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The impact of cloud fraction and cloud type on the heating rate (HR) of black and brown carbon (HRBC and HRBrC) was experimentally determined using a methodology developed in a previous study (Ferrero et al., 2018). High time-resolution measurements of the aerosol absorption coefficient at multiple-wavelengths (Aethalometer AE33 calibrated in COLOSSAL Campaign, Ferrero et al., 2021a) were coupled with spectral measurements of the direct, diffuse and surface reflected irradiance (Multiplexer-Radiometer-Irradiometer coupled with LSI-Lastem DPA154 and C201R, class 1 radiometers), and with lidar-ceilometer (Jenoptik Nimbus 15k biaxial lidar-ceilometer) during a one year field campaign in Milan, Po Valley (Italy).The set-up allowed the experimental determination of the total HR (and its speciation: HRBC and HRBrC) in all sky conditions (from clear-sky to cloudy) with the highest total HR values found in the middle of winter (1.43±0.05 K day-1). The HRBrC accounted for 13.7±0.2% of the total HR (BrC absorption Angstrom exponent: 3.49±0.01).Sky conditions were classified in terms of cloudiness (fraction of sky covered by clouds: oktas) and cloud types: stratus (St), cumulus (Cu), stratocumulus (Sc), altostratus (As), altocumulus (Ac), cirrus (Ci) and cirrocumulus-cirrostratus (Cc-Cs). During the campaign, clear sky conditions were present 23% of the time, the remaining time (77%) being characterized by cloudy conditions. The average cloudiness was 3.58±0.04 oktas (highest in February: 4.56±0.07 oktas, lowest in November: 2.91±0.06 oktas). St were mostly responsible of overcast conditions (oktas=7-8, frequency: 87 and 96%).HR measurements showed a constant decrease with increasing cloudiness allowing to quantify the bias (in %) of the aerosol HR introduced by the simplified assumption of clear-sky conditions in radiative transfer model calculations. Results showed that the HR of light absorbing aerosol was ~20-30% lower in low cloudiness (oktas=1-2) up to 80% lower in complete overcast conditions (i.e., oktas=7-8), compared to clear sky ones. The impact of different cloud types on the HR was also investigated. Cirrus were found to have a modest impact, decreasing the HRBC and HRBrC by -5% at most. Cumulus decreased the HRBC and HRBrC by -31±12 and -26±7%, respectively; cirrocumulus-cirrostratus decreased the HRBC and HRBrC by -60±8 and -54±4%, which was comparable to the impact of altocumulus (-60±6 and -46±4%). A higher impact on HRBC and HRBrC suppression was found for stratocumulus (-63±6 and -58±4%, respectively) and altostratus (-78±5 and -73±4%, respectively). The highest impact was associated to stratus, suppressing the HRBC and HRBrC by -85±5 and -83±3%, respectively. The presence of clouds caused a decrease of both HRBC and HRBrC (normalized to the absorption coefficient of the respective species) of -11.8±1.2% and -12.6±1.4% per okta (Ferrero et al., 2021b) allowing to parametrize the BC and BrC radiative impact in non clear sky conditions around the world.References:Ferrero L., et al., 2018. Environ. Sci. Tech., 52, 3546−3555, DOI: 10.1021/acs.est.7b04320, 2018.Ferrero, L., et al., 2021a. Science of the Total Environment 791. doi:10.1016/j.scitotenv.2021.148277.Ferrero, L., et al. 2021b. Atmospheric Chemistry and Physics 21, 4869–4897. doi:10.5194/acp-21-4869-2021.

The COVID-19 pandemic has surprised the entire population. The world has had to face an unprecedented pandemic. Only, Spanish flu had similar disastrous consequences. As a result, drastic measures (lockdown) have been adopted worldwide. Healthcare service has been overwhelmed by the extraordinary influx of patients, often requiring high intensity of care. Mortality has been associated with severe comorbidities, including chronic diseases. Patients with frailty were, therefore, the victim of the SARS-COV-2 infection. Allergy and asthma are the most prevalent chronic disorders in children and adolescents, so they need careful attention and, if necessary, an adaptation of their regular treatment plans. Fortunately, at present, young people are less suffering from COVID-19, both as incidence and severity. However, any age, including infancy, could be affected by the pandemic.Based on this background, the Italian Society of Pediatric Allergy and Immunology has felt it necessary to provide a Consensus Statement. This expert panel consensus document offers a rationale to help guide decision-making in the management of children and adolescents with allergic or immunologic diseases.

Airborne particulate (PM) components from fossil fuel combustion can induce oxidative stress initiated by reactive oxygen species (ROS) that are strongly correlated with airway inflammation and asthma. A valid biomarker of airway inflammation is fractionated exhaled nitric oxide (FENO). The oxidative potential of PM2.5 can be evaluated with the dithiothreitol (DTT) dosage, which represents both ROS chemically produced and intracellular ROS of macrophages. This correlates with quality indicators of the internal environment and ventilation strategies such as dilution and removal of airborne contaminants.

The most important parameter to obtain an appropriate preservation condition of museum environments concerns the indoor air quality. The exposure of artwork and materials to gaseous and particulate pollutants introduced by visitors and either indoor or outdoor sources contributes to their decay. In this work, we evaluated the possible monitoring of the visitors’ influence using the stable carbon isotopic ratio of CO2 and the concentration of NH3 as a real-time tool. The study was done in the Refectory of Santa Maria delle Grazie (Milan, Italy) which houses one of the most important paintings of Leonardo da Vinci, the Last Supper, and had more than 400,000 visitors in 2019. The results confirmed a good correlation between the presence of tourists inside the museum and the variation of δ13C value during the visits and the closure of the museum. The variation of indoor atmospheric δ13C was influenced by the presence of visitors in the Refectory and delineates the way done from the entrance to the exit. In the same way, the concentration of NH3 was influenced by the presence of visitors and confirmed the role of this one on preservation methodology for indoor air quality in the museum. This new methodology can be used as a supplemental and non-invasive tool to help in calibrating microclimatic conditions through the ventilation rate and air filtration systems in the museum and to manage the number of visitors per turn.

In this study, the applicability of a benchtop polar photometer (PP_UniMI) to retrieve multi-wavelength aerosol absorption coefficient data by off-line measurements of the Multi-Angle Absorption Photometer (MAAP) sample spots is presented. MAAP is a widespread single wavelength online instrument providing the aerosol absorption coefficient and the equivalent black carbon concentration. In this work, MAAP samples collected during four different campaigns were analysed off-line with PP_UniMI. First of all, data from PP_UniMI and MAAP were compared to investigate contributions to measurement uncertainties. In particular, the role of the following assumptions performed in the MAAP was investigated: 1) reconstructing angular distribution of light scattered by filter samples from measurements at three fixed angles using analytical functions; 2) setting the fraction of the back-scattered radiation by the blank filter (BM) at a fixed value BM = 0.7; 3) assuming a fixed value for the asymmetry factor g = 0.75. Samples collected at several sites showed an agreement within 5% when data from the two instruments were retrieved using the same approximations (i.e. backscattered radiation from the filter matrix BM set at a fixed value, phase functions reconstructed by analytical functions from measurements at 3 angles, same asymmetry factor) in the data retrieval algorithm. Conversely, larger differences (14% on average) between off-line measurements and averaged MAAP data were obtained when the high-angular resolved information available by PP_UniMI was exploited. By analysing the role of MAAP assumptions for σap retrieval, it resulted that fixing BM = 0.7 was the main responsible for the detected differences. Indeed, high-angular resolved off-line measurements by PP_UniMI allow to directly measure BM, obtaining BM = 0.88 on white spots. It is noteworthy that the observed results were similar at all investigated sites, so they proved to be independent of the aerosol type and can likely be attributed to instrumental effects. Moreover, a sensitivity test was carried out also to check the impact of the fixed value used for the asymmetry factor (set at g = 0.75 in both instruments). Varying g values within the typical range for ambient aerosol (0.50–0.75) the estimate of aerosol absorbance ABS (directly obtained from PP_UniMI measurements and linked to σap) was affected by 8% at most, thus being a minor source of uncertainty in the calculation. The effect of the variability in blank spots used for off-line analyses was also evaluated and resulted in a contribution smaller than 3% to the uncertainty of the methodology employed. Finally, the possibility of exploiting multi-wavelength assessment of absorption coefficients is an added value of PP_UniMI; indeed, it allows to estimate the contribution of different aerosol sources and components to the absorption coefficient using MAAP tapes used in present or past campaigns., The authors acknowledge the Italian Ministry of Research and the National Institute of Nuclear Physics for having supported this research in the PRIN2007-project and the INFN-TRACCIA experiment, respectively. The authors are also grateful to the GEMMA centre in the framework of project MIUR “Dipartimenti di Eccellenza 2018–2022”. Measurements at Spanish sites (Montseny, Montsec and Barcelona) were supported by the Spanish Ministry of Economy, Industry and Competitiveness and FEDER funds under the project HOUSE (CGL2016-78594-R) and by the Generalitat de Catalunya (AGAUR 2014 SGR33, AGAUR 2017 SGR41 and the DGQA).

In the frame of the EMEP/ACTRIS/COLOSSAL campaign in Milan during winter 2018, equivalent black carbon measurements using the Aethalometer 31 (AE31), the Aethalometer 33 (AE33), and the Multi-Angle Absorption Photometer (MAAP) were carried out together with levoglucosan analyses on 12-h resolved PM2.5 samples collected in parallel. From AE31 and AE33 data, the loading-corrected aerosol attenuation coefficients (bATN) were calculated at 7 wavelengths (λs, where λ = 370, 470, 520, 590, 660, 880, 950 nm). Aerosol absorption coefficient at 637 nm (babs_MAAP) was determined by MAAP measurements. Furthermore, babs was also measured at 4 wavelengths (405, 532, 635, 780 nm) on the 12-h resolved PM2.5 samples by a polar photometer (PP_UniMI). After comparing PP_UniMI and MAAP results, we exploited PP_UniMI data to evaluate the filter multiple-scattering enhancement parameter at different wavelengths for AE31 and AE33. We obtained instrument- and wavelength-dependent multiple-scattering parameters by linear regression of the Aethalometer bATN against the babs measured by PP_UniMI. We found significant filter material, and hence instrumental, dependence of the multiple-scattering enhancement parameter with the difference up to 30 % between the AE31 and the AE33 tapes. The wavelength dependence and day/night variations were small – the difference between the smallest and largest value was up to 6 %. Data from the different instruments were used as input to the so-called “Aethalometer model” for optical source apportionment and instrument-dependence of the results was investigated. Inconsistencies among the source apportionment were found fixing the AE31 and AE33 multiple-scattering enhancement parameters to their usual values. Opposite, optimised multiple-scattering enhancement parameters led to 5 % agreement among the approaches. Also, the component-apportionment “MWAA model” was applied to the dataset. It resulted less sensitive to the instrument and the number of wavelengths, whereas significant differences in the determination of the absorption Ångström exponent for brown carbon were found (up to 22 %).

We experimentally quantified the impact of cloud fraction and cloud type on the heating rates (HRs) of black and brown carbon (HRBC and HRBrC).In particular, in this work, we examine in more detail the average cloud effect (Ferrero et al., 2018) using high time-resolution measurements of aerosol absorption at multiple-wavelengths coupled with spectral measurements of the direct, diffuse and surface reflected radiation and lidar data in the Po Valley. The experimental set-up allowed a direct determination of HRBC and HRBrC in any sky condition. The highest values of total HR were found in the middle of the winter (1.43 ± 0.05 K day−1) while the lowest in spring (0.54 ± 0.02 K day−1) Overall the HRBrC accounted for 13.7 ± 0.2 % of the total HR, the BrC being characterized by an AAE of 3.49 ± 0.01. Simultaneously, sky conditions were classified (from clear-sky to cloudy) in terms of fraction of sky covered by clouds (oktas) and cloud types. Cloud types were grouped as a function of altitude into the following classes: 1) low level ( 7 km) cirrus, cirrocumulus-cirrostratus. Measurements carried out in different sky conditions at high-time resolution showed a constant decrease of HR with increasing cloudiness of the atmosphere enabling us to quantify for the first time the bias (in %) in the aerosol HR introduced by improperly assuming clear-sky conditions in radiative transfer calculations. In fact, during the campaign, clear sky conditions were only present 23 % of the time while the remaining time (77 %) was characterized by cloudy conditions. Our results show that, by incorrectly assuming clear-sky conditions, the HR of light absorbing aerosol can be largely overestimated (by 50 % in low cloudiness, oktas = 1–2), up to over 400 % (in complete overcast conditions, i.e., oktas = 7–8). The impact of different cloud types on the HR compared to a clear sky condition was also investigated. Cirrus were found to have a modest impact, decreasing the HRBC and HRBrC by −1– −5 %. Cumulus decreased the HRBC and HRBrC by −31 ± 12 and −26 ± 7 %, respectively, while cirrocumulus-cirrostratus by −60 ± 8 and −54 ± 4 %, which was comparable to the impact of altocumulus (−60 ± 6 and −46 ± 4 %). A high impact on HRBC and HRBrC was found for stratocumulus (−63 ± 6 and −58 ± 4 %, respectively) and altostratus (−78 ± 5 and −73 ± 4 %, respectively), although the highest impact was found to be associated to stratus that suppressed the HRBC and HRBrC by −85 ± 5 and −83 ± 3 %, respectively. Additionally, the cloud influence on the radiation spectrum that interacts with the absorbing aerosol was investigated. Black and brown carbon (BC and BrC) have different spectral responses (a different absorption Angstrom exponent, AAE) and our results show that the presence of clouds causes a greater decrease for the HRBC with respect to to HRBrC going clear sky to complete overcast conditions; the observed the difference is 12 ± 6 %. This means that, compared to BC, BrC is more efficient in heating the surrounding atmosphere in cloudy conditions than in clear sky. Overall, this study extends the results of a previous work (Ferrero et al., 2018), highlighting the need to take into account both the role of cloudiness and of different cloud types to better estimate the HR associated to both BC and BrC, and in turn decrease the uncertainties associated to the quantification of the impact of these species on radiation and climate.

Black carbon (BC) and Brown Carbon (BrC) absorbs sunlight and heat the atmosphere. The heating rate (HR) can be determined from the divergence of the net radiative flux with altitude (vertical profiles) or from the modelling activity; however, it determination is, up to now, too sparse, does not account for light-absorbing-aerosol (LAA) speciation and for the influence of different cloudy sky conditions on the BC induced heating rate (HR) in the atmospheric layer below clouds. This work applies a new method (Ferrero et al., 2018) to experimentally determine (at high time resolution) the HR induced by the LAA from mid-latidudes to the Arctic along two years (2018-2019, June-August) of oceanographic cruises moving from 54°N to 81°N and from 2°W to 25°E.The HR was experimentally determined at high time resolution and apportioned in the context of LAA species (BC, BrC), and sources (fossil fuel, FF; biomass burning, BB) as reported in Ferrero et al. (2018) equipping the Oceania vessel of the Polish Academy of Science with the following instrumentation:1) Aethalometer (AE-33, Magee Scientific, 7-λ), 2) Multiplexer-Radiometer-Irradiometer ROX (diffuse, direct and reflected radiance: 350-1000 nm, 1 nm resolution), 3) a SPN1 radiometer (global and diffuse radiation), 4) High volume sampler (TSP ECHO-PUF Tecora). Samples were analysed for ions (Dionex IC) and by EC/OC by using DRI Model 2015 Multi-Wavelength Thermal/Optical Carbon Analyzer. Radiometers were compensated for the ship pitch and roll by an automatic gimbal. AE33 absorption coefficient accuracy was determined through comparison with a MAAP (Thermo-Fischer).The HR showed a clear latitudinal behavior with higher values in the harbor of Gdansk (0.29±0.01 K/day) followed by the Baltic Sea (0.04±0.01 K/day), the Norvegian Sea (0.01±0.01 K/day) and finally with the lowest values in the pure Arctic Ocean (0.003±0.001 K/day).They followed the decrease of both BC concentrations and global radiation from 1189±21 ng/m3 and 230±6 W/m2 (Gdansk) to 27±1 ng/m3 and 111±3 W/m2 (Arctic Ocean). The latitunal gradient of the HR clearly demonstrate that the warming of the Arctic could be influenced by a heat transport. In this respect, the LAA added about 300 J/m3 at mid-latitudes and only 3 J/m3 close to the North Pole. Moreover, above the Arctic circle, 70% of the HR was due to the diffuse radiation induced by cloud presence, a condition that climate models in clear-sky assumption cannot capture. In addition, in the Arctic the BrC experienced an increase of 60% in determining the HR compared to mid-latitudes.Acknowledgements: GEMMA Center - Project MIUR – Dipartimenti di Eccellenza 2018–2022.Reference: Ferrero, L., et al (2018) Environ. Sci Tech., 52, 3546−3555

The role of the elemental carbon (EC), in synergy with hygroscopic ionic species, was investigated to study the formation of electrical bridging phenomena once the aerosol deliquescence is achieved. Ambient aerosol samples were collected on hydrophobic surfaces in urban and rural sites in Northern Italy, their conductance was measured in an Aerosol Exposure Chamber (AEC) while varying the relative humidity. An electric signal was detected on 64% of the collected samples with conductance values (11.20 &plusmn, 7.43 &mu, S) above the failure threshold (1 &mu, S) of printed circuit boards. The ionic content was higher for non-electrically conductive samples (43.7 &plusmn, 5.6%) than for electrically conductive ones (37.1 &plusmn, 5.6%). Conversely, EC was two times higher for electrically conductive samples (26.4 &plusmn, 4.1 &mu, g cm&minus, 2, 8.4 &plusmn, 1.7%) than for non-electrical ones (12.0 &plusmn, 5.2 &plusmn, 1.9%) suggesting that the synergy between the ionic and carbonaceous fractions is necessary to promote a bridging phenomenon. Synthetic aerosols (EC only, saline only, mixed saline and EC) were generated in laboratory and their conductance was measured in the AEC to verify the ambient results. Only in case of a contemporary presence of both EC and ionic components the bridging phenomenon occurred in keeping with the theoretical deliquescence values of each salt (R2 = 0.996).

Accurate and temporally consistent measurements of light absorbing aerosol (LAA) heating rate (HR) and of its source apportionment (fossil-fuel, FF; biomass-burning, BB) and speciation (black and brown Carbon; BC, BrC) are needed to evaluate LAA short-term climate forcing. For this purpose, wavelength- and time-dependent accurate LAA absorption coefficients are required. HR was experimentally determined and apportioned (sources/species) in the EMEP/ACTRIS/COLOSSAL-2018 winter campaign in Milan (urban-background site). Two Aethalometers (AE31/AE33) were installed together with a MAAP, CPC, OPC, a low volume sampler (PM2.5) and radiation instruments. AE31/AE33 multiple-scattering correction factors (C) were determined using two reference systems for the absorption coefficient: 1) 5-wavelength PP_UniMI with low time resolution (12 h, applied to PM2.5 samples); 2) timely-resolved MAAP data at a single wavelength. Using wavelength- and time-independent C values for the AE31 and AE33 obtained with the same reference device, the total HR showed a consistency (i.e. reproducibility) with average values comparable at 95% probability. However, if different reference devices/approaches are used, i.e. MAAP is chosen as reference instead of a PP_UniMI, the HR can be overestimated by 23–30% factor (by both AE31/AE33). This became more evident focusing on HR apportionment: AE33 data (corrected by a wavelength- and time-independent C) showed higher HRFF (+24 ± 1%) and higher HRBC (+10 ± 1%) than that of AE31. Conversely, HRBB and HRBrC were −28 ± 1% and −29 ± 1% lower for AE33 compared to AE31. These inconsistencies were overcome by introducing a wavelength-dependent Cλ for both AE31 and AE33, or using multi-wavelength apportionment methods, highlighting the need for further studies on the influence of wavelength corrections for HR determination. Finally, the temporally-resolved determination of C resulted in a diurnal cycle of the HR not statistically different whatever the source- speciation- apportionment used.

A closure experiment was conducted over Svalbard by comparing Lidar measurements and optical aerosol properties calculated from aerosol vertical profiles measured using a tethered balloon. Arctic Haze was present together with Icelandic dust. Chemical analysis of filter samples, aerosol size distribution and a full set of meteorological parameters were determined at ground. Moreover, scanning electron microscopy coupled with energy-dispersive X-ray (SEM-EDS) data were at disposal showing the presence of several mineralogical phases (i.e., sheet silicates, gypsum, quartz, rutile, hematite). The closure experiment was set up by calculating the backscattering coefficients from tethered balloon data and comparing them with the corresponding lidar profiles. This was preformed in three subsequent steps aimed at determining the importance of a complete aerosol speciation: (i) a simple, columnar refractive index was obtained by the closest Aerosol Robotic Network (AERONET) station, (ii) the role of water-soluble components, elemental carbon and organic matter (EC/OM) was addressed, (iii) the dust composition was included. When considering the AERONET data, or only the ionic water-soluble components and the EC/OM fraction, results showed an underestimation of the backscattering lidar signal up to 76, 53 and 45% (355, 532 and 1064 nm). Instead, when the dust contribution was included, the underestimation disappeared and the vertically-averaged, backscattering coefficients (1.45±0.30, 0.69±0.15 and 0.34±0.08 Mm-1 sr-1, at 355, 532 and 1064 nm) were found in keeping with the lidar ones (1.60±0.22, 0.75±0.16 and 0.31±0.08 Mm-1 sr-1). Final results were characterized by low RMSE (0.36, 0.08 and 0.04 Mm-1 sr-1) and a high linear correlation (R2 of 0.992, 0.992 and 0.994) with slopes close to one (1.368, 0.931 and 0.977, respectively). This work highlighted the importance of all the aerosol components and of the synergy between single particle and bulk chemical analysis for the optical property characterization in the Arctic .

Satellite data are fundamental for air quality monitoring. Despite this, several algorithms are present in literature leaving to the reader a choice on the best approach without considering the physical – spatial – temporal inconsistencies concerning the problem of relating satellite with ground-based data. In order to overcome this dilemma, the present work was carried out developing a general methodological approach to overcome the aforementioned inconsistencies obtaining in any region the best retrieval. In this respect, the particulate matter phenomenology (both at ground and vertically) was considered in order to select the best approach for the AOD to PM conversion starting from the knowledge of PM properties, meteorology and vertical behaviour. In this respect, multiple years of particulate matter vertical profiles, chemical composition, hygroscopicity, meteorology and optical properties were used to define an optimized satellite AOD-ground PM relationship. A hybrid algorithm (physically based and statistical) was developed to be applied over the Milan conurbation (Po Valley) to determine ground-level PM1, PM2.5 and PM10 concentrations from satellite aerosol optical depth (AOD) data. The developed algorithm (based on aerosol optical depth, mixing height, wind speed and PM concentrations of the previous day) showed high accuracy enabling to predict ground particulate matter concentrations with very low RMSE in prediction (5.48 μg/m3, 9.89 μg/m3 and 10.64 μg/m3 for PM1, PM2.5 and PM10) and rather high R2 (≥0.83 on the evaluation set of data).

This work discusses the sources of model biases in reconstructing the Planetary Boundary Layer (PBL) height among five commonly used PBL parameterizations. The Weather Research and Forecasting (WRF) Model was applied over the critical area of Northern Italy with 5 km of horizontal resolution, and compared against a wide set of experimental data for February 2008. Three non-local closure PBL schemes (Asymmetrical Convective Model version 2, ACM2; Medium Range Forecast, MRF; Yonsei University, YSU) and two local closure parameterizations (Mellor Yamada Janjic, MYJ; University of Washington Moist Turbulence, UW) were selected for the analysis. Vertical profiles of aerosol number concentrations and Lidar backscatter profiles were collected in the metropolitan area of Milan in order to derive the PBL hourly evolution. Moreover, radio-soundings of Milano Linate airport as well as surface temperature, mixing ratio and wind speed of several meteorological stations were considered too. Results show that all five parameterizations produce similar performances in terms of temperature, mixing ratio and wind speed in the city of Milan, implying some systematic errors in all simulations. However, UW and ACM2 use the same local closure during nighttime conditions, allowing smaller mean biases (MB) of temperature (ACM2 MB = 0.606 K, UW MB = 0.209 K), and wind speed (ACM2 MB = 0.699 m s−1, UW MB = 0.918 m s−1). All schemes have the same variations of the diurnal PBL height, since over predictions of temperature and wind speed are found to cause a general overestimation of mixing during its development in winter. In particular, temperature estimates seem to impact the early evolution of the PBL height, while entrainment fluxes parameterizations have major influence on the afternoon development. MRF, MYJ and ACM2 use the same approach in reconstructing the entrainment process, producing the largest overestimations of PBL height (MB ranges from 85.51–179.10 m). On the contrary, the best agreement between model and both Lidar and balloon observations was identified for YSU (MB = −27.54 m and 30.15 m, respectively).

The collection of atmospheric particles on not-filtering substrates via dry deposition, and the subsequent study of the particle-induced material decay, is trivial due to the high number of variables simultaneously acting on the investigated surface. This work reports seasonally resolved data of chemical composition and size distribution of particulate matter deposed on stone and surrogate surfaces obtained using a new method, especially developed at this purpose. A “Deposition Box” was designed allowing the particulate matter dry deposition to occur selectively removing, at the same time, variables that can mask the effect of airborne particles on material decay. A pitched roof avoided rainfall and wind variability; a standardised gentle air exchange rate ensured a continuous “sampling” of ambient air leaving unchanged the sampled particle size distribution and, at the same time, leaving quite calm condition inside the box, allowing the deposition to occur. Thus, the “Deposition Box” represents an affordable tool that can be used complementary to traditional exposure systems. With this system, several exposure campaigns, involving investigated stone materials (ISMs) (Carrara Marble, Botticino limestone, Noto calcarenite and Granite) and surrogate (Quartz, PTFE, and Aluminium) substrates, have been performed in two different sites placed in Milan (Italy) inside and outside the low emission zone. Deposition rates (30–90 μg cm−2 month−1) showed significant differences between sites and seasons, becoming less evident considering long-period exposures due to a positive feedback on the deposition induced by the deposited particles. Similarly, different stone substrates influenced the deposition rates too. The collected deposits have been observed with optical and scanning electron microscopes and analysed by ion chromatography. Ion deposition rates were similar in the two sites during winter, whereas it was greater outside the low emission zone during summer and considering the long-period exposure. The dimensional distribution of the collected deposits showed a significant presence of fine particles in agreement with deposition rate of the ionic fraction. The obtained results allowed to point out the role of the fine particles fraction and the importance of making seasonal studies.

The effects of hygroscopic atmospheric particles are investigated in relation to the corrosion of tin. Surface insulation resistance test boards were directly contaminated both with ambient particles sampled in the field at Milan, Italy, and with pure saline particles generated in the laboratory. An innovative particle deposition device was used to uniformly coat circular spots on to the test board surfaces. Deliquescence and crystallization of the water-soluble compounds were detected by observing the impedance response to varying relative humidity (RH) conditions with a gradual and continuous ramps. The effects of the adsorption/desorption kinetics and of the temperature on the deliquescence and crystallization RH values were also investigated. Leakage current measurements at 5-V dc highlighted the ability of atmospheric particles to promote corrosion and electrochemical migration at RH levels far below condensing conditions (100% RH).

EU emission standards for vehicles do not include many particulate (PM) and gaseous species, despite their considerable impact on air pollution and health. Emission factors (EFs) were measured for unregulated species, i.e. polycyclic aromatic hydrocarbons (PAHs) and n-alkanes (ALKs) in the particle phase, and, for the first time, EFs for phenols in both particle and gas phases. Exhaust samples were collected under controlled operating conditions (chassis dynamometer tests) for in-service vehicles (private cars, PCs and light duty vehicles, LDVs) from different EURO classes. EFs of trace organics were highest for the old EURO 1 vehicles (the tested EURO 1 vehicles were without emission-control devices), and lowest for the more recent EURO 3 and 4 vehicles. ALKs (C20–C32) were the most abundant trace organic compounds found in PM vehicle exhaust, and their EF ranged between 2034 and 101 μg km−1 (Euro 1–4 LDVs). PM-phased phenols EFs were in the range 0.42–2.50 μg km−1, and 4-nitrophenol was the most abundant one. The highest EFs were measured for phenols in the gas phase (dominated by the presence of phenol) for gasoline EURO 1 (43.16 ± 9.99 μg km−1). Emissions of PAHs changed depending on the fuel used. The PAH EFs of diesel-driven PCs were 4–5 times higher than those of gasoline vehicles, with PAHs diesel exhaust being mainly enriched in low 4-ring PAHs (85%), while 5–6 ring PAHs were prevalent (55%) in gasoline vehicles. Results of source profiles from chassis dynamometer tests were compared with ambient data, and the traffic PAH source profile derived from a tunnel study (Milan) agreed with the estimated emissions from a mix of diesel and gasoline vehicles circulating in the same area. Moreover, the impact of EURO regulatory changes on exhaust emissions was calculated, and this made it possible to estimate the downward trend of PAH emissions in the Province of Milan in the period 2005–2020.

During the summers of 2011 and 2012, two scientific cruises were carried out over the Arctic Ocean aiming at the determination of the aerosol chemical composition in this pristine environment. First, mass spectrometry was applied to study the concentration and gas/particle partitioning of polycyclic aromatic hydrocarbons (PAHs) and n-alkanes. Experimental and modelled data of phase partitioning were compared: results demonstrated an equilibrium between gas and particle phase for PAHs, while n-alkanes showed a particle-oriented partitioning, due to the local marine origin of them, confirmed by the extremely low value of their carbon preference index. Moreover, the inorganic and organic ions (carboxylic acids and amines) concentrations, together with those of elemental carbon (EC) and organic matter (OM), were analyzed: 63% of aerosol was composed of ionic compounds (&gt, 90% from sea-salt) and the OM content was very high (30.5%, close to 29.0% of Cl&minus, ) in agreement with n-alkanes&rsquo, marine signature. Furthermore, the amines&rsquo, (dimethylamine, trimethylamine, diethylamine) concentrations were 3.98 &plusmn, 1.21, 1.70 &plusmn, 0.82, and 1.06 &plusmn, 0.56 p.p.t.v., respectively, fully in keeping with concentration values used in the CLOUD (Cosmics Leaving OUtdoor Droplet)-chamber experiments to simulate the ambient nucleation rate in a H2SO4-DMA-H2O system, showing the amines&rsquo, importance in polar regions to promote new particle formation. Finally, high resolution mass spectrometry was applied to determine trace elements, including Rare Earth Elements (REEs), highlighting the dominant natural versus anthropic inputs for trace metals (e.g., Fe, Mn, Ti vs. As, Cd, Ni) and possible signatures of such anthropic activity.

The energy demands of data centers (DCs) worldwide are rapidly increasing, as are their environmental and economic costs. This paper presents a study conducted at Sannazzaro de' Burgondi (Po Valley), Italy, specifically aimed at optimizing the operating conditions of a DC designed for the Italian Oil and Gas Company (Eni) (5200 m(2) of Information Technology installed, 30 MW) and based on a direct free cooling (DFC) system. The aim of the study was to save the largest possible quantity of energy, while at the same time preventing aerosol corrosion. The aerosol properties (number size distribution, chemical composition, deliquescence relative humidity (DRH), acidity) and meteorological parameters were monitored and utilized to determine the potential levels of aerosol entering the DC (equivalent ISO class), together with its DRH. These data enabled us both to select the DC's filtering system (MERV13 filters) and to optimize the cooling cycle through calculation of the most reliable humidity cycle (60% of maximum allowed RH) applicable to the DFC. A potential energy saving of 81%, compared to a traditional air conditioning cooling system, was estimated: in one year, for 1 kW of installed information technology, the estimated energy saving is 7.4 MWh, resulting in 2.7 fewer tons of CO2 being emitted, and a financial saving of € 1100.

In this paper we present results from a systematic study of vertical profiles of aerosol number size distribution and black carbon (BC) concentrations conducted in the Arctic, over Ny-Ålesund (Svalbard). The campaign lasted 2 years (2011–2012) and resulted in 200 vertical profiles measured during the spring and summer seasons. In addition, chemical analysis of filter samples, aerosol size distribution and a full set of meteorological parameters were determined at ground to put on a firmer grounds the analysis of the vertical profiles. The collected experimental data allowed a classification of the vertical profiles into different typologies which allowed to describe a seasonal phenomenology of vertical aerosol properties in the Arctic. During spring, four main types of profiles were found and their behaviour was related to the main aerosol and atmospheric dynamics occurring at the measuring site. Background conditions generated homogenous profiles. Transport events caused an increase of aerosol concentration with altitude. High Arctic haze pollution trapped below thermal inversions promoted a decrease of aerosol concentration with altitude. Finally, ground-based plumes of locally formed secondary aerosol determined profiles with decreasing aerosol concentration located at different altitude in function of size. During the summer season, the impact from shipping caused aerosol and BC pollution plumes constrained close to the ground, indicating that increasing shipping emissions in the Arctic could bring anthropogenic aerosol and BC in the summer Arctic affecting the climate.

During the 2013 Arctic campaign, direct measurements and size-segregated samplings of atmospheric aerosol were carried out from March to September at the Gruvebadet observatory in Ny-lesund (78A degrees 56'N, 11A degrees 56'E; Svalbard Islands). Continuous size distribution measurements (104 size classes) were performed both in the nano- (TSI-SMPS system) and micro-metric (TSI-APS device) range with a resolution of 10 min. Aerosol sampling was carried out on daily basis (PM10 fraction, 00:01-23:59 UTC) and with a 4-day resolution (four-stage cascade impactor). A back-trajectory analysis was performed for specific events to understand transport processes and possible source areas of aerosol reaching Ny-lesund. Aerosol samples were analyzed for ion composition (inorganic cations and anions, selected organic anions) by a three-chromatograph system after extraction in ultra-sonic bath. Special attention was spent in identifying and interpreting the seasonal pattern of natural and anthropic chemical markers. Sea spray aerosol was evenly distributed along all the sampling period with maxima related to wind speed. Its size distribution peaks in 1.0-2.5 or 2.5-10 A mu m, depending on the transport conditions and distance from source areas. Anthropic sulfate dominates the spring aerosol load (Arctic Haze), both in acidic form (H2SO4) and in partially or totally neutralized ammonium salts. Biogenic contributions, marked by methanesulfonic acid, are relatively relevant in late spring-early summer and are distributed in the finest aerosol fraction (< 1.0 A mu m).

Daily PM10 aerosol samples were collected at the Gruvebadet observatory, Ny-Ålesund (Svalbard Islands), during the spring-summer 2014 Italian Arctic Campaign. A total of 136 samples were analysed for ion (inorganic anions and cations, selected organic anions) composition aiming to evaluate the seasonal pattern of sulfate, as a key component of the Arctic haze. Ionic balances indicated a strong sulfate seasonality with mean spring concentration about 1.5 times higher than that measured in summer. The spring and summer aerosol was almost neutral, indicating that ammonia was the major neutralizing agent for atmospheric acidic species. The linear regression between sulfate from potential acidic sources (non-sea salt sulfate and non-crustal sulfate) and ammonium indicated that the mean sulfate/ammonium ratio was intermediate between semi-(NH4HSO4) and complete ((NH4)2SO4) neutralization. Using sea-salt sodium as sea-spray marker, non-sea-salt calcium as crustal marker and methanesulfonic acid as biogenic marker, a detailed source apportionment for sulfate was carried out. The anthropogenic input (calculated as the differences between total sulfate and the sum of sea-salt, crustal and biogenic contributes) was found to be the most relevant contribution to the sulfate budget in the Ny-Ålesund aerosol in summer and, especially, in spring. In this last season, crustal, sea-salt, biogenic and anthropogenic sources accounted for 3.3, 12.0, 11.5 and 74.8 %, respectively.

Recent epidemiological evidence support the hypothesis that health effects from inhalation of air particles are governed by more than just particle mass, since specific chemical components have been identified as important contributors to mortality and hospitality admissions.We studied the chemical composition and the oxidative potential (OP) of total suspended particle (TSP) samples from Milan at two sites with different traffic loads: a site in the low emission zone (LEZ) and a traffic site (TR) outside. Two a-cellular assays; dithiothreitol (OPDTT) and 2',7' dichlorofluorescin (OPDCFH) were used to characterize the OP of the soluble fraction of particles.TSP samples from LEZ showed significantly lower concentrations of traffic-related chemical components compared to TR. The decrease in the concentrations from TR to LEZ was maximum for EC, with a LEZ/TR ratio of 0.64 (±0.18), and a significant reduction (p < 0.01) was also observed for PAHs (LEZ/TR = 0.73 ± 0.16), elements (Mn, Cu, Zn, Cd, Pb: LEZ/TR ranged between 0.64 and 0.82), OC (LEZ/TR = 0.85 ± 0.12) and NH4+ (LEZ/TR = 0.92 ± 0.07).OP measures, expressed as OP/m3 or OP/mg, were comparable between sites both for OPDTT and OPDCFH, thus not showing any significant impact of local traffic on OP values at sites. OPDTT and OPDCFH showed contrasting seasonal and daily trends, indicating that the two a-cellular assays gave complementary information on the OP of particles in Milan. The two OP assays resulted to be sensitive to different chemical properties of PM samples. OPDTT correlated positively only with Global Radiation (Spearman's rs = 0.38, p < 0.05), which could be considered as a proxy for high concentrations of secondary oxidizing organics, while OPDCFH was related to various PM chemical species, mainly correlated with total mass (rs = 0.65; p < 0.01), elements (e.g. Zn, rs = 0.67; As, rs = 0.65; p < 0.01) and the sum of sulfate and nitrate (rs = 0.63; p < 0.01), a proxy for secondary aerosol.

Pollen aeroallergens are present in atmospheric particulate matter (PM) where they can be found in coarse biological particles such as pollen grains (aerodynamic diameter dae > 10 μm), as well as fragments in the finest respirable particles (PM2.5; dae < 2.5 μm). Nitration of tyrosine residues in pollen allergenic proteins can occur in polluted air, and inhalation and deposition of these nitrated proteins in the human respiratory tract may lead to adverse health effects by enhancing the allergic response in population. Previous studies investigated protein nitration by atmospheric gaseous pollutants such as nitrogen dioxide and ozone. In this work we report, for the first time, a study on protein nitration by nitrate ion in aqueous solution, at nitrate concentrations and pH conditions simulating those occurring in the atmospheric aerosol liquid water phase. Experiments have been carried out on the Bovine serum albumin (BSA) protein and the recombinant Phleum pratense allergen (Phl p 2) both in the dark and under UV-A irradiation (range 4–90 W m− 2) to take into account thermal and/or photochemical nitration processes. For the latter protein, modifications in the allergic response after treatment with nitrate solutions have been evaluated by immunoblot analyses using sera from grass-allergic patients. Experimental results in bulk solutions showed that protein nitration in the dark occurs only in dilute nitrate solutions and under very acidic conditions (pH < 3 for BSA; pH < 2.2 for Phl p 2), while nitration is always observed (at pH 0.5–5) under UV-A irradiation, both in dilute and concentrated nitrate solutions, being significantly enhanced at the lowest pH values. In some cases, protein nitration resulted in an increase of the allergic response.

Atmospheric aerosols deliquescence and crystallization relative humidity (DRH and CRH) are rarely measured compared to the worldwide number of hygroscopicity measurements; this feature comes from the lack of an efficient method able to capture the whole complexity of chemical composition of aerosols. Despite this, the knowledge of both DRH and CRH are crucial for a correct parameterization of the aerosol hygroscopic growth used in different applications, among which the remote sensing is very important. In this paper, a newly developed technique (direct current conductance method) was applied in an aerosol chamber to Milan PM2.5 samples, to identify aerosol DRH and CRH both during winter and summer. These results were compared with those independently obtained by gravimetric measurements conducted in the chamber using a microbalance. Microbalance data allowed also the determination of the mass hygroscopic growth factor on the collected PM2.5 samples. Results evidenced first a good agreement between the two methods (RMSE = 2.7% and 2.3% for DRH and CRH, respectively). Collected data evidenced the hysteresis behavior of ambient particles and variability in both DRH and CRH between the two seasons. Summer samples showed higher DRH and CRH (on average 71.4 ± 1.0% RH and 62.6 ± 1.2% RH, respectively) than the winter ones (on average 55.2 ± 0.7% RH and 46.9 ± 0.6% RH). This behavior was related to the higher content of sulfates during the summer season. Conversely, the mass hygroscopic growth factor at 90% RH was higher for winter samples (2.76 ± 0.06) with respect to the summer ones (1.91 ± 0.11). Since hysteresis behavior affects optical properties of aerosols, when RH conditions are within the loop, the hygroscopic growth factor could be assigned in a wrong way. Thus, the growth factor was calculated within the hysteresis loop for both upper and lower branches: results showed that difference in hygroscopic growth factor could reach up the 24%.

Aerosol size distributions and chemical compositions were characterized during extensive balloon soundings over the Terni valley (central Italy). The evolution of aerosol size distributions across the mixing layer, and further up, revealed features similar in many aspects to those observed over Milan (the Po Valley) and attributed to sedimentation and ageing dynamics. Sedimentation led to a lower vertical mixing of coarse particles than of fine ones. This also resulted in a decline in the mean volume of coarse particles across the mixing height (−50.5 ± 15.1% and −47.2 ± 12.4% over Terni and Milan, respectively) accompanied by a reduction in crustal components. Conversely, fine particles were subject to ageing, resulting in an increase in their mean volume above the mixing height (+10.9 ± 4.8% and +4.0 ± 3.1% over Terni and Milan, respectively); this process was accompanied by an increase in secondary aerosol components, and a greater correlation between different aerosol size-classes. These results were obtained over basins of different sizes and geographical location; as such, they corroborate the presence of common forms of behaviour driven by comparable meteorological and orographic conditions, which seem to characterize polluted basin valleys in general.

Polycyclic aromatic hydrocarbons (PAHs) and nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) were identified from both air particulate matter and soils. For air sampling, a six-stage cascade impactor was situated in an urban area (Catania, Italy) that is recognized for its high traffic volume. The soil samples were collected every 1.5 km from under the grass by the side of the median of a Catania road along its full length (8.2 km). HPLC in electrochemical-fluorescence detection mode was used for selective separation, identification and quantification of analytes in air and soil samples, providing both good selectivity and sensitivity. The seasonal trends, effects of urban traffic, and source profiles are discussed herein. Higher PM10 concentrations were observed for summer (43 μg m−3) in comparison to winter (24 μg m−3). Conversely, the PAHs contained in PM10 were higher in winter (0.48 ng m−3 for fluoranthene) than in summer (0.14 ng m−3 for fluoranthene). Analysis of the size-segregated urban par...

The results presented summarise the ones obtained in the coordinated research project Tosca, which extensively analysed the impact of Milan urban PM on human health. The molecular markers of exposure and effects of seasonally and size-fractionated PMs (summer and winter PM10, PM2.5) were investigated in in vitro (human lung cell lines) and in vivo (mice) systems. The results obtained by the analyses of cytotoxic, pro-inflammatory and genotoxic parameters demonstrate that the biological responses are strongly dependent upon the PM samples seasonal and dimensional variability, that ultimately reflect their chemical composition and source. In fact summer PM10, enriched in crustal elements and endotoxins, was the most cytotoxic and pro-inflammatory fraction, while fine winter PMs induced genotoxic effects and xenobiotic metabolizing enzymes (like CYP1B1) production, likely as a consequence of the higher content in combustion derived particles reach in PAHs and heavy toxic metals. These outcomes outline the need of a detailed knowledge of the PMs physico-chemical composition on a local scale, coupled with the biological hazard directly associated to PM exposure. Apparently this is the only way allowing scientists and police-makers to establish the proper relationships between the respirable PM quantity/quality and the health outcomes described by clinicians and epidemiologists.

A novel approach for measuring vertical profiles of HCs and particle number concentrations was described and applied in the low troposphere over Milan (Italy) during typical spring and summer days. Particle profiles yielded nearly homogeneous concentrations below the mixing height, with level-to-ground concentration ratios of 92–97%, while HCs showed a more pronounced decrease (74–95%). Vertical mixing and photochemical loss of HCs were demonstrated to cause these gradients. Much lower concentrations were observed for the profiles above the mixing height, where the HC mixtures showed also a different composition, which was partially explained by the horizontal advection of air with HC sources different to those prevailing at the site. The application of pseudo-first order kinetics for reactions between HCs and the hydroxyl radical allowed for the estimation of the vertical mixing time scale in the order of 100 ± 20 min.

Vertical profiles of particle number concentration, potential temperature and relative humidity were measured in the Po Valley using an optical particle counter and a portable meteorological station attached to a tethered balloon. The field campaign covered the period 2006–2008, providing an extended dataset of vertical profiles in both stable and convective boundary-layer conditions. These vertical profiles were used to estimate an experimentally retrieved mixing height (MH). The MM5 meteorological model was also used to simulate the atmospheric dispersion characteristics for the same period, using a variety of different boundary-layer and land surface parameterization schemes (Medium-Range Forecast; high-resolution Blackadar; Gayno–Seaman; and Pleim–Chang). The model simulated MHs were compared among themselves, and then with that measured from balloon soundings. MRF parameterization represented the best compromise solution to simulate increasing MHs in the Po Valley. The MM5 simulations showed the regional character of meteorological forcing on PM ground-concentrations in the Po Valley.

Vertical aerosol profiles were directly measured over the city of Milan during three years (2005–2008) of field campaigns. An optical particle counter, a portable meteorological station and a miniaturized cascade impactor were deployed on a tethered balloon. More than 300 vertical profiles were measured, both in winter and summer, mainly in conditions of clear, dry skies. The mixing height was determined from the observed vertical aerosol concentration gradient, and from potential temperature and relative humidity profiles. Results show that inter-consistent mixing heights can be retrieved highlighting good correlations between particle dispersion in the atmosphere and meteorological parameters. Mixing height growth speed was calculated for both winter and summer showing the low potential atmospheric dispersion in winter. Aerosol number size distribution and chemical composition profiles allowed us to investigate particle behaviour along height. Aerosol measurements showed changes in size distribution according to mixing height. Coarse particle profiles (dp>1.6 μm) were distributed differently than the fine ones (dp

Fine particulate matter (PM1 and PM2.5) was collected in Milan over the summer (August-September) and winter (January-March) seasons of 2007/2008. Particles were analyzed for their chemical composition (inorganic ions, elements and PAHs) and the effects produced on the human lung carcinoma epithelial cell line A549. In vitro tests were performed to assess cell viability with MTT assay, cytokine release (IL-6 and IL-8) with ELISA, and DNA damage with COMET assay. Results were investigated by bivariate analysis and multivariate data analysis (Principal Component Analysis, PCA) to investigate the relationship between PM chemical composition and the biological effects produced by cell exposure to 12 microg cm(-2). The different seasonal chemical composition of PM showed to influence some biological properties. Summer PM samples had a high mass contribution of SO(4)(=) (13+/-2%) and were enriched in some elements, like Al, As, Cr, Cu, and Zn, compared to winter PM samples. Cell viability reduction was two times higher for summer PM samples in comparison with winter ones (27+/-5% and 14+/-5%, respectively), and the highest correlation coefficients between cell viability reduction and single chemical components were with As (R(2)=0.57) and SO(4)(=) (R(2)=0.47). PM1 affected cell viability reduction and induced IL-8 release, and these events were interrelated (R(2)=0.95), and apparently connected with the same chemical compounds. PM2.5 fraction, which was enriched in Ca(++) and Mg(++) (from soil dust), and Al, Fe, Zn, Ba Mn, produced cell viability reduction and DNA damage (R(2)=0.73).

Within the framework of air quality monitoring, measurements by Earth-observing satellite sensors are combined here with regional meteorological and chemical transport models. Two satellite-derived products developed within the QUITSAT project, regarding significant pollutants including PM2.5 and NO2, are presented. Estimates of PM2.5 concentrations at ground level were obtained using moderate resolution imaging spectroradiometer (Terra-Aqua/NASA) aerosol optical properties. The semi-empirical approach adopted takes into account PM2.5 sampling and meteorological descriptions of the area studied, as simulated by MM5, to infer aerosol optical properties to PM projection coefficients. Daily maps of satellite-based PM2.5 concentrations over northern Italy are derived. Monthly average values were compared with in situ PM2.5 samplings showing good agreement. Ozone monitoring instrument (OMI) (Aura/NASA) NO2 tropospheric contents are merged using the GAMES chemical model simulations. The method employs a weighted rescaling of the model column in the troposphere according to the OMI observations. The weightings take into account measurement errors and model column variances within the satellite ground pixel. The obtained ground-level concentrations of NO2 show good agreement with the environmental agencies’ in situ. The capabilities of Earth observation satellites have greatly improved over the last few years, with gradual improvements in temporal and spatial resolutions and enhancements in radiometric accuracy, thus encouraging further studies on the use of satellite data to assess air quality (AQ). Within this context, the synoptic view and the daily repetition cycle of satellite-based measurements strengthen the potential for monitoring air pollution transport and directly evaluating the spatial distribution of various air pollutant concentrations. These evaluations are in compliance with the regulations of

Elemental concentrations of air particulates collected by gravimetric method in a scrap iron and steel smelter industry were determined using a combination of four different techniques: total reflection X-ray fluorescence (TXRF), the conventional energy dispersive X-ray fluorescence (EDXRF), the modified (polarized) energy dispersive X-ray fluorescence ED(P)XRF, and the inductively coupled plasma optical emission spectroscopy (ICP-OES) analytical techniques. A number of elements were detected by all the techniques, some by one or two while some are better detected by a particular technique. The ICP-OES and TXRF techniques have low detection limits worth of consideration despite the risk of contamination possible during sample preparation. The techniques are observed to be adequate for analytes above K except for Br and Pb, which are significantly lost during digestion of samples. The Mo-target EDXRF, just like ICP-OES and TXRF, cannot detect elements below K but substitute well for them in the analysis of volatile elements like Br and Pb despite its higher detection limits for the said elements. The Mo-target EDXRF is also observed to be inadequate for rare earth elements with energies close to that of Mo as a result of possible poor resolution of the energy peaks. The ED(P)XRF is more adequate in the analysis of low Z elements as well as volatile ones. Where volatile elements like Cl, Br, and Pb and/ or low Z elements are of primary interest, the use of techniques involving no elaborate sample preparation should be considered. © 2009 Taylor & Francis.