Formation of highly oxidized multifunctional compounds : autoxidation of peroxy radicals formed in the ozonolysis of alkenes - deduced from structure-product relationships

It has been postulated that secondary organic particulate matter plays a pivotal role in the early growth of newly formed particles in forest areas. The recently detected class of extremely low volatile organic compounds (ELVOC) provides the missing organic vapors and possibly contributes a significant fraction to atmospheric SOA (secondary organic aerosol). The sequential rearrangement of peroxy radicals and subsequent O-2 addition results in ELVOC which are highly oxidized multifunctional molecules (HOM). Key for efficiency of such HOM in early particle growth is that their formation is induced by one attack of the oxidant (here O-3), followed by an autoxidation process involving molecular oxygen. Similar mechanisms were recently observed and predicted by quantum mechanical calculations e.g., for isoprene. To assess the atmospheric importance and therewith the potential generality, it is crucial to understand the formation pathway of HOM. To elucidate the formation path of HOM as well as necessary and sufficient structural prerequisites of their formation we studied homologous series of cycloalkenes in comparison to two monoterpenes. We were able to directly observe highly oxidized multifunctional peroxy radicals with 8 or 10 O atoms by an Atmospheric Pressure interface High Resolution Time of Flight Mass Spectrometer (APi-TOF-MS) equipped with a NO3--chemical ionization (CI) source. In the case of O-3 acting as an oxidant, the starting peroxy radical is formed on the so-called vinylhydroperoxide path. HOM peroxy radicals and their termination reactions with other peroxy radicals, including dimerization, allowed for analyzing the observed mass spectra and narrowing down the likely formation path. As consequence, we propose that HOM are multifunctional percarboxylic acids, with carbonyl, hydroperoxy, or hydroxy groups arising from the termination steps. We figured that aldehyde groups facilitate the initial rearrangement steps. In simple molecules like cycloalkenes, autoxidation was limited to both terminal C atoms and two further C atoms in the respective alpha positions. In more complex molecules containing tertiary H atoms or small, constrained rings, even higher oxidation degrees were possible, either by simple H shift of the tertiary H atom or by initialization of complex ring-opening reactions.Peer reviewe

Collaborative Multi-Robot Search and Rescue: Planning, Coordination, Perception, and Active Vision

Search and rescue (SAR) operations can take significant advantage from supporting autonomous or teleoperated robots and multi-robot systems. These can aid in mapping and situational assessment, monitoring and surveillance, establishing communication networks, or searching for victims. This paper provides a review of multi-robot systems supporting SAR operations, with system-level considerations and focusing on the algorithmic perspectives for multi-robot coordination and perception. This is, to the best of our knowledge, the first survey paper to cover (i) heterogeneous SAR robots in different environments, (ii) active perception in multi-robot systems, while (iii) giving two complementary points of view from the multi-agent perception and control perspectives. We also discuss the most significant open research questions: shared autonomy, sim-to-real transferability of existing methods, awareness of victims' conditions, coordination and interoperability in heterogeneous multi-robot systems, and active perception. The different topics in the survey are put in the context of the different challenges and constraints that various types of robots (ground, aerial, surface, or underwater) encounter in different SAR environments (maritime, urban, wilderness, or other post-disaster scenarios). The objective of this survey is to serve as an entry point to the various aspects of multi-robot SAR systems to researchers in both the machine learning and control fields by giving a global overview of the main approaches being taken in the SAR robotics area

Muscle activity and inactivity periods during normal daily life

Recent findings suggest that not only the lack of physical activity, but also prolonged times of sedentary behaviour where major locomotor muscles are inactive, significantly increase the risk of chronic diseases. The purpose of this study was to provide details of quadriceps and hamstring muscle inactivity and activity during normal daily life of ordinary people. Eighty-four volunteers (44 females, 40 males, 44.1±17.3 years, 172.3±6.1 cm, 70.1±10.2 kg) were measured during normal daily life using shorts measuring muscle electromyographic (EMG) activity (recording time 11.3±2.0 hours). EMG was normalized to isometric MVC (EMGMVC) during knee flexion and extension, and inactivity threshold of each muscle group was defined as 90% of EMG activity during standing (2.5±1.7% of EMGMVC). During normal daily life the average EMG amplitude was 4.0±2.6% and average activity burst amplitude was 5.8±3.4% of EMGMVC (mean duration of 1.4±1.4 s) which is below the EMG level required for walking (5 km/h corresponding to EMG level of about 10% of EMGMVC). Using the proposed individual inactivity threshold, thigh muscles were inactive 67.5±11.9% of the total recording time and the longest inactivity periods lasted for 13.9±7.3 min (2.5–38.3 min). Women had more activity bursts and spent more time at intensities above 40% EMGMVC than men (p<0.05). In conclusion, during normal daily life the locomotor muscles are inactive about 7.5 hours, and only a small fraction of muscle\u27s maximal voluntary activation capacity is used averaging only 4% of the maximal recruitment of the thigh muscles. Some daily non-exercise activities such as stair climbing produce much higher muscle activity levels than brisk walking, and replacing sitting by standing can considerably increase cumulative daily muscle activity

Impacts of soil moisture on de novo monoterpene emissions from European beech, Holm oak, Scots pine, and Norway spruce

Impacts of soil moisture on de novo monoterpene (MT) emissions from Holm oak, European beech, Scots pine, and Norway spruce were studied in laboratory experiments. The volumetric water content of the soil, Θ, was used as the reference quantity to parameterize the dependency of MT emissions on soil moisture and to characterize the severity of the drought.When Θ dropped from 0.4 m3 × m−3 to ~0.2 m3 × m−3 slight increases of de novo MT emissions were observed but with further progressing drought the emissions decreased to almost zero. In most cases the increases of MT emissions observed under conditions of mild drought were explainable by increases of leaf temperature due to lowered transpirational cooling. When Θ fell below certain thresholds, MT emissions decreased simultaneously with Θ and the relationship between Θ and MT emissions was approximately linear. The thresholds of Θ (0.044–0.19 m3 × m−3) were determined, as well as other parameters required to describe the soil moisture dependence of de novo MT emissions for application in the Model of Emissions of Gases and Aerosols from Nature, MEGAN.A factorial approach was found appropriate to describe the impacts of Θ, temperature, and light. Temperature and Θ influenced the emissions largely independently from each other, and, in a similar manner, light intensity and Θ acted independently on de novo MT emissions. The use of Θ as the reference quantity in a factorial approach was tenable in predicting constitutive de novo MT emissions when Θ changed on a time scale of days. Empirical parameterization with Θ as a reference was only unsuccessful when soil moisture changed rapidl

Effects of NOx and SO2 on the Secondary Organic Aerosol Formation from Photooxidation of α-pinene and Limonene

Anthropogenic emissions such as NOx and SO2 influence the biogenic secondary organic aerosol (SOA) formation, but detailed mechanisms and effects are still elusive. We studied the effects of NOx and SO2 on the SOA formation from the photooxidation of α-pinene and limonene at ambient relevant NOx and SO2 concentrations (NOx: < 1to 20 ppb, SO2: < 0.05 to 15 ppb). In these experiments, monoterpene oxidation was dominated by OH oxidation. We found that SO2 induced nucleation and enhanced SOA mass formation. NOx strongly suppressed not only new particle formation but also SOA mass yield. However, in the presence of SO2 which induced a high number concentration of particles after oxidation to H2SO4, the suppression of the mass yield of SOA by NOx was completely or partly compensated for. This indicates that the suppression of SOA yield by NOx was largely due to the suppressed new particle formation, leading to a lack of particle surface for the organics to condense on and thus a significant influence of vapor wall loss on SOA mass yield. By compensating for the suppressing effect on nucleation of NOx, SO2 also compensated for the suppressing effect on SOA yield. Aerosol mass spectrometer data show that increasing NOx enhanced nitrate formation. The majority of the nitrate was organic nitrate (57–77 %), even in low-NOx conditions (<  ∼  1 ppb). Organic nitrate contributed 7–26 % of total organics assuming a molecular weight of 200 g mol−1. SOA from α-pinene photooxidation at high NOx had a generally lower hydrogen to carbon ratio (H ∕ C), compared to low NOx. The NOx dependence of the chemical composition can be attributed to the NOx dependence of the branching ratio of the RO2 loss reactions, leading to a lower fraction of organic hydroperoxides and higher fractions of organic nitrates at high NOx. While NOx suppressed new particle formation and SOA mass formation, SO2 can compensate for such effects, and the combining effect of SO2 and NOx may have an important influence on SOA formation affected by interactions of biogenic volatile organic compounds (VOCs) with anthropogenic emissions.published versionpeerReviewe

Effects of NO_<i>x</i> and SO₂ on the secondary organic aerosol formation from photooxidation of <i>α</i>-pinene and limonene

Anthropogenic emissions such as NOx and SO2 influence the biogenic secondary organic aerosol (SOA) formation, but detailed mechanisms and effects are still elusive. We studied the effects of NOx and SO2 on the SOA formation from the photooxidation of α-pinene and limonene at ambient relevant NOx and SO2 concentrations (NOx: &lt; 1to 20 ppb, SO2: &lt; 0.05 to 15 ppb). In these experiments, monoterpene oxidation was dominated by OH oxidation. We found that SO2 induced nucleation and enhanced SOA mass formation. NOx strongly suppressed not only new particle formation but also SOA mass yield. However, in the presence of SO2 which induced a high number concentration of particles after oxidation to H2SO4, the suppression of the mass yield of SOA by NOx was completely or partly compensated for. This indicates that the suppression of SOA yield by NOx was largely due to the suppressed new particle formation, leading to a lack of particle surface for the organics to condense on and thus a significant influence of vapor wall loss on SOA mass yield. By compensating for the suppressing effect on nucleation of NOx, SO2 also compensated for the suppressing effect on SOA yield. Aerosol mass spectrometer data show that increasing NOx enhanced nitrate formation. The majority of the nitrate was organic nitrate (57–77 %), even in low-NOx conditions (&lt;  ∼  1 ppb). Organic nitrate contributed 7–26 % of total organics assuming a molecular weight of 200 g mol−1. SOA from α-pinene photooxidation at high NOx had a generally lower hydrogen to carbon ratio (H ∕ C), compared to low NOx. The NOx dependence of the chemical composition can be attributed to the NOx dependence of the branching ratio of the RO2 loss reactions, leading to a lower fraction of organic hydroperoxides and higher fractions of organic nitrates at high NOx. While NOx suppressed new particle formation and SOA mass formation, SO2 can compensate for such effects, and the combining effect of SO2 and NOx may have an important influence on SOA formation affected by interactions of biogenic volatile organic compounds (VOCs) with anthropogenic emissions

Impact of NOx and OH on secondary organic aerosol formation from β-pinene photooxidation

In this study, the NOx dependence of secondary organic aerosol (SOA) formation from photooxidation of the biogenic volatile organic compound (BVOC) β-pinene was comprehensively investigated in the Jülich Plant Atmosphere Chamber. Consistent with the results of previous NOx studies we found increases of SOA yields with increasing [NOx] at low-NOx conditions ([NOx]0    10 ppbC ppb−1). Furthermore, increasing [NOx] at high-NOx conditions ([NOx]0  >  30 ppb, [BVOC]0 ∕ [NOx]0  ∼  10 to  ∼  2.6 ppbC ppb−1) suppressed the SOA yield. The increase of SOA yield at low-NOx conditions was attributed to an increase of OH concentration, most probably by OH recycling in NO + HO2  →  NO2 + OH reaction. Separate measurements without NOx addition but with different OH primary production rates confirmed the OH dependence of SOA yields. After removing the effect of OH concentration on SOA mass growth by keeping the OH concentration constant, SOA yields only decreased with increasing [NOx]. Measuring the NOx dependence of SOA yields at lower [NO] ∕ [NO2] ratio showed less pronounced increase in both OH concentration and SOA yield. This result was consistent with our assumption of OH recycling by NO and to SOA yields being dependent on OH concentrations. Our results furthermore indicated that NOx dependencies vary for different NOx compositions. A substantial fraction of the NOx-induced decrease of SOA yields at high-NOx conditions was caused by NOx-induced suppression of new particle formation (NPF), which subsequently limits the particle surface where low volatiles condense. This was shown by probing the NOx dependence of SOA formation in the presence of seed particles. After eliminating the effect of NOx-induced suppression of NPF and NOx-induced changes of OH concentrations, the remaining effect of NOx on the SOA yield from β-pinene photooxidation was moderate. Compared to β-pinene, the SOA formation from α-pinene photooxidation was only suppressed by increasing NOx. However, basic mechanisms of the NOx impacts were the same as that of β-pinene