Rice consumption is the major pathway for human methylmercury (MeHg) exposure in inland China, especially in mercury (Hg) contaminated regions. MeHg production, a microbially driven process, depends on both the chemical speciation of inorganic divalent mercury, Hg(II), that determines Hg bioavailability for methylation. Studies have shown that Hg(II) speciation in contaminated paddy soils is mostly controlled by natural organic matter and sulfide levels, which are typically thought to limit Hg mobility and bioavailability. Yet, high levels of MeHg are found in rice, calling for reconsideration of the nature of Hg species bioavailable to methylators in paddy soils. Here, we conducted incubation experiments using a multi-isotope tracer technique including ¹⁹⁸Hg(NO₃)₂, natural organic matter bond Hg(II) (NOM-¹⁹⁹Hg(II)), ferrous sulfide sorbed Hg(II) (≡FeS-²⁰⁰Hg(II)), and nanoparticulate mercuric sulfide (nano-²⁰²HgS), to investigate the relative importance of geochemically diverse yet relevant Hg(II) species on Hg methylation in paddy soils across a Hg concentration gradient. We show that methylation rates for all Hg(II) species tested decreased with increasing Hg concentrations, and that methylation rates using NOM-¹⁹⁹Hg(II) and nano-²⁰²HgS as substrates were similar or greater than rates obtained using the labile ¹⁹⁸Hg(NO₃)₂ substrate. ≡FeS-²⁰⁰Hg(II) yielded the lowest methylation rate in all sites, and thus the formation of FeS is likely a sink for labile ¹⁹⁸Hg(NO₃)₂ in sulfide-rich paddy soils. Moreover, the variability in the methylation data for a given site (1 to 5-fold variation depending on the Hg species) was smaller than what was observed across the Hg concentration gradient (10³–10⁴ fold variation between sites). These findings emphasize that at broad spatial scales, site-specific characteristics, such as microbial community structure, need to be taken into consideration, alongside the nature of the Hg substrate available for methylation, to determine net MeHg production. This study highlights the importance of developing site-specific strategies for remediating Hg pollution.

Biomass burning (BB) is one of the largest sources of carbonaceous aerosols with adverse impacts on air quality, visibility, health and climate. BB emits a few specific aromatic acids (p-hydroxybenzoic, vanillic, syringic and dehydroabietic acids) which have been widely used as key indicators for source identification of BB-derived carbonaceous aerosols in various environmental matrices. In addition, measurement of p-hydroxybenzoic and vanillic acids in snow and ice cores have revealed the historical records of the fire emissions. Despite their uniqueness and importance as tracers, our current understanding of analytical methods, concentrations, diagnostic ratios and degradation processes are rather limited and scattered in literature. In this review paper, firstly we have summarized the most established methods and protocols for the measurement of these aromatic acids in aerosols and ice cores. Secondly, we have highlighted the geographical variability in the abundances of these acids, their diagnostic ratios and degradation processes in the environments. The review of the existing data indicates that the concentrations of aromatic acids in aerosols vary greatly with locations worldwide, typically more abundant in urban atmosphere where biomass fuels are commonly used for residential heating and/or cooking purposes. In contrast, their concentrations are lowest in the polar regions which are avoid of localized emissions and largely influenced by long-range transport. The diagnostic ratios among aromatic acids can be used as good indicators for the relative amounts and types of biomass (e.g. hardwood, softwood and herbaceous plants) as well as photochemical oxidation processes. Although studies suggest that the degradation processes of the aromatic acids may be controlled by light, pH and hygroscopicity, a more careful investigation, including closed chamber studies, is highly appreciated.

Cryoconite is a dark, dusty aggregate of mineral particles, organic matter, and microorganisms transported by wind and deposited on glacier surfaces. It can accelerate glacier melting and alter glacier mass balances by reducing the surface albedo of glaciers. Biomass burning in the Tibetan Plateau, especially in the glacier cryoconites, is poorly understood. Retene, levoglucosan, mannosan and galactosan can be generated by the local fires or transported from the biomass burning regions over long distances. In the present study, we analyzed these four molecular markers in cryoconites of seven glaciers from the northern to southern Tibetan Plateau. The highest levels of levoglucosan and retene were found in cryoconites of the Yulong Snow Mountain and Tienshan glaciers with 171.4 ± 159.4 ng g⁻¹ and 47.0 ± 10.5 ng g⁻¹ dry weight (d.w.), respectively. The Muztag glacier in the central Tibetan Plateau contained the lowest levels of levoglucosan and retene with mean values of 59.8 ng g⁻¹ and 0.4 ± 0.1 ng g⁻¹ d.w., respectively. In addition, the vegetation changes and the ratios of levoglucosan to mannosan and retene indicate that combustion of conifers significantly contributes to biomass burning of the cryoconites in the Yulong Snow Mountain and Tienshan glacier. Conversely, biomass burning tracers in cryoconites of Dongkemadi, Yuzhufeng, Muztag, Qiyi and Laohugou glaciers are derived from the combustion of different types of biomass including softwood, hardwood and grass.

Organic tracers are useful for investigating the sources of carbonaceous aerosols but there are still no adequate studies in China. To obtain insights into the diurnal variations, properties, and the influence of regional emission controls on carbonaceous aerosols in Beijing, day-/nighttime PM₂.₅ samples were collected before (Oct. 15th – Nov. 2nd) and during (Nov. 3rd – Nov. 12th) the 2014 Asia-Pacific Economic Cooperation (APEC) summit. Eleven organic compound classes were analysed using gas chromatography/mass spectrometry (GC/MS). In addition, the stable carbon isotope ratios (δ¹³CTC) of total carbon (TC) were detected using an elemental analyser/isotope ratio mass spectrometry (EA/irMS). Most of the organic compounds were more abundant during the night than in the daytime, and their concentrations generally decreased during the APEC. These features were associated with the strict regional emission controls and meteorological conditions. The day/night variations of δ¹³CTC were smaller during the APEC than those before the APEC the summit, suggesting that regionally transported aerosols are potentially played an important role in the loading of organic aerosols in Beijing before the APEC summit. The source apportionment based on the organic tracers suggested that biomass burning, plastic and microbial emissions, and fossil fuel combustion were important sources of organic aerosols in Beijing. Furthermore, a similar contribution of biomass burning to OC before and during the APEC suggests biomass burning was a persistent contributor to PM₂.₅ in Beijing and its surroundings.

Fine particulate matter (PM2.5) samples were collected using a high-volume air sampler and pre-combusted quartz filters during May 2013 to January 2014 at a background rural site (47∘35 N, 133∘31 E) in Sanjiang Plain, Northeast China. A homologous series of dicarboxylic acids (C2-C11) and related compounds (oxoacids, α-dicarbonyls and fatty acids) were analyzed by using a gas chromatography (GC) and GC-MS method employing a dibutyl ester derivatization technique. Intensively open biomass-burning (BB) episodes during the harvest season in fall were characterized by high mass concentrations of PM2.5, dicarboxylic acids and levoglucosan. During the BB period, mass concentrations of dicarboxylic acids and related compounds were increased by up to >20 times with different factors for different organic compounds (i.e., succinic (C4) acid > oxalic (C2) acid > malonic (C3) acid). High concentrations were also found for their possible precursors such as glyoxylic acid (ωC2), 4-oxobutanoic acid, pyruvic acid, glyoxal, and methylglyoxal as well as fatty acids. Levoglucosan showed strong correlations with carbonaceous aerosols (OC, EC, WSOC) and dicarboxylic acids although such good correlations were not observed during non-biomass-burning seasons. Our results clearly demonstrate biomass burning emissions are very important contributors to dicarboxylic acids and related compounds. The selected ratios (e.g., C3/C4, maleic acid/fumaric acid, C2/ωC2, and C2/levoglucosan) were used as tracers for secondary formation of organic aerosols and their aging process. Our results indicate that organic aerosols from biomass burning in this study are fresh without substantial aging or secondary production. The present chemical characteristics of organic compounds in biomass-burning emissions are very important for better understanding the impacts of biomass burning on the atmosphere aerosols.

Based on the 12-hour PM2.5 samples collected in an urban site of Beijing, sixteen PM2.5-bound Polycyclic Aromatic Hydrocarbons (PAHs) were measured to investigate the characteristics and potential source regions of particulate PAHs in Beijing. The study period included the summer period in July–August 2014, the APEC source control period during the Asia-Pacific Economic Cooperation (APEC) meeting in the first half of November 2014, and the heating period in the second half of November 2014. Compared to PM2.5, sum of 16 PM2.5-bound PAHs exhibited more significant seasonal variation with the winter concentration largely exceeding the summer concentration. Temperature appeared to be the most crucial meteorological factor during the summer and heating periods, while PM2.5-bound PAHs showed stronger correlation with relative humidity and wind speed during the APEC source control period. Residential heating significantly increased the concentrations of higher-ring-number (≥4) PAHs measured in PM2.5 fraction. Potential source contribution function (PSCF) and concentration weighted trajectory (CWT) analysis as well as the (3 + 4) ring/(5 + 6) ring PAH ratio analysis revealed the seasonal difference in the potential source area of PM2.5-bound PAHs in Beijing. Southern Hebei was the most likely potential source area in the cold season. Using black carbon (BC) and carbon monoxide (CO) as the PAH tracers, regional residential, transportation and industry emissions all contributed to the PAH pollution in Beijing.

The chemical composition of single particles deposited on industrial filters located in three different chimneys of an iron-manganese (Fe–Mn) alloy manufacturing plant have been compared using aerosol time-of-flight mass spectrometry (ATOFMS) and scanning electron microscopy–energy dispersive X-ray spectrometry (SEM-EDX). Very similar types of particles were observed using both analytical techniques. Calcium-containing particles dominated in the firing area of the sintering unit, Mn and/or Al-bearing particles were observed at the cooling area of the sintering unit, while Mn-containing particles were dominant at the smelting unit. SEM-EDX analysis of particles collected downstream of the industrial filters showed that the composition of the particles emitted from the chimneys is very similar to those collected on the filters. ATOFMS analysis of ore samples was also performed to identify particulate emissions that could be generated by wind erosion and manual activities. Specific particle types have been identified for each emission source (chimneys and ore piles) and can be used as tracers for source apportionment of ambient PM measured in the vicinity of the industrial site.

Magnetic particles (MP) emitted by an iron smelter were used to investigate the exposure of cows grazing on a grassland polluted by these MP and by large amounts of potentially toxic elements (PTE). The morphology as well as the chemical composition of the MP separated from cow dung were studied. Large amounts of typical MP were found (1.1 g kg−1 dry weight) in the cow dung sampled from the exposed site, whereas these particles were absent from the reference unpolluted site. The ingested MP were mainly technogenic magnetic particles (TMP) emitted by the smelter. Considering the MP concentration in the grazed grass on the exposed site, it was concluded that cows absorb the MP not only from the grass but also from the soil surface. The results of a mild acidic leaching of the MP suggested that the particles were possibly submitted to a superficial dissolution in the abomasum, pointing at a potential route of transfer of the PTE originating from the TMP and leading into food chains. TMP were only a small part of the anthropogenic contamination having affected the soil and the dung. However, due to their unequivocal signature, TMP are a powerful tracer of the distribution of PTE in the different compartments constituting the food chains and the ecosystems. Furthermore, the measurement of the particle sizes gave evidence that a noticeable proportion of the MP could enter the respiratory tract.

Sewage impacted soil, sludge and water samples were studied to understand the occurrence and formation of thiosteranes and to determine the relevance of these compounds as tracers for sewage input into the environment. Soils were collected from wastewater irrigation fields (Wroclaw, Poland), water from the Nexapa River Basin (Mexico), which also received wastewater and wastewater treatment plant (WWTP) effluent, and water and sludge from the Norman WWTP (USA) at different treatment stages. Thiosteranes represented a high proportion of the steroid fraction in the Wroclaw irrigation field and the Nexapa River Basin samples. Small amounts of thiosteranes were found in anaerobically digested sludge from the Norman WWTP. A good correlation between coprostanone and thiosterane concentrations suggests thiosteranes were produced by stanone sulphurization under anoxic conditions. Thiosterane stability under anoxic and suboxic conditions indicates their potential use as tracers for environmental input of sewage products or land application of sewage sludge.

Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD) are bioaccumulative flame retardants. PBDEs increased in many ecosystems during the late 20th century, but recently have declined in some environments. To examine trends in the northern Pacific, we analysed PBDEs, HBCDD and carbon and nitrogen stable isotopes (δ13C and δ15N) to account for dietary effects in archived eggs of three seabird species from British Columbia, Canada, 1990–2011 (rhinoceros auklets, Cerorhinca monocerata; Leach's storm-petrels, Oceanodroma leucorhoa; ancient murrelets, Synthliboramphus antiquus, 2009 only). PBDEs increased until approximately 2000 and then decreased, while HBCDD increased exponentially throughout the examined period. No significant changes in dietary tracers were observed. HBCDD and ΣPBDE levels varied among species; ΣPBDE also varied among sites. Temporal changes in contaminant concentrations are unlikely to have been caused by dietary changes, and likely reflect the build-up followed by decreases associated with voluntary phase-outs and regulations implemented in North America to control PBDEs.