Revisiting nitrous acid (HONO) emission from on-road vehicles: A tunnel study with a mixed fleet

Nitrous acid (HONO) is an important precursor of OH radicals in the atmosphere. In urban areas, emissions from vehicles are the main source of air pollutants, including reactive nitrogen. Previously reported emission ratios of HONO (HONO/NO_x) from vehicles were measured in the late 1990s and need to be updated due to the significant changes in emission control technologies. We measured the emission ratio of a fleet of vehicles (38% diesel on average) from March 11 to 21, 2015, in a road tunnel in Hong Kong. The emission ratio of 1.24% (±0.35%) obtained is greater than the commonly adopted 0.8% or 0.3%. The elevated emission ratio is found to be related to the presence of vehicles equipped with diesel particle filters (DPFs). Positive correlation between HONO and black carbon (BC) shows that HONO and BC were emitted together, while the lack of correlation or even anticorrelation between HONO/NO_x and BC indicates that the BC-mediated conversion of NO₂ to HONO in the dark was insignificant in the immediate vicinity of the emission sources.

Implications: Vehicular emission is a key source for HONO in the urban atmosphere. However, the most commonly used emission ratio HONO/NO_x in modeling studies was measured more than 15 years ago. Our tunnel study suggests that a mixed fleet nowadays has a higher emission ratio, possibly because of the diesel particle filter (DPF) retrofit program and the growing share of Euro IV or more advanced diesel vehicles. Our study also provides new insight into the role of black carbon in HONO formation from vehicles.     

Formation and mitigation of PCDD/Fs in iron ore sintering

The sintering of iron ore is presently a significant industrial source of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) worldwide owing to the fundamental requirement of the operation of a high temperature process to pre-treat fines and to recycle plant by-products arising from the integrated iron and steelworks. The process is a noteworthy contributor of PCDD/F indirectly due to decreasing PCDD/F releases from municipal solid waste incineration. Commonly PCDD/F formation from the process is associated with the addition of oily mill scales although raw material containing a combination of C, Cl and specific metal catalyst has been shown to drastically increase PCDD/F formation in the process. The degenerate graphitic structure of carbon present in coke fuel and soot formed and the chemistry of catalytic metals and Cl are important factors. A review on PCDD/F emission in this process has been carried out, including examination of its formation mechanism, congener distribution, contributing factors and mitigation strategies, with emphasis on the use of inhibiting compound to achieve suppression. A detailed analysis of the de novo and precursor theories of formation and the contributing factor is given since the subject of PCDD/F formation is still controversial. The de novo formation pathway identified in sinter plants and controlled studies performed in the laboratory as well as at pilot-scale are discussed; where appropriate, a comparison is drawn between sintering and other thermal processes emitting PCDD/Fs. Summary of the latest developments in PCDD/F downstream abatement strategies presently employed in full scale industrial plants is provided. Potential inhibiting compounds are discussed in terms of their mode of action and merits under sintering conditions.     

Interpretation of air quality in relation to monitoring station's surroundings

This study explores the appropriateness of the locality of air monitoring stations which are meant to indicate air quality in the area. Daily variations in NO₂ and PM₁₀ concentrations at 14 monitoring stations in Hong Kong are examined. The daily variations in NO₂ at a number of background monitoring stations exhibit patterns similar to variations in traffic volume while variations in PM₁₀ concentration exhibit less discernible pattern. Principal component analysis (PCA) and cluster analysis (CA) are applied to analyse NO₂ and PM₁₀ measurements between January 2001 and December 2005. The results show that NO₂ concentrations at background stations within the urban area are highly influenced by vehicle emissions. The effect vehicle emission has on NO₂ at stations within new towns is smaller. CA results also show that variations in PM₁₀ concentrations are distinguished by the area the station is located in. PCA results show that there are two principal components (PC's) associated with variations in roadside concentration of PM₁₀. The strong influence of roadside emissions towards concentrations of NO₂ and PM₁₀ at a number of urban background stations may be due to their close proximity to busy roadways and the high density of surrounding tall buildings, which creates an enclosure that hinders dispersion of roadside emissions and results in air pollution behaviour that reflects variation in traffic.     

Carbon content of common airborne fungal species and fungal contribution to aerosol organic carbon in a subtropical city

Interest in the role and contribution of fungi to atmospheric aerosols and processes grows in the past decade. Substantial data or information such as fungal mass or carbon loading to ambient aerosols is however still lacking. This study aimed to quantify the specific organic carbon content (OC per spore) of eleven fungal species commonly found airborne in the subtropics, and estimated their contribution to organic carbon in aerosols. The specific OC contents showed a size-dependent relationship (r = 0.64, p < 0.05) and ranged from 3.6 to 201.0 pg carbon per spore or yeast cell, giving an average of 6.0 pg carbon per spore (RSD 51%) for spore or cell size less than 10 μm. In accounting for natural variations in the composition and abundance of fungal population, weighted-average carbon content for field samples was adopted using the laboratory determined specific OC values. An average of 5.97 pg carbon per spore (RSD 3.8%) was enumerated from 28 field samples collected at the university campus. The mean fungal OC concentration was 3.7, 6.0 and 9.7 ng m^?3 in PM_2.5, PM_2.5–10 and PM₁₀, respectively. These corresponded to 0.1%, 1.2% and 0.2% of the total OC in PM_2.5, PM_2.5–10 and PM₁₀, respectively. In the study period, rain provided periods with low total OC but high fungal prevalence and fungi contributed 7–32% OC in PM_2.5–10 or 2.4–7.1% OC in PM₁₀. More extensive studies are deserved to better understand the spatial-, temporal- and episodic dependency on the fungal OC contribution to the atmospheric aerosols.     

Source analysis of high particulate matter days in Hong Kong

This study identifies major contributing sources of high particulate matter (PM) days in Hong Kong and conducive meteorological conditions leading to high PM. The PM₁₀ chemical composition of 3393 ambient samples collected at ten monitoring stations in Hong Kong during 1998–2005 were used as input for positive matrix factorization (PMF) modeling to identify and quantify the aerosol sources in Hong Kong. Days with PM₁₀ levels exceeding 56 μg m^?3, the average plus one standard deviation of the mass concentration of all samples, are defined as high PM days. A total of 401 samples fell in the high PM category during the study period. Biomass burning, secondary sulfate and secondary nitrate were found to be the major contributors leading to high PM, responsible for 68–73% of PM₁₀ mass on high PM days. The contributions by these sources on high PM days were 140–180% higher than their respective average concentration contributions. These sources were identified to be regional sources on the grounds of little spatial variation in their concentrations among the monitoring stations and a temporal pattern of higher in the winter and lower in the summer. Sampling days of high PM in 2004 and 2005 were individually examined for weather charts and regional surface wind maps. Weak high pressures over mainland China were the most important synoptic event leading to high PM days in the fall and winter, while typhoon episodes were responsible for most summer cases. Approximately 80% of the high PM days were in the fall and winter months (September–February). Almost all the high PM days were associated with northwesterly, northerly or northeasterly regional transport. Anthropogenic primary sources (coal combustion, vehicular exhaust, and residue oil combustion) showed the highest contributions associated with northwesterly wind, indicating the strong influence of the more urbanized areas to the northwest of Hong Kong in the Pearl River Delta region.     

Use of high-resolution MM5/CALMET/CALPUFF system: SO2 apportionment to air quality in Hong Kong

Recent research has highlighted the substantial health-related costs of air pollution in the Hong Kong Special Administrative Region (HKSAR) and the potential threat from air pollution to HKSARs economic competitiveness. In order to address the air pollution problems, this paper seeks to analyse the individual contributions of major sulphur dioxide (SO₂) sources in the Pearl River Delta Region (PRDR) (Pearl River Delta + HKSAR) on the air quality in the HKSAR. This study employed the coupling of the MM5/CALMET system with the CALPUFF, the multi-layer, non-steady-state puff dispersion model, where major power plants, marine vessels and vehicles, all in the PRDR, are taken into account. The observation data and simulation results at 11 Hong Kong Environmental Protection Department (HKEPD) general (non-road-side) stations are analyzed. Urban (in-zone) and Rural (out-zone) stations are defined in order to examine the SO₂ contribution of different emission sources in different regions of the HKSAR. The model results show that the contribution of the HKSAR marine sources is significant both in summer and in winter, especially for the locations around the in-zone stations (in general 60%, and 55% in summer and winter respectively). In addition, the contribution of the HKSAR power plants is slightly higher than that of the PRD power plants in early summer, with a contribution difference of up to 20% when the prevailing wind is from the south. However, in late summer, this situation reverses. In winter, the contribution of the PRD power plants is two to three times greater than that of the HKSAR power plants. Moreover, Yantian port affects the northern part of the HKSAR when a northeasterly wind dominates the HKSAR. In order to solve these air pollution problems, the main implication of these results suggests that the HKSAR government, in close co-operation with the Guangdong government, needs to take immediate action.     

Degradation Kinetics of Biofilter Media Treating Reduced Sulfur Odors and VOCs

ABSTRACT

A lab-scale study was conducted to determine the rate and extent of decomposition of three biofilter media materials—compost, hog fuel, and a mixture of the two in 1:1 ratio—used in biofiltration applied to removal of reduced sulfur odorous compounds from pulp mill air emissions. The rate of carbon mineralization, as a measure of biofilter media degradation, was determined by monitoring respiratory CO₂ evolution and measuring the changes in carbon and nitrogen fractions of the biofilter materials over a period of 127 days. Both ambient air and air containing reduced sulfur (RS) compounds were used, and the results were compared. After 127 days of incubation with ambient air, about 17% of the media carbon was evolved as CO₂ from compost as compared to 6 and 12% from hog fuel and the mixture, respectively. The decomposition showed sequential breakdown of carbon moieties, and three distinct stages were observed for each of the biofilter media. First-order rate kinetics were used to describe the decomposition stages. Decomposition rates in the initial stages were at least twice those of the following stages. Carbon mineralization showed close dependence on the C/N ratio of the biofilter material. Media decomposition was enhanced in the presence of RS gases as a result of increased bioactivity by sulfur-oxidizing bacteria and other microorganisms, thus reducing the media half-life by more than 50%. At higher concentrations of RS gases, the CO₂ evolution rates were proportionally lower than those at the low concentrations because of the limited acid buffering capacity of the biofilter materials.     

An 'artificial mussel' for monitoring heavy metals in marine environments

A new chemical sampling device, artificial mussel (AM), has been developed for monitoring metals in marine environments. This device consists of a polymer ligand suspended in artificial seawater within a Perspex tubing, and enclosed with semi-permeable gel at both ends. Laboratory and field experiments were carried out to examine the uptake of five metals (Cd, Cr, Cu, Pb and Zn) by the AM. Uptake of metals by AM was proportional to the exposure metal concentrations, and the AM was able to accumulate the ASV labile fractions of metals. Uptake and release of the metals of AM are similar to those of the mussel Perna viridis, but less affected by salinity and temperature. Field studies demonstrated that the AM can not only provide a time-integrated estimate of metals concentrations, but also allows comparisons of metal levels in different environments and geographical areas beyond the natural distribution limits of biomonitors.     

Health risk assessment for polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins and dibenzofurans, and polychlorinated naphthalenes in seafood from Guangzhou and Zhoushan, China

This study determined the concentrations of organochlorine contaminants in common seafood in two Chinese coastal cities (Guangzhou and Zhoushan), and assessed the health risk due to the daily consumption of contaminated seafood. Twenty-six pooled samples, belonging to five food categories (fish, bivalves, shrimp, crab, and cephalopods), were purchased from local markets in Guangzhou and Zhoushan in 2003 and 2004. These samples were analyzed for total polychlorinated biphenyls (PCBs), non- and mono-ortho-PCBs (coplanar PCBs), polychlorinated naphthalenes (PCNs), and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/DFs). The concentrations of total PCBs and coplanar PCBs in fish samples were higher in Guangzhou than in Zhoushan, while the levels of PCNs and PCDDs/DFs were comparable between the two cities. The total daily intake values of dioxin-like compounds were 1.05 and 0.86pg WHO-TEQ/kg body weight in Guangzhou and Zhoushan, respectively. Hazard ratios of non-cancer risk in the two cities were all less than unity.     

PCDD/F and dioxin-like PCB in Hong Kong air in relation to their regional transport in the Pearl River Delta region

PCDD/F and dioxin-like PCB were measured in 142 air samples of Hong Kong. The annual average PCDD/F and dioxin-like PCB concentrations obtained for Hong Kong air at Tap Mun (PCDD/F: 1724+/-1984; dioxin-like PCB: 1572+/-1170 fg m(-3)), Yuen Long (PCDD/F: 2927+/-2695; dioxin-like PCB: 4331+/-1962 fg m(-3)) and Tsuen Wan (PCDD/F: 1875+/-1502; dioxin-like PCB: 2972+/-1510 fg m(-3)) from January 2004 to March 2005 were comparable to other urban centers around the world and were within the Japanese and USA ambient air quality guidelines. A clear seasonal pattern was observed for PCDD/F, generally with a 50-60 times higher air concentration in winter when background northerly wind was weaker and land-sea breeze prevailed, resulting in regional transport; and a lower concentration in summer, due to the inflow of clean oceanic southeasterly wind from the South China Sea. A higher WHO-TEQ value of dioxin-like PCB (mainly attributed to the relatively higher WHO-TEQ value of PCB 126) in Yuen Long during winter, compared with other months, could also be related to the regional transport by the winter monsoon wind and the low mixing height in winter. Spatially, air concentrations of PCDD/F and dioxin-like PCB demonstrated a west-to-east gradient (with Yuen Long>Tsuen Wan>Tap Mun). It is suggested that PCDD/F and dioxin-like PCB were transported into the western airshed of Hong Kong from the Pearl River Delta by land-sea breeze circulation and confined to the northwestern part, due to the blocking effect of the northwestern airshed in Hong Kong.