Roles of photochemical consumption of VOCs on regional background O3 concentration and atmospheric reactivity over the pearl river estuary, Southern China.

Understanding of the photochemical ozone (O3) pollution over the Pearl River Estuary (PRE) of southern China remains limited. We performed an in-depth analysis of volatile organic compounds (VOCs) data collected on an island (i.e., the Da Wan Shan Island, DWS) located at the downwind of Pearl River Delta (PRD) from 26 November to 15 December 2021. Abundances of O3 and its precursors were measured when the air masses originated from the inland PRD. We observed that the VOCs levels at the DWS site were lower, while the mixing ratio of O3 was higher, compared to those reported at inland PRD, indicating the occurrence of photochemical consumption of VOCs during the air masses transport, which was further confirmed by the composition and diurnal variations of VOCs, as well as ratios of specific VOCs. The simulation results from a photochemical box model showed that the O3 level in the outflow air masses of inland PRD (O3(out-flow)) was the dominant factor leading to the intensification of O3 pollution and the enhancement of atmospheric radical concentrations (ARC) over PRE, which was mainly contributed by the O3 production via photochemical consumption of VOCs during air masses transport. Overall, our findings provided direct quantitative evidence for the roles of outflow O3 and its precursors from inland PRD on O3 abundance and ARC over the PRE area, highlighting that alleviation of O3 pollution over PRE should focus on the impact of photochemical loss of VOCs in the outflow air masses from inland PRD.

Comparative analysis for the impacts of VOC subgroups and atmospheric oxidation capacity on O3 based on different observation-based methods at a suburban site in the North China Plain.

The persistent O3 pollution in the Beijing-Tianjin-Hebei (BTH) region remains unresolved, largely due to limited comprehension of O3-precursor relationship and photochemistry drivers. In this work, intraday O3 sensitivity evolution from VOC-limited (volatile organic compound) regime in the forenoon to transition regime in the late afternoon was inferred by relative incremental reactivity (RIR) in summer 2019 at Xianghe, a suburban site in BTH region, suggesting that VOC-focused control policy could combine with stringent afternoon NOx control. Then detailed impacts of VOC subgroups on O3 formation were further comprehensively quantified by parametric OH reactivity (KOH), O3 formation potential (OFP), as well as RIR weighted value and O3 formation path tracing (OFPT) approach based on photochemical box model. O3 episode days corresponded to stronger O3 formation, depicted by higher KOH (10.4 s-1), OFP (331.7 µg m-3), RIR weighted value (1.2), and F(O3)-OFPT (15.5 ppbv h-1). High proportions of isoprene and OVOCs (oxygenated VOCs) to the total KOH and the OFPT method were demonstrated whereas results of OFP and RIR-weighted presented extra great impacts of aromatics on O3 formation. The OFPT approach captured the process that has already happened and included final O3 response to the original VOC, thus reliable for replicating VOC impacts. The comparison results of the four methods showed similarities when utilizing KOH and OFPT methods, which reveals that the potential applicability of simple KOH for contingency VOC control and more complex OFPT method for detailed VOC- and source-oriented control during policy-making. To investigate propulsion of VOC-involved O3 photochemistry, atmospheric oxidation capacity (AOC) was quantified by two atmospheric oxidation indexes (AOI). Both AOIp_G (7.0 × 107 molec cm-3 s-1, potential AOC calculated by oxidation reaction rates) and AOIe_G (8.5 µmol m-3, estimated AOC given redox electron transfer for oxidation products) were stronger on O3 episode days, indicating that AOC promoted the radical cycling initiated from VOC oxidation and subsequent O3 production. Result-oriented AOIe_G reasonably characterized actual AOC inferred by good linear correlation between AOIe_G and O3 concentrations compared to process-oriented AOIp_G. Therefore, with continuous NOx abatement, AOIe_G should be considered to represent actual AOC, also O3-inducing ability.

Roles of semivolatile and intermediate-volatility organic compounds in secondary organic aerosol formation and its implication: A review.

Secondary organic aerosol (SOA) is a very important component of fine particulate matter (PM2.5) in the atmosphere. However, the simulations of SOA, which could help to elucidate the detailed mechanism of SOA formation and quantify the roles of various precursors, remains unsatisfactory, as SOA levels are frequently underestimated. It has been found that the performance of SOA formation models can be significantly improved by incorporating the emission and evolution of semivolatile and intermediate-volatility organic compounds (S/IVOCs). In order to explore the roles of S/IVOCs in SOA formation, this study reviews some simulation models which could consider S/IVOCs for SOA formation as well as the development of emission inventories of S/IVOCs and S/IVOC modules for SOA formation. In addition, the future research directions for simulations of the effect of S/IVOCs on SOA formation are suggested.

Secondary Formation and Impacts of Gaseous Nitro-Phenolic Compounds in the Continental Outflow Observed at a Background Site in South China.

Nitro-phenolic compounds (NPs) have attracted increasing attention because of their health risks and impacts on visibility, climate, and atmospheric chemistry. Despite many measurements of particulate NPs, the knowledge of their gaseous abundances, sources, atmospheric fates, and impacts remains incomplete. Here, 18 gaseous NPs were continuously measured with a time-of-flight chemical ionization mass spectrometer at a background site in South China in autumn and winter. Abundant NPs were observed in the continental outflows from East Asia, with a total concentration up to 122.1 pptv. Secondary formation from the transported aromatics dominated the observed NPs, with mono-NPs exhibiting photochemical daytime peaks and nighttime enrichments of di-NPs and Cl-substituted NPs. The budget analysis indicates that besides the •OH oxidation of aromatics, the NO3• oxidation also contributed significantly to the daytime mono-NPs, while the further oxidation of mono-NPs by NO3• dominated the nocturnal formation of di-NPs. Photolysis was the main daytime sink of NPs and produced substantial HONO, which would influence atmospheric oxidation capacity in downwind and background regions. This study provides quantitative insights on the formation and impacts of gaseous NPs in the continental outflow and highlights the role of NO3• chemistry in the secondary nitro-aromatics production that may facilitate regional pollution.

Molecular Composition of Oxygenated Organic Molecules and Their Contributions to Organic Aerosol in Beijing.

The understanding at a molecular level of ambient secondary organic aerosol (SOA) formation is hampered by poorly constrained formation mechanisms and insufficient analytical methods. Especially in developing countries, SOA related haze is a great concern due to its significant effects on climate and human health. We present simultaneous measurements of gas-phase volatile organic compounds (VOCs), oxygenated organic molecules (OOMs), and particle-phase SOA in Beijing. We show that condensation of the measured OOMs explains 26-39% of the organic aerosol mass growth, with the contribution of OOMs to SOA enhanced during severe haze episodes. Our novel results provide a quantitative molecular connection from anthropogenic emissions to condensable organic oxidation product vapors, their concentration in particle-phase SOA, and ultimately to haze formation.

Long-term variations of C1-C5 alkyl nitrates and their sources in Hong Kong.

Investigating the long-term trends of alkyl nitrates (RONO2) is of great importance for evaluating the variations of photochemical pollution. Mixing ratios of C1-C5 RONO2 were measured in autumn Hong Kong from 2002 to 2016, and the average level of 2-butyl nitrate (2-BuONO2) always ranked first. The C1-C4 RONO2 all showed increasing trends (p < 0.05), and 2-BuONO2 had the largest increase rate. The enhancement in C3 RONO2 was partially related to elevated propane, and dramatic decreases (p < 0.05) in both nitrogen monoxide (NO) and nitrogen dioxide (NO2) also led to the increased RONO2 formation. In addition, an increase of hydroxyl (OH) and hydroperoxyl (HO2) radicals (p < 0.05) suggested enhanced atmospheric oxidative capacity, further resulting in the increases of RONO2. Source apportionment of C1-C4 RONO2 specified three typical sources of RONO2, including biomass burning emission, oceanic emission, and secondary formation, of which secondary formation was the largest contributor to ambient RONO2 levels. Mixing ratios of total RONO2 from each source were quantified and their temporal variations were investigated. Elevated RONO2 from secondary formation and biomass burning emission were two likely causes of increased ambient RONO2. By looking into the spatial distributions of C1-C5 RONO2, regional transport from the Pearl River Delta (PRD) was inferred to build up RONO2 levels in Hong Kong, especially in the northwestern part. In addition, more serious RONO2 pollution was found in western PRD region. This study helps build a comprehensive understanding of RONO2 pollution in Hong Kong and even the entire PRD.

Photochemistry of ozone pollution in autumn in Pearl River Estuary, South China.

To explore the photochemical O3 pollution over the Pearl River Estuary (PRE), intensive measurements of O3 and its precursors, including trace gases and volatile organic compounds (VOCs), were simultaneously conducted at a suburban site on the east bank of PRE (Tung Chung, TC) in Hong Kong and a rural site on the west bank (Qi'ao, QA) in Zhuhai, Guangdong in autumn 2016. Throughout the sampling period, 3 days with high O3 levels (maximum hourly O3 > 100 ppbv) were captured at both sites (pattern 1) and 13 days with O3 episodes occurred only at QA (pattern 2). It was found that O3 formation at TC was VOC-limited in both patterns because of the large local NOx emissions. However, the O3 formation at QA was co-limited by VOCs and NOx in pattern 1, but VOC-limited in pattern 2. In both patterns, isoprene, formaldehyde, xylenes and trimethylbenzenes were the top 4 VOCs that modulated local O3 formation at QA, while they were isoprene, formaldehyde, xylenes and toluene at TC. In pattern 1, the net O3 production rate at QA (13.1 ± 1.6 ppbv h-1) was high, and comparable (p = 0.40) to that at TC (12.1 ± 1.5 ppbv h-1), so was the hydroxyl radical (i.e., OH), implying high atmospheric oxidative capacity over PRE. In contrast, the net O3 production rate was significantly higher (p < 0.05) at QA (16.3 ± 0.4 ppbv h-1) than that at TC (4.7 ± 0.2 ppbv h-1) in pattern 2, and the OH concentration and cycling rate were also higher, indicating much stronger photochemical reactions at QA. These findings enhanced our understanding of O3 photochemistry in the Pearl River estuary, which could be extended to other estuaries.

A gridded emission inventory of semi-volatile and intermediate volatility organic compounds in China.

An emission inventory of precursors is a prerequisite for the simulation of secondary organic aerosol (SOA), which could provide valuable information on the evolution of precursors, formation of SOA, and its influence on fine particle (PM2.5) abundance, oxidative capacity, and climate change. However, an emission inventory of semi-volatile and intermediate volatility organic compounds (S/IVOCs), the key precursor of SOA, particularly the gridded inventory that is appropriate for input into regional air quality models, remains limited in China, leading to an incomplete understanding of S/IVOCs sources and roles in SOA formation and the atmospheric environment. Therefore, a gridded emission inventory of S/IVOCs in China for 2016 was developed based on ample source-specific measured data on emission ratios of S/IVOCs to primary organic aerosols (POA) from literatures. The total emission of S/IVOCs was estimated to be 9.6 Tg, and industry and residential sectors were major sources of S/IVOCs, with contributions of 48.0% and 30.2%, respectively. The spatial variations suggested that S/IVOC emissions were mainly distributed in the highly industrialized and urbanized regions in China, such as Beijing-Tianjin-Hebei (BTH), the Yangtze River Delta (YRD), the Pearl River Delta (PRD), and the Sichuan-Chongqing (SC) regions, though the contributions and temporal patterns varied between different regions. Furthermore, uncertainty of the emission inventory was estimated to be within the range of -66%-153%, which was mainly attributed to emission ratios of IVOCs/POA for industry, transportation, and power plants. The gridded emission inventory developed in this study can be used to estimate the emissions of S/IVOCs in different regions, and can be applied to different models for a better understanding of the environmental effects of S/IVOCs.

Overview on the spatial-temporal characteristics of the ozone formation regime in China.

Ozone (O3), a main component in photochemical smog, is a secondary pollutant formed through complex photochemical reactions involving nitrogen oxides (NOx) and volatile organic compounds (VOCs). In the past few decades, with the rapid economic development, industrialization and urbanization, the mixing ratio of O3 has increased substantially in China. O3 non-attainment days have been frequently observed. Despite great efforts made in the past few years, it is still difficult to alleviate O3 pollution in China, due to its non-linear relationship with the precursors. In view of the severe situation in China, this study presents a comprehensive review on the spatial-temporal variations of the relationship between O3 and its precursors (i.e. O3 formation regime), built upon the previous reviews of the spatial-temporal variations of O3 and its precursor levels. Valuable findings from previous studies are laid out for a better understanding of O3 pollution, followed by implications for the control of O3 pollution. This literature review indicates that O3 formation in most areas of the North China Plain (NCP), Yangtze River Delta (YRD) and Pearl River Delta (PRD) regions is in a VOC-limited regime during the high-O3 seasons due to dramatic emissions from human activities in cities. Outside these metropolitan areas, a NOx-limited regime dominates rural/remote areas. From summer to winter, the O3 formation regime over China shows a tendency to shift to a VOC-limited regime. Furthermore, O3 formation in China shifted toward increasing sensitivity to VOC emissions before the 12th Five-Year-Plan. However, after the 12th Five-Year-Plan, successful reduction of NOx slowed down this trend. Further effective control of VOCs is expected to achieve sustained O3 attainment in the future. To timely solve the current O3 pollution problem, precise control of O3 precursors is proposed, together with the joint prevention and control of regional air pollution.

Photochemical evolution of continental air masses and their influence on ozone formation over the South China Sea.

To investigate photochemical ozone (O3) pollution over the South China Sea (SCS), an intensive sampling campaign was conducted from August to November simultaneously at a continental site (Tung Chung, TC) and a marine site (Wan Shan Island, WSI). It was found that when continental air masses intruded the SCS, O3 episodes often occurred subsequently. To discover the causes, a photochemical trajectory model (PTM) coupled with the near-explicit Master Chemical Mechanism (MCM) was adopted, and the photochemical processes of air masses during the transport from TC to WSI were investigated. The simulated O3 and its precursors (i.e. NOx and VOCs) showed a reasonably good agreement with the observations at both TC and WSI, indicating that the PTM was capable of simulating O3 formation for air masses traveling from TC to WSI. The modeling results revealed that during the transport of air masses from TC to WSI, both VOC and NOx decreased in the morning while O3 increased significantly, mainly due to rapid chemical reactions with elevated radicals over the SCS. The elevated radicals over the SCS were attributable to the fact that higher NOx at TC consumed more radicals, whereas the concentration of radicals increased from TC to WSI because of NOx dilution and destruction. Subsequently, the photochemical cycling of radicals accelerated, leading to high O3 mixing ratios over the SCS. Furthermore, based on the source profiles of the emission inventory used, the contributions of six sources, i.e. gasoline vehicle exhaust, diesel vehicle exhaust, gasoline evaporation and LPG usage, solvent usage, biomass and coal burning, and biogenic emissions, to maritime O3 formation were evaluated. The results suggested that gasoline vehicles exhaust and solvent usage largely contributed the O3 formation over the SCS (about 5.2 and 3.8 ppbv, respectively). This is the first time that the contribution of continental VOC sources to the maritime O3 formation was quantified.

Sources of methacrolein and methyl vinyl ketone and their contributions to methylglyoxal and formaldehyde at a receptor site in Pearl River Delta.

Methacrolein (MACR) and methyl vinyl ketone (MVK) are two major intermediate products from the photochemical oxidation of isoprene, the most important biogenic volatile organic compound. In addition, MACR and MVK have primary emissions. Investigating the sources and evolution of MACR and MVK could provide helpful information for the oxidative capacity of the atmosphere. In this study, hourly measurements of isoprene, MACR, and MVK were conducted at a receptor site in the Pearl River Delta region (PRD), i.e., the Heshan site (HS), from 22 October to 20 November, 2014. The average mixing ratios of isoprene, MACR and MVK were 151 ±â€¯17, 91 ±â€¯6 and 79 ±â€¯6 pptv, respectively. The daily variations and the ratios of MVK/MACR during daytime and nighttime suggested that other sources besides isoprene photooxidation influenced the MACR and MVK abundances at the HS. Positive matrix factorization was utilized to resolve the sources of MACR and MVK. Five sources were identified and quantified, including biogenic emissions, biomass burning, secondary formation, diesel, and gasoline vehicular emissions. Among them, secondary formation made the greatest contribution to observed MACR and MVK with average contributions of ~45% and ~70%, respectively. Through the yields of secondary products from the oxidation of MACR and MVK by the OH radical and the concentrations of MACR and MVK, it was found that methylglyoxal and formaldehyde were the main oxidation products of MACR and MVK at the HS site. Overall, this study evaluated the roles of primary emissions on ambient levels of MACR and MVK and advanced the understanding of photochemical oxidation of MACR and MVK in the PRD.

Photochemical Formation of C1-C5 Alkyl Nitrates in Suburban Hong Kong and over the South China Sea.

Alkyl nitrates (RONO2) are important reservoirs of atmospheric nitrogen, regulating nitrogen cycling and ozone (O3) formation. In this study, we found that propane and n-butane were significantly lower at the offshore site (WSI) in Hong Kong ( p < 0.05), whereas C3-C4 RONO2 were comparable to the suburban site (TC) ( p > 0.05). Stronger oxidative capacity at WSI led to more efficient RONO2 formation. Relative incremental reactivity (RIR) was for the first time used to evaluate RONO2-precursor relationships. In contrast to a consistently volatile organic compounds (VOC)-limited regime at TC, RONO2 formation at WSI switched from VOC-limited regime during O3 episodes to VOC and nitrogen oxides (NO x) colimited regime during nonepisodes. Furthermore, unlike the predominant contributions of parent hydrocarbons to C4-C5 RONO2, the production of C1-C3 RONO2 was more sensitive to other VOCs like aromatics and carbonyls, which accounted for ∼40-90% of the productions of C1-C3 alkylperoxy (RO2) and alkoxy radicals (RO) at both sites. This resulted from the decomposition of larger RO2/RO and the change of OH abundance under the photochemistry of other VOCs. This study advanced our understanding of the photochemical formation of RONO2, particularly the relationships between RONO2 and their precursors, which were not confined to the parent hydrocarbons.

Factors dominating 3-dimensional ozone distribution during high tropospheric ozone period.

Data from an in situ monitoring network and five ozone sondes are analysed during August of 2012, and a high tropospheric ozone episode is observed around the 8th of AUG. The Community Multi-scale Air Quality (CMAQ) model and its process analysis tool were used to study factors and mechanisms for high ozone mixing ratio at different levels of ozone vertical profiles. A sensitive scenario without chemical initial and boundary conditions (ICBCs) from MOZART4-GEOS5 was applied to study the impact of stratosphere-troposphere exchange (STE) on vertical ozone. The simulation results indicated that the first high ozone peak near the tropopause was dominated by STE. Results from process analysis showed that: in the urban area, the second peak at approximately 2 km above ground height was mainly caused by local photochemical production. The third peak (near surface) was mainly caused by the upwind transportation from the suburban/rural areas; in the suburban/rural areas, local photochemical production of ozone dominated the high ozone mixing ratio from the surface to approximately 3 km height. Furthermore, the capability of indicators to distinguish O3-precursor sensitivity along the vertical O3 profiles was investigated. Two sensitive scenarios, which had cut 30% anthropogenic NOX or VOC emissions, showed that O3-precursor indicators, specifically the ratios of O3/NOy, H2O2/HNO3 or H2O2/NOZ, could partly distinguish the O3-precursor sensitivity between VOCs-sensitive and NOx-sensitive along the vertical profiles. In urban area, the O3-precursor relationship transferred from VOCs-sensitive within the boundary layer to NOx-sensitive at approximately 1-3 km above ground height, further confirming the dominant roles of transportation and photochemical production in high O3 peaks at the near-ground layer and 2 km above ground height, respectively.

Seasonal variations of C1-C4 alkyl nitrates at a coastal site in Hong Kong: Influence of photochemical formation and oceanic emissions.

Five C1-C4 alkyl nitrates (RONO2) were measured at a coastal site in Hong Kong in four selected months of 2011 and 2012. The total mixing ratios of C1-C4 RONO2 (Σ5RONO2) ranged from 15.4 to 143.7 pptv with an average of 65.9 ± 33.0 pptv. C3-C4 RONO2 (2-butyl nitrate and 2-propyl nitrate) were the most abundant RONO2 during the entire sampling period. The mixing ratios of C3-C4 RONO2 were higher in winter than those in summer, while the ones of methyl nitrate (MeONO2) were higher in summer than those in winter. Source analysis suggests that C2-C4 RONO2 were mainly derived from photochemical formation along with biomass burning (58.3-71.6%), while ocean was a major contributor to MeONO2 (53.8%) during the whole sampling period. The photochemical evolution of C2-C4 RONO2 was investigated, and found to be dominantly produced by the parent hydrocarbon oxidation. The notable enrichment of MeONO2 over C3-C4 RONO2 was observed in a summer episode when the air masses originating from the South China Sea (SCS) and MeONO2 was dominantly derived from oceanic emissions. In order to improve the accuracy of ozone (O3) prediction in coastal environment, the relative contribution of RONO2 from oceanic emissions versus photochemical formation and their coupling effects on O3 production should be taken into account in future studies.

Surface O3 photochemistry over the South China Sea: Application of a near-explicit chemical mechanism box model.

A systematic field measurement was conducted at an island site (Wanshan Island, WSI) over the South China Sea (SCS) in autumn 2013. It was observed that mixing ratios of O3 and its precursors (such as volatile organic compounds (VOCs), nitrogen oxides (NOx = NO + NO2) and carbon monoxide (CO)) showed significant differences on non-episode days and episode days. Additional knowledge was gained when a photochemical box model incorporating the Master Chemical Mechanism (PBM-MCM) was applied to further investigate the differences/similarities of O3 photochemistry between non-episode and episode days, in terms of O3-precursor relationship, atmospheric photochemical reactivity and O3 production. The simulation results revealed that, from non-O3 episode days to episode days, 1) O3 production changed from both VOC and NOx-limited (transition regime) to VOC-limited; 2) OH radicals increased and photochemical reaction cycling processes accelerated; and 3) both O3 production and destruction rates increased significantly, resulting in an elevated net O3 production over the SCS. The findings indicate the complexity of O3 pollution over the SCS.

The toxic effects of indoor atmospheric fine particulate matter collected from allergic and non-allergic families in Wuhan on mouse peritoneal macrophages.

Recent studies have shown that fine particulate matter (PM2.5) is associated with multiple adverse health outcomes and PM2.5-induced oxidative stress is now commonly known as a proposed mechanism of PM2.5-mediated toxicity. However, the association between allergic symptoms in children and exposure to PM2.5 has not been fully elucidated, particularly the role of PM2.5 on the indoor environment involved in allergy or non-allergy is unknown. The aim of the present study was to explore whether indoor PM2.5 from the homes of children with allergic symptoms had more increased risks of allergy than that of healthy ones and then compare the toxicity and inflammatory response of them. In this study, indoor PM2.5 was collected from the homes of schoolchildren with allergic symptoms and those of healthy ones respectively, and components of PM2.5 were analyzed. PM2.5-mediated oxidative damage and inflammatory response were further evaluated in mouse peritoneal macrophages based on its effects on the levels of reactive oxygen species accumulation, lipid peroxidation, DNA damage or cytokine production. It seems that oxidative stress may contribute to PM2.5-induced toxicity, and PM2.5 from the allergic indoor environment produced more serious toxic effects and an inflammatory response on mouse peritoneal macrophages than that from a non-allergic indoor environment.

Metallic corrosion in the polluted urban atmosphere of Hong Kong.

This study aimed to explore the relationship between air pollutants, particularly acidic particles, and metallic material corrosion. An atmospheric corrosion test was carried out in spring-summer 2012 at a polluted urban site, i.e., Tung Chung in western Hong Kong. Nine types of metallic materials, namely iron, Q235 steel, 20# steel, 16Mn steel, copper, bronze, brass, aluminum, and aluminum alloy, were selected as specimens for corrosion tests. Ten sets of the nine materials were all exposed to ambient air, and then each set was collected individually after exposure to ambient air for consecutive 6, 13, 20, 27, 35, 42, 49, 56, 63, and 70 days, respectively. After the removal of the corrosion products on the surface of the exposed specimens, the corrosion rate of each material was determined. The surface structure of materials was observed using scanning electron microscopy (SEM) before and after the corrosion tests. Environmental factors including temperature, relative humidity, concentrations of gaseous pollutants, i.e., sulfur dioxide (SO2), nitrogen dioxide (NO2), carbon monoxide (CO), ozone (O3), and particulate-phase pollutants, i.e., PM2.5 (FSP) and PM10 (RSP), were monitored. Correlation analysis between environmental factors and corrosion rate of materials indicated that iron and carbon steel were damaged by both gaseous pollutants (SO2 and NO2) and particles. Copper and copper alloys were mainly corroded by gaseous pollutants (SO2 and O3), while corrosion of aluminum and aluminum alloy was mainly attributed to NO2 and particles.

Tracer-based source apportionment of polycyclic aromatic hydrocarbons in PM2.5 in Guangzhou, southern China, using positive matrix factorization (PMF).

From 28 November to 23 December 2009, 24-h PM2.5 samples were collected simultaneously at six sites in Guangzhou. Concentrations of 18 polycyclic aromatic hydrocarbons (PAHs) together with certain molecular tracers for vehicular emissions (i.e., hopanes and elemental carbon), coal combustion (i.e., picene), and biomass burning (i.e., levoglucosan) were determined. Positive matrix factorization (PMF) receptor model combined with tracer data was applied to explore the source contributions to PAHs. Three sources were identified by both inspecting the dominant tracer(s) in each factor and comparing source profiles derived from PMF with determined profiles in Guangzhou or in the Pearl River Delta region. The three sources identified were vehicular emissions (VE), biomass burning (BB), and coal combustion (CC), accounting for 11 ± 2%, 31 ± 4%, and 58 ± 4% of the total PAHs, respectively. CC replaced VE to become the most important source of PAHs in Guangzhou, reflecting the effective control of VE in recent years. The three sources had different contributions to PAHs with different ring sizes, with higher BB contributions (75 ± 3%) to four-ring PAHs such as pyrene and higher CC contributions (57 ± 4%) to six-ring PAHs such as benzo[ghi]perylene. Temporal variations of VE and CC contributions were probably caused by the change of weather conditions, while temporal variations of BB contributions were additionally influenced by the fluctuation of BB emissions. Source contributions also showed some spatial variations, probably due to the source emission variations near the sampling sites.

A preliminary investigation on the occurrence and distribution of antibiotic resistance genes in the Beijiang River, South China.

The occurrence of antibiotic resistance genes (ARGs) was investigated and quantified in 20 water samples collected in the Beijiang River, South China. Sulfonamide- and tetracycline-resistant bacteria were present in 17 and 14 of the collected 20 samples. For sulfonamide ARGs, sulII and sulII were frequently observed in the Beijiang River. The levels of sulI were higher than sulII (p < 0.05), with the mean values of (1.41 +/- 1.12) x 10(-2) and (1.58 +/- 1.71) x 10(-3) copies/16S rDNA, respectively. For tetracycline ARGs, tetG had the highest frequency, 100%, followed by tetA (85%), tetO (85%), tetC (70%), tetX (60%), tetM (40%) and tetQ (20%), while tetE and tetS were not detected in all the samples from the Beijiang River. On the other hand, tetC had the highest concentration, ranging from 8.30 x 10(-2) to 13.20 copies/16S rDNA. The poor correlation between ARGs and antibiotic concentrations revealed that the self-amplification and persistence of ARGs were the reasons that made ARGs exist in the water environment even though the antibiotic selecting pressure was absent. Because so few field measurements have been conducted for investigating the levels of ARGs in rivers in South China, this study provides an important insight on better understanding the occurrence and spread of ARGs in such an ecosystem.

Polycyclic aromatic hydrocarbons in PM2.5 in Guangzhou, southern China: spatiotemporal patterns and emission sources.

Fine particulate samples were simultaneously collected at six sites in Guangzhou in November-December 2009. Eighteen polycyclic aromatic hydrocarbons (PAHs) and tracers, i.e. hopanes, elemental carbon, picene and levoglucosan were measured. Three high level episodes were observed during the sampling period, likely due to accumulation effects. Back trajectory analysis revealed that the air masses for the three episodes were from eastern inland Pearl River Delta (PRD) region. There was no obvious concentration gradient for total and 5-6 ring PAHs such as benzo[g,h,i]perylene (BghiP) from urban to rural sites. However, 4-ring PAHs such as pyrene (Pyr) exhibited significantly higher levels at rural site than that at urban/suburban sites (p<0.01). BghiP correlated well with hopanes, elemental carbon and picene, indicating vehicular emissions and coal combustion were the sources of 5-6 ring PAHs, which were further confirmed by comparing the four tracers/BghiP ratios and IcdP/BghiP ratios in ambient samples with those from source profiles. Results indicated that vehicular emissions were no longer the dominant sources in winter season in Guangzhou.