Review of ozone and temperature lidar validations performed within the framework of the Network for the Detection of Stratospheric Change

The use of assimilation tools for satellite validation requires true estimates of the accuracy of the reference data. Since its inception, the Network for Detection of Stratospheric Change (NDSC) has provided systematic lidar measurements of ozone and temperature at several places around the world that are well adapted for satellite validations. Regular exercises have been organised to ensure the data quality at each individual site. These exercises can be separated into three categories: large scale intercomparisons using multiple instruments, including a mobile lidar; using satellite observations as a geographic transfer standards to compare measurements at different sites; and comparative investigations of the analysis software. NDSC is a research network, so each system has its own history, design, and analysis, and has participated differently in validation campaigns. There are still some technological differences that may explain different accuracies. However, the comparison campaigns performed over the last decade have always proved to be very helpful in improving the measurements. To date, more efforts have been devoted to characterising ozone measurements than to temperature observations. The synthesis of the published works shows that the network can potentially be considered as homogeneous within +/-2% between 20-35 km for ozone and +/-1 K between 35-60 km for temperature. Outside this altitude range, larger biases are reported and more efforts are required. In the lower stratosphere, Raman channels seem to improve comparisons but such capabilities were not systematically compared. At the top of the profiles, more investigations on analysis methodologies are still probably needed. SAGE II and GOMOS appear to be excellent tools for future ozone lidar validations but need to be better coordinated and take more advantage of assimilation tools. Also, temperature validations face major difficulties caused by atmospheric tides and therefore require intercomparisons with the mobile systems, at all sites.     

Influence of x-ray diffraction sample preparation on quantitative mineralogy: implications for chromate waste treatment

Powders of chromite ore processing residue (COPR) were mineralogically evaluated using quantitative X-ray powder diffraction (XRPD) to illustrate the impacts of sample preparation procedures. Chromite ore processing residue is strongly alkaline, reactive, contains minerals of varying hardness and absorption coefficients, and exhibits significant amorphicity. This poses a challenge to produce powders for XRPD analysis that are sufficiently fine and of uniform particle size while avoiding mineral reactions and overgrinding effects. Dry, hand pulverization to different grain sizes, and wet, mechanical pulverization (micromilling) using four milling liquids (cyclohexane, isopropanol, ethanol, and water), and variable milling durations (up to 15 min) were evaluated. Micromilling with a light, nonpolar, highly evaporative liquid such as cyclohexane with a milling time of 5 min mitigated systematic errors such as microabsorption and preferred orientation as it produced finer and more uniform particle size distributions than the hand-pulverized powders, while simultaneously affording the least time for sample preparation. Conversely, the use of water as milling liquid resulted in extensive hydration reactions during sample preparation, causing mischaracterization and significant underestimation of its reactive brownmillerite content, which can complicate the remediation design process for COPR. Hand pulverization emerged as a necessary complement to quantify Cr(VI)-containing, softer minerals destroyed during mechanical milling, the quantification of which has also important implications for COPR treatment design. The findings of this study may be applicable in a variety of geochemically complicated and reactive environmental media (metal-contaminated soils, stabilized/solidified media, inorganic waste), and points to the importance of the sample preparation method to obtain reliable quantitative XRPD results.     

Sensitivity of shortwave radiative fluxes to the vertical distribution of aerosol single scattering albedo in the presence of a desert dust layer

The aim of this work is to quantify the sensitivity of shortwave radiative fluxes to changes in the vertical distribution of aerosol absorption, taken into account through the aerosol Single Scattering Albedo (SSA). The case study represents a real atmospheric situation with a desert dust layer (DDL) in the mid troposphere over an urban Boundary Layer (BL) observed at Rome on 20 June 2007. A moderately high aerosol optical depth (AOD), 0.292 at 550 nm, and low Ångström exponent of 0.30 were measured. The observed case was reconstructed with a radiative transfer model, in which the SSA of the boundary layer aerosols was varied from that of a highly absorbing aerosol type (urban) to a highly scattering one (clear marine). The SSA of the DDL is determined keeping fixed the measured SSA of the whole atmospheric column. The simulations show notable changes in the surface and top of the atmosphere (TOA) diffuse fluxes depending on the boundary layer aerosol properties. The aerosol radiative forcing (ARF) at the surface changes by 6–19 W m^?2, depending on the solar zenith angle, when urban or clean marine particles are included in the boundary layer. The ARF differences observed at TOA are between 1 and 5 W m^?2 when urban and clean marine aerosol types in the BL are respectively used, showing a smaller dependency on the solar zenith angle than at the surface.     

Quantification of Saharan dust contribution to PM10 concentrations over Italy during 2003–2005

Italy is frequently affected by Saharan dust intrusions, which result in high PM₁₀ concentrations in the atmosphere and can cause the exceedances of the PM₁₀ daily limits (50 μg m^?3) set by the European Union (EU/2008/50). The estimate of African dust contribution to PM₁₀ concentrations is therefore a key issue in air quality assessment and policy formulation. This study presents a first identification of Saharan dust outbreaks as well as an estimate of the African dust contribution to PM₁₀ concentrations during the period 2003–2005 over Italy. The identification of dust events has been carried out by looking at different sources of information such as monitoring network observations, satellite images, ground measurements of aerosol optical properties, dust model simulations and air mass backward trajectory analysis. The contribution of Saharan dust to PM₁₀ monthly concentrations has been estimated at seven Italian locations. The results are both spatially (with station) and temporally (with month and year) variable, as a consequence of the variability of the meteorological conditions. However, excluding the contribution of severe dust events (21st February 2004, 25th–28th September 2003, 23rd–27th March 2005), the monthly contribution of dust varies approximately between 1 μg m^?3 and 10 μg m^?3 throughout year 2005 and between 1 μg m^?3 and 8 μg m^?3 throughout year 2003. In 2004 the dust concentration is lower than 2003 and 2005 (<5 μg m^?3 at all sites). The reduction in the number of daily exceedances of the limit value (50 μg m^?3) after subtraction of the dust contribution is also calculated at each station: it varies with station between 20% and 50% in 2005 and between 5% and 25% in 2003 and 2004.     

Degradation of chlordecone and beta-hexachlorocyclohexane by photolysis, (photo-)fenton oxidation and ozonation

Intensive use of chlorinated pesticides from the 1960s to the 1990s has resulted in a diffuse contamination of soils and surface waters in the banana-producing areas of the French West Indies. The purpose of this research was, for the first time, to examine the degradation of two of these persistent pollutants – chlordecone (CLD) and beta-hexachlorocyclohexane (β-HCH) in 1 mg L^?1 synthetic aqueous solutions by means of photolysis, (photo-) Fenton oxidation and ozonation processes. Fenton oxidation is not efficient for CLD and yields less than 15% reduction of β-HCH concentration in 5 h. Conversely, both molecules can be quantitatively converted under UV-Vis irradiation reaching 100% of degradation in 5 h, while combination with hydrogen peroxide and ferrous iron does not show any significant improvement except in high wavelength range (>280 nm). Ozonation exhibits comparable but lower degradation rates than UV processes. Preliminary identification of degradation products indicated that hydrochlordecone was formed during photo-Fenton oxidation of CLD, while for β-HCH the major product peak exhibited C₃H₃Cl₂ as most abundant fragment.     

Use of molecular and In Silico bioinformatic tools to investigate pesticide binding to insect (Lepidoptera) phenoloxidases (PO): Insights to toxicological aspects

In the present work, the promising bioinformatic tools, based on structure–affinity analysis, allowed to screen several pesticides supposed to bind to the insect immune Phenoloxidases (PO). First, the binding of aminoparathion, a reference compound, to the PO was structurally (3D) validated in accordance with previous reports. Second, using the same docking conditions, a range of pesticides was checked for their binding ability to the crystal 3D structure (PDB 3HSS) of the insect Manduca sexta (Lepidoptera) PO. The obtained data showed that many of the tested pesticides were able to bind, in silico, to M. sexta PO. The combination of in vitro (chemical and biochemical) and in silico (automated docking) approaches was found advantageous to elucidate the behavior of phenolic pesticides as substrate-analogues when binding to the active site of insect POs. Our findings emphasize new ecotoxicological aspects of pesticide residues in the agro-chemical and environmental circles.     

Residential radon concentration in the Abruzzo region (Italy): a different perspective for identifying radon prone areas

Indoor radon is an important risk factor for human health. Indeed radon inhalation is considered the second cause of lung cancer after smoking. During the last decades, in many countries huge efforts have been made in order to measuring, mapping and predicting radon levels in dwellings. Various researches have been devoted to identify those areas within the country where high radon concentrations are more likely to be found. Data collected through indoor radon surveys have been analysed adopting various statistical approaches, among which hierarchical Bayesian models and geostatistical tools are worth noting. The essential goal of this paper regards the identification of high radon concentration areas (the so-called radon prone areas) in the Abruzzo Region (Italy). In order to accurately pinpoint zones deserving attention for mitigation purpose, we adopt spatial cluster detection techniques, traditionally employed in epidemiology. As a first step, we assume that indoor radon measurements do not arise from a continuous spatial process; thus the geographic locations of dwellings where the radon measurements have been taken can be viewed as a realization of a spatial point process. Following this perspective, we adopt and compare recent cluster detection techniques: the simulated annealing scan statistic, the case event approach based on distance regression on the selection order and the elliptic spatial scan statistic. The analysis includes data collected during surveys carried out by the Regional Agency for the Environment Protection of Abruzzo (ARTA) in 1,861 random sampled dwellings across 277 municipalities of the Abruzzo region. The radon prone areas detected by the selected approaches are provided along with the summary statistics of the methods. Finally, the methodologies considered in this paper are tested on simulated data in order to evaluate their power and the precision of cluster location detection.     

Influence of transport and trends in atmospheric CO2 at Lampedusa

The study of the CO₂ 15-year records at Lampedusa (35° 31′N, 12° 37′E) is presented in this work. Short- and long-term CO₂ variability has been investigated. No significant diurnal variations are observable thus remarking the background character and representativeness of the observation site. The CO₂ long-term trend shows a mean linear growth rate (GR) of 1.9 ppm yr^?1. The periodic behaviour of the time series has been analysed and the mean seasonal cycle amplitude has been found to be 8.72 ppm. The seasonal cycle amplitude shows a marked interannual variability. The lowest value of the seasonal cycle amplitude has been detected in 2003, in concomitance with the strong anomalous heat wave recorded in Europe. CO₂ GR behaviour has been related to global processes such as El Niño Southern Oscillation (ENSO) and global temperature (T_g). The influence of ENSO event on GR is remarkable only during 1998. CO₂ GR curve shows peaks in the periods 1995, 2001 and 2005 (1.9, 3.7, 3.2 ppm yr^?1 respectively) that are characterized by high T_g values and by intense biomass burning events. The anomalous decrease in the GR during the warm 2003 has been attributed to changes in the atmospheric circulation regime. Evaluation of the influence of transport on CO₂ variability has been carried out using backward air-mass trajectory analysis and highlights the effect of the regional distribution of sources and sinks. The industrial activities and forests located in the Eastern European and Russian sector strongly affect the CO₂ mixing ratio. The CO₂ content of air-masses originating from this region is influenced in summertime by the high efficiency of the vegetation sink while in the winter period prevails the effect of industrial emissions.     

Tropospheric halocompounds and nitrous oxide monitored at a remote site in the Mediterranean

Analysis of time series and trends of nitrous oxide (N₂O) and halocompounds weekly monitored at the Mediterranean island of Lampedusa are discussed. Atmospheric N₂O levels showed a linear upward growth rate of 0.78 ppb yr^?1 and mixing ratios comparable with Northern Hemisphere global stations. CFC-11 and CFC-12 time series displayed a decline consistent with their phase-out. Chlorofluorocarbons (CFCs) replacing compounds and SF₆ exhibited an increasing temporal behaviour. The most rapid growth rate was recorded for HFC-134a with a value of 9.6% yr^?1. The industrial solvents CCl₄ and CH₃CCl₃, banned by the Montreal Protocol, showed opposite trends. While CH₃CCl₃ reported an expected decay of ?1.8 ppt yr^?1, an increasing rate of 5.7 ppt yr^?1 was recorded for CCl₄ and it is probably related to its relatively long lifetime and persisting emissions. Chlorinated halomethanes showed seasonality with a maximum in early April and a minimum at the end of September. Halon-1301 and Halon-1211 displayed a decreasing trend consistent with industry emission estimates.An interspecies correlation analysis gave positive high correlations between HCFC-22 and HFC-134a (+0.84) highlighting the common extensive employment as refrigerants. Sharing sources inferred the high coupling between CH₃Cl and CH₃Br (+0.73) and between CHCl₃ and CH₂Cl₂ (+0.77). A singular strong relationship (+0.55) between HFC-134a and CH₃I suggested the influence of an unknown anthropogenic source of CH₃I.Constraining of source and sink distribution was carried out by transport studies. Results were compared with the European Environment Agency (EEA) emission database. In contrast with the emission database results, our back trajectory analysis highlighted the release of large amounts of HFC-134a and SF₆ from Eastern Europe. Observations also showed that African SF₆ emissions may be considerable. Leakages from SF₆ insulated electrical equipments located in the industrialized Northern African areas justify our observations.