Ozone stress response of leaf BVOC emission and photosynthesis in mountain birch (Betula pubescens spp. czerepanovii) depends on leaf age.

Oxidative stress from ozone (O3) causes plants to alter their emission of biogenic volatile organic compounds (BVOC) and their photosynthetic rate. Stress reactions from O3 on birch trees can result in prohibited plant growth and lead to increased BVOC emission rates as well as changes in their compound blend to emit more monoterpenes (MT) and sesquiterpenes (SQT). BVOCs take part in atmospheric reactions such as enhancing the production of secondary organic aerosols (SOA). As the compound blend and emission rate change with O3 stress, this can influence the atmospheric conditions by affecting the production of SOA. Studying the stress responses of plants provides important information on how these reactions might change, which is vital to making better predictions of the future climate. In this study, measurements were taken to find out how the leaves of mature mountain birch trees (Betula pubescens ssp. czerepanovii) respond to different levels of elevated O3 exposure in situ depending on leaf age. We found that leaves from both early and late summers responded with induced SQT emission after exposure to 120 ppb O3. Early leaves were, however, more sensitive to increased O3 concentrations, with enhanced emission of green leaf volatiles (GLV) and tendencies of both induced leaf senescence as well as poor recovery in the photosynthetic rate between exposures. Late leaves had more stable photosynthetic rates throughout the experiment and responded less to exposure at different O3 levels.

Widespread Pesticide Distribution in the European Atmosphere Questions their Degradability in Air.

Risk assessment of pesticide impacts on remote ecosystems makes use of model-estimated degradation in air. Recent studies suggest these degradation rates to be overestimated, questioning current pesticide regulation. Here, we investigated the concentrations of 76 pesticides in Europe at 29 rural, coastal, mountain, and polar sites during the agricultural application season. Overall, 58 pesticides were observed in the European atmosphere. Low spatial variation of 7 pesticides suggests continental-scale atmospheric dispersal. Based on concentrations in free tropospheric air and at Arctic sites, 22 pesticides were identified to be prone to long-range atmospheric transport, which included 15 substances approved for agricultural use in Europe and 7 banned ones. Comparison between concentrations at remote sites and those found at pesticide source areas suggests long atmospheric lifetimes of atrazine, cyprodinil, spiroxamine, tebuconazole, terbuthylazine, and thiacloprid. In general, our findings suggest that atmospheric transport and persistence of pesticides have been underestimated and that their risk assessment needs to be improved.

Modeling non-linear changes in an urban setting: From pro-environmental affordances to responses in behavior, emissions and air quality.

Interactions in urban environment were investigated using a multidisciplinary model combination, with focus on traffic, emissions and atmospheric particles. An agent-based model was applied to simulate the evolution of unsustainable human behavior (usage of combustion-based personal vehicles) as a function of pro-environmental affordances (opportunities for sustainable choices). Scenarios regarding changes in multi-pollutant emissions were derived, and the non-linear implications to atmospheric particles were simulated with a box model. Based on the results for a Nordic city, increasing pro-environmental affordances by 10%, 50% or 100% leads to emission reductions of 15%, 30% and 40% within 2 years. To reduce ambient particle mass, emissions from traffic should decrease by > 15%, while the lung deposited surface area decreases in all scenarios ([Formula: see text], [Formula: see text] and [Formula: see text], correspondingly). The presented case is representative of one season, but the approach is generic and applicable to simulating a full year, given meteorological and pollution data that reflects seasonal variation. This work emphasizes the necessity to consider feedback mechanisms and non-linearities in both human behavior and atmospheric processes, when predicting the outcomes of changes in an urban system.

Emissions of biogenic volatile organic compounds from adjacent boreal fen and bog as impacted by vegetation composition.

Peatland ecosystems emit biogenic volatile organic compounds (BVOC), which have a net cooling impact on the climate. However, the quality and quantity of BVOC emissions, and how they are regulated by vegetation and peatland type remain poorly understood. Here we measured BVOC emissions with dynamic enclosures from two major boreal peatland types, a minerotrophic fen and an ombrotrophic bog situated in Siikaneva, southern Finland and experimentally assessed the role of vegetation by removing vascular vegetation with or without the moss layer. Our measurements from four campaigns during growing seasons in 2017 and 2018 identified emissions of 59 compounds from nine different chemical groups. Isoprene accounted for 81 % of BVOC emissions. Measurements also revealed uptake of dichloromethane. Total BVOC emissions and the emissions of isoprene, monoterpenoids, sesquiterpenes, homoterpenes, and green leaf volatiles were tightly connected to vascular plants. Isoprene and sesquiterpene emissions were associated with sedges, whereas monoterpenoids and homoterpenes were associated with shrubs. Additionally, isoprene and alkane emissions were higher in the fen than in the bog and they significantly contributed to the higher BVOC emissions from intact vegetation in the fen. During an extreme drought event in 2018, emissions of organic halides were absent. Our results indicate that climate change with an increase in shrub cover and increased frequency of extreme weather events may have a negative impact on total BVOC emissions that otherwise are predicted to increase in warmer temperatures. However, these changes also accompanied a change in BVOC emission quality. As different compounds differ in their capacity to form secondary organic aerosols, the ultimate climate impact of peatland BVOC emissions may be altered.

Role of Secondary Organic Matter on Soot Particle Toxicity in Reconstituted Human Bronchial Epithelia Exposed at the Air-Liquid Interface.

Secondary organic matter (SOM) formed from gaseous precursors constitutes a major mass fraction of fine particulate matter. However, there is only limited evidence on its toxicological impact. In this study, air-liquid interface cultures of human bronchial epithelia were exposed to different series of fresh and aged soot particles generated by a miniCAST burner combined with a micro smog chamber (MSC). Soot cores with geometric mean mobility diameters of 30 and 90 nm were coated with increasing amounts of SOM, generated from the photo-oxidation of mesitylene and ozonolysis of α-pinene. At 24 h after exposure, the release of lactate dehydrogenase (LDH), indicating cell membrane damage, was measured and proteome analysis, i.e. the release of 102 cytokines and chemokines to assess the inflammatory response, was performed. The data indicate that the presence of the SOM coating and its bioavailability play an important role in cytotoxicity. In particular, LDH release increased with increasing SOM mass/total particle mass ratio, but only when SOM had condensed on the outer surface of the soot cores. Proteome analysis provided further evidence for substantial interference of coated particles with essential properties of the respiratory epithelium as a barrier as well as affecting cell remodeling and inflammatory activity.

Equal abundance of summertime natural and wintertime anthropogenic Arctic organic aerosols.

Aerosols play an important yet uncertain role in modulating the radiation balance of the sensitive Arctic atmosphere. Organic aerosol is one of the most abundant, yet least understood, fractions of the Arctic aerosol mass. Here we use data from eight observatories that represent the entire Arctic to reveal the annual cycles in anthropogenic and biogenic sources of organic aerosol. We show that during winter, the organic aerosol in the Arctic is dominated by anthropogenic emissions, mainly from Eurasia, which consist of both direct combustion emissions and long-range transported, aged pollution. In summer, the decreasing anthropogenic pollution is replaced by natural emissions. These include marine secondary, biogenic secondary and primary biological emissions, which have the potential to be important to Arctic climate by modifying the cloud condensation nuclei properties and acting as ice-nucleating particles. Their source strength or atmospheric processing is sensitive to nutrient availability, solar radiation, temperature and snow cover. Our results provide a comprehensive understanding of the current pan-Arctic organic aerosol, which can be used to support modelling efforts that aim to quantify the climate impacts of emissions in this sensitive region.

Decomposition of spruce wood and release of volatile organic compounds depend on decay type, fungal interactions and enzyme production patterns.

Effect of three wood-decaying fungi on decomposition of spruce wood was studied in solid-state cultivation conditions for a period of three months. Two white rot species (Trichaptum abietinum and Phlebia radiata) were challenged by a brown rot species (Fomitopsis pinicola) in varying combinations. Wood decomposition patterns as determined by mass loss, carbon to nitrogen ratio, accumulation of dissolved sugars and release of volatile organic compounds (VOCs) were observed to depend on both fungal combinations and growth time. Similar dependence of fungal species combination, either white or brown rot dominated, was observed for secreted enzyme activities on spruce wood. Fenton chemistry suggesting reduction of Fe3+ to Fe2+ was detected in the presence of F. pinicola, even in co-cultures, together with substantial degradation of wood carbohydrates and accumulation of oxalic acid. Significant correlation was perceived with two enzyme activity patterns (oxidoreductases produced by white rot fungi; hydrolytic enzymes produced by the brown rot fungus) and wood degradation efficiency. Moreover, emission of four signature VOCs clearly grouped the fungal combinations. Our results indicate that fungal decay type, either brown or white rot, determines the loss of wood mass and decomposition of polysaccharides as well as the pattern of VOCs released upon fungal growth on spruce wood.

Interannual and Seasonal Dynamics of Volatile Organic Compound Fluxes From the Boreal Forest Floor.

In the northern hemisphere, boreal forests are a major source of biogenic volatile organic compounds (BVOCs), which drive atmospheric processes and lead to cloud formation and changes in the Earth's radiation budget. Although forest vegetation is known to be a significant source of BVOCs, the role of soil and the forest floor, and especially interannual variations in fluxes, remains largely unknown due to a lack of long-term measurements. Our aim was to determine the interannual, seasonal and diurnal dynamics of boreal forest floor volatile organic compound (VOC) fluxes and to estimate how much they contribute to ecosystem VOC fluxes. We present here an 8-year data set of forest floor VOC fluxes, measured with three automated chambers connected to the quadrupole proton transfer reaction mass spectrometer (quadrupole PTR-MS). The exceptionally long data set shows that forest floor fluxes were dominated by monoterpenes and methanol, with relatively comparable emission rates between the years. Weekly mean monoterpene fluxes from the forest floor were highest in spring and in autumn (maximum 59 and 86 µg m-2 h-1, respectively), whereas the oxygenated VOC fluxes such as methanol had highest weekly mean fluxes in spring and summer (maximum 24 and 79 µg m-2 h-1, respectively). Although the chamber locations differed from each other in emission rates, the inter-annual dynamics were very similar and systematic. Accounting for this chamber location dependent variability, temperature and relative humidity, a mixed effects linear model was able to explain 79-88% of monoterpene, methanol, acetone, and acetaldehyde fluxes from the boreal forest floor. The boreal forest floor was a significant contributor in the forest stand fluxes, but its importance varies between seasons, being most important in autumn. The forest floor emitted 2-93% of monoterpene fluxes in spring and autumn and 1-72% of methanol fluxes in spring and early summer. The forest floor covered only a few percent of the forest stand fluxes in summer.

New Perspectives on CO2, Temperature, and Light Effects on BVOC Emissions Using Online Measurements by PTR-MS and Cavity Ring-Down Spectroscopy.

Volatile organic compounds (VOC) play important roles in atmospheric chemistry, plant ecology, and physiology, and biogenic VOC (BVOC) emitted by plants is the largest VOC source. Our knowledge about how environmental drivers (e.g., carbon, light, and temperature) may regulate BVOC emissions is limited because they are often not controlled. We combined a greenhouse facility to manipulate atmospheric CO2 ([CO2]) with proton-transfer-reaction mass spectrometry (PTR-MS) and cavity ring-down spectroscopy to investigate the regulation of BVOC in Norway spruce. Our results indicate a direct relationship between [CO2] and methanol and acetone emissions, and their temperature and light dependencies, possibly related to substrate availability. The composition of monoterpenes stored in needles remained constant, but emissions of mono-(linalool) and sesquiterpenes (ß-farnesene) increased at lower [CO2], with the effects being most pronounced at the highest air temperature. Pulse-labeling suggested an immediate incorporation of recently assimilated carbon into acetone, mono- and sesquiterpene emissions even under 50 ppm [CO2]. Our results provide new perspectives on CO2, temperature and light effects on BVOC emissions, in particular how they depend on stored pools and recent photosynthetic products. Future studies using smaller but more seedlings may allow sufficient replication to examine the physiological mechanisms behind the BVOC responses.

Size distribution and chemical composition of airborne particles in south-eastern Finland during different seasons and wildfire episodes in 2006.

The inorganic main elements, trace elements and PAHs were determined from selected PM(1), PM(2.5) and PM(10) samples collected at the Nordic background station in Virolahti during different seasons and during the wildfire episodes in 2006. Submicron particles are those most harmful to human beings, as they are able to penetrate deep into the human respiratory system and may cause severe health effects. About 70-80%, of the toxic trace elements, like lead, cadmium, arsenic and nickel, as well as PAH compounds, were found in particles smaller than 1 microm. Furthermore, the main part of the copper, zinc, and vanadium was associated with submicron particles. In practice, all the PAHs found in PM(10) were actually in PM(2.5). For PAHs and trace elements, it is more beneficial to analyse the PM(2.5) or even the PM(1) fraction instead of PM(10), because exclusion of the large particles reduces the need for sample cleaning to minimize the matrix effects during the analysis. During the wildfire episodes, the concentrations of particles smaller than 2.5 microm, as well as those of submicron particles, increased, and also the ratio PM(1)/PM(10) increased to about 50%. On the fire days, the mean potassium concentration was higher in all particle fractions, but ammonium and nitrate concentrations rose only in particles smaller than 1.0 microm. PAH concentrations rose even to the same level as in winter.

Determination of the aerosol yield of isoprene in the presence of an organic seed with carbon isotope analysis.

We examined a new method to determine the aerosol yield of precursors of secondary organic aerosols in the presence of organic seed particles. To distinguish between the oxidation products of the compound in question and the organic seed, the compound was labeled with stable isotopes and aerosol samples were analyzed by isotope ratio mass spectrometry (IRMS). 13C labeled isoprene was obtained from isoprene emitting plants that were exposed to (13)CO2. The aerosol yield of isoprene was determined from the 13C/12C ratio measured in the aerosol. Measurements at organic aerosol mass concentrations as low as 10 microg m(-3) were performed. Three different methods of aerosolsampling procedureswere evaluated: impactor, filter, and electrostatic deposition. The excess-% 13C measured by the three sampling methods agreed well. The aerosol yield of isoprene derived from these measurements showed a strong dependence on further oxidation of first-generation products and is within the range of reported yield values (1-5%) obtained so far from pure isoprene experiments.

Using proton transfer reaction mass spectrometry for online analysis of secondary organic aerosols.

Proton-transfer-reaction mass spectrometry (PTR-MS) is a useful tool in ambient trace gas analysis, especially for the analysis of oxygenated volatile organic compounds (OVOC). Many OVOCs are produced during photooxidation of volatile organic compounds and contribute to both the gas phase and secondary organic aerosols (SOA). The inlet system of the PTR-MS instrument was modified to allow also for the measurement of the particulate phase of an aerosol with a high time resolution. The new inlet consists mainly of a denuder to strip off the gas phase, and a heater (120/150 degrees C) to vaporize the aerosol particles. This inlet system was tested with pinonic acid particles generated with a nebulizer and SOA particles formed during the photooxidation of 1,3,5-trimethylbenzene and alpha-pinene with NO(x) in a smog chamber. The performance of this new technique is discussed and the partitioning coefficients for the oxidation products are estimated.

Ambient air concentrations, source profiles, and source apportionment of 71 different C2-C10 volatile organic compounds in urban and residential areas of Finland.

Ambient air concentrations and source contributions of 71 volatile organic compounds (VOCs) including C2-C10 nonmethane hydrocarbons, halogenated hydrocarbons, and carbonyls were studied at urban and residential sites in Finland. On the basis of the emission profile and concentration measurements, the contributions of different sources were estimated using a chemical mass balance (CMB) receptor model. It was shown that it is possible to apply CMB in the case of a large number of different compounds with different properties. However, the performance of the model varies significantly for the different compounds. According to the CMB analysis, major sources for these VOCs at the urban site were traffic and distant sources. At the residential site, the contribution due to traffic was minor while distant sources, liquid gasoline, and wood combustion made higher contributions. However, different compound groups or compounds were found to have totally different sources. It was also shown that a biogenic compound, isoprene, also has significant anthropogenic sources and that at some locations wood combustion can be an important source for some VOCs usually considered as traffic-related compounds (e.g., benzene).

Aromatic hydrocarbon and methyl tert-butyl ether measurements in ambient air of Helsinki (Finland) using diffusive samplers.

The diffusive sampling method was evaluated for measuring benzene, toluene, ethylbenzene, xylenes, styrene, propylbenzene, ethyltoluenes, trimethylbenzenes and methyl tert-butyl ether (MTBE) in the urban air of Helsinki, Finland. Concentrations were measured in 2-week periods at four different sites during the year 2000. Tube type adsorbent tubes were pre-packed with Carbopack-B (60/80). Analysis was conducted using thermal desorption and gas chromatograph coupled to a mass spectrometer. In different seasons, during five diffusive sampling periods, parallel measurements were conducted using pumped and online sampling. The compared techniques agreed reasonably well for other compounds than trimethylbenzenes. Based on comparisons, diffusive uptake rates for ethyltoluenes, styrene, propylbenzene and MTBE were determined, and for trimethylbenzenes, uptake rates were revised. The concentrations of aromatic compounds in Helsinki metropolitan area were also compared to the concentrations of a rural, forested site in Central Finland.