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1.
Irradiation of aqueous (pH = 5) mixtures containing hydrogen peroxide (1 mM) and phenolic compounds (10 mM) were found to produce visible light absorbing solutions over the course of several hours. The kinetics and products of these reactions were studied by UV–VIS absorbance, electrospray mass spectrometry, FTIR, fluorescence, and NMR and compared to humic-like substances commonly found in atmospheric particulate matter. It was determined the reactions leading to formation of color are quite general to this compound class, and the reactions proceeded more rapidly with hydroxyl or methoxy substitution ortho to the phenolic OH. However, para substitution generally slowed formation of colored compounds compared to the unsubstituted form. Mass spectrometry confirms compounds of several hundred Da formed in the reaction mixtures. The IR spectra of the reaction products bear similarity to that observed for authentic aerosol humic-like substances. The results indicate radical coupling of phenols and methoxylated phenols in tropospheric waters may contribute to humic-like particulate matter.  相似文献   

2.
Extracellular polymeric substances (EPS) were extracted from four anaerobic granular sludges with different procedures to study their involvement in biosorption of metallic elements. EPS extracts are composed of closely associated organic and mineral fractions. The EPS macromolecules (proteins, polysaccharides, humic-like substances, nucleic, and uronic acids) have functional groups potentially available for the binding of metallic elements. The acidic constants of these ionizable groups are: pK a1 (4–5) corresponding to the carboxyl groups; pK a2 (6–7) corresponding to the phosphoric groups; pK a3 (8–10) and pK a4 (≈10) corresponding to the phenolic, hydroxyl, and amino groups. The polarographic study confirms the higher affinity of the EPS to bind to lead than to cadmium. Moreover, the binding of these metallic compounds with the EPS is a mix of several sorption mechanisms including surface complexation, ion exchange, and flocculation. Inorganic elements were found as ions linked to organic molecules or as solid particles. The mineral fraction affects the binding properties of the EPS, as the presence of salts decreases the EPS binding ability. Calcite and apatite particles observed on SEM images of EPS extracts can also sorb metallic elements through ion exchange or surface complexation.  相似文献   

3.
This work intends to quantify the variation in optical properties of aerosol by in-situ spectroscopic monitoring the ozonolysis of a mixture of typical biomass burning compounds. The reaction occurs on silica and glass particles in the presence of simulated sunlight.Fused silica particles (Aerosil) were coated with a thin film of a 1:1 mixure of 4-phenoxyphenol with 4-carboxyphenone as a photosensitizer. UV–VIS spectra of dichloromethane extracts from the particles recorded before and after treatment, show development of a new band after prolonged ozone and light exposure.Changes in optical properties are reported, and variations of spectroscopic features are discussed. We show that the ozone-induced heterogeneous photochemical reaction does produce species absorbing light in the solar spectral range. Further, we demonstrate that the heterogeneous photosensitized reactions at 200 ppb ozone (strongly ozone polluted regions) for a time period of 7 h aging process, can increase light absorption of atmospheric aerosols in the tropospheric actinic window (>290 nm) by 0.4 absorption units ng-C?1 O3 ppm?1 in the region 290–358 nm and by 1.0 absorption units ng-C?1 O3 ppm?1 in the region 360–448 nm.Chemical changes of such surface films were identified by diffuse reflectance infrared Fourier transform spectroscopy of coated glass spheres, and we suggest formation of humic-like substances comparable to those reported in continental aerosol.  相似文献   

4.
Fogwater and air samples were collected in Baton Rouge between November 2004–February 2005 and during February 2006 at Houston. Organic compounds present in the fog samples were detected, quantified and then grouped into different compound classes based on molecular size, solubility and polarity using gas chromatography/mass spectrometry, high performance liquid chromatography with diode array detection and ion chromatography. Organic compounds were grouped as n-alkanes, aromatics and polycyclic aromatics, carbonyls, alcohols, amides and esters. Organic compounds in fog and air samples in Houston indicated clear urban/industrial anthropogenic origin, while compounds detected in Baton Rouge fog and air samples showed a mix of both agricultural and urban/industrial anthropogenic inputs. Among the various polycyclic aromatic compounds detected, the total concentration of naphthalene and its derivatives was 2.8 μg m?3 in Houston and 0.08 μg m?3 in Baton Rouge air. Analysis of concentrations of organic compounds pre- and post- fog revealed that compounds with low vapor pressure had higher scavenging efficiency in fog sampled at the two locations. Concentrations of organic compounds in fog samples were higher than those predicted by conventional air-water Henry's law equilibrium. Observed higher concentrations in the aqueous phase were modeled accounting for surface adsorption and accumulation of gas phase species and the presence of humic-like substances in fogwater.  相似文献   

5.
Dissolved organic matter (DOM) present in fogwater samples collected in southeastern Louisiana and central-eastern China has been characterized using excitation–emission matrix fluorescence spectroscopy. The goal of the study was to illustrate the utility of fluorescence for obtaining information on the large fraction of organic carbon in fogwaters (typically >40% by weight) that defies characterization in terms of specific chemical compounds without the difficulty inherent in obtaining sufficient fogwater volume to isolate DOM for assessment using other spectroscopic and chemical analyses. Based on the findings of previous studies using other characterization methods, it was anticipated that the unidentified organic carbon fraction would have characteristic peaks associated with humic substances and fluorescent amino acids. Both humic- and protein-like fluorophores were observed in the fogwater spectra and fluorescence-derived indices for the fogwater had similar values to those of soil and sediment porewater. Greater biological character was observed in samples with higher organic carbon concentrations. Fogwaters are shown to contain a mixture of terrestrially- and microbially-derived fluorescent organic material, which is expected to be derived from an array of different sources, such as suspended soil and dust particles, biogenic emissions and organic substances generated by atmospheric processes. The fluorescence results indicate that much of the unidentified organic carbon present in fogwater can be represented by humic-like and biologically-derived substances similar to those present in other aquatic systems, though it should be noted that fluorescent signatures representative of DOM produced by atmospheric processing of organic aerosols may be contributing to or masked by humic-like fluorophores.  相似文献   

6.
Compost leachates were collected to investigate the influence of the composition and removal of volatile fatty acids (VFAs), humic-like substances (HSs), and dissolved organic nitrogen (DON) on heavy metal distribution during the leachate treatment process. The results showed that acetic and propionic acids accounted for 81.3 to 93.84 % of VFAs, and that these acids were removed by the anaerobic-aerobic process. Humic- and fulvic-like substances were detected by excitation–emission matrix spectroscopy coupled with parallel factor analysis, and their content significantly decreased after the anaerobic and membrane treatments. DON in compost leachates ranged from 26.53 mg L-1 to 919.46 mg L-1, comprised of dissolved free amino acids and the protein-like matter bound to humic- and fulvic-like substances, and was removed by the aerobic process. Correlation analysis showed that Mn, Ni, and Pb were bound to VFAs and protein-, fulvic-, and humic-like substances in the leachates. Co was primarily bound to fulvic- and humic-like matter and inorganic sulfurs, whereas Cu, Zn, and Cd interacted with inorganic sulfur.  相似文献   

7.
A method based on photolysis was developed for the appropriate treatment of organic pollutants in air exhausting from breweries upon wort decoction, and thereby causing smell nuisance. A continuous flow stirred photoreactor was built-up exclusively, allowing OH radicals to react with selected odorous compounds contained in exhaust vapours, such as: 2-methylpropanal, 3-methylbutanal, 2-methylbutanal, 3-methyl-1-butanol, n-hexanal, 2-methylbutyl isobutyrate, 2-undecanone, phenyl acetaldehyde, myrcene, limonene, linalool, humulene, dimethylsulphide, and dimethyltrisulphide. These substances were quantified in brewery broth before and after UV irradiation using high-resolution gas chromatography–mass spectrometry (HRGC–MS). For odour analysis, high-resolution gas chromatography-flame ionisation detection (HRGC-FID) coupled with sensory methods was used. Determined quantum yields of about 10−3 for phenyl acetaldehyde, myrcene, and humulene pointed out that direct photolysis contributed to their decay. Quantum yields of below 10−4 for the other substances indicated that UV irradiation did not contribute significantly to their degradation processes. Hydroxyl radical reaction rate constants and Henry constants of organic compounds were also measured. Substances accompanied with low Henry constants converted rapidly, whereas those with higher ones, relatively slowly. Determined aroma values concluded that after UV–H2O2 treatment, only dimethylsulphide and myrcene remained as important odorous compounds, but in significantly reduced concentrations. The UV–H2O2 treatment of brewery broth has been proved effective to reduce smell-irritating substances formed upon wort decoction.  相似文献   

8.
Using the relative kinetic technique the kinetics of the gas-phase reactions of Br radicals with acrolein, methacrolein and methylvinyl ketone have been investigated at (301±3) K in 1013 mbar of (N2+O2) bath gas at varying proportions. In 1013 mbar of synthetic air the following rate coefficients have been obtained (in units of cm3 molecule−1 s−1): acrolein (3.21±0.11)×10−12; methacrolein (2.33±0.08)×10−11; methyl vinyl ketone (1.87±0.06)×10−11. This study represents the first determination of the rate coefficients for these compounds. As for other unsaturated hydrocarbons the rate coefficient with Br was found to increase with increasing partial pressure of O2. From the product studies of the reactions it has been established that addition of Br radicals to the terminal C-atom is the major pathway in all three cases. However, for acrolein H atom abstraction from the -CO–H group is also significant. Mechanisms are proposed to explain the observed products, mainly β-brominated carbonyl compounds.  相似文献   

9.
Numerous chemical products are dispersed into the environment, and the consequences can be sometimes harmful to humans and ecosystems. Pharmaceutical compounds and hormone steroids are among these substances that concern the scientific community. Currently, little data are available on the presence and fate of these compounds in the environment and, in particular, for solid matrices. Therefore, the aim of this work was to perform soil column experiments to evaluate the accumulation, transfer and degradation of these substances in soil. The analyses were based on efficient sample preparation followed by sensitive and selective liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). For this purpose, 23 compounds were chosen including both pharmaceutical compounds as well as steroid hormones. In addition, this experiment was performed on two soils with different properties (% clay, pH, etc.). To the best of our knowledge, no soil column experiments have been performed previously on a large number of pharmaceutical compounds and steroid hormones. Significant transfer was observed only for sulphonamides that can be justified by their polarity (log K ow ?相似文献   

10.
To investigate the effect of organic matter evolution on heavy metal sorption, fluorescence excitation–emission matrix (EEM) spectra combined with parallel factor (PARAFAC) analysis were employed to characterize the evolution and metal-complexing potential of fluorescent water-extractable organic matter (WEOM) from composted municipal solid wastes (MSWs). The WEOMs examined comprised humic-, fulvic-, tryptophan-, and tyrosine-like substances. Composting treatment increased the content of humic- and fulvic-like matter, and changed the existence pattern of tryptophan- and tyrosine-like substances (i.e., the tryptophan- and tyrosine-like substances from uncomposted MSWs were mainly bound in protein-like matter, whereas those from composted MSWs were primarily bound in humic- and fulvic-like substances). Furthermore, composting treatment increased the polar functional group, aromaticity, and humification degree of the WEOMs, but decreased the aliphatic and hydroxyl group. These evolutions decreased the Cu(II) affinities of fulvic- and humic-like substances and the Pb(II) affinities and complexing capacities of fulvic-like substances, but increased the Cu(II) complexing capacities of fulvic- and humic-like substances. These results reveal that mature composts from the MSWs can be used for the remediation of Cu- and Pb-contaminated soils in situ, whereas immature composts can enhance the metal transferability from soil to plant.  相似文献   

11.
The CROMIS AhR kit, a simple and rapid yeast bioassay kit, was developed and used to detect dioxins and dioxin-like compounds in 20 gas and solid samples collected from refuse incineration plants in Japan. The World Health Organization toxic equivalent (WHO-TEQ) values of the samples were also calculated using high-resolution gas chromatography/high--resolution mass spectrometry. The WHO-TEQ values of the samples varied greatly, ranging from 0.0021–6.3 ng/g to 0.00013–16 ng/m3N (normal cubic meter) in the solid and gas samples, respectively. 2,3,4,7,8-Pentachlorodibenzofuran (23478-PeCDF) and 1,2,3,7,8-pentachlorodibenzo-p-dioxin (12378-PeCDD) were the major contributors to the samples’ WHO-TEQ values. The yeast in the bioassay responded to these congeners, and the EC50 values of 2,3,7,8-tetrachlorodibenzo-p-dioxin (2378-TeCDD), 12378-PeCDD, and 2,3,4,7,8-PeCDF were 490, 560, and 590 nM, respectively. The incinerator samples were subjected to the bioassay to obtain 2378-TeCDD equivalent values (CROMIS-TEQ values). The CROMIS-TEQ values of the solid and gas samples ranged from 0.0019 to 5.64 ng/g and from 0.14 to 20 ng/m3N, respectively. The CROMIS-TEQ and WHO-TEQ values displayed good correlations (r 2?=?0.94 and 0.95 in the solid and gas samples, respectively), except for those of the samples with low dioxin concentrations (below the Japanese emission standards). Therefore, the CROMIS AhR kit is a useful tool for the initial screening of samples containing dioxin-like compounds.  相似文献   

12.
《Chemosphere》2013,90(11):1426-1436
Volatile organic compounds (VOCs) from several different municipal solid wastes’ treatment plants in Mallorca (Spain) have been analysed by thermal desorption–gas chromatography–mass spectrometry (TD–GC–MS). Ambient (immission) air was collected during February and March 2011 by active sampling onto sorbents Tenax™ TA and Carboxen™ 1000. The study presents the chemical characterisation of 93 volatile organic compounds (VOCs) from an overall set of 84 immission air samples. 70 VOCs were positively identified.The linear fit for all 93 external standard calibration, from 10 mg L−1 to 150 mg L−1 (n = 4), was within the range 0.974 < r2 < 0.998. Limits of detection of the method (LOD) for all the standards were within the range 1.1–4,213 pg, as the absolute standard amount spiked into sorbent tubes in 1 μL standard mixture (dissolved in methanol).Overall results stated systematic correlation between waste’s nature and VOCs’ air composition. Organic wastes show main contribution of terpenes, waste water sludge residues’ of reduced sulphured compounds (RSCs) and municipal solid wastes show contribution of a wide sort of VOCs. The use of a chemometric approach for variable’s reduction to 12 principal components enables evaluation of similarities and dissimilarities between facilities. PCA clearly related samples to its corresponding facility on the basis of their VOCs composition and the ambient temperature.  相似文献   

13.
The variety of chemical substances present in modern building products, household products and furnishings provides potential for chemical reactions in the material (case 1), on the material surface (case 2) and in the gas phase (case 3). Such “indoor chemistry” is known as one of the main reasons for primary and secondary emissions. The conditions of production often cause unwanted side reactions and a number of new compounds can be found in finished products. Elevated temperatures are responsible for the degradation of cellulose, decomposition of non-heat-resistant additives and other thermally induced reactions like Diels–Alder synthesis. Heterogeneous chemistry takes place on the surface of materials. Well-known examples are the formation of aliphatic aldehydes from the oxidation of unsaturated fatty acids or the cleavage of photoinitiators under the influence of light. In case of composite flooring structures hydrolysis is one of the major pathways for the appearance of alcohols from esters. If different kinds of material are fixed together, emissions of new VOCs formed by inter-species reactions are possible. Other indoor air pollutants are formed by rearrangement of cleavage products or by metabolism. Compounds with –CC– bonds like terpenes, styrene, 4-phenylcyclohexene, etc. undergo gas phase reactions with O3, NOx, OH and other reactive gases. It has been shown that such products derived from indoor-related reactions may have a negative impact on indoor air quality due to their low odor threshold or health-related properties. Therefore, the understanding of primary and secondary emissions and the chemical processes behind is essential for the evaluation of indoor air quality. This publication gives an overview on the current state of research and new findings regarding primary and secondary emissions from building products and furnishings.  相似文献   

14.
A highly selective and sensitive method based on gas chromatography-tandem mass spectrometry (GC-MS/MS) to identify and quantify persistent organochlorine pesticides, (18 compounds including primary compounds and metabolites), in animal internal organs (kidneys, liver, and brain) has been developed. Tandem mass spectrometric conditions were individually optimized for each target compound in Multiple Reaction Monitoring (MRM) mode to obtain maximum sensitivity. Prior to instrumental analysis, a sample preparation method based on matrix solid phase dispersion (MSPD) followed by acidic digestion with sulfuric acid to reduce matrix co-extractives was employed. Analyses of real samples were carried out on coypus (Myocastor coypus) from the autumn slaughter of 19 animals. In the analyzed samples, three of the target compounds, namely DDE-pp′ (DDT metabolite), HCB and lindane, were detected. Their concentration levels fell in the ranges of 0.003–0.007, 0.003–0.025, and 0.003–0.021 mg kg?1 (0.005, 0.010, and 0.010 mg kg?1 on average) in the case of DDE-pp′, HCB and lindane, respectively. Although low quantities of organochlorine pesticides do not pose an immediate danger to consumers' health, they should be of public health concern considering long-term, low-dose exposure.  相似文献   

15.
This work describes the analysis of 15 pharmaceutical compounds, belonging to different therapeutic classes (anti-inflammatory/analgesics, lipid regulators, antiepileptics, β-blockers and antidepressants) and with diverse physical–chemical properties, in Spanish soils with different farmland uses. The studied compounds were extracted from soil by ultrasound-assisted extraction (UAE) and determined, after derivatization, by gas chromatography with mass spectrometric detection (GC–MS). The limits of detection (LODs) ranged from 0.14 ng g?1 (naproxen) to 0.65 ng g?1 (amitriptyline). At least two compounds where detected in all samples, being ibuprofen, salicylic acid, and paracetamol, the most frequently detected compounds. The highest levels found in soil were 47 ng g?1 for allopurinol and 37 ng g?1 for salicylic acid. The influence of the type of crop and the sampling area on the levels of pharmaceuticals in soil, as well as their relationship with soil physical–chemical properties, was studied. The frequent and widespread detection of some of these compounds in agricultural soils show a diffuse contamination, although the low levels found do not pose a risk to the environment or the human health.  相似文献   

16.
Baker A  Elliott S  Lead JR 《Chemosphere》2007,67(10):2035-2043
Fluorescence of organic matter from six contrasting freshwaters was analysed after filtration (1.2 microm and 0.2 microm filter sizes) and pH perturbation (+/-2 pH units from ambient conditions). Two fluorophores were compared in detail: tryptophan-like fluorescence, whose filtration and pH characteristics are relatively poorly understood, and humic-like fluorescence, which is better characterised. Although there was some variability in both fluorophores, the tryptophan-like fluorescence showed the most significant decrease in fluorescence intensity between raw and 1.2 microm filter samples, and a much smaller decrease between 1.2 and 0.2 microm, demonstrating a significant source associated with particulate material as well as a significant <0.2 microm fraction. In contrast, humic-like fluorescence shows little change with filtration, suggesting that the majority of this fluorescence is associated with truly dissolved material. The pH perturbation experiments demonstrate that tryptophan-like fluorescence is less impacted by pH than with filter fraction. For humic-like fluorescence, pH effects are weak and are not as consistent as those reported in the literature for extracted humic substances. pH perturbation of the freshwaters shows a wide range of sample specific pH responses, significantly more variable than that observed in experiments using extracted humic substances and tryptophan standards, demonstrating the natural variability of freshwater dissolved organic matter.  相似文献   

17.
In this study, we present the analysis of functional groups of humic-like substances (HULIS) isolated from atmospheric aerosols (<1 μm). Aerosol samples were collected in an urban area (Dübendorf, Switzerland) both in summer and winter. Quantification of carboxylic, arylic, phenolic and aliphatic functional groups of HULIS was performed by a specially adapted and optimized H-NMR method. The concentrations of carboxylic, arylic, phenolic and aliphatic functional groups were between 9×10−11 and 6×10−8 mol/m3 for all samples, corresponding up to 14% of the total HULIS mass. A good correlation between the H-NMR results and the potentiometric titration of carboxylic groups was observed for all winter and summer samples. The pK distributions of carboxylic groups of HULIS were calculated from potentiometric titration data. pK spectra showed that pK values of most carboxylic groups is between 3 and 5. The H-NMR data show that the content of aromatic groups is higher in winter than in summer. This may either be due to emission of aromatic compounds by wood burning or to slower degradation reaction of aromatics in winter.  相似文献   

18.
Traffic has long been recognized as the major contributor to polycyclic aromatic hydrocarbon (PAH) emissions to the urban atmosphere. Stationary combustion sources, including residential space heating systems, are also a major contributor to PAH emissions. The aim of this study was to determine the profile and concentration of PAHs in stack flue gas emissions from different kinds of space heaters in order to increase the understanding of the scale of the PAH pollution problem caused by this source. This study set out to first assess the characteristics of PAHs and their corresponding benzo[a]pyrene equivalent emissions from a few types of domestic heaters and central heating systems to the urban atmosphere. The study, enabled for the first time, the characterization of PAHs in stationary combustion sources in the city of Damascus, Syria. Nine different types of heating systems were selected with respect to age, design, and type of fuel burned. The concentrations of 15 individual PAH compounds in the stack flue gas were determined in the extracts of the collected samples using high-performance liquid chromatography system (HPLC) equipped with ultraviolet–visible and fluorescence detectors. In general, older domestic wood stoves caused considerably higher PAH emissions than modern domestic heaters burning diesel oil. The average concentration of ΣPAH (sum of 15 compounds) in emissions from all types of studied heating systems ranged between 43?±?0.4 and 316?±?1.4 μg/m3. Values of total benzo[a]pyrene equivalent ranged between 0.61 and 15.41 μg/m3.  相似文献   

19.
A series of source tests was performed to evaluate the chemical composition of particle emissions from the woodstove combustion of four prevalent Portuguese species of woods: Pinus pinaster (maritime pine), Eucalyptus globulus (eucalyptus), Quercus suber (cork oak) and Acacia longifolia (golden wattle). Analyses included water-soluble ions, metals, radionuclides, organic and elemental carbon (OC and EC), humic-like substances (HULIS), cellulose and approximately l80 organic compounds. Particle (PM10) emission factors from eucalyptus and oak were higher than those from pine and acacia. The carbonaceous matter represented 44–63% of the particulate mass emitted during the combustion process, regardless of species burned. The major organic components of smoke particles, for all the wood species studied, with the exception of the golden wattle (0.07–1.9% w/w), were anhydrosugars (0.2–17% w/w). Conflicting with what was expected, only small amounts of cellulose were found in wood smoke. As for HULIS, average particle mass concentrations ranged from 1.5% to 3.0%. The golden wattle wood smoke presented much higher concentrations of ions and metal species than the emissions from the other wood types. The results of the analysis of radionuclides revealed that the 226Ra was the naturally occurring radionuclide more enriched in PM10. The chromatographically resolved organics included n-alkanes, n-alkenes, PAH, oxygenated PAH, n-alkanals, ketones, n-alkanols, terpenoids, triterpenoids, phenolic compounds, phytosterols, alcohols, n-alkanoic acids, n-di-acids, unsaturated acids and alkyl ester acids.  相似文献   

20.
The mass concentrations of inorganic ions, water-soluble organic carbon, water-insoluble organic carbon and black carbon were determined in atmospheric aerosol collected at three European background sites: (i) the Jungfraujoch, Switzerland (high-alpine, PM2.5 aerosol); (ii) K-puszta, Hungary (rural, PM1.0 aerosol); (iii) Mace Head, Ireland (marine, total particulate matter). At the Jungfraujoch and K-puszta the contribution of carbonaceous compounds to the aerosol mass was higher than that of inorganic ions by 33% and 94%, respectively. At these continental sites about 60% of the organic carbon was water soluble, 55–75% of the total carbon proved to be refractory and a considerable portion of the water soluble, refractory organic matter was composed of humic-like substances. At Mace Head the mass concentration of organic matter was found to be about twice than that of nonsea-salt ions, 40% of the organic carbon was water soluble and the amount of highly refractory carbon was low. Humic-like substances were not detected but instead low molecular weight carboxylic acids were responsible for about one-fifth of the water-soluble organic mass. These results imply that the influence of carbonaceous compounds on aerosol properties (e.g. hygroscopic, optical) might be significant.  相似文献   

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