Measurements of hydroxyl (OH) and hydroperoxy (HO2*) radical concentrations were made at the Pasadena ground site during the CalNex‐LA 2010 campaign using the laser‐induced fluorescence‐fluorescence ...assay by gas expansion technique. The measured concentrations of OH and HO2* exhibited a distinct weekend effect, with higher radical concentrations observed on the weekends corresponding to lower levels of nitrogen oxides (NOx). The radical measurements were compared to results from a zero‐dimensional model using the Regional Atmospheric Chemical Mechanism‐2 constrained by NOx and other measured trace gases. The chemical model overpredicted measured OH concentrations during the weekends by a factor of approximately 1.4 ± 0.3 (1σ), but the agreement was better during the weekdays (ratio of 1.0 ± 0.2). Model predicted HO2* concentrations underpredicted by a factor of 1.3 ± 0.2 on the weekends, while measured weekday concentrations were underpredicted by a factor of 3.0 ± 0.5. However, increasing the modeled OH reactivity to match the measured total OH reactivity improved the overall agreement for both OH and HO2* on all days. A radical budget analysis suggests that photolysis of carbonyls and formaldehyde together accounted for approximately 40% of radical initiation with photolysis of nitrous acid accounting for 30% at the measurement height and ozone photolysis contributing less than 20%. An analysis of the ozone production sensitivity reveals that during the week, ozone production was limited by volatile organic compounds throughout the day during the campaign but NOx limited during the afternoon on the weekends.
Key Points
Measurements of OH and HO2 during CalNex‐LA displayed a weekend effect
Modeled OH and HO2 agreed with measurements after accounting for missing OH reactivity
Ozone production was VOC limited on the weekdays but NOx limited on the weekends
The serotonin 5-HT2C receptor (5-HT2CR) is localized to the limbic-corticostriatal circuit, which plays an integral role in mediating attention, motivation, cognition, and reward processes. The ...5-HT2CR is linked to modulation of mesoaccumbens dopamine neurotransmission via an activation of γ-aminobutyric acid (GABA) neurons in the ventral tegmental area (VTA). However, we recently demonstrated the expression of the 5-HT2CR within dopamine VTA neurons suggesting the possibility of a direct influence of the 5-HT2CR upon mesoaccumbens dopamine output. Here, we employed double-label fluorescence immunochemistry with the synthetic enzymes for dopamine (tyrosine hydroxylase; TH) and GABA (glutamic acid decarboxylase isoform 67; GAD-67) and retrograde tract tracing with FluoroGold (FG) to uncover whether dopamine and GABA VTA neurons that possess 5-HT2CR innervate the nucleus accumbens (NAc). The highest numbers of FG-labeled cells were detected in the middle versus rostral and caudal levels of the VTA, and included a subset of TH- and GAD-67 immunoreactive cells, of which >50% also contained 5-HT2CR immunoreactivity. Thus, we demonstrate for the first time that the 5-HT2CR colocalizes in DA and GABA VTA neurons which project to the NAc, describe in detail the distribution of NAc-projecting GABA VTA neurons, and identify the colocalization of TH and GAD-67 in the same NAc-projecting VTA neurons. These data suggest that the 5-HT2CR may exert direct influence upon both dopamine and GABA VTA output to the NAc. Further, the indication that a proportion of NAc-projecting VTA neurons synthesize and potentially release both dopamine and GABA adds intriguing complexity to the framework of the VTA and its postulated neuroanatomical roles.
Celotno besedilo
Dostopno za:
DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
An equilibrium between proinflammatory and anti-inflammatory immune responses is essential for maternal tolerance of the fetus throughout gestation. To study the participation of fetal tissue-derived ...factors in this delicate immune balance, we analyzed the effects of human chorionic gonadotropin (hCG) on murine Treg cells and Th17 cells
in vitro
, and on pregnancy outcomes, fetal and placental growth, blood flow velocities and remodeling of the uterine vascular bed
in vivo
. Compared with untreated CD4
+
CD25
+
T cells, hCG increased the frequency of Treg cells upon activation of the LH/CG receptor. hCG, with the involvement of IL-2, also interfered with induced differentiation of CD4
+
T cells into proinflammatory Th17 cells. In already differentiated Th17 cells, hCG induced an anti-inflammatory profile. Transfer of proinflammatory Th17 cells into healthy pregnant mice promoted fetal rejection, impaired fetal growth and resulted in insufficient remodeling of uterine spiral arteries, and abnormal flow velocities. Our works show that proinflammatory Th17 cells have a negative influence on pregnancy that can be partly avoided by
in vitro
re-programming of proinflammatory Th17 cells with hCG.
Nitrous Acid (HONO) plays an important role in tropospheric chemistry as a precursor of the hydroxyl radical (OH), the most important oxidizing agent in the atmosphere. Nevertheless, the formation ...mechanisms of HONO are still not completely understood. Recent field observations found unexpectedly high daytime HONO concentrations in both urban and rural areas, which point to unrecognized, most likely photolytically enhanced HONO sources. Several gas-phase, aerosol, and ground surface chemistry mechanisms have been proposed to explain elevated daytime HONO, but atmospheric evidence to favor one over the others is still weak. New information on whether HONO formation occurs in the gas-phase, on aerosol, or at the ground may be derived from observations of the vertical distribution of HONO and its precursor nitrogen dioxide, NO2, as well as from its dependence on solar irradiance or actinic flux. Here we present field observations of HONO, NO2 and other trace gases in three altitude intervals (30–70 m, 70–130 m and 130–300 m) using UCLA's long path DOAS instrument, as well as in situ measurements of OH, NO, photolysis frequencies and solar irradiance, made in Houston, TX, during the Study of Houston Atmospheric Radical Precursor (SHARP) experiment from 20 April to 30 May 2009. The observed HONO mixing ratios were often ten times larger than the expected photostationary state with OH and NO. Larger HONO mixing ratios observed near the ground than aloft imply, but do not clearly prove, that the daytime source of HONO was located at or near the ground. Using a pseudo steady-state (PSS) approach, we calculated the missing daytime HONO formation rates, Punknown, on four sunny days. The NO2-normalized Punknown, Pnorm, showed a clear symmetrical diurnal variation with a maximum around noontime, which was well correlated with actinic flux (NO2 photolysis frequency) and solar irradiance. This behavior, which was found on all clear days in Houston, is a strong indication of a photolytic HONO source. HONO/NO2 ratios also showed a clear diurnal profile, with maxima of 2–3% around noon. PSS calculations show that this behavior cannot be explained by the proposed gas-phase reaction of photoexcited NO2 (NO2*) or any other gas-phase or aerosol photolytic process occurring at similar or longer wavelengths than that of HONO photolysis. HONO formation by aerosol nitrate photolysis in the UV also seems to be unlikely. Pnorm correlated better with solar irradiance (average R2 = 0.85/0.87 for visible/UV) than with actinic flux (R2 = 0.76) on the four sunny days, clearly pointing to HONO being formed at the ground rather than on the aerosol or in the gas-phase. In addition, the observed HONO/NO2 diurnal variation can be explained if the formation of HONO depends on solar irradiance, but not if it depends on the actinic flux. The vertical mixing ratio profiles, together with the stronger correlation with solar irradiance, support the idea that photolytically enhanced NO2 to HONO conversion on the ground was the dominant source of HONO in Houston.
Nitrous acid (HONO) acts as a major precursor of the hydroxyl radical (OH) in the urban atmospheric boundary layer in the morning and throughout the day. Despite its importance, HONO formation ...mechanisms are not yet completely understood. It is generally accepted that conversion of NO sub(2) on surfaces in the presence of water is responsible for the formation of HONO in the nocturnal boundary layer, although the type of surface on which the mechanism occurs is still under debate. Recent observations of higher than expected daytime HONO concentrations in both urban and rural areas indicate the presence of unknown daytime HONO source(s). Various formation pathways in the gas phase, and on aerosol and ground surfaces have been proposed to explain the presence of daytime HONO. However, it is unclear which mechanism dominates and, in the cases of heterogeneous mechanisms, on which surfaces they occur. Vertical concentration profiles of HONO and its precursors can help in identifying the dominant HONO formation pathways. In this study, daytime HONO and NO sub(2) vertical profiles, measured in three different height intervals (20-70, 70-130, and 130-300 m) in Houston, TX, during the 2009 Study of Houston Atmospheric Radical Precursors (SHARP) are analyzed using a one-dimensional (1-D) chemistry and transport model. Model results with various HONO formation pathways suggested in the literature are compared to the the daytime HONO and HONO/NO sub(2) ratios observed during SHARP. The best agreement of HONO and HONO/NO sub(2) ratios between model and observations is achieved by including both a photolytic source of HONO at the ground and on the aerosol. Model sensitivity studies show that the observed diurnal variations of the HONO/NO sub(2) ratio are not reproduced by the model if there is only a photolytic HONO source on aerosol or in the gas phase from NO sub(2) super(*) + H sub(2)O. Further analysis of the formation and loss pathways of HONO shows a vertical dependence of HONO chemistry during the day. Photolytic HONO formation at the ground is the major formation pathway in the lowest 20 m, while a combination of gas-phase, photolytic formation on aerosol, and vertical transport is responsible for daytime HONO between 200-300 m a.g.l. HONO removal is dominated by vertical transport below 20 m and photolysis between 200-300 m a.g.l.
The role of chlorine atoms (Cl) in atmospheric oxidation has been traditionally thought to be limited to the marine boundary layer, where they are produced through heterogeneous reactions involving ...sea salt. However, recent observation of photolytic Cl precursors (ClNO2 and Cl2) formed from anthropogenic pollution has expanded the potential importance of Cl to include coastal and continental urban areas. Measurements of ClNO2 in Los Angeles during CalNex (California Nexus – Research at the Nexus of Air Quality and Climate Change) showed it to be an important primary (first generation) radical source. Evolution of ratios of volatile organic compounds (VOCs) has been proposed as a method to quantify Cl oxidation, but we find no evidence from this approach for a significant role of Cl oxidation in Los Angeles. We use a box model with the Master Chemical Mechanism (MCM v3.2) chemistry scheme, constrained by observations in Los Angeles, to examine the Cl sensitivity of commonly used VOC ratios as a function of NOx and secondary radical production. Model results indicate VOC tracer ratios could not detect the influence of Cl unless the ratio of OH to Cl was less than 200 for at least a day. However, the model results also show that secondary (second generation) OH production resulting from Cl oxidation of VOCs is strongly influenced by NOx, and that this effect obscures the importance of Cl as a primary oxidant. Calculated concentrations of Cl showed a maximum in mid-morning due to a photolytic source from ClNO2 and loss primarily to reactions with VOCs. The OH to Cl ratio was below 200 for approximately 3 h in the morning, but Cl oxidation was not evident from the measured ratios of VOCs. Instead, model simulations show that secondary OH production causes VOC ratio evolution to follow that expected for OH oxidation, despite the significant input of primary Cl from ClNO2 photolysis in the morning. Even though OH is by far the dominant oxidant in Los Angeles, Cl atoms do play an important role in photochemistry there, constituting 9% of the primary radical source. Furthermore, Cl–VOC reactivity differs from that of OH, being more than an order of magnitude larger and dominated by VOCs, such as alkanes, that are less reactive toward OH. Primary Cl is also slightly more effective as a radical source than primary OH due to its greater propensity to initiate radical propagation chains via VOC reactions relative to chain termination via reaction with nitrogen oxides.
We collected mercury observations as part of the Nitrogen, Oxidants, Mercury, and Aerosol Distributions, Sources, and Sinks (NOMADSS) aircraft campaign over the southeastern US between 1 June and ...15 July 2013. We use the GEOS-Chem chemical transport model to interpret these observations and place new constraints on bromine radical initiated mercury oxidation chemistry in the free troposphere. We find that the model reproduces the observed mean concentration of total atmospheric mercury (THg) (observations: 1.49 ± 0.16 ng m−3, model: 1.51 ± 0.08 ng m−3), as well as the vertical profile of THg. The majority (65 %) of observations of oxidized mercury (Hg(II)) were below the instrument's detection limit (detection limit per flight: 58–228 pg m−3), consistent with model-calculated Hg(II) concentrations of 0–196 pg m−3. However, for observations above the detection limit we find that modeled Hg(II) concentrations are a factor of 3 too low (observations: 212 ± 112 pg m−3, model: 67 ± 44 pg m−3). The highest Hg(II) concentrations, 300–680 pg m−3, were observed in dry (RH < 35 %) and clean air masses during two flights over Texas at 5–7 km altitude and off the North Carolina coast at 1–3 km. The GEOS-Chem model, back trajectories and observed chemical tracers for these air masses indicate subsidence and transport from the upper and middle troposphere of the subtropical anticyclones, where fast oxidation of elemental mercury (Hg(0)) to Hg(II) and lack of Hg(II) removal lead to efficient accumulation of Hg(II). We hypothesize that the most likely explanation for the model bias is a systematic underestimate of the Hg(0) + Br reaction rate. We find that sensitivity simulations with tripled bromine radical concentrations or a faster oxidation rate constant for Hg(0) + Br, result in 1.5–2 times higher modeled Hg(II) concentrations and improved agreement with the observations. The modeled tropospheric lifetime of Hg(0) against oxidation to Hg(II) decreases from 5 months in the base simulation to 2.8–1.2 months in our sensitivity simulations. In order to maintain the modeled global burden of THg, we need to increase the in-cloud reduction of Hg(II), thus leading to faster chemical cycling between Hg(0) and Hg(II). Observations and model results for the NOMADSS campaign suggest that the subtropical anticyclones are significant global sources of Hg(II).
Sun-lit snow is increasingly recognized as a chemical reactor that plays an active role in uptake, transformation, and release of atmospheric trace gases. Snow is known to influence boundary layer ...air on a local scale, and given the large global surface coverage of snow may also be significant on regional and global scales. We present a new detailed one-dimensional snow chemistry module that has been coupled to the 1-D atmospheric boundary layer model MISTRA. The new 1-D snow module, which is dynamically coupled to the overlaying atmospheric model, includes heat transport in the snowpack, molecular diffusion, and wind pumping of gases in the interstitial air. The model includes gas phase chemical reactions both in the interstitial air and the atmosphere. Heterogeneous and multiphase chemistry on atmospheric aerosol is considered explicitly. The chemical interaction of interstitial air with snow grains is simulated assuming chemistry in a liquid-like layer (LLL) on the grain surface. The coupled model, referred to as MISTRA-SNOW, was used to investigate snow as the source of nitrogen oxides (NOx) and gas phase reactive bromine in the atmospheric boundary layer in the remote snow covered Arctic (over the Greenland ice sheet) as well as to investigate the link between halogen cycling and ozone depletion that has been observed in interstitial air. The model is validated using data taken 10 June–13 June, 2008 as part of the Greenland Summit Halogen-HOx experiment (GSHOX). The model predicts that reactions involving bromide and nitrate impurities in the surface snow can sustain atmospheric NO and BrO mixing ratios measured at Summit, Greenland during this period.
Highlights • Cue reactivity incubates during forced abstinence from cocaine- or sucrose-taking. • Incubation aligns with lower potency of 5-HT2C R agonist to suppress cocaine cue reactivity. • ...Incubation of cocaine cue reactivity associates with lower 5-HT2C R expression in mPFC. • Membrane to cytoplasmic 5-HT2C R ratio inversely correlates with cocaine cue reactivity.
Nitrous acid (HONO) often plays an important role in tropospheric photochemistry as a major precursor of the hydroxyl radical (OH) in early morning hours and potentially during the day. However, the ...processes leading to formation of HONO and its vertical distribution at night, which can have a considerable impact on daytime ozone formation, are currently poorly characterized by observations and models. Long-path differential optical absorption spectroscopy (LP-DOAS) measurements of HONO during the 2006 TexAQS II Radical and Aerosol Measurement Project (TRAMP), near downtown Houston, TX, show nocturnal vertical profiles of HONO, with mixing ratios of up to 2.2 ppb near the surface and below 100 ppt aloft. Three nighttime periods of HONO, NO2 and O3 observations during TRAMP were used to perform model simulations of vertical mixing ratio profiles. By adjusting vertical mixing and NOx emissions the modeled NO2 and O3 mixing ratios showed very good agreement with the observations. Using a simple conversion of NO2 to HONO on the ground, direct HONO emissions, as well as HONO loss at the ground and on aerosol, the observed HONO profiles were reproduced by the model for 1–2 and 7–8 September in the nocturnal boundary layer (NBL). The unobserved increase of HONO to NO2 ratio (HONO/NO2) with altitude that was simulated by the initial model runs was found to be due to HONO uptake being too small on aerosol and too large on the ground. Refined model runs, with adjusted HONO uptake coefficients, showed much better agreement of HONO and HONO/NO2 for two typical nights, except during morning rush hour, when other HONO formation pathways are most likely active. One of the nights analyzed showed an increase of HONO mixing ratios together with decreasing NO2 mixing ratios that the model was unable to reproduce, most likely due to the impact of weak precipitation during this night. HONO formation and removal rates averaged over the lowest 300 m of the atmosphere showed that NO2 to HONO conversion on the ground was the dominant source of HONO, followed by traffic emission. Aerosol did not play an important role in HONO formation. Although ground deposition was also a major removal pathway of HONO, net HONO production at the ground was the main source of HONO in our model studies. Sensitivity studies showed that in the stable NBL, net HONO production at the ground tends to increase with faster vertical mixing and stronger NOx emission. Vertical transport was found to be the dominant source of HONO aloft.
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