Oxidative properties of ambient PM2.5 and elemental composition: Heterogeneous associations in 19 European cities

We assessed the extent to which constituents of PM_2.5 (transition metals, sodium, chloride) contribute to the ability to generate hydroxyl radicals (OH) in vitro in PM_2.5 sampled at 20 locations in 19 European centres participating in the European Community Respiratory Health Survey. PM_2.5 samples (n = 716) were collected on filters over one year and the oxidative activity of particle suspensions obtained from these filters was then assessed by measuring their ability to generate OH in the presence of hydrogen peroxide. Associations between OH formation and the studied PM constituents were heterogeneous. The total explained variance ranged from 85% in Norwich to only 6% in Albacete. Among the 20 centres, 15 showed positive correlations between one or more of the measured transition metals (copper, iron, manganese, lead, vanadium and titanium) and OH formation. In 9 of 20 centres OH formation was negatively associated with chloride, and in 3 centres with sodium. Across 19 European cities, elements which explained the largest variations in OH formation were chloride, iron and sodium.     

White clover clones as a cost-effective indicator of phytotoxic ozone: 10 years of experience from central Italy

Data collected at one site in central Italy using the NC-S/NC-R clover (Trifolium repens) biotype system during 1997-2007 were analysed in order to assess: (a) its performance under Mediterranean conditions; (b) variations of ozone damage linked with meteorological conditions; (c) if critical level approach is a good predictor of ozone risk on vegetation. NC-S dry biomasses were systematically lower than those of NC-R, the mean ratio being 0.7. Relevant relationship between ozone visible injury and cumulated values of AOT40 were also reported. Temperature and number of rainy days were the most important factors associated with ozone presence and, as a consequence, with leaf injury index. Photosynthetic gas exchange properties indicate that NC-S has higher values of stomatal conductance.     

DOC removal paradigms in highly humic aquatic ecosystems

Background, aim, and scope  Dissolved humic substances (HS) usually comprise 50–80% of the dissolved organic carbon (DOC) in aquatic ecosystems. From a trophic and biogeochemical perspective, HS has been considered to be highly refractory and is supposed to accumulate in the water. The upsurge of the microbial loop paradigm and the studies on HS photo-degradation into labile DOC gave rise to the belief that microbial processing of DOC should sustain aquatic food webs in humic waters. However, this has not been extensively supported by the literature, since most HS and their photo-products are often oxidized by microbes through respiration in most nutrient-poor humic waters. Here, we review basic concepts, classical studies, and recent data on bacterial and photo-degradation of DOC, comparing the rates of these processes in highly humic ecosystems and other aquatic ecosystems. Materials and methods  We based our review on classical and recent findings from the fields of biogeochemistry and microbial ecology, highlighting some odd results from highly humic Brazilian tropical lagoons, which can reach up to 160 mg C L⁻¹. Results and discussion  Highly humic tropical lagoons showed proportionally lower bacterial production rates and higher bacterial respiration rates (i.e., lower bacterial growth efficiency) than other lakes. Zooplankton showed similar δ¹³C to microalgae but not to humic DOC in these highly humic lagoons. Thus, the data reviewed here do not support the microbial loop as an efficient matter transfer pathway in highly humic ecosystems, where it is supposed to play its major role. In addition, we found that some tropical humic ecosystems presented the highest potential DOC photo-chemical mineralization (PM) rates reported in the literature, exceeding up to threefold the rates reported for temperate humic ecosystems. We propose that these atypically high PM rates are the result of a joint effect of the seasonal dynamics of allochthonous humic DOC input to these ecosystems and the high sunlight incidence throughout the year. The sunlight action on DOC is positive to microbial consumption in these highly humic lagoons, but little support is given to the enhancement of bacterial growth efficiency, since the labile photo-chemical products are mostly respired by microbes in the nutrient-poor humic waters. Conclusions  HS may be an important source of energy for aquatic bacteria in humic waters, but it is probably not as important as a substrate to bacterial growth and to aquatic food webs, since HS consumption is mostly channeled through microbial respiration. This especially seems to be the case of humic-rich, nutrient-poor ecosystems, where the microbial loop was supposed to play its major role. Highly humic ecosystems also present the highest PM rates reported in the literature. Finally, light and bacteria can cooperate in order to enhance total carbon degradation in highly humic aquatic ecosystems but with limited effects on aquatic food webs. Recommendations and perspectives  More detailed studies using C- and N-stable isotope techniques and modeling approaches are needed to better understand the actual importance of HS to carbon cycling in highly humic waters.     

Validation of a Lagrangian dispersion model implementing different kernel methods for density reconstruction

In this paper the inert version of a Lagrangian particle model named photochemical Lagrangian particle model (PLPM) is described and validated. PLPM implements four density reconstruction algorithms based on the kernel density estimator. All these methods are fully grid-free but they differ each other in considering local or global features of the particles distribution, in treating the Cartesian directions separately or together and in being based on receptors or particles positions in space. Each kernel has been shown to have both advantages and disadvantages, but the overall good performances of the model when compared with the well known Copenhagen and Kincaid data sets are very encouraging in view of its extension to fully chemically active simulations, currently under development.     

Photochemical oxidation of reduced sulfur compounds in an urban location based on short time monitoring data

This study examines the oxidation of reduced sulfur compounds (RSCs) in urban ambient air. The photochemical conversions of RSC (such as DMS, CS₂, H₂S, DMDS, and CH₃SH) to a further oxidized form (e.g., SO₂, MSA, and H₂SO₄) were assessed using a photochemical box model. For our model simulation of RSC oxidation, measurements were taken at an urban monitoring station in Seoul, Korea (37.6° N, 127° E) during three separate time periods (e.g., Sept. 17–18, Oct. 23, and Oct. 27–28, 2003). The results indicate that DMS and H₂S were the dominant RSCs with concentrations of 370 ± 140 and 110 ± 60 pptv, respectively. The photochemical conversion of DMDS to SO₂ was found to occur more efficiently than other RSCs. The overall results of our study suggest that photochemical conversion of RSCs accounted for less than 15% of the observed SO₂ during the measurement period. The SO₂ production from DMS oxidation (mainly by the reaction with OH) was found to be affected primarily by the abstraction channel due to high NO_x levels during the experimental conditions.     

Contribution of anthropogenic pollutants to the increase of tropospheric ozone levels in the Oporto Metropolitan Area, Portugal since the 19th century

The main purpose of this study was to evaluate the contribution of anthropogenic pollutants to the increase of tropospheric ozone levels in the Oporto Metropolitan Area (Portugal) since the 19th century. The study was based on pre-industrial and recent data series, the results being analyzed according to the atmospheric chemistry. The treatment of ozone and meteorological data was performed by classical statistics and by time-series analysis. It was concluded that in the 19th century the ozone present in the troposphere was not of photochemical origin, being possible to consider the respective concentrations as reference values. For recent data a cycle of 8h for ozone concentrations could be related to traffic. Compared to the 19th century, the current concentrations were 147% higher (252% higher in May) due to the increased photochemical production associated with the increased anthropogenic emissions.     

Phytoremediation of polyaromatic hydrocarbons, anilines and phenols

Phytoremediation technologies based on the combined action of plants and the microbial communities that they support within the rhizosphere hold promise in the remediation of land and waterways contaminated with hydrocarbons but they have not yet been adopted in large-scale remediation strategies. In this review plant and microbial degradative capacities, viewed as a continuum, have been dissected in order to identify where bottle-necks and limitations exist. Phenols, anilines and polyaromatic hydrocarbons (PAHs) were selected as the target classes of molecule for consideration, in part because of their common patterns of distribution, but also because of the urgent need to develop techniques to overcome their toxicity to human health. Depending on the chemical and physical properties of the pollutant, the emerging picture suggests that plants will draw pollutants including PAHs into the plant rhizosphere to varying extents via the transpiration stream. Mycorrhizosphere-bacteria and -fungi may play a crucial role in establishing plants in degraded ecosystems. Within the rhizosphere, microbial degradative activities prevail in order to extract energy and carbon skeletons from the pollutants for microbial cell growth. There has been little systematic analysis of the changing dynamics of pollutant degradation within the rhizosphere; however, the importance of plants in supplying oxygen and nutrients to the rhizosphere via fine roots, and of the beneficial effect of microorganisms on plant root growth is stressed. In addition to their role in supporting rhizospheric degradative activities, plants may possess a limited capacity to transport some of the more mobile pollutants into roots and shoots via fine roots. In those situations where uptake does occur (i.e. only limited microbial activity in the rhizosphere) there is good evidence that the pollutant may be metabolised. However, plant uptake is frequently associated with the inhibition of plant growth and an increasing tendency to oxidant stress. Pollutant tolerance seems to correlate with the ability to deposit large quantities of pollutant metabolites in the 'bound' residue fraction of plant cell walls compared to the vacuole. In this regard, particular attention is paid to the activities of peroxidases, laccases, cytochromes P450, glucosyltransferases and ABC transporters. However, despite the seemingly large diversity of these proteins, direct proof of their participation in the metabolism of industrial aromatic pollutants is surprisingly scarce and little is known about their control in the overall metabolic scheme. Little is known about the bioavailability of bound metabolites; however, there may be a need to prevent their movement into wildlife food chains. In this regard, the application to harvested plants of composting techniques based on the degradative capacity of white-rot fungi merits attention.     

化学氧化剂对水华蓝藻的控制研究

对比了过氧化氢（H₂O₂）、高铁酸钾（K₂FeO₄）和过碳酸钠（Na₂CO₄）3种氧化剂对自然水体中群体蓝藻生长和光合活性的影响.结果发现,3种氧化剂对蓝藻均有快速的抑制效应,且随着氧化剂浓度的增加抑制效果增强.相同氧化剂浓度下,H₂O₂对水华蓝藻的去除能力强于K₂FeO₄和Na₂CO₄,对蓝藻光合系统Ⅱ的最大光量子产量（F_v/F_m）和有效光量子产量（F_v'/F_m'）的抑制效果也更显著.H₂O₂对不同浓度水华蓝藻的控制实验结果表明,初始藻细胞浓度对H₂O₂控藻效果影响较大,细胞密度越大,H₂O₂降解率增加,抑藻效果急剧下降.当初始藻密度为10μg/L和100μg/L,5mg/L H₂O₂的48h降解率分别为64.9%和97.5%,对藻细胞F_v/F_m的抑制率分别为10%和1%.因此,实施H₂O₂控制蓝藻水华的措施应该尽量在蓝藻水华形成早期,即藻密度较低的时候使用.     

Observation and analysis of atmospheric volatile organic compounds in a typical petrochemical area in Yangtze River Delta, China

Volatile organic compounds (VOCs) are a kind of important precursors for ozone photochemical formation. In this study, VOCs were measured from November 5th, 2013 to January 6th, 2014 at the Second Jinshan Industrial Area, Shanghai, China. The results showed that the measured VOCs were dominated by alkanes (41.8%), followed by aromatics (20.1%), alkenes (17.9%), and halo-hydrocarbons (12.5%). The daily trend of the VOC concentration showed a bimodal feature due to the rush-hour traffic in the morning and at nightfall. Based on the VOC concentration, a receptor model of Positive Matrix Factorization (PMF) coupled with the information related to VOC sources was applied to identify the major VOC emissions. The result showed five major VOC sources: solvent use and industrial processes were responsible for about 30% of the ambient VOCs, followed by rubber chemical industrial emissions (23%), refinery and petrochemical industrial emissions (21%), fuel evaporations (13%) and vehicular emissions (13%). The contribution of generalized industrial emissions was about 74% and significantly higher than that made by vehicle exhaust. Using a propylene-equivalent method, alkenes displayed the highest concentration, followed by aromatics and alkanes. Based on a maximum incremental reactivity (MIR) method, the average hourly ozone formation potential (OFP) of VOCs is 220.49?ppbv. The most significant source for ozone chemical formation was identified to be rubber chemical industrial emissions, following one by vehicular emission. The data shown herein may provide useful information to develop effective VOC pollution control strategies in industrialized area.     

Insights into the formation of secondary organic carbon in the summertime in urban Shanghai

To investigate formation mechanisms of secondary organic carbon(SOC) in Eastern China,measurements were conducted in an urban site in Shanghai in the summer of 2015. A period of high O_3 concentrations(daily peak 120 ppb) was observed, during which daily maximum SOC concentrations exceeding 9.0 μg/(C·m~3). Diurnal variations of SOC concentration and SOC/organic carbon(OC) ratio exhibited both daytime and nighttime peaks. The SOC concentrations correlated well with O_x(= O_3+ NO_2) and relative humidity in the daytime and nighttime, respectively, suggesting that secondary organic aerosol formation in Shanghai is driven by both photochemical production and aqueous phase reactions. Single particle mass spectrometry was used to examine the formation pathways of SOC. Along with the daytime increase of SOC, the number fraction of elemental carbon(EC) particles coated with OC quickly increased from 38.1% to 61.9% in the size range of 250–2000 nm, which was likely due to gas-to-particle partitioning of photochemically generated semi-volatile organic compounds onto EC particles. In the nighttime, particles rich in OC components were highly hygroscopic, and number fraction of these particles correlated well with relative humidity and SOC/OC nocturnal peaks. Meanwhile, as an aqueous-phase SOC tracer, particles that contained oxalate-Fe(III) complex also peaked at night. These observations suggested that aqueous-phase processes had an important contribution to the SOC nighttime formation. The influence of aerosol acidity on SOC formation was studied by both bulk and single particle level measurements, suggesting that the aqueous-phase formation of SOC was enhanced by particle acidity.