A Boltzmann model for rod alignment and schooling fish

We consider a Boltzmann model introduced by Bertin, Droz and Greegoire as a binary interaction model of the Vicsek alignment interaction. This model considers particles lying on the circle. Pairs of particles interact by trying to reach their mid-point (on the circle) up to some noise. We study the equilibria of this Boltzmann model and we rigorously show the existence of a pitchfork bifurcation when a parameter measuring the inverse of the noise intensity crosses a critical threshold. The analysis is carried over rigorously when there are only finitely many non-zero Fourier modes of the noise distribution. In this case, we can show that the critical exponent of the bifurcation is exactly 1/2. In the case of an infinite number of non-zero Fourier modes, a similar behavior can be formally obtained thanks to a method relying on integer partitions first proposed by Ben-Naim and Krapivsky.Comment: 22 pages, 3 figure

Nitrogen oxides and PAN in plumes from boreal fires during ARCTAS-B and their impact on ozone: an integrated analysis of aircraft and satellite observations

We determine enhancement ratios for NO_x, PAN, and other NO_y species from boreal biomass burning using aircraft data obtained during the ARCTAS-B campaign and examine the impact of these emissions on tropospheric ozone in the Arctic. We find an initial emission factor for NO_x of 1.06 g NO per kg dry matter (DM) burned, much lower than previous observations of boreal plumes, and also one third the value recommended for extratropical fires. Our analysis provides the first observational confirmation of rapid PAN formation in a boreal smoke plume, with 40% of the initial NO_x emissions being converted to PAN in the first few hours after emission. We find little clear evidence for ozone formation in the boreal smoke plumes during ARCTAS-B in either aircraft or satellite observations, or in model simulations. Only a third of the smoke plumes observed by the NASA DC8 showed a correlation between ozone and CO, and ozone was depleted in the plumes as often as it was enhanced. Special observations from the Tropospheric Emission Spectrometer (TES) also show little evidence for enhanced ozone in boreal smoke plumes between 15 June and 15 July 2008. Of the 22 plumes observed by TES, only 4 showed ozone increasing within the smoke plumes, and even in those cases it was unclear that the increase was caused by fire emissions. Using the GEOS-Chem atmospheric chemistry model, we show that boreal fires during ARCTAS-B had little impact on the median ozone profile measured over Canada, and had little impact on ozone within the smoke plumes observed by TES

Near-IR photodissociation of peroxy acetyl nitrate

Measurements of the C-H overtone transition strengths combined with estimates of the photodissociation cross sections for these transitions suggest that near-IR photodissociation of peroxy acetyl nitrate (PAN) is less significant (Jnear−IR ~3×10^−8 s^−1 at noon) in the lower atmosphere than competing sinks resulting from unimolecular decomposition and ultraviolet photolysis. This is in contrast to the photochemical behavior of a related peroxy nitrate, pernitric acid (PNA), that undergoes rapid near-IR photolysis in the atmosphere with Jnear−IR ~10^−5 s^−1 at noon (Roehl et al., 2002). This difference is attributed to the larger binding energy and larger number of vibrational degrees of 10 freedom in PAN, which make 4[Greek nu]CH the lowest overtone excitation with a high photodissociation yield (as opposed to 2[Greek nu]OH in PNA)

New Methods for Measurements of Photosynthesis from Space

Our ability to close the Earth's carbon budget and predict feedbacks in a warming climate depends critically on knowing where, when, and how carbon dioxide (CO2) is exchanged between the land and atmosphere. In particular, determining the rate of carbon fixation by the Earth's biosphere (commonly referred to as gross primary productivity, or GPP) and the dependence of this productivity on climate is a central goal. Historically, GPP has been inferred from spectral imagery of the land and ocean. Assessment of GPP from the color of the land and ocean requires, however, additional knowledge of the types of plants in the scene, their regulatory mechanisms, and climate variables such as soil moisture—just the independent variables of interest! Sunlight absorbed by chlorophyll in photosynthetic organisms is mostly used to drive photosynthesis, but some can also be dissipated as heat or re‐radiated at longer wavelengths (660–800 nm). This near‐infrared light re‐emitted from illuminated plants is termed solarinduced fluorescence (SIF), and it has been found to strongly correlate with GPP. To advance our understanding of SIF and its relation to GPP and environmental stress at the planetary scale, the Keck Institute for Space Studies (KISS) convened a workshop—held in Pasadena, California, in August 2012—to focus on a newly developed capacity to monitor chlorophyll fluorescence from terrestrial vegetation by satellite. This revolutionary approach for retrieving global observations of SIF promises to provide direct and spatially resolved information on GPP, an ideal bottom‐up complement to the atmospheric net CO2 exchange inversions. Workshop participants leveraged our efforts on previous studies and workshops related to the European Space Agency’s FLuorescence EXplorer (FLEX) mission concept, which had already targeted SIF for a possible satellite mission and had developed a vibrant research community with many important publications. These studies, mostly focused on landscape, canopy, and leaf‐level interpretation, provided the ground‐work for the workshop, which focused on the global carbon cycle and synergies with atmospheric net flux inversions. Workshop participants included key members of several communities: plant physiologists with experience using active fluorescence methods to quantify photosynthesis; ecologists and radiative transfer experts who are studying the challenge of scaling from the leaf to regional scales; atmospheric scientists with experience retrieving photometric information from space‐borne spectrometers; and carbon cycle experts who are integrating new observations into models that describe the exchange of carbon between the atmosphere, land and ocean. Together, the participants examined the link between “passive” fluorescence observed from orbiting spacecraft and the underlying photochemistry, plant physiology and biogeochemistry of the land and ocean. This report details the opportunity for forging a deep connection between scientists doing basic research in photosynthetic mechanisms and the more applied community doing research on the Earth System. Too often these connections have gotten lost in empiricism associated with the coarse scale of global models. Chlorophyll fluorescence has been a major tool for basic research in photosynthesis for nearly a century. SIF observations from space, although sensing a large footprint, probe molecular events occurring in the leaves below. This offers an opportunity for direct mechanistic insight that is unparalleled for studies of biology in the Earth System. A major focus of the workshop was to review the basic mechanisms that underlie this phenomenon, and to explore modeling tools that have been developed to link the biophysical and biochemical knowledge of photosynthesis with the observable—in this case, the radiance of SIF—seen by the satellite. Discussions led to the identification of areas where knowledge is still lacking. For example, the inability to do controlled illumination observations from space limits the ability to fully constrain the variables that link fluorescence and photosynthesis. Another focus of the workshop explored a “top‐down” view of the SIF signal from space. Early studies clearly identified a strong correlation between the strength of this signal and our best estimate of the rate of photosynthesis (GPP) over the globe. New studies show that this observation provides improvements over conventional reflectance‐based remote sensing in detecting seasonal and environmental (particularly drought related) modulation of photosynthesis. Apparently SIF responds much more quickly and with greater dynamic range than typical greenness indices when GPP is perturbed. However, discussions at the workshop also identified areas where top‐down analysis seemed to be “out in front” of mechanistic studies. For example, changes in SIF based on changes in canopy light interception and the light use efficiency of the canopy, both of which occur in response to drought, are assumed equivalent in the top‐down analysis, but the mechanistic justification for this is still lacking from the bottom‐up side. Workshop participants considered implications of these mechanistic and empirical insights for large‐scale models of the carbon cycle and biogeochemistry, and also made progress toward incorporating SIF as a simulated output in land surface models used in global and regional‐scale analysis of the carbon cycle. Comparison of remotely sensed SIF with modelsimulated SIF may open new possibilities for model evaluation and data assimilation, perhaps leading to better modeling tools for analysis of the other retrieval from GOSAT satellite, atmospheric CO2 concentration. Participants also identified another application for SIF: a linkage to the physical climate system arising from the ability to better identify regional development of plant water stress. Decreases in transpiration over large areas of a continent are implicated in the development and “locking‐in” of drought conditions. These discussions also identified areas where current land surface models need to be improved in order to enable this research. Specifically, the radiation transport treatments need dramatic overhauls to correctly simulate SIF. Finally, workshop participants explored approaches for retrieval of SIF from satellite and ground‐based sensors. The difficulty of resolving SIF from the overwhelming flux of reflected sunlight in the spectral region where fluorescence occurs was once a major impediment to making this measurement. Placement of very high spectral resolution spectrometers on GOSAT (and other greenhouse gas–sensing satellites) has enabled retrievals based on infilling of solar Fraunhofer lines, enabling accurate fluorescence measurements even in the presence of moderately thick clouds. Perhaps the most interesting challenge here is that there is no readily portable ground‐based instrumentation that even approaches the capability of GOSAT and other planned greenhouse gas satellites. This strongly limits scientists’ ability to conduct ground‐based studies to characterize the footprint of the GOSAT measurement and to conduct studies of radiation transport needed to interpret SIF measurement. The workshop results represent a snapshot of the state of knowledge in this area. New research activities have sprung from the deliberations during the workshop, with publications to follow. The introduction of this new measurement technology to a wide slice of the community of Earth System Scientists will help them understand how this new technology could help solve problems in their research, address concerns about the interpretation, identify future research needs, and elicit support of the wider community for research needed to support this observation. Somewhat analogous to the original discovery that vegetation indices could be derived from satellite measurements originally intended to detect clouds, the GOSAT observations are a rare case in which a (fortuitous) global satellite dataset becomes available before the research community had a consolidated understanding on how (beyond an empirical correlation) it could be applied to understanding the underlying processes. Vegetation indices have since changed the way we see the global biosphere, and the workshop participants envision that fluorescence can perform the next indispensable step by complementing these measurements with independent estimates that are more indicative of actual (as opposed to potential) photosynthesis. Apart from the potential FLEX mission, no dedicated satellite missions are currently planned. OCO‐2 and ‐3 will provide much more data than GOSAT, but will still not allow for regional studies due to the lack of mapping capabilities. Geostationary observations may even prove most useful, as they could track fluorescence over the course of the day and clearly identify stress‐related down‐regulation of photosynthesis. Retrieval of fluorescence on the global scale should be recognized as a valuable tool; it can bring the same quantum leap in our understanding of the global carbon cycle as vegetation indices once did

Cis-cis and trans-perp HOONO: Action spectroscopy and isomerization kinetics

The weakly bound HOONO product of the OH + NO_2 + M reaction is studied using the vibrational predissociation that follows excitation of the first OH overtone (2nu1). We observe formation of both cis-cis and trans-perp conformers of HOONO. The trans-perp HOONO 2nu1 band is observed under thermal (223–238 K) conditions at 6971 cm^(–1). We assign the previously published (warmer temperature) HOONO spectrum to the 2nu1 band at 6365 cm^(–1) and 2nu1-containing combination bands of the cis-cis conformer of HOONO. The band shape of the trans-perp HOONO spectrum is in excellent agreement with the predicted rotational contour based on previous experimental and theoretical results, but the apparent origin of the cis-cis HOONO spectrum at 6365 cm^(–1) is featureless and significantly broader, suggesting more rapid intramolecular vibrational redistribution or predissociation in the latter isomer. The thermally less stable trans-perp HOONO isomerizes rapidly to cis-cis HOONO with an experimentally determined lifetime of 39 ms at 233 K at 13 hPa (in a buffer gas of predominantly Ar). The temperature dependence of the trans-perp HOONO lifetime in the range 223–238 K yields an isomerization barrier of 33±12 kJ/mol. New ab initio calculations of the structure and vibrational mode frequencies of the transition state perp-perp HOONO are performed using the coupled cluster singles and doubles with perturbative triples [CCSD(T)] model, using a correlation consistent polarized triple zeta basis set (cc-pVTZ). The energetics of cis-cis, trans-perp, and perp-perp HOONO are also calculated at this level [CCSD(T)/cc-pVTZ] and with a quadruple zeta basis set using the structure determined at the triple zeta basis set [CCSD(T)/cc-pVQZ//CCSD(T)/cc-pVTZ]. These calculations predict that the anti form of perp-perp HOONO has an energy of DeltaE0 = 42.4 kJ/mol above trans-perp HOONO, corresponding to an activation enthalpy of DeltaH298[double-dagger]0 = 41.1 kJ/mol. These results are in good agreement with statistical simulations based on a model developed by Golden, Barker, and Lohr. The simulated isomerization rates match the observed decay rates when modeled with a trans-perp to cis-cis HOONO isomerization barrier of 40.8 kJ/mol and a strong collision model. The quantum yield of cis-cis HOONO dissociation to OH and NO2 is also calculated as a function of photon excitation energy in the range 3500–7500 cm^(–1), assuming D0 = 83 kJ/mol. The quantum yield is predicted to vary from 0.15 to 1 over the observed spectrum at 298 K, leading to band intensities in the action spectrum that are highly temperature dependent; however, the observed relative band strengths in the cis-cis HOONO spectrum do not change substantially with temperature over the range 193–273 K. Semiempirical calculations of the oscillator strengths for 2nu1(cis-cis HOONO) and 2nu1(trans-perp HOONO) are performed using (1) a one-dimensional anharmonic model and (2) a Morse oscillator model for the OH stretch, and ab initio dipole moment functions calculated using Becke, Lee, Yang, and Parr density functional theory (B3LYP), Møller-Plesset pertubation theory truncated at the second and third order (MP2 and MP3), and quadratic configuration interaction theory using single and double excitations (QCISD). The QCISD level calculated ratio of 2nu1 oscillator strengths of trans-perp to cis-cis HOONO is 3.7:1. The observed intensities indicate that the concentration of trans-perp HOONO early in the OH + NO2 reaction is significantly greater than predicted by a Boltzmann distribution, consistent with statistical predictions of high initial yields of trans-perp HOONO from the OH + NO_2 + M reaction. In the atmosphere, trans-perp HOONO will isomerize nearly instantaneously to cis-cis HOONO. Loss of HOONO via photodissociation in the near-IR limits the lifetime of cis-cis HOONO during daylight to less than 45 h, other loss mechanisms will reduce the lifetime further

Exploring Oxidation in the Remote Free Troposphere: Insights from Atmospheric Tomography (ATom)

Earth's atmosphere oxidizes the greenhouse gas methane and other gases, thus determining their lifetimes and oxidation products. Much of this oxidation occurs in the remote, relatively clean free troposphere above the planetary boundary layer, where the oxidation chemistry is thought to be much simpler and better understood than it is in urban regions or forests. The NASA airborne Atmospheric Tomography study (ATom) was designed to produce cross sections of the detailed atmospheric composition in the remote atmosphere over the Pacific and Atlantic Oceans during four seasons. As part of the extensive ATom data set, measurements of the atmosphere's primary oxidant, hydroxyl (OH), and hydroperoxyl (HO₂) are compared to a photochemical box model to test the oxidation chemistry. Generally, observed and modeled median OH and HO₂ agree to with combined uncertainties at the 2σ confidence level, which is ~±40%. For some seasons, this agreement is within ~±20% below 6 km altitude. While this test finds no significant differences, OH observations increasingly exceeded modeled values at altitudes above 8 km, becoming ~35% greater, which is near the combined uncertainties. Measurement uncertainty and possible unknown measurement errors complicate tests for unknown chemistry or incorrect reaction rate coefficients that would substantially affect the OH and HO₂ abundances. Future analysis of detailed comparisons may yield additional discrepancies that are masked in the median values

The hatching larva of the priapulid worm Halicryptus spinulosus

Despite their increasing evolutionary importance, basic knowledge about the priapulid worms remains limited. In particular, priapulid development has only been partially documented. Following previous description of hatching and the earliest larval stages of Priapulus caudatus, we here describe the hatching larva of Halicryptus spinulosus. Comparison of the P. caudatus and the H. spinulosus hatching larvae allows us to attempt to reconstruct the ground pattern of priapulid development. These findings may further help unravelling the phylogenetic position of the Priapulida within the Scalidophora and hence contribute to the elucidation of the nature of the ecdysozoan ancestor

Tropospheric methane retrieved from ground-based near-IR solar absorption spectra

High-resolution near-infrared solar absorption spectra recorded between 1977 and 1995 at the Kitt Peak National Solar Observatory are analyzed to retrieve column abundances of methane (CH_4), hydrogen fluoride (HF), and oxygen (O_2). Employing a stratospheric “slope equilibrium” relationship between CH_4 and HF, the varying contribution of stratospheric CH_4 to the total column is inferred. Variations in the CH_4 column due to changes in surface pressure are determined from the O_2 column abundances. By this technique, CH_4 tropospheric volume mixing ratios are determined with a precision of ∼0.5%. These display behavior similar to Mauna Loa in situ surface measurements, with a seasonal peak-to-peak amplitude of approximately 30 ppbv and a nearly linear increase between 1977 and 1983 of 18.0 ± 0.8 ppbv yr^(−1), slowing significantly after 1990

α-pinene photooxidation under controlled chemical conditions – Part 2: SOA yield and composition in low- and high-NO_x environments

The gas-phase oxidation of α-pinene produces a large amount of secondary organic aerosol (SOA) in the atmosphere. A number of carboxylic acids, organosulfates and nitrooxy organosulfates associated with α-pinene have been found in field samples and some are used as tracers of α-pinene oxidation. α-pinene reacts readily with OH and O_3 in the atmosphere followed by reactions with both HO_2 and NO. Due to the large number of potential reaction pathways, it can be difficult to determine what conditions lead to SOA. To better understand the SOA yield and chemical composition from low- and high-NO_x OH oxidation of α-pinene, studies were conducted in the Caltech atmospheric chamber under controlled chemical conditions. Experiments used low O_3 concentrations to ensure that OH was the main oxidant and low α-pinene concentrations such that the peroxy radical (RO_2) reacted primarily with either HO_2 under low-NO_x conditions or NO under high-NO_x conditions. SOA yield was suppressed under conditions of high-NO_x. SOA yield under high-NO_x conditions was greater when ammonium sulfate/sulfuric acid seed particles (highly acidic) were present prior to the onset of growth than when ammonium sulfate seed particles (mildly acidic) were present; this dependence was not observed under low-NO_x conditions. When aerosol seed particles were introduced after OH oxidation, allowing for later generation species to be exposed to fresh inorganic seed particles, a number of low-NO_x products partitioned to the highly acidic aerosol. This indicates that the effect of seed acidity and SOA yield might be under-estimated in traditional experiments where aerosol seed particles are introduced prior to oxidation. We also identify the presence of a number of carboxylic acids that are used as tracer compounds of α-pinene oxidation in the field as well as the formation of organosulfates and nitrooxy organosulfates. A number of the carboxylic acids were observed under all conditions, however, pinic and pinonic acid were only observed under low-NO_x conditions. Evidence is provided for particle-phase sulfate esterification of multi-functional alcohols

Patterns of CO2 and radiocarbon across high northern latitudes during International Polar Year 2008

High-resolution in situ CO2 measurements were conducted aboard the NASA DC-8 aircraft during the ARCTAS/POLARCAT field campaign, a component of the wider 2007-2008 International Polar Year activities. Data were recorded during large-scale surveys spanning the North American sub-Arctic to the North Pole from 0.04 to 12 km altitude in spring and summer of 2008. Influences on the observed CO2 concentrations were investigated using coincident CO, black carbon, CH3CN, HCN, O3, C2Cl4, and Δ14CO2 data, and the FLEXPART model. In spring, the CO2 spatial distribution from 55̊N to 90̊N was largely determined by the long-range transport of air masses laden with Asian anthropogenic pollution intermingled with Eurasian fire emissions evidenced by the greater variability in the mid-to-upper troposphere. At the receptor site, the enhancement ratios of CO2 to CO in pollution plumes ranged from 27 to 80 ppmv ppmv-1 with the highest anthropogenic content registered in plumes sampled poleward of 80̊N. In summer, the CO2 signal largely reflected emissions from lightning-ignited wildfires within the boreal forests of northern Saskatchewan juxtaposed with uptake by the terrestrial biosphere. Measurements within fresh fire plumes yielded CO2 to CO emission ratios of 4 to 16 ppmv ppmv-1 and a mean CO2 emission factor of 1698 ± 280 g kg-1 dry matter. From the 14C in CO2 content of 48 whole air samples, mean spring (46.6 ± 4.4%) and summer (51.5 ± 5%) D14CO2 values indicate a 5%seasonal difference. Although the northern midlatitudes were identified as the emissions source regions for the majority of the spring samples, depleted Δ14CO2 values were observed in <1% of the data set. Rather, ARCTAS Δ14CO2 observations (54%) revealed predominately a pattern of positive disequilibrium (1-7%) with respect to background regardless of season owing to both heterotrophic respiration and fire-induced combustion of biomass. Anomalously enriched Δ14CO2 values (101-262%) measured in emissions from Lake Athabasca and Eurasian fires speak to biomass burning as an increasingly important contributor to the mass excess in Δ14CO2 observations in a warming Arctic, representing an additional source of uncertainty in the quantification of fossil fuel CO2