E. Kleist

A large source of low-volatility secondary organic aerosol

Forests emit large quantities of volatile organic compounds (VOCs) to the atmosphere. Their condensable oxidation products can form secondary organic aerosol, a significant and ubiquitous component of atmospheric aerosol, which is known to affect the Earth’s radiation balance by scattering solar radiation and by acting as cloud condensation nuclei. The quantitative assessment of such climate effects remains hampered by a number of factors, including an incomplete understanding of how biogenic VOCs contribute to the formation of atmospheric secondary organic aerosol. The growth of newly formed particles from sizes of less than three nanometres up to the sizes of cloud condensation nuclei (about one hundred nanometres) in many continental ecosystems requires abundant, essentially non-volatile organic vapours, but the sources and compositions of such vapours remain unknown. Here we investigate the oxidation of VOCs, in particular the terpene α-pinene, under atmospherically relevant conditions in chamber experiments. We find that a direct pathway leads from several biogenic VOCs, such as monoterpenes, to the formation of large amounts of extremely low-volatility vapours. These vapours form at significant mass yield in the gas phase and condense irreversibly onto aerosol surfaces to produce secondary organic aerosol, helping to explain the discrepancy between the observed atmospheric burden of secondary organic aerosol and that reported by many model studies. We further demonstrate how these low-volatility vapours can enhance, or even dominate, the formation and growth of aerosol particles over forested regions, providing a missing link between biogenic VOCs and their conversion to aerosol particles. Our findings could help to improve assessments of biosphere–aerosol–climate feedback mechanisms, and the air quality and climate effects of biogenic emissions generally.

Gas phase formation of extremely oxidized pinene reaction products in chamber and ambient air

This manuscript presents elemental composition data of highly oxidized compounds as clusters of nitrate ion, NO3-, and biogenic volatile organic compounds, especially a-pinene, oxidation products. The authors present a brief description of the APi-ToF instrument and mass calibration procedure for a large mass range, followed by comparison of mass spectra from Jülich chamber and the Hyytiälä field site along with a hypotheses for the formation mechanism of the highly oxidized compounds. Finally, the authors estimate the concentration of neutral molecules from the observed ion clusters. The data presented is very convincing and the manuscript is suitable for publication in ACP after the following comments are addressed.

Methanol emissions from deciduous tree species: dependence on temperature and light intensity

Methanol emissions from several deciduous tree species with predominantly mature leaves were measured under laboratory and field conditions. The emissions were modulated by temperature and light. Under constant light conditions in the laboratory, methanol emissions increased with leaf temperature, by up to 12% per degree. At constant temperatures, emissions doubled when light intensity (PAR) increased from darkness to 800 micromol x m(-2) x s(-1). A phenomenological description of light and temperature dependencies was derived from the laboratory measurements. This description was successfully applied to reproduce the diel cycle of methanol emissions from an English oak measured in the field. Labelling experiments with (13)CO(2) provided evidence that less than 10% of the emitted methanol was produced de novo by photosynthesis directly prior to emission. Hence, the light dependence of the emissions cannot be explained by instantaneous production from CO(2) fixation. Additional experiments with selective cooling of plant roots indicated that a substantial fraction of the emitted methanol may be produced in the roots or stem and transported to stomata by the transpiration stream. However, the transpiration stream cannot be considered as the main factor that determines methanol emissions by the investigated plants.

Aerosol Mass Spectrometric Features of Biogenic SOA: Observations from a Plant Chamber and in Rural Atmospheric Environments

Secondary organic aerosol (SOA) is known to form from a variety of anthropogenic and biogenic precursors. Current estimates of global SOA production vary over 2 orders of magnitude. Since no direct measurement technique for SOA exists, quantifying SOA remains a challenge for atmospheric studies. The identification of biogenic SOA (BSOA) based on mass spectral signatures offers the possibility to derive source information of organic aerosol (OA) with high time resolution. Here we present data from simulation experiments. The BSOA from tree emissions was characterized with an Aerodyne quadrupole aerosol mass spectrometer (Q-AMS). Collection efficiencies were close to 1, and effective densities of the BSOA were found to be 1.3 +/- 0.1 g/cm(3). The mass spectra of SOA from different trees were found to be highly similar. The average BSOA mass spectrum from tree emissions is compared to a BSOA component spectrum extracted from field data. It is shown that overall the spectra agree well and that the mass spectral features of BSOA are distinctively different from those of OA components related to fresh fossil fuel and biomass combustions. The simulation chamber mass spectrum may potentially be useful for the identification and interpretation of biogenic SOA components in ambient data sets.

RNAi-mediated suppression of isoprene biosynthesis in hybrid poplar impacts ozone tolerance

Isoprene is the most abundant volatile compound emitted by vegetation. It influences air chemistry and is thought to take part in plant defense reactions against abiotic stress such as high temperature or ozone. However, whether or not isoprene emission impacts ozone tolerance of plants is still in discussion. In this study, we exploited the transgenic non-isoprene emitting grey poplar (Populus x canescens (Aiton) Sm.) in a biochemical and physiological model study to investigate the effect of acute ozone stress on the elicitation of defense-related emissions of plant volatiles, on photosynthesis and on the antioxidative system. We recorded that non-isoprene emitting poplars were more resistant to ozone as indicated by less damaged leaf area and higher assimilation rates compared to ozone-exposed wild-type (WT) plants. The integral of green leaf volatile emissions was different between the two poplar phenotypes and was a reliable early marker for subsequent leaf damage. For other stress-induced volatiles, such as mono-, homo- and sesquiterpenes and methyl salicylate, similar time profiles, pattern and emission intensities were observed in both transgenic and WT plants. However, unstressed non-isoprene emitting poplars are characterized by elevated levels of ascorbate and alpha-tocopherol as well as by a more effective de-epoxidation ratio of xanthophylls than the WT. Since ozone quenching properties of ascorbate are much higher than those of isoprene and furthermore alpha-tocopherol is also an essential antioxidant, non-isoprene emitting poplars might benefit from changes within the antioxidative system by providing them with enhanced ozone tolerance.

Atmospheric benzenoid emissions from plants rival those from fossil fuels

Despite the known biochemical production of a range of aromatic compounds by plants and the presence of benzenoids in floral scents, the emissions of only a few benzenoid compounds have been reported from the biosphere to the atmosphere. Here, using evidence from measurements at aircraft, ecosystem, tree, branch and leaf scales, with complementary isotopic labeling experiments, we show that vegetation (leaves, flowers, and phytoplankton) emits a wide variety of benzenoid compounds to the atmosphere at substantial rates. Controlled environment experiments show that plants are able to alter their metabolism to produce and release many benzenoids under stress conditions. The functions of these compounds remain unclear but may be related to chemical communication and protection against stress. We estimate the total global secondary organic aerosol potential from biogenic benzenoids to be similar to that from anthropogenic benzenoids (~10 Tg y−1), pointing to the importance of these natural emissions in atmospheric physics and chemistry.

Formation of octachloroacenaphthylene in the pyrolysis of decachlorobiphenyl

Abstract The pyrolytic degradation of decachlorobiphenyl (PCB 209) in the temperature range of 700 – 1000°C and at a pyrolysis time of 10 seconds generated one main chloroaromatic product. This Compound has been identified by HPLC-UV, GC-MS, GC-FTIR and 13 C-NMR as octachloroacenaphthylene (OCAN). The mechanism of the nearly quantitative formation of octachloroacenaphthylene (OCAN) occurs via a nonachlorobenzobarrylene radical (ZIR) as an intermediate followed by a rearrangement and further dechlorination to for OCAN. Calculations with the program THERM based on the Benson-group-theory indicated that this mechanism is not possible for lower nonchlorinated biphenyls.

Modelling new particle formation from Jülich plant atmosphere chamber and CERN CLOUD chamber measurements

An MALTE-BOX model is used to study the effects of oxidation of SO2 and BVOCs to new particle formation from Julich Plant Atmosphere Chamber and CERN CLOUD chamber measurements. Several days of continuously measurements were chosen for the simulation. Our preliminary results show that H2SO4 is one of the critical compounds in nucleation process. Nucleation involving the oxidation of BVOCs shows better agreements with measurements.

Probing aerosol formation by comprehensive measurements of gas phase oxidation products

A comprehensive suite of chemical ionization mass spectrometers (CIMS) were deployed for chamber studies of monoterpene oxidation. The CIMS instruments were able to detect several different groups of compounds ranging from volatile to practically non-volatile. The compound groups showed very different behavior and correlations with aerosol number and mass. Results suggest that major gas phase contributors are not considered in current models.

Aerosol Formation from Plant Emissions: The Jülich Plant Chamber Experiments

We have performed measurements of particle formation and growth in a setup consisting of a plant and a reaction chamber, using live plants as well as an α-pinene source. The nucleation rates observed varied between 0.04 and 260 cm �3 s �1 , while the growth rates were 10-30 nm/h. We found that the formation and growth rates of particles increased with increasing amounts of carbon emitted by the plants, but there was significant variation between the plants. We have also modeled the formation of the aerosol using a continuously stirred tank reactor concept, and found that the basic physics and chemistry of the chamber are captured well.