Degradation of anti-inflammatory drug ketoprofen by electro-oxidation: comparison of electro-Fenton and anodic oxidation processes

The electrochemical degradation of the nonsteroidal anti-inflammatory drug ketoprofen in tap water has been studied using electro-Fenton (EF) and anodic oxidation (AO) processes with platinium (Pt) and boron-doped diamond (BDD) anodes and carbon felt cathode. Fast degradation of the parent drug molecule and its degradation intermediates leading to complete mineralization was achieved by BDD/carbon felt, Pt/carbon felt, and AO with BDD anode. The obtained results showed that oxidative degradation rate of ketoprofen and mineralization of its aqueous solution increased by increasing applied current. Degradation kinetics fitted well to a pseudo-first-order reaction. Absolute rate constant of the oxidation of ketoprofen by electrochemically generated hydroxyl radicals was determined to be (2.8?±?0.1)?×?10⁹ M^?1 s^?1 by using competition kinetic method. Several reaction intermediates such as 3-hydroxybenzoic acid, pyrogallol, catechol, benzophenone, benzoic acid, and hydroquinone were identified by high-performance liquid chromatography (HPLC) analyses. The formation, identification, and evolution of short-chain aliphatic carboxylic acids like formic, acetic, oxalic, glycolic, and glyoxylic acids were monitored with ion exclusion chromatography. Based on the identified aromatic/cyclic intermediates and carboxylic acids as end products before mineralization, a plausible mineralization pathway was proposed. The evolution of the toxicity during treatments was also monitored using Microtox method, showing a faster detoxification with higher applied current values.     

Kinetics of acetaminophen degradation by Fenton oxidation in a fluidized-bed reactor

Acetaminophen (ACT), an analgesic and antipyretic substance, is one of the most commonly detected pharmaceutical compound in surface waters and wastewaters. In this study, fluidized-bed Fenton (FB-Fenton) was used to decompose ACT into its final degradation products. The 1.45-L cylindrical glass reactor had inlet, outlet and recirculating sections. SiO₂ carrier particles were supported by glass beads with 2–4 mm in diameter. ACT concentration was determined by high performance liquid chromatography (HPLC). During the first 40 min of reaction, a fast initial ACT removal was observed and the “two-stage” ACT degradation conformed to a pseudo reaction kinetics. The effects of ferrous ion dosage and [Fe²⁺]/[H₂O₂] (FH ratio) were integrated into the derived pseudo second-order kinetic model. A reaction pathway was proposed based on the intermediates detected through SPME/GC–MS. The aromatic intermediates identified were hydroquinone, benzaldehydes and benzoic acids while the non-aromatic substances include alcohols, ketones, aldehydes and carboxylic acids. Rapid initial ACT degradation rate can be accomplished by high initial ferrous ion concentration and/or low FH ratio.     

Primary photoproducts and half-lives

The photolytically induced decomposition of fluoroquinolone carboxylic acids (enrofloxacin, danofloxacin, ciprofloxacin and norfloxacin) at concentrations of 10 mg/l in pure water and an irradiation intensity of 200 W/m² (xenon lamp) led to half-lives from 20.6 min (danofloxacin) to 105.9 min (norfloxacin). The environmental half-life of enrofloxacin was calculated by the GCSOLAR program and resulted in 1.8 to 55.4 hours, depending on the season and degree of latitude. During the irradiation procedure, products were built up which primarily demonstrated alterations involving the piperazine ring as compared with the parent compounds. The amount of¹⁴CO₂ evolved by the photomineralization of¹⁴C-labeled enrofloxacin reached 26.4 % of the applied radioactivity. The main photoproducts were isolated by HPLC and their structural elucidation was carried out by different spectroscopic methods (MS, GC/MS and¹H-NMR).     

A rapid and high-throughput quantum dots bioassay for monitoring of perfluorooctane sulfonate in environmental water samples

Currently HPLC/MS is the state of the art tool for environmental/drinking water perfluorooctane sulfonate (PFOS) monitoring. PFOS can bind to peroxisomal proliferator-activated receptor-alpha (PPARα), which forms heterodimers with retinoid X receptors (RXRs) and binds to PPAR response elements. In this bioassay free PFOS in water samples competes with immobilized PFOS in ELISA plates for a given amount of PPARα-RXRα. It can be determined indirectly by immobilizing PPARα-RXRα-PFOS complex to another plate coated with PPARα antibody and subsequent measuring the level of PPARα-RXRα by using biotin-modified PPARα-RXRα probes-quantum dots-streptavidin detection system. The rapid and high-throughput bioassay demonstrated a detection limit of 2.5 ng L⁻¹ with linear range between 2.5 ng L⁻¹ and 75 ng L⁻¹. Detection results of environmental water samples were highly consistent between the bioassay and HPLC/MS.     

Identification of microcystins from three collection strains of Microcystis aeruginosa

Microcystins (MCs) are toxic cyclic heptapeptides produced by various cyanobacteria genera, especially Microcystis. We identified 10 out of 12 MCs produced by three Microcystis aeruginosa strains from cyanobacteria collections, UTEX 2666, UTEX 2670 and UAM 1303, by using two analytical methods: Matrix-assisted Laser Desorption Ionization Time of Flight Mass Spectrometry (MALDI-TOF/MS) and HPLC Photodiode Array Detector coupled to a hybrid Quadrupole Time of Flight Mass Spectrometry (HPLC-PDA-QTOF/MS). MALDI-TOF/MS failed to detect non-polar MCs, such as MC-LY and MC-LW. HPLC-QTOF/MS permitted the accurate identification of most MCs present in methanolic extracts. Besides, three new MCs, namely: [D-Glu(OCH₃)⁶, D-Asp³] MC-LAba, MC-YL and MC-YM were detected by HPLC-QTOF/MS.     

Degradation of anthraquinone dye C.I. Reactive Blue 19 in aqueous solution by ozonation

This study investigated the degradation of anthraquinone reactive dye C.I. Reactive Blue 19 (RB-19) with initial concentration of 100 mg L⁻¹ in aqueous solution by ozone oxidation. The results of UV/VIS and FTIR spectra showed that the anthraquinone structures, nitrogen linkages and amino groups of RB-19 were destroyed under direct ozone reaction. The identification by LC–MS and GC–MS analyses indicated that some organic acids (e.g., phthalic acids) and 1,3-indanone could be the primary degradation products, respectively. The Microtox toxicity of the ozonated RB-19 solution initially increased but subsequently decreased when ozonation time increased. This detoxification accompanied biodegradability enhancement revealed by BOD/COD ratio increasing from 0.15 to 0.33 after 10 min of ozonation.     

Sediments as a sink for UV filters and benzotriazoles: the case study of Upper Iguaçu watershed,Curitiba (Brazil)

Ingredients in home and personal care products, including UV filters and benzotriazoles, are high production volume chemicals extensively used in our daily life, despite several studies revealed their potential eco-toxicity and endocrine-disrupting capacity. Due to some features, such as high lipophilicity, low degradability, and persistence of many of these compounds, sediments can be considered a sink for them in the aquatic environment. In the present study, nine organic UV filters and three benzotriazoles were investigated for the first time in sediments from four urban rivers in Brazil. The contaminants were analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The results revealed that octocrylene (OC), etylhexyl-methoxycinnamate (EHMC), benzophenone-3 (oxybenzone, BP3), and benzotriazole (BZT) were the predominant compounds adsorbed on the sediments, with concentrations ranging from 5.6 to 322.2 ng g⁻¹ dry weight. The results reported in this work constitute the first data on the accumulation of polar benzotriazoles and lipophilic organic UV filters in sediments from Brazil.

     

Detailed characterization of polar compounds of residual oil in contaminated soil revealed by Fourier transform ion cyclotron resonance mass spectrometry

Effects of remediation technologies on polar compounds of crude oil in contaminated soils have not been well understood when compared to hydrocarbons. In this study, ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to characterize the changes in NSO polar compounds of crude oil and residual oil after long-term natural attenuation, biostimulation and subsequent ozonation following biostimulation of contaminated soils. N₁ and O₁ species, which were abundant in the crude oil, were selectively biodegraded, and species with higher double bond equivalent values and smaller carbon numbers appeared to be more resistant to microbial alteration. O₂-O₆ species were enriched by biodegradation and contained a large number of compounds with a high degree of unsaturation. Ozone could react with a variety of polar compounds in residual oil after biodegradation and showed high reactivity with polar species containing aromatic or multi-aliphatic rings, including the residual N₁ and O₁ species, naphthenic acids and unsaturated O₃-O₆ compounds. Fatty acids and O₃-O₈ species dominated by saturated alkyl compounds were resistant to ozonation or the primarily incomplete ozonation products. Principal component analysis of identified peaks in the FT-ICR MS spectra provided a comprehensive overview of the complex samples at the molecular level and the results were consistent with the detailed analysis. Taken together, these results showed the high complexity of polar compounds in residual oils after biodegradation or ozonation in contaminated soil and would contribute to a better understanding of bioremediation and ozonation processes.     

Oxidation of ofloxacin by Oxone/Co2+: identification of reaction products and pathways

Oxidative degradation of ofloxacin (OFX) by sulfate free radicals (SO₄ ^??) in the UV/Oxone/Co²⁺oxidation process was investigated for the first time, with a special focus upon identifying the transformation products as well as understanding the reaction pathways. Thirteen main compounds were identified after the initial transformation of OFX; the detailed structural information of which were characterized by high-performance liquid chromatography–high resolution mass spectrometry and MS fragmentation analysis. The degradation pathways mainly encompassed ring openings at both the piperazinyl substituent and the quinolone moiety, indicating that the usage of SO₄ ^?? aided the oxidative degradation of OFX to undergo more facile routes compared to those in previous reports by using OH^?/h⁺ as the oxidant, where the initial transformation attacks were mainly confined to the piperazine moiety. Moreover, in this study, smart control over the pH conditions of the oxidation system via different modes of Oxone dosage resulted in the selective degradation of the functional sites of OFX molecule, where it was shown that the SO₄ ^??-driven destruction of the quinolone moiety of OFX molecule favored the neutral pH conditions. This would be beneficial for the reduction of bacterial resistance against quinolones in the aqueous environment.     

Degradation dynamics,residues and risk assessment of Dufulin enantiomers in corn plants and corn by LC/MS/MS

ABSTRACT

The degradation dynamics and terminal residues of dufulin enantiomers were investigated in two typical corn plants. A convenient and precise chiral method by high-performance liquid chromatography coupled with tandem triple quadrupole mass spectrometry (HPLC/MS/MS) using a Chiralpak IC column was developed and validated for measuring dufulin enantiomers in corn plants and corn. The two enantiomers of dufulin quickly dissipated in the corn plant, and no noticeable stereoselectivity was observed during degradation or in the final residues. After 30% rac-dufulin wettable powder with a 1- to 1.5-fold dose of the recommended value was sprayed two to three times on corn plants, the residue levels of S-(+)-dufulin and R-(-)-dufulin in corn from both sites were lower than or equal to 0.0520 mg kg^–1 on days 7, 14 and 21 after the last application. The dietary risk assessment indicated that dufulin did not exhibit obvious dietary health risks in corn samples when good agricultural practices were implemented. The findings from this study may be used to better understand the chiral profiles of dufulin in the environment and the effect of dufulin residues in corn on health.     

Trace analysis of parabens preservatives in drinking water treatment sludge,treated, and mineral water samples

Parabens have been widely used as antimicrobial agents, mainly in food products, pharmaceuticals, and cosmetics. Although they are known as safe preservatives, they also cause some harm to human health, which has been discussed lately. Therefore, the aim of this study was to evaluate the occurrence of nine parabens (including isomers) in mineral and drinking waters, besides in drinking water treatment sludge (DWTS) samples with determination by liquid chromatography tandem mass spectrometry (LC-MS/MS). Both methods solid phase extraction (SPE) and QuEChERS were validated. Calibration curves showed a correlation coefficient of 0.99 for all compounds. LOQ values ranged from 0.04 to 4 μg L^?1 in aqueous matrices and from 5 to 500 ng g^?1 in DWTS. Recoveries between 70 and 115% were reached with RSD below 20% for all compounds in SPE whereas recoveries between 62 and 119% were found with RSD below 20% for almost all compounds in QuEChERS. Matrix effect had low values (<?20%); it was only above 20% for methylparaben in the SPE and for pentylparaben in the QuEChERS. Using a quick and simple extraction procedures with SPE, QuEChERS, and LC-MS/MS analyses, these methods proved to be selective and sensitive. They were successfully applied to real samples (treated water, mineral water, and sludge), and methylparaben was detected at concentration levels below 0.242 μg L^?1 in mineral and treated water samples and 10 ng g^?1 in DWTS samples.     

Determination of polycyclic aromatic hydrocarbons and substitutes (Nitro-, Oxy-PAHs) in urban soil and airborne particulate by GC-MS and NCI-MS/MS

A method involving high resolution gas chromatography combined with ion trap (HRGC-MS/MS) and negative chemical ionisation (NCI) was developed for the determination of nitrated or oxygenated polycyclic aromatic hydrocarbons (nitro-PAHs, oxy-PAHs) and other electrophilic substitutes in soil samples. Efficient clean-up was achieved by a combination of methods for the determination of PAHs in soil and nitro-PAHs in aerosol using solid phase extraction (SPE) and semipreparative high performance liquid chromatography (HPLC). In samples of surface soil from the city of Basle (Switzerland), nitro-PAHs (mainly 3-nitrofluoranthene and 1-nitropyrene) were found in concentrations between 30 and 800 ng/kg dry weight. Oxy-PAHs and parent PAHs revealed 10²-10⁴-fold higher levels. Nitro-PAHs which are up to 10⁵ times more mutagenic seem to be less persistent in soil than the parent forms, although their entire mutagenic potential has to be estimated as being on the same order of magnitude. In urban air particulate matter, the amounts of nitro-PAHs (2–62 pg/m³) were 10–100 times lower than oxyPAHs and parent PAHs which were both found in a similar range. 3-nitrobenzanthrone, a recently described suspected human carcinogen has not yet been detected. Using multivariate statistical analysis, it was possible to elucidate similarities or special characteristics of substances in a given matrix reflecting their chemical properties or specific emission sources.     

Radical-driven carbonyl-to-acid conversion and acid degradation in tropospheric aqueous systems studied by CAPRAM

Model studies on the aqueous phase radical-driven processing of carbonyl compounds and acids in clouds and deliquescent particles were performed. The model exposed that aqueous radical conversions of carbonyl compounds and its oxidation products can contribute potentially to the formation of functionalised organic acids. The main identified C₂–C₄ organic gas phase precursors are ethylene glycol, glycolaldehyde, glyoxal, methylglyoxal and 1,4-butenedial. The aqueous phase is shown to contribute significantly with about 93%/63%, 47%/8%, 31%/4%, 7%/4%, 36%/8% to the multiphase oxidative fate of these compounds under remote/urban conditions. Interestingly, the studies revealed that aqueous chemical processing is not only limited to in-cloud conditions but also proceeds in deliquescent particle phase with significant fluxes. Oxalic acid is shown to be formed preferably in deliquescent particles subsequent to the in-cloud oxidations. Mean aqueous phase oxalate formation fluxes of about 12, 42 and 0.4 ng m^?3 h^?1 in the remote, urban and maritime scenario, respectively. Additionally, the turnovers of the oxidation of organics such as methylglyoxal by NO₃ radical reactions are identified to be competitive to their OH pendants. At the current state of CAPRAM, mean C₂–C₄ in-cloud oxidation fluxes of about 0.12 and 0.5 μg m^?3 h^?1 are modelled under the idealised remote and urban cloud conditions.Finally, turnovers from radical oxidations were compared with those of thermal reactions. It is demonstrated that, based on the sparse kinetic data available organic accretion reaction might be of interest in just a few cases for cloud droplets and aqueous particles but generally do not reach the oxidative conversion rates of the main radical oxidants OH and NO₃. Interestingly, oxidation reactions of H₂O₂ are shown to be competitive to the OH radical conversions in cases when H₂O₂ is not readily used up by the S(IV) oxidation.     

Distribution of14C-TNT and derivatives in different biochemical compartments ofPhaseolus vulgaris

¹⁴C-TNT was used to quantify the uptake rate and metabolic turnover of TNT inPhaseolus vulgaris. Seventeen plants were analysed by a special cell fractionation method with polar and nonpolar solvents and enzymes. We obtained three cytoplasmic fractions and five cell wall derived fractions. The recovery rate was 72% as measured by liquid scintillation counting.¹⁴C partitioned almost in equal amounts with approximately 50% in the cytoplasm and in the cell wall. The majority of the TNT-metabolites are present in the cytoplasm as was shown by GC/ ECD and thin layer chromatography. The¹⁴C in the cell wall is bound probably resulting in long-term immobilisation of these metabolites. We conclude that plants may also be a model for nitroaromatic turnover and immobilisation in soil components.     

Monofluorinated analogues of polychlorinated biphenyls (F-PCBs): synthesis using the Suzuki-coupling, characterization, specific properties and intended use

An improved method, a palladium-catalyzed cross-coupling reaction the so-called Suzuki-coupling, was used to synthesize 19 monofluorinated analogues (F-PCBs) of polychlorinated biphenyls (PCBs), including analogues of PCBs 28, 52 and 81. The coupling of chlorinated and/or fluorinated isomers of aryl boronic acids with bromo- and/or iodobenzenes gave the desired F-PCB congeners in good to excellent yields. The self-coupling product of the aryl boronic acids was the major impurity, but this limitation could be minimized. The influence of ortho-substitution by chlorine on the reaction time was studied in detail. The F-PCBs were characterized by means of ¹H and ¹⁹F NMR and mass spectrometry (MS). F-PCBs show remarkably similar characteristics in many aspects to those of the corresponding non-fluorinated parent PCBs. Since fluorine is generally resistant to degradation, once incorporated into a substrate it functions as an indelible label that can be used to monitor structures and dynamics. F-PCBs may prove their usefulness as markers and tracers in mechanistic and toxicological studies. The aim of further research will be to test the suitability of fluorine as a sensitive probe in a broad range of applications, including synthesis, analytical, mechanistic and toxicological studies.     

Photochemical production and loss of organic acids in high Arctic aerosols during long-range transport and polar sunrise ozone depletion events

Unique daily measurements of water-soluble organics in fine (<2 μm) and coarse (>2 μm) aerosols were conducted at Alert in the Canadian Arctic in winter to spring of 1992. They yield insight into photochemical production and loss of organics during long-range transport and ozone depletion events following polar sunrise. Comprehensive analyses of α, ω-dicarboxylic acids (C₂–C₁₂), ω-oxocarboxylic acids (C₂–C₉) and α-dicarbonyls (C₂, C₃) as well as pyruvic acid and aromatic (phthalic) diacid were conducted using GC and GC/MS techniques. Oxalic (C₂) acid was generally the dominant diacid species in both fine and coarse fractions, followed by malonic (C₃) and succinic (C₄) acids. Concentrations of total diacids in the fine aerosol fraction (0.2–64 ng m⁻³) were 5–60 times higher than those in the coarse fraction (0.01–3 ng m⁻³). After polar sunrise in early-March, the total concentration of fine aerosol diacids increased by a factor of 3–5 while the coarse mode did not change significantly. From dark winter to sunlit spring, temporal changes in correlations and ratios of these water-soluble organics to vanadium and sulfate measured simultaneously suggest that atmospheric diacids and related organic compounds are largely controlled by long-range atmospheric transport of polluted air during winter, but they are significantly affected by photochemical production. The latter can occur in sunlight either during transport to the Arctic or during photochemical events associated with surface ozone depletion and bromine chemistry near Alert in spring. Conversion of gaseous precursors to particulate matter via photochemical oxidation was intensified at polar sunrise, resulting in a peak in the ratio of total diacids to V. During ozone depletion events, complex patterns are indicated in photochemical production and loss depending on the diacid compound. Unsaturated (maleic and phthalic) diacids were inversely correlated with particulate Br whereas saturated diacids (C₂–C₄) positively correlated with particulate Br. These results suggest that Br chemistry associated with ozone depletion leads to degradation of unsaturated diacids and to the production of smaller saturated diacids.     

Spatial distribution of perfluoroalkyl acids in the Pearl River of Southern China

An intensive campaign was conducted in September 2012 to collect surface water samples along the tributaries of the Pearl River in southern China. Thirteen perfluoroalkyl acids (PFAAs), including perfluorocarboxylates (PFCAs, C4–C11) and perfluorosulfonates (PFSAs, C4, C6–C8, and C10), were determined using high-performance liquid chromatography/negative electrospray ionization–tandem mass spectrometry (HPLC/(-)ESI–MS/MS). The concentrations of total PFAAs (ΣPFAAs) ranged from 3.0 to 52 ng L⁻¹, with an average of 19 ± 12 ng L⁻¹. The highest concentrations of ΣPFAAs were detected in the surface water of the Dong Jiang tributary (17–52 ng L⁻¹), followed by the main stream (13–26 ng L⁻¹) and the Sha Wan stream (3.0–4.5 ng L⁻¹). Perfluorooctanoate (PFOA), perfluorobutane sulfonate (PFBS), and perfluorooctane sulfonate (PFOS) were the three most abundant PFAAs and on average accounted for 20%, 24%, and 19% of ΣPFAAs, respectively. PFBS was the most abundant PFAA in the Dong Jiang tributary, and PFOA was the highest PFAA in the samples from the main stream of the Pearl River. A correlation was found between PFBS and PFOA, which suggests that both of these PFAAs originate from common source(s) in the region. Nevertheless, the slope of PFBS/PFOA was different in the different tributaries sampled, which indicates a spatial difference in the source profiles of the PFAAs.     

Metabolism of the14C-labeled herbicide clodinafop-propargyl in plant cell cultures of wheat and tobacco

The metabolism of ¹⁴C-clodinafop-propargyl (CfP) was examined in cell cultures of wheat (Triticum aestivum L. cv. ‘Heines Koga II’) and tobacco (Nicotiana tabacum L.). Besides the non-transgenic tobacco culture, cultures transformed separately with cDNA of human cytochrome P450-monooxygenases (P450s) CYP1A1, CYP1A2, CYP3A4, CYP2B6 and CYP2C19 were examined. Experiments with wheat were executed in the presence and absence of safener cloquintocet-mexyl (CqM). After 48 h of incubation, only about 10% of applied ¹⁴C was found in media (both tobacco and wheat). Non-extractable residues of ¹⁴C-CfP in wheat cells were 16.54% (without CqM) and 30.87% (with CqM). In all tobacco cultures, 82.41–92.46% of applied radioactivity was recovered in cell extracts. In contrast to wheat, non-extractable residues amounted only to 1.50–2.82%. As determined by radio-thin layer chromatography (TLC) and -high-performance liquid chromatography (HPLC), the parent CfP was not found in the cell extracts of wheat; in tobacco cell extracts, only traces of CfP were detected. After a hydrolysis of assumed carbohydrate conjugates of CfP derived polar ¹⁴C-labeled compounds, TLC and HPLC analysis showed that in wheat, a more complex pattern of metabolites of CfP were observed as compared to all tobacco cultures. In hydrolysates resulting from wheat, the identity of three primary products was confirmed by means of GC-EI-MS: free acid clodinafop (Cf), hydroxy-Cf hydroxylated at the pyridinyl moiety, and 4-(5-chloro-3-fluoropyridin-2-yloxy)phenol. In hydrolysates derived from all tobacco cultures, main metabolite was Cf besides only traces of further unidentified products. Differences among the different tobacco cultures (non-transgenic, transgenic) did not emerge. According to kinetics of disappearance of primary metabolite Cf as well as formation of polar soluble products and non-extractable residues, metabolization of CfP proceeded at a noticeably higher rate in wheat cells treated with safener CqM than in cells without CqM treatment. Thus, these results indicated a stimulation of CfP's metabolism by CqM, although metabolic profiles observed in CqM treated and non-treated cells (after hydrolysis) were qualitatively similar. The findings obtained from all tobacco cultures suggested that with the exception of ester cleavage to Cf, CfP cannot be metabolized by tobacco itself or by the human P450s examined.     

矸石基X型分子筛对水中Co2+、Cu2+、Cd2+和Cr3+的去除

以煤矸石为原料,采用碱熔后水热合成法制备X型分子筛并进行XRD、SEM、BET和Zeta电位分析。研究其对水中Co2+、Cu2+、Cd2+和Cr3+4种离子的吸附性能,包括吸附等温线、吸附动力学以及初始金属离子浓度、pH值对吸附性能的影响。所合成的矸石基X型分子筛的BET比表面积为676.02 m2/g,微孔孔容为0.263 cm3/g。吸附实验表明,矸石基X型分子筛能有效去除上述4种离子,同时实现煤矸石的资源化和金属离子的去除。4种离子的平衡吸附量均随初始浓度的增大而增大,相同条件下平衡吸附量的大小顺序为Cd2+>Cr3+>Cu2+>Co2+。准二级动力学模型能很好地描述4种离子的吸附动力行为。Langmuir模型对Co2+、Cu2+和Cd2+吸附的拟合较Freundlich模型高,说明其主要表现为物理吸附过程。4种离子的吸附速率均由液膜扩散和颗粒内扩散共同控制。     

PM2.5 source apportionment with organic markers in the Southeastern Aerosol Research and Characterization (SEARCH) study

Positive matrix factorization (PMF) and effective variance (EV) solutions to the chemical mass balance (CMB) were applied to PM_2.5 (particulate matter with an aerodynamic diameter <2.5 μm) mass and chemically speciated measurements for samples taken from 2008 to 2010 at the Atlanta, Georgia, and Birmingham, Alabama, sites. Commonly measured PM_2.5 mass, elemental, ionic, and thermal carbon fraction concentrations were supplemented with detailed nonpolar organic speciation by thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS). Source contribution estimates were calculated for motor vehicle exhaust, biomass burning, cooking, coal-fired power plants, road dust, vegetative detritus, and secondary sulfates and nitrates for Atlanta. Similar sources were found for Birmingham, with the addition of an industrial source and the separation of biomass burning into open burning and residential wood combustion. EV-CMB results based on conventional species were qualitatively similar to those estimated by PMF-CMB. Secondary ammonium sulfate was the largest contributor, accounting for 27–38% of PM_2.5, followed by biomass burning (21–24%) and motor vehicle exhaust (9–24%) at both sites, with 4–6% of PM_2.5 attributed to coal-fired power plants by EV-CMB. Including organic compounds in the EV-CMB reduced the motor vehicle exhaust and biomass burning contributions at both sites, with a 13–23% deficit for PM_2.5 mass. The PMF-CMB solution showed mixing of sources within the derived factors, both with and without the addition of speciated organics, as is often the case with complex source mixtures such as those at these urban-scale sites. The nonpolar TD-GC/MS compounds can be obtained from existing filter samples and are a useful complement to the elements, ions, and carbon fractions. However, they should be supplemented with other methods, such as TD-GC/MS on derivitized samples, to obtain a wider range of polar compounds such as sterols, sugars, and organic acids. The PMF and EV solutions to the CMB equations are complementary to, rather than replacements for, each other, as comparisons of their results reveal uncertainties that are not otherwise evident.

Implications:?Organic markers can be measured on currently acquired PM_2.5 filter samples by thermal methods. These markers can complement element, ion, and carbon fraction measurements from long-term speciation networks. Applying the positive matrix factorization and effective variance solutions for the chemical mass balance equations provides useful information on the accuracy of the source contribution estimates. Nonpolar compounds need to be complemented with polar compounds to better apportion cooking and secondary organic aerosol contributors.