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The HUmic-LIke Substances (HULIS) fraction isolated from aerosol samples collected at a rural location of the Pearl River Delta Region (PRD), China, during the harvest season was analyzed by both positive and negative mode electrospray ionization (ESI) coupled with an ultrahigh resolution mass spectrometer (UHRMS). With the remarkable resolving power and mass accuracy of ESI-UHRMS, thousands of elemental formulas were identified. Formulas detected in the positive (ESI+) and the negative (ESI-) mode complement each other due to differences in the ionization mechanism, and the use of both provides a more complete characterization of HULIS. Compounds composed of C, H, and O atoms were preferentially detected in ESI- by deprotonation, implying their acidic properties. Tandem MS and Kendrick Mass Defect analysis implies that carboxyl groups are abundant in the CHO compounds. This feature is similar to those of natural fulvic acids, but relatively smaller molecular weights are observed in the HULIS samples. A greater number of reduced nitrogen organic compounds were observed in the ESI+ compared to ESI-. Compounds with biomass burning origin including alkaloids, amino acids, and their derivatives are their probable constituents. Sulfur-containing species were dominantly detected in ESI-. The presence of sulfate fragments in the MS/MS spectra of these species and their high O/S ratios implies that they are mainly organosulfates. Organosulfates and nitrooxy-organosulfates were often the most intensive peaks in the ESI- spectra. They are believed to be products of reactive uptake of photooxidation products of reactive volatile organic compounds by acidic sulfate particles. The elemental compositions deduced from the UHRMS analysis confirm the conclusion from our previous study that biomass burning and SOA formation are both important sources of HULIS in the PRD region.

A laboratory intercomparison of organic carbon (OC) and elemental carbon (EC) measurements of atmospheric particulate matter samples collected on quartz filters was conducted among eight participants of the ACE-Asia field experiment The intercomparison took place in two stages: the first round of the intercomparison was conducted when filter samples collected during the ACE-Asia experiment were being analyzed for OC and EC, and the second round was conducted after the ACE-Asia experiment and included selected samples from the ACE-Asia experiment Each participant operated ECOC analyzers from the same manufacturer and utilized the same analysis protocol for their measurements. The precision of OC measurements of quartz fiber filters was a function of the filter's carbon loading but was found to be in the range of 4-13% for OC loadings of 1.0-25 microg of C cm(-2). For measurements of EC, the precision was found to be in the range of 6-21% for EC loadings in the range of 0.7-8.4 microg of C cm(-2). It was demonstrated for three ambient samples, four source samples, and three complex mixtures of organic compounds that the relative amount of total evolved carbon allocated as OC and EC (i.e., the ECOC split) is sensitive to the temperature program used for analysis, and the magnitude of the sensitivity is dependent on the types of aerosol particles collected. The fraction of elemental carbon measured in wood smoke and an extract of organic compounds from a wood smoke sample were sensitive to the temperature program used for the ECOC analysis. The ECOC split for the three ambient samples and a coal fly ash sample showed moderate sensitivity to temperature program, while a carbon black sample and a sample of secondary organic aerosol were measured to have the same split of OC and EC with all temperature programs that were examined.

Atmospheric oxidation of hydrocarbons by hydroxyl radicals and ozone leads to products containing -COOH, -OH, and -CdO functional groups. The high polarity of such compounds precludes direct GC-MS analysis. In addition, many such compounds often exist in a single sample at trace levels. An analytical method has been developed to identify compounds containing one or more functional groups of carbonyl, carboxy, and hydroxy in atmospheric samples. In the method, -CdO groups are derivatized using O-(2,3,4,5,6-pentafluorobenzyl) hydroxy amine (PFBHA), and -COOH and -OH groups are derivatized using a silylation reagent N,O-bis(trimethylsilyl)-trifluoroacetamide (BSTFA). The derivatives are easily resolved by a GC column. The chemical ionization mass spectra of these derivatives exhibit several pseudomolecular ions, allowing unambiguous determination of molecular weights. Functional group identification is accomplished by monitoring the ions in the electron ionization mass spectra that are characteristic of each functional group derivative: m/z 181 for carbonyl and m/z 73 and 75 for carboxyl and hydroxy groups. The method is used to identify products in laboratory studies of ozone oxidation of R-pinene and ∆ 3carene. Among products from ozone oxidation of R-pinene, we have detected pinonaldehyde, norpinonaldehyde, pinonic acid, norpinonic acid, C 10 hydroxy dicarbonyls, pinic acid, 2,2-dimethyl-3-(formylmethyl)-cyclobutaneformic acid, and a product that has a molecular weight of 156 and contains a CdO and a COOH/OH group. The latter two products have not been reported previously. ∆ 3 -Carene is structurally analogous to R-pinene in that both have an internal unsaturated bond where ozone oxidation takes place. We have also identified the corresponding analogous products, of which all but caronaldehyde are reported for the first time.

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Humic-like substances (HULIS) in ambient aerosols collected at seven locations in East Asia were analyzed using electrospray ionization (ESI) coupled with an ultra-high-resolution mass spectrometer (UHRMS). Locations included a 3 km high mountaintop site in Taiwan, rural, suburban, and urban locations in the Pearl River Delta (PRD), South China, and in Taiwan. Organosulfates (OS) in the HULIS fraction were tentatively identified through accurate mass measurements and MS/MS spectra interpretation. In the two mountaintop samples collected in regional background atmosphere, little OS were detected, while a few hundred OS formulas were identified in the six samples taken in Taiwan and PRD. Many of the OS ions were among the most intense peaks in the negative ESI-UHRMS spectra, and their elemental formulas were identical to OS derived from biogenic volatile organic compounds (BVOCs) (e.g., monoterpenes) that have been identified in chamber studies. With OS having less than 6 carbon atoms too hydrophilic to be effectively retained in the HULIS fraction, OS containing 10 carbon atoms were the most abundant, indicating monoterpenes as important precursors of OS in the HULIS fraction. Clear spatial variation in abundance of OS was found among different atmospheric environments, with enhanced coupling of BVOCs with anthropogenic acidic aerosols observed in the PRD samples over the Taiwan samples. The double bond equivalent (DBE) values indicate the majority of OS (>90%) in the HULIS fraction are aliphatic. The elemental compositions of OS compounds containing N atoms (defined as CHONS) indicate that they are probably nitrooxy OS. Some insights into OS formation mechanisms are also gained through examining the presence/absence of perceived reactant-product formula pairs in the mass spectra. The results suggest the dominant epoxide intermediate pathway for formation of OS compounds without N atoms (defined as CHOS) and confirm the more readily hydrolyzed characteristics of the --ONO₂ group than the --OSO₃ group. There is a lack of evidence for the epoxide pathway to account for the formation of OS in the CHONS subgroup.

BackgroundOsteoarthritis (OA) is the most common joint disease worldwide. In the past decade, mesenchymal stem cells (MSCs) have been used widely for the treatment of OA. A potential mechanism of MSC-based therapies has been attributed to the paracrine secretion of trophic factors, in which exosomes may play a major role. In this study, we aimed to compare the effectiveness of exosomes secreted by synovial membrane MSCs (SMMSC-Exos) and exosomes secreted by induced pluripotent stem cell-derived MSCs (iMSC-Exos) on the treatment of OA.MethodsInduced pluripotent stem cell-derived MSCs and synovial membrane MSCs were characterized by flow cytometry. iMSC-Exos and SMMSC-Exos were isolated using an ultrafiltration method. Tunable resistive pulse-sensing analysis, transmission electron microscopy, and western blots were used to identify exosomes. iMSC-Exos and SMMSC-Exos were injected intra-articularly in a mouse model of collagenase-induced OA and the efficacy of exosome injections was assessed by macroscopic, histological, and immunohistochemistry analysis. We also evaluated the effects of iMSC-Exos and SMMSC-Exos on proliferation and migration of human chondrocytes by cell-counting and scratch assays, respectively.ResultsThe majority of iMSC-Exos and SMMSC-Exos were approximately 50–150 nm in diameter and expressed CD9, CD63, and TSG101. The injection of iMSC-Exos and SMMSC-Exos both attenuated OA in the mouse OA model, but iMSC-Exos had a superior therapeutic effect compared with SMMSC-Exos. Similarly, chondrocyte migration and proliferation were stimulated by both iMSC-Exos and SMMSC-Exos, with iMSC-Exos exerting a stronger effect.ConclusionsThe present study demonstrated that iMSC-Exos have a greater therapeutic effect on OA than SMMSC-Exos. Because autologous iMSCs are theoretically inexhaustible, iMSC-Exos may represent a novel therapeutic approach for the treatment of OA.Electronic supplementary materialThe online version of this article (doi:10.1186/s13287-017-0510-9) contains supplementary material, which is available to authorized users.

Oxalic acid is often the single most abundant watersoluble organic compound identified in ambient aerosols, but its precursors have not been identified, and its formation mechanism is not well understood. On the contrary, sulfate as a major aerosol component, its formation pathways have been established, and in-cloud processing is recognized as its major production pathway. Our measurements of aerosol sulfate and oxalate collected across a wide geographical span in the East Asia region, up to Beijing in the north and down to Hong Kong in the south, indicate that the two species are highly correlated among samples collected at the same location and among samples collected at different locations in the Pearl River Delta region. This good correlation is also found in measurements made elsewhere by other researchers. We argue that a common dominant formation pathway, likely in-cloud processing, explains the close tracking of the two chemically distinct species. This also highlights the potential importance of in-cloud processing as a pathway leading to formation of secondary organic aerosols.