An annual assessment of air quality with the CALIOPE modeling system over Spain

The CALIOPE project, funded by the Spanish Ministry of the Environment, aims at establishing an air quality forecasting system for Spain. With this goal, CALIOPE modeling system was developed and applied with high resolution (4 km × 4 km, 1 h) using the HERMES emission model (including emissions of resuspended particles from paved roads) specifically built up for Spain. The present study provides an evaluation and the assessment of the modeling system, coupling WRF-ARW/HERMES/CMAQ/BSC-DREAM8b for a full-year simulation in 2004 over Spain. The evaluation focuses on the capability of the model to reproduce the temporal and spatial distribution of gas phase species (NO2, O3, and SO2) and particulate matter (PM10) against ground-based measurements from the Spanish air quality monitoring network. The evaluation of the modeling results on an hourly basis shows a strong dependency of the performance of the model on the type of environment (urban, suburban and rural) and the dominant emission sources (traffic, industrial, and background). The O3 chemistry is best represented in summer, when mean hourly variability and high peaks are generally well reproduced. The mean normalized error and bias meet the recommendations proposed by the United States Environmental Protection Agency (US-EPA) and the European regulations. Modeled O3 shows higher performance for urban than for rural stations, especially at traffic stations in large cities, since stations influenced by traffic emissions (i.e., high-NOx environments) are better characterized with a more pronounced daily variability. NOx/O3 chemistry is better represented under non-limited-NO2 regimes. SO2 is mainly produced from isolated point sources (power generation and transformation industries) which generate large plumes of high SO2 concentration affecting the air quality on a local to national scale where the meteorological pattern is crucial. The contribution of mineral dust from the Sahara desert through the BSC-DREAM8b model helps to satisfactorily reproduce episodic high PM10 concentration peaks at background stations. The model assessment indicates that one of the main air quality-related problems in Spain is the high level of O3. A quarter of the Iberian Peninsula shows more than 30 days exceeding the value 120 μg m−3 for the maximum 8-h O3 concentration as a consequence of the transport of O3 precursors downwind to/from the Madrid and Barcelona metropolitan areas, and industrial areas and cities in the Mediterranean coast

Assessment of Kalman filter bias-adjustment technique to improve the simulation of ground-level ozone over Spain

The CALIOPE air quality modelling system has been used to diagnose ground level O3 concentration for the year 2004, over the Iberian Peninsula. We investigate the improvement in the simulation of daily O3 maximum by the use of a post-processing such as the Kalman filter bias-adjustment technique. The Kalman filter bias-adjustment technique is a recursive algorithm to optimally estimate bias-adjustment terms from previous measurements and model results. The bias-adjustment technique improved the simulation of daily O3 maximum for the entire year and the all the stations considered over the whole domain. The corrected simulation presents improvements in statistical indicators such as correlation, root mean square error, mean bias, and gross error. After the post-processing the exceedances of O3 concentration limits, as established by the European Directive 2008/50/CE, are better reproduced and the uncertainty of the modelling system, as established by the European Directive 2008/50/CE, is reduced from 20% to 7.5%. Such uncertainty in the model results is under the established EU limit of the 50%. Significant improvements in the O3 timing and amplitude of the daily cycle are also observed after the post-processing. The systematic improvements in the O3 maximum simulations suggest that the Kalman filter post-processing method is a suitable technique to reproduce accurate estimate of ground-level O3 concentration. With this study we evince that the adjusted O3 concentrations obtained after the post-process of the results from the CALIOPE system are a reliable means for real near time O3 forecasts

On the determination of a cloud condensation nuclei from satellite : Challenges and possibilities

We use aerosol size distributions measured in the size range from 0.01 to 10+ μm during Transport and Chemical Evolution over the Pacific (TRACE-P) and Aerosol Characterization Experiment-Asia (ACE-Asia), results of chemical analysis, measured/modeled humidity growth, and stratification by air mass types to explore correlations between aerosol optical parameters and aerosol number concentration. Size distributions allow us to integrate aerosol number over any size range expected to be effective cloud condensation nuclei (CCN) and to provide definition of a proxy for CCN (CCNproxy). Because of the internally mixed nature of most accumulation mode aerosol and the relationship between their measured volatility and solubility, this CCNproxy can be linked to the optical properties of these size distributions at ambient conditions. This allows examination of the relationship between CCNproxy and the aerosol spectral radiances detected by satellites. Relative increases in coarse aerosol (e.g., dust) generally add only a few particles to effective CCN but significantly increase the scattering detected by satellite and drive the Angstrom exponent (α) toward zero. This has prompted the use of a so-called aerosol index (AI) on the basis of the product of the aerosol optical depth and the nondimensional α, both of which can be inferred from satellite observations. This approach biases the AI to be closer to scattering values generated by particles in the accumulation mode that dominate particle number and is therefore dominated by sizes commonly effective as CCN. Our measurements demonstrate that AI does not generally relate well to a measured proxy for CCN unless the data are suitably stratified. Multiple layers, complex humidity profiles, dust with very low α mixed with pollution, and size distribution differences in pollution and biomass emissions appear to contribute most to method limitations. However, we demonstrate that these characteristic differences result in predictable influences on AI. These results suggest that inference of CCN from satellites will be challenging, but new satellite and model capabilities could possibly be integrated to improve this retrieval

Airborne sunphotometer, airborne in-situ, space-borne, and ground-based measurements of tropospheric aerosol in ACE-2

The North Atlantic Regional Aerosol Characterization Experiment (ACE-2) of the International Global Atmospheric Chemistry Project (IGAC) ran from 16 June to 25 July 1997. The results presented in this study are part of the "Clear-sky column closure experiment" (CLEARCOLUMN) activity, one of 6 ACE-2 activities [1]. Clear-sky column closure experiments call for characterization of aerosol layers by simultaneous measurements using different techniques that can be related using models [2]. A wide range of aerosol types was encountered throughout the ACE-2 area, including background Atlantic marine, European pollution-derived and African mineral dust. In a series of papers, we reported on ACE-2 CLEARCOLUMN results obtained by combining airborne sunphotometer and in-situ measurements taken aboard the Pelican aircraft, spaceborne NOAA/VHRR data and ground-based lidar and sunphotometer measurements [3]-[10]. Those and other CLEARCOLUMN results have been summarized in [11]. In this paper we only report on results not shown in this form in [3]-[11]

In situ aerosol-size distributions and clear-column radiative closure during ACE-2

As part of the second Aerosol Characterization Experiment (ACE-2) during June and July of 1997, aerosol-size distributions were measured on board the CIRPAS Pelican aircraft through the use of a DMA and 2 OPCs. During the campaign, the boundary-layer aerosol typically possessed characteristics representative of a background marine aerosol or a continentally influenced aerosol, while the free-tropospheric aerosol was characterized by the presence or absence of a Saharan dust layer. A range of radiative closure comparisons were made using the data obtained during vertical profiles flown on 4 missions. Of particular interest here are the comparisons made between the optical properties as determined through the use of measured aerosol-size distributions and those measured directly by an airborne 14-wavelength sunphotometer and 3 nephelometers. Variations in the relative humidity associated with each of the direct measurements required consideration of the hygroscopic properties of the aerosol for size-distribution-based calculations. Simultaneous comparison with such a wide range of directly-measured optical parameters not only offers evidence of the validity of the physicochemical description of the aerosol when closure is achieved, but also provides insight into potential sources of error when some or all of the comparisons result in disagreement. Agreement between the derived and directly-measured optical properties varied for different measurements and for different cases. Averaged over the 4 case studies, the derived extinction coefficient at 525 nm exceeded that measured by the sunphotometer by 2.5% in the clean boundary layer, but underestimated measurements by 13% during pollution events. For measurements within the free troposphere, the mean derived extinction coefficient was 3.3% and 17% less than that measured by the sunphotometer during dusty and non-dusty conditions, respectively. Likewise, averaged discrepancies between the derived and measured scattering coefficient were −9.6%, +4.7%, +17%, and −41% for measurements within the clean boundary layer, polluted boundary layer, free troposphere with a dust layer, and free troposphere without a dust layer, respectively. Each of these quantities, as well as the majority of the >100 individual comparisons from which they were averaged, were within estimated uncertainties

Direct radiative effects during intense Mediterranean desert dust outbreaks

The direct radiative effect (DRE) during 20 intense and widespread dust outbreaks, which affected the broader Mediterranean basin over the period March 2000–February 2013, has been calculated with the NMMB-MONARCH model at regional (Sahara and European continent) and short-term temporal (84 h) scales. According to model simulations, the maximum dust aerosol optical depths (AODs) range from  ∼  2.5 to  ∼  5.5 among the identified cases. At midday, dust outbreaks locally induce a NET (shortwave plus longwave) strong atmospheric warming (DREATM values up to 285 W m−2; Niger–Chad; dust AODs up to  ∼  5.5) and a strong surface cooling (DRENETSURF values down to −337 W m−2), whereas they strongly reduce the downward radiation at the ground level (DRESURF values down to −589 W m−2 over the Eastern Mediterranean, for extremely high dust AODs, 4.5–5). During night-time, reverse effects of smaller magnitude are found. At the top of the atmosphere (TOA), positive (planetary warming) DREs up to 85 W m−2 are found over highly reflective surfaces (Niger–Chad; dust AODs up to  ∼  5.5) while negative (planetary cooling) DREs down to −184 W m−2 (Eastern Mediterranean; dust AODs 4.5–5) are computed over dark surfaces at noon. Dust outbreaks significantly affect the mean regional radiation budget, with NET DREs ranging from −8.5 to 0.5 W m−2, from −31.6 to 2.1 W m−2, from −22.2 to 2.2 W m−2 and from −1.7 to 20.4 W m−2 for TOA, SURF, NETSURF and ATM, respectively. Although the shortwave DREs are larger than the longwave ones, the latter are comparable or even larger at TOA, particularly over the Sahara at midday. As a response to the strong surface day-time cooling, dust outbreaks cause a reduction in the regional sensible and latent heat fluxes by up to 45 and 4 W m−2, respectively, averaged over land areas of the simulation domain. Dust outbreaks reduce the temperature at 2 m by up to 4 K during day-time, whereas a reverse tendency of similar magnitude is found during night-time. Depending on the vertical distribution of dust loads and time, mineral particles heat (cool) the atmosphere by up to 0.9 K (0.8 K) during day-time (night-time) within atmospheric dust layers. Beneath and above the dust clouds, mineral particles cool (warm) the atmosphere by up to 1.3 K (1.2 K) at noon (night-time). On a regional mean basis, negative feedbacks on the total emitted dust (reduced by 19.5 %) and dust AOD (reduced by 6.9 %) are found when dust interacts with the radiation. Through the consideration of dust radiative effects in numerical simulations, the model positive and negative biases for the downward surface SW or LW radiation, respectively, with respect to Baseline Surface Radiation Network (BSRN) measurements, are reduced. In addition, they also reduce the model near-surface (at 2 m) nocturnal cold biases by up to 0.5 K (regional averages), as well as the model warm biases at 950 and 700 hPa, where the dust concentration is maximized, by up to 0.4 K. However, improvements are relatively small and do not happen in all episodes because other model first-order errors may dominate over the expected improvements, and the misrepresentation of the dust plumes' spatiotemporal features and optical properties may even produce a double penalty effect. The enhancement of dust forecasts via data assimilation techniques may significantly improve the results.The MDRAF project has received funding from the European Union’s Seventh Framework Programme for research, technological development and demonstration under grant agreement no. 622662. Oriol Jorba and Sara Basart acknowledge the grant CGL2013-46736 and the AXA Research Fund. Carlos Pérez García-Pando acknowledges long-term support from the AXA Research Fund, as well as the support received through the Ramón y Cajal programme (grant RYC-2015-18690) and grant CGL2017-88911-R of the Spanish Ministry of Economy and Competitiveness. The authors acknowledge support from the EU COST Action CA16202 “International Network to Encourage the Use of Monitoring and Forecasting Dust Products (InDust)”. Simulations were performed with the Marenostrum Supercomputer at the Barcelona Supercomputing Center (BSC). We would like to thank the principal investigators maintaining the BSRN sites used in the present work. The authors would like thank the Arnon Karnieli for his effort in establishing and maintaining SEDE_BOKER AERONET site.Peer ReviewedPostprint (published version

Evidence of activation of the Toll-like receptor-4 proinflammatory pathway in patients with schizophrenia

BACKGROUND: Alterations in the innate immune/inflammatory system may underlie the pathophysiology of schizophrenia, but we do not understand the mechanisms involved. The main agents of innate immunity are the Toll-like receptors (TLRs), which detect molecular patterns associated with damage and pathogens. The TLR first reported was TLR4, and it is still the most studied one. METHODS: We aimed to describe putative modifications to the TLR4 proinflammatory pathway using 2 different strategies in 2 cohorts of patients with schizophrenia and matched controls: 1) quantification of protein and mRNA expression in postmortem prefrontal cortex samples from 30 patients with schizophrenia and 30 controls, and 2) identification of single nucleotide polymorphisms associated with the risk of schizophrenia using whole blood samples from 214 patients with schizophrenia and 216 controls. RESULTS: We found evidence of alterations in the expression of the initial elements of the TLR4 signalling pathway (TLR4, Myeloid differentiation primary response gene 88 [MyD88] and nuclear factor-κ B [NF-κB]) in the PFC of patients with schizophrenia. These alterations seem to depend on the presence/absence of antipsychotic treatment at death. Moreover, a polymorphism within the MyD88 gene was significantly associated with schizophrenia risk. LIMITATIONS: The use of 2 different approaches in 2 different cohorts, the lack of a complementary neuropsychiatric group, the possible confounding effects of antipsychotic treatment and suicide are the main limitations of our study. CONCLUSION: The evidence from this dual approach suggests there is an altered innate immune response in patients with chronic schizophrenia in which the TLR4 proinflammatory pathway could be affected. Improved understanding of the stimuli and mechanisms responsible for this response could lead to improved schizophrenia treatment and better control of the side effects of current antipsychotics

Iron oxide minerals in dust-source sediments from the Bodélé Depression, Chad: Implications for radiative properties and Fe bioavailability of dust plumes from the Sahara

Atmospheric mineral dust can influence climate and biogeochemical cycles. An important component of mineral dust is ferric oxide minerals (hematite and goethite) which have been shown to influence strongly the optical properties of dust plumes and thus affect the radiative forcing of global dust. Here we report on the iron mineralogy of dust-source samples from the Bodélé Depression (Chad, north-central Africa), which is estimated to be Earth’s most prolific dust producer and may be a key contributor to the global radiative budget of the atmosphere as well as to long-range nutrient transport to the Amazon Basin. By using a combination of magnetic property measurements, Mössbauer spectroscopy, reflectance spectroscopy, chemical analysis, and scanning electron microscopy, we document the abundance and relative amounts of goethite, hematite, and magnetite in dust-source samples from the Bodélé Depression. The partition between hematite and goethite is important to know to improve models for the radiative effects of ferric oxide minerals in mineral dust aerosols. The combination of methods shows (1) the dominance of goethite over hematite in the source sediments, (2) the abundance and occurrences of their nanosize components, and (3) the ubiquity of magnetite, albeit in small amounts. Dominant goethite and subordinate hematite together compose about 2% of yellow-reddish dust-source sediments from the Bodélé Depression and contribute strongly to diminution of reflectance in bulk samples. These observations imply that dust plumes from the Bodélé Depression that are derived from goethite-dominated sediments strongly absorb solar radiation. The presence of ubiquitous magnetite (0.002-0.57 wt. %) is also noteworthy for its potentially higher solubility relative to ferric oxide and for its small sizes, including PM<0.1m. For all examined samples, the average iron apportionment is estimated at about 33% in ferric oxide minerals, 1.4 % in magnetite, and 65% in ferric silicates. Structural iron in clay minerals may account for much of the iron in the ferric silicates. We estimate that the mean ferric oxides flux exported from the Bodélé Depression is 0.9 Tg/yr with greater than 50% exported as ferric oxide nanoparticles (<0.1m). The high surface-to-volume ratios of ferric oxide nanoparticles once entrained into dust plumes may facilitate increased atmospheric chemical and physical processing and affect iron solubility and bioavailability to marine and terrestrial ecosystems

A longitudinal study of gene expression in first-episode schizophrenia; exploring relapse mechanisms by co-expression analysis in peripheral blood

Little is known about the pathophysiological mechanisms of relapse in first-episode schizophrenia, which limits the study of potential biomarkers. To explore relapse mechanisms and identify potential biomarkers for relapse prediction, we analyzed gene expression in peripheral blood in a cohort of first-episode schizophrenia patients with less than 5 years of evolution who had been evaluated over a 3-year follow-up period. A total of 91 participants of the 2EPs project formed the sample for baseline gene expression analysis. Of these, 67 provided biological samples at follow-up (36 after 3 years and 31 at relapse). Gene expression was assessed using the Clariom S Human Array. Weighted gene co-expression network analysis was applied to identify modules of co-expressed genes and to analyze their preservation after 3 years of follow-up or at relapse. Among the 25 modules identified, one module was semi-conserved at relapse (DarkTurquoise) and was enriched with risk genes for schizophrenia, showing a dysregulation of the TCF4 gene network in the module. Two modules were semi-conserved both at relapse and after 3 years of follow-up (DarkRed and DarkGrey) and were found to be biologically associated with protein modification and protein location processes. Higher expression of DarkRed genes was associated with higher risk of suffering a relapse and early appearance of relapse (p = 0.045). Our findings suggest that a dysregulation of the TCF4 network could be an important step in the biological process that leads to relapse and suggest that genes related to the ubiquitin proteosome system could be potential biomarkers of relapse. © 2021, The Author(s)