SOM was more thermostable and less polar than amorphous SOM. Condensed SOM was relatively low in O-alkyl C and carboxyl C and it was likely to contain only small amounts of labile organic components (carbohydrates, peptides, fatty acids). Apart from these general characteristics, the composition of the condensed and amorphous domains appeared to be highly dependent on the origin and nature of the SOM investigated. Condensed domains in relatively undecomposed SOM were enriched in aliphatic C, whereas condensed domains in relatively weathered SOM were enriched in aromatic C. Altogether, the compositional changes upon persulfate oxidation were similar to the compositional changes upon humification, which supports the idea that weathered SOM is more condensed than the original material.     

Relating dissolved organic matter fluorescence and functional properties

The fluorescence excitation–emission matrix properties of 25 dissolved organic matter samples from three rivers and one lake are analysed. All sites are sampled in duplicate, and the 25 samples include ten taken from the lake site, and nine from one of the rivers, to cover variations in dissolved organic matter composition due to season and river flow. Fluorescence properties are compared to the functional properties of the dissolved organic matter; the functional assays provide quantitative information on photochemical fading, buffering capacity, copper binding, benzo[a]pyrene binding, hydrophilicity and adsorption to alumina. Optical (absorbance and fluorescence) characterization of the dissolved organic matter samples demonstrates that (1) peak C (excitation 300–350 nm; emission 400–460 nm) fluorescence emission wavelength; (2) the ratio of peak T (excitation 220–235 nm; emission 330–370 nm) to peak C fluorescence intensity; and (3) the peak C fluorescence intensity: absorbance at 340 nm ratio have strong correlations with many of the functional assays. Strongest correlations are with benzo[a]pyrene binding, alumina adsorption, hydrophilicity and buffering capacity, and in many cases linear regression equations with a correlation coefficient >0.8 are obtained. These optical properties are independent of freshwater dissolved organic carbon concentration (for concentrations <10 mg L⁻¹) and therefore hold the potential for laboratory, field and on-line monitoring and prediction of organic matter functional properties.     

Spatial variability in chromophoric dissolved organic matter for an artificial coastal lake (Shiwha) and the upstream catchments at two different seasons

Selected water quality parameters and spectroscopic characteristics of dissolved organic matter (DOM) were examined during two different seasons for an artificial coastal lake (Shiwha Lake in South Korea), which are affected by seawater exchange due to the operation of a tidal power plant and external organic loadings from the upstream catchments. The coastal lake exhibited much lower concentrations of organic matter and nutrients than the upstream sources. The spectroscopic properties of the lake DOM were easily distinguished from those of the catchment sources as revealed by a lower absorption coefficient, lower degree of humification, and higher spectral slopes. The observed DOM properties suggest that the lake DOM may be dominated by smaller molecular size and less condensed structures. For the lake and the upper streams, higher absorption coefficients and fluorescence peak intensities but lower spectral slopes and humification index were found for the premonsoon versus the monsoon season. However, such seasonal differences were less pronounced for the industrial channels in the upper catchments. Three distinctive fluorophore groups including microbial humic-like, tryptophan-like, and terrestrial humic-like fluorescence were decomposed from the fluorescence excitation-emission matrix (EEM) of the DOM samples by parallel factor analysis (PARAFAC) modeling. The microbial humic-like component was the most abundant for the industrial channels, suggesting that the component may be associated with anthropogenic organic pollution. The terrestrial humic-like component was predominant for the upper streams, and its relative abundance was higher for the rainy season. Our principal component analysis (PCA) results demonstrated that exchange of seawater and seasonally variable input of allochthonous DOM plays important roles in determining the characteristics of DOM in the lake.     

A comparative characterization of dissolved organic matter by means of original aqueous samples and isolated humic substances

The aim of our study is to test the use of less time-consuming spectroscopic methods applied on original water samples in order to obtain information about DOM composition without any sample preparation. These results were directly compared with results from a conventional isolation and characterization procedure of dissolved humic substances (fulvic acids – FA) isolated from the same water sample. FAs were characterized by UV-, fluorescence-, FTIR spectroscopy and elemental composition. UV absorbance and fluorescence behavior of FAs and original water samples follow the same pattern. A lower UV absorbance and a lower humification index (derived from the synchronous fluorescence spectra) of about 15% is typical for water samples compared to the FAs. We computed linear relationships between properties of the original water sample (UV-, synchronous fluorescence spectra) and the isolated FA (IR absorption, C/N ratio). The application of synchronous fluorescence and UV spectroscopy of aqueous samples has been proved to result in similar information about DOM composition as the characterization of isolated humic substances concerning the content of aromatic structures and the degree of humification.     

Spectroscopic characterization of water extractable organic matter during composting of municipal solid waste

This paper aims to characterize the evolution of water extractable organic matter (WEOM) during the composting of municipal solid waste (MSW), and investigate the correlation between maturity and WEOM characteristics. WEOM was extracted at different stages of MSW composting (0, 7, 14, 21, and 51 d) and characterized by FTIR, UV-Vis, and fluorescence spectroscopy. The results obtained show that the composting process decreased aliphatics, alcohols, polysaccharides, as well as protein-like materials, and increased aromatic polycondensation, humification, oxygen-containing functional groups, molecular weight, and humic-like materials. The maturity of MSW during composting was characterized by the presence of the peak with an excitation/emission wavelength pair of 289/421 nm in excitation-emission matrix spectra.     

Studies of metal-binding sites in natural organic matter and their role in the generation of disinfection by-products using lanthanide ion probes

In this study, the complexation of Tb3+ with natural organic matter (NOM) was studied by the method of time-resolved fluorescence spectroscopy. In the presence of NOM, the excitation of Tb3+ was observed in a wide range of wavelengths, for which virtually no excitation of free Tb3+ took place. The pseudo-quantum yield spectra (excitation intensity normalized by corresponding light absorbance values) had a maximum at 282 nm. This indicated that the excitation of NOM-bound Tb3+ proceeds through energy transfer from aromatic groups in NOM. The concentration of the metal-binding sites (C(L)) was determined by titration with Tb3+ and was found to range from 0.21% to 0.83% of total moles of organic carbon. The actual number of the carbon atoms that comprise these functionalities was hypothesized to be at least seven times higher. The C(L) values were well correlated with the reactivity of NOM with chlorine quantified by total organic halogen formation potential and with the contribution of polyhydroxyaromatic moieties determined by pyrolysis-GC/MS method. The correlation of C(L) with the contributions of aromatic and carboxylic moieties in NOM determined by 13C NMR was poor. Based on the data, it was concluded that the metal binding functionalities in NOM are closely associated with halogen attack sites.     

Assessing the importance of heterogeneous reactions of polycyclic aromatic hydrocarbons in the urban atmosphere using the Multimedia Urban Model

The Multimedia Urban Model (MUM-Fate) of Diamond, M.L., Priemer, D.A., Law, N.L., 2001. Developing a multimedia model of chemical dynamics in an urban area. Chemosphere 44, 1655–1667 was used to evaluate the contribution of heterogeneous reactions of polycyclic aromatic hydrocarbons (PAHs) with gas-phase ozone to the total loss of these compounds in an illustrative urban environment. Recent laboratory studies by Kahan, T.F., Kwamena, N.-O.A., Donaldson, D.J., 2006. Heterogeneous ozonation kinetics of polycyclic aromatic hydrocarbons on organic films. Atmospheric Environment 40, 3448–3459 and Kwamena, N.-O.A., Thornton, J.A., Abbatt, J.P.D., 2004. Kinetics of surface-bound benzo[a] pyrene and ozone on solid organic and salt aerosols. Journal of Physical Chemistry A 108, 11626–11634 provided half-lives for these heterogeneous reactions on surface films and atmospheric particulate matter, respectively. Two model scenarios were studied, representing urban environments with varying amounts of impervious surface coverage. We investigated six PAHs spanning a wide range of physical and chemical properties; results for anthracene, pyrene and benzo[a]pyrene are presented here. Advection from air was the dominant loss process for all PAHs investigated. Heterogeneous reactions primarily on surface films but also on atmospheric particulate matter accounted for up to 75% of the reactive losses of lower volatility PAHs, which accumulate in condensed phases. The results suggest that surface films can be efficient reactive sinks for lower volatility PAHs.