Senchao Lai

Occurrence and dry deposition of organophosphate esters in atmospheric particles over the northern South China Sea

Nine organophosphate esters (OPEs) in airborne particles were measured during a cruise campaign over the northern South China Sea (SCS) from September to October 2013. The concentration of the total OPEs (∑OPEs) was 47.1-160.9 pg m(-3), which are lower than previous measurements in marine atmosphere environments. Higher OPE concentrations were observed in terrestrially influenced samples, suggesting that OPE concentrations were significantly influenced by air mass transport. Chlorinated OPEs were the dominant OPEs, accounting for 65.8-83.7% of the ∑OPEs. Tris-(2-chloroethyl) phosphate (TCEP) was the predominant OPE compound in the samples (45.0±12.1%), followed by tris-(1-chloro-2-propyl) phosphates (TCPPs) (28.8±8.9%). Dry particle-bound deposition fluxes ranged from 8.2 to 27.8 ng m(-2) d(-1) for the ∑OPEs. Moreover, the dry deposition input of the ∑OPEs was estimated to be 4.98 ton y(-1) in 2013 in a vast area of northern SCS. About half of the input was found to relate to air masses originating from China.

Seasonal variations of anhydrosugars in PM2.5 in the Pearl River Delta Region, China

Anhydrosugars including levoglucosan and mannosan are the most effective organic tracers for biomass burning aerosol in the atmosphere. In this study, to investigate the contribution of biomass burning emissions to the aerosol burden in the Pearl River Delta (PRD) region, China, 24-hour integrated PM2.5 samples were collected simultaneously at four locations, (i) Guangzhou (GZ), (ii) Zhaoqing (ZQ) in Guangdong province, (iii) Hok Tsui (HT) and (iv) Hong Kong Polytechnic University (PU) in Hong Kong, in four seasons between 2006 and 2007. Levoglucosan and mannosan, together with water-soluble inorganic ions and water-soluble organic carbon (WSOC), were determined to elucidate the seasonal and spatial variations in biomass burning contributions. The concentrations of levoglucosan and mannosan were on average 82.4±123 and 5.8±8.6 ng m−3, respectively. The WSOC concentrations ranged from 0.2 to 9.4 µg m−3, with an average of 2.1±1.6 µg m−3. The relative contributions of biomass burning emissions to OC were 33% in QZ, 12% in GZ, 4% at PU and 5% at HT, respectively, estimated by the measured levoglucosan to organic carbon ratio (LG/OC) relative to literature-derived LG/OC values. The contributions from biomass burning emissions were in general 1.7–2.8 times higher in winter than those in other seasons. Further, it was inferred from diagnostic tracer ratios that a significant fraction of biomass burning emissions was derived from burning of hard wood and likely also from field burning of agricultural residues, such as rice straw, in the PRD region. Our results highlight the contributions from biomass/biofuel burning activities on the regional aerosol budget in South China.

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.

Air Pollution and Climate Change Effects on Allergies in the Anthropocene: Abundance, Interaction, and Modification of Allergens and Adjuvants

Air pollution and climate change are potential drivers for the increasing burden of allergic diseases. The molecular mechanisms by which air pollutants and climate parameters may influence allergic diseases, however, are complex and elusive. This article provides an overview of physical, chemical and biological interactions between air pollution, climate change, allergens, adjuvants and the immune system, addressing how these interactions may promote the development of allergies. We reviewed and synthesized key findings from atmospheric, climate, and biomedical research. The current state of knowledge, open questions, and future research perspectives are outlined and discussed. The Anthropocene, as the present era of globally pervasive anthropogenic influence on planet Earth and, thus, on the human environment, is characterized by a strong increase of carbon dioxide, ozone, nitrogen oxides, and combustion- or traffic-related particulate matter in the atmosphere. These environmental factors can enhance the abundance and induce chemical modifications of allergens, increase oxidative stress in the human body, and skew the immune system toward allergic reactions. In particular, air pollutants can act as adjuvants and alter the immunogenicity of allergenic proteins, while climate change affects the atmospheric abundance and human exposure to bioaerosols and aeroallergens. To fully understand and effectively mitigate the adverse effects of air pollution and climate change on allergic diseases, several challenges remain to be resolved. Among these are the identification and quantification of immunochemical reaction pathways involving allergens and adjuvants under relevant environmental and physiological conditions.

Influence of continental organic aerosols to the marine atmosphere over the East China Sea: Insights from lipids, PAHs and phthalates

Total suspended particle (TSP) samples were collected during a marine cruise in the East China Sea from May 18 to June 12, 2014. They were analyzed for solvent extractable organic compounds (lipid compounds, PAHs and phthalates) using gas chromatography/mass spectrometry (GC/MS) to better understand the sources and source apportionment of aerosol pollution in the western North Pacific. Higher concentrations were observed in the terrestrially influenced aerosol samples on the basis of five-day backward air mass trajectories, especially for aerosols collected near coastal areas. Phthalates were found to be the dominant species among these measured compound classes (707±401ngm-3 for daytime and 313±155ngm-3 for nighttime), followed by fatty acids, fatty alcohols, n-alkanes and PAHs. In general, the daytime abundances for these compounds are higher than nighttime, possibly attributable to more intensive anthropogenic activities during the daytime. The factor analysis indicates that biomass burning, fungal activities and fossil fuel combustion maybe the main emission sources for organic aerosols over the East China Sea. This study demonstrates that the East Asian continent can be a natural emitter of biogenic and anthropogenic organics to the marine atmosphere through long-range transport, which controls the chemical composition and concentration of organic aerosols over the East China Sea.

Release of free amino acids upon oxidation of peptides and proteins by hydroxyl radicals

Hydroxyl radical-induced oxidation of proteins and peptides can lead to the cleavage of the peptide, leading to a release of fragments. Here, we used high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) and pre-column online ortho-phthalaldehyde (OPA) derivatization-based amino acid analysis by HPLC with diode array detection and fluorescence detection to identify and quantify free amino acids released upon oxidation of proteins and peptides by hydroxyl radicals. Bovine serum albumin (BSA), ovalbumin (OVA) as model proteins, and synthetic tripeptides (comprised of varying compositions of the amino acids Gly, Ala, Ser, and Met) were used for reactions with hydroxyl radicals, which were generated by the Fenton reaction of iron ions and hydrogen peroxide. The molar yields of free glycine, aspartic acid, asparagine, and alanine per peptide or protein varied between 4 and 55%. For protein oxidation reactions, the molar yields of Gly (∼32–55% for BSA, ∼10–21% for OVA) were substantially higher than those for the other identified amino acids (∼5–12% for BSA, ∼4–6% for OVA). Upon oxidation of tripeptides with Gly in C-terminal, mid-chain, or N-terminal positions, Gly was preferentially released when it was located at the C-terminal site. Overall, we observe evidence for a site-selective formation of free amino acids in the OH radical-induced oxidation of peptides and proteins, which may be due to a reaction pathway involving nitrogen-centered radicals.

Non-polar organic compounds in marine aerosols over the northern South China Sea: influence of continental outflow.

Filter samples of total suspended particle (TSP) collected during a cruise campaign over the northern South China Sea (SCS) from September to October 2013 were analyzed for non-polar organic compounds (NPOCs) as well as organic carbon (OC), elemental carbon (EC) and water-soluble ions. A total of 115 NPOCs species in groups of n-alkanes, polycyclic aromatic hydrocarbons (PAHs), iso-/antiso-alkanes, hopanes, steranes, methylalkanes, branched alkanes, cycloalkanes, alkenes and phthalates were detected. The characteristics of NPOCs in marine TSP samples were investigated to understand the sources from the Asian continent and other regions. The concentrations of total NPOCs ranged from 19.8 to 288.2 ng/m(3) with an average of 87.9 ng/m(3), which accounted for 0.8-1.7% (average 1.0%) of organic matter (OM). n-Alkanes was the predominant group, accounting for 43.1-79.5%, followed by PAHs (5.5-44.4%) and hopanes (1.6-11.4%). We found that primary combustion (biomass burning/fossil fuel combustion) was the dominant source for the majority of NPOCs (89.1%). Biomass burning in southern/southeastern China via long-range transport was proposed to be a major contributor of NPOCs in marine aerosols over the northern SCS, suggested by the significant correlations between nss-K(+) and NPOCs groups as well as the analysis of air mass back-trajectory and fire spots. For the samples with strong continental influence, the strong enhancement in concentrations of n-alkanes, PAHs, hopanes and steranes were attributed to fossil fuel (coal/petroleum) combustion. In addition, terrestrial plants waxes were another contributor to NPOCs.

Metaproteomic analysis of atmospheric aerosol samples

AbstractMetaproteomic analysis of air particulate matter provides information about the abundance and properties of bioaerosols in the atmosphere and their influence on climate and public health. We developed and applied efficient methods for the extraction and analysis of proteins from glass fiber filter samples of total, coarse, and fine particulate matter. Size exclusion chromatography was applied to remove matrix components, and sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) was applied for protein fractionation according to molecular size, followed by in-gel digestion and LC-MS/MS analysis of peptides using a hybrid Quadrupole-Orbitrap MS. Maxquant software and the Swiss-Prot database were used for protein identification. In samples collected at a suburban location in central Europe, we found proteins that originated mainly from plants, fungi, and bacteria, which constitute a major fraction of primary biological aerosol particles (PBAP) in the atmosphere. Allergenic proteins were found in coarse and fine particle samples, and indications for atmospheric degradation of proteins were observed. Graphical abstractWorkflow for the metaproteomic analysis of atmospheric aerosol samples

Organophosphate Esters in Air, Snow, and Seawater in the North Atlantic and the Arctic

The concentrations of eight organophosphate esters (OPEs) have been investigated in air, snow and seawater samples collected during the cruise of ARK-XXVIII/2 from sixth June to third July 2014 across the North Atlantic and the Arctic. The sum of gaseous and particle concentrations (ΣOPE) ranged from 35 to 343 pg/m3. The three chlorinated OPEs accounted for 88 ± 5% of the ΣOPE. The most abundant OPE was tris(2-chloroethyl) phosphate (TCEP), with concentrations ranging from 30 to 227 pg/m3, followed by three major OPEs, such as tris(1-chloro-2-propyl) phosphate (TCPP, 0.8 to 82 pg/m3), tri-n-butyl phosphate (TnBP, 2 to 19 pg/m3), and tri-iso-butyl phosphate (TiBP, 0.3 to 14 pg/m3). The ΣOPE concentrations in snow and seawater ranged from 4356 to 10561 pg/L and from 348 to 8396 pg/L, respectively. The atmospheric particle-bound dry depositions of TCEP ranged from 2 to 12 ng/m2/day. The air-seawater gas exchange fluxes were dominated by net volatilization from seawater to air for TCEP (mean, 146 ± 239 ng/m2/day), TCPP (mean, 1670 ± 3031 ng/m2/day), TiBP (mean, 537 ± 581 ng/m2/day) and TnBP (mean, 230 ± 254 ng/m2/day). This study highlighted that OPEs are subject to long-range transport via both air and seawater from the European continent and seas to the North Atlantic and the Arctic.

Simultaneous determination of nitrated and oligomerized proteins by size exclusion high-performance liquid chromatography coupled to photodiode array detection

Chemical modifications such as nitration and cross-linking may enhance the allergenic potential of proteins. The kinetics and mechanisms of the underlying chemical processes, however, are not yet well understood. Here, we present a size-exclusion chromatography/spectrophotometry method (SEC-HPLC-DAD) that allows a simultaneous detection of mono-, di-, tri-, and higher protein oligomers, as well as their individual nitration degrees (NDs). The ND results of proteins from this new method agree well with the results from an alternative well-established method, for the analysis of tetranitromethane (TNM)- and nitrogen dioxide and ozone (NO2/O3)-nitrated protein samples. Importantly, the NDs for individual oligomer fractions can be obtained from the new method, and also, we provide a proof of principle for the calculation of the concentrations for individual protein oligomer fractions by their determined NDs, which will facilitate the investigation of the kinetics and mechanism for protein tyrosine nitration and cross-linking.