Publications

Time-resolved particle emissions from a conventional wood stove were investigated with aerosol mass spectrometry to provide links between combustion conditions, emission factors, mixing state of refractory black carbon and implications for organic tracer methods. The addition of a new batch of fuel results in low temperature pyrolysis as the fuel heats up, resulting in strong, short-lived, variable emission peaks of organic aerosol-containing markers of anhydrous sugars, such as levoglucosan (fragment at m/z 60). Flaming combustion results in emissions dominated by refractory black carbon co-emitted with minor fractions of organic aerosol and markers of anhydrous sugars. Full cycle emissions are an external mixture of larger organic aerosol-dominated and smaller thinly coated refractory black carbon particles. A very high burn rate results in increased full cycle mass emission factors of 66, 2.7, 2.8 and 1.3 for particulate polycyclic aromatic hydrocarbons, refractory black carbon, total organic aerosol and m/z 60, respectively, compared to nominal burn rate. Polycyclic aromatic hydrocarbons are primarily associated with refractory black carbon-containing particles. We hypothesize that at very high burn rates, the central parts of the combustion zone become air starved, leading to a locally reduced combustion temperature that reduces the conversion rates from polycyclic aromatic hydrocarbons to refractory black carbon. This facilitates a strong increase of polycyclic aromatic hydrocarbons emissions. At nominal burn rates, full cycle emissions based on m/z 60 correlate well with organic aerosol, refractory black carbon and particulate matter. However, at higher burn rates, m/z 60 does not correlate with increased emissions of polycyclic aromatic hydrocarbons, refractory black carbon and organic aerosol in the flaming phase. The new knowledge can be used to advance source apportionment studies, reduce emissions of genotoxic compounds and model the climate impacts of refractory black carbon, such as absorption enhancement by lensing.

Personal monitors based on unipolar diffusion charging (miniDiSC/DiSCmini, NanoTracer, Partector) can be used to assess the individual exposure to nanoparticles in different environments. The charge acquired by the aerosol particles is nearly proportional to the particle diameter and, by coincidence, also nearly proportional to the alveolar lung-deposited surface area (LDSA), the metric reported by all three instruments. In addition, the miniDiSC/DiSCmini and the NanoTracer report particle number concentration and mean particle size. In view of their use for personal exposure studies, the comparability of these personal monitors was assessed in two measurement campaigns. Altogether 29 different polydisperse test aerosols were generated during the two campaigns, covering a large range of particle sizes, morphologies and concentrations. The data provided by the personal monitors were compared with those obtained from reference instruments: a scanning mobility particle sizer (SMPS) for
LDSA and mean particle size and a ultrafine particle counter (UCPC) for number concentration. The results indicated that the LDSA concentrations and the mean particle sizes provided by all investigated instruments in this study were in the order of ±30% of the reference value obtained from the SMPS when the particle sizes of the test aerosols generatedwerewithin 20–400 nm and the instruments were properly calibrated. Particle size, morphology and concentration did not have a major effect within the aforementioned limits. The comparability of the number concentrations was found to be slightly worse and in the range of ±50% of the reference value obtained from the UCPC. In addition, a minor effect of the particle morphology on the number concentration measurements was observed. The presence of particles >400nm can drastically bias the measurement results of all instruments and all metrics determined.

Levels of neurotoxic methylmercury (MeHg) in phytoplankton are strongly associated to water MeHg concentrations. Because uptake by phytoplankton is the first and largest step of bioaccumulation in aquatic food webs many studies have investigated factors controlling seasonal changes in water MeHg concentrations. However organic matter (OM), widely accepted as an important driver of MeHg production and uptake by phytoplankton, is known for strong interannual variability in concentrations and composition within systems. In this study, we explore the role of OM on spatial and interannual variability of MeHg in a subarctic coastal sea, the northern Baltic Sea. Using MeHg (2014: 80±25 fM; 2015: <LOD fM; 2016: 21±9 fM) and OM measurements during late summer/early fall, we find that dissolved organic carbon (DOC) and humic matter content explain 60% of MeHg variability. We find that while labile DOC increases MeHg levels in the water, humic content reduces it. We propose that the positive association between MeHg and labile DOC shows that labile DOC is a proxy for OM remineralization rate in nearshore and offshore waters. This is consistent with other studies finding that in situ MeHg production in the water column occurs during OM remineralization. The negative association between water humic content and MeHg concentration is most likely due to humic matter decreasing inorganic mercury (HgII) bioavailability to methylating microbes. With these relationships, we develop a statistical model and use it to calculate MeHg concentrations in late summer nearshore and offshore waters between 2006 and 2016 using measured values for water DOC and humic matter content. We find that MeHg concentrations can vary by up to an order of magnitude between years, highlighting the importance of considering interannual variability in water column MeHg concentrations when interpreting both short and long term MeHg trends in biota.