Size-dependent Composition Research Articles

Size-dependent composition and in-situ structure analysis of the milk fat globule membrane in buffalo milk

This study provides insights into the composition and in-situ structures of the milk fat globule membrane (MFGM) in buffalo milk with different fat globule sizes (0.55 μm and 8.04 μm). Small fat globules contained a higher amount of MFGM proteins and polar lipids, while the content of MFGM components (except for ADPH) was greater per unit membrane area in large fat globules. A total of 386 differentially expressed proteins were identified, with many of the most differentially expressed proteins being associated with human diseases, such as cancer and elderly diseases. The coverage of sphingomyelin and certain MFGM proteins (BTN and PAS 6/7) on large fat globules was higher, potentially linked to the presence of larger, irregular lipid rafts and patch-shaped glycocalyxes, respectively. These findings suggest that small fat globules are suitable for nutritional fortification of buffalo milk, while large fat globules are appropriate for the preparation of functional dairy-based ingredients.

Response of size-dependent chemical composition of dissolved organic and inorganic species to land use types in tropical coastal headstreams

Land-use types dramatically affect the source, composition, behavior and fate of headstream chemical species. However, the influence of land-use types on the size-dependent composition of dissolved organic matter (DOM) and dissolved inorganic matter (DIM) is still unclear. Here, we evaluated the size-dependent concentration, composition and relationship of chemical species from 9 coastal headstreams (i.e. forested, agricultural and wetland headstreams) using multiple spectroscopic techniques including absorbance, excitation-emission matrix, near-edge X-ray absorption fine structure spectroscopy (NEXAFS), X-ray diffraction (XRD), scanning electron microscopy combined with energy dispersive spectroscopy (SEM-EDS) and synchrotron-based micro-X-ray fluorescence (μ-XRF). Results showed that 68.57%-85.78% of dissolved organic carbon (DOC) with abundant humic/fulvic-like substances were distributed in the <1 kDa fraction in all samples, with a higher percentage in wetland samples. Agricultural land-use increased the export of aluminosilicate minerals in >1 kDa fractions and terrestrial fulvic/humic-like substances from land to stream. Forested streams showed high DOC in the 1 kDa-0.2 μm fraction, predominance of autochthonous DOM rich in amides, amines, carboxyl and O-alkyl groups, and abundance whitlockite and ferromanganese oxides. Wetland streams were characterized by abundant halite, sylvite, and microbially-transformed humic-like DOM rich in aromatic and phenolic groups. Morphology and correlation analysis implied DIM was closely combined with fluorescent DOM (FDOM) and colored DOM (CDOM), resulting in more irregular organo-inorganic complexes in forested and agricultural streams, and more halite and sylvite crystal blocks encapsulating by smooth and close organic–inorganic complexes in wetland streams. Redundancy analysis (RDA) analysis suggested that land-use types (17.20%) and molecular weight (14.29%) were the prominent factors impacting the composition and relationship of DOM and DIM. Land-use types altered the sources and transport patterns of chemical species in headstreams, influencing their size-dependent compositions and associated biogeochemical processes. Such information is imperative for monitoring and developing land-use policies in coastal regions undergoing intense anthropogenic alterations.

Resonant-XRD Characterization of Nanoalloyed Au-Pd Catalysts for the Direct Synthesis of H2O2: Quantitative Analysis of Size Dependent Composition of the Nanoparticles †

The focus of this work is on the relationship between the quantitative structural characterization of bimetallic Au-Pd nanoparticles dispersed in an amorphous polymer matrix and their catalytic activity in the direct synthesis of hydrogen peroxide (DS reaction). Resonant X-ray powder diffraction with synchrotron radiation was employed to probe selectively and to reveal fine details of the structure of bimetallic nanoparticles embedded in the support. The semi-quantitative analysis of the resonant X-ray powdered diffraction data, made on a large number of metal nanoparticles, shows that in one of the polymer-supported Au-Pd catalyst for the DS reaction (P75) featured by an overall molar Pd/Au of about 5.54, the smallest metal nanoparticles (MNPs), which account for more than 99.9% of the total MNPs number and for more than 95% of the metal surface, are formed by practically pure palladium. The relative number of bimetallic alloyed nanoparticles is very small (less than 4 × 102 ppm) and they contribute to only about 2% of the total metal surface. In a second gold-enriched catalyst (P50) with an overall molar Pd/Au of 1.84, the proportion of the bimetallic alloyed nanoparticles increased to about 97% and they account for about 99% of the metal surface. As a result of the metal intermixing, the catalytic productivity for the DS reaction increased from 97 to 109 mmolH2O2/molH2, owing to the gold-promotion of palladium.

Aircraft and ground measurements of dust aerosols over the west African coast in summer 2015 during ICE-D and AER-D

Abstract. During the summertime, dust from the Sahara can be efficiently transported westwards within the Saharan air layer (SAL). This can lead to high aerosol loadings being observed above a relatively clean marine boundary layer (MBL) in the tropical Atlantic Ocean. These dust layers can impart significant radiative effects through strong visible and IR light absorption and scattering, and can also have indirect impacts by altering cloud properties. The processing of the dust aerosol can result in changes in both direct and indirect radiative effects, leading to significant uncertainty in climate prediction in this region. During August 2015, measurements of aerosol and cloud properties were conducted off the coast of west Africa as part of the Ice in Cloud Experiment – Dust (ICE-D) and AERosol properties – Dust (AER-D) campaigns. Observations were obtained over a 4-week period using the UK Facility for Atmospheric Airborne Measurements (FAAM) BAe 146 aircraft based on Santiago Island, Cabo Verde. Ground-based observations were collected from Praia (14∘57′ N, 23∘29′ W; 100 m a.s.l.), also located on Santiago Island. The dust in the SAL was mostly sampled in situ at altitudes of 2–4 km, and the potential dust age was estimated by backward trajectory analysis. The particle mass concentration (at diameter d = 0.1–20 µm) decreased with transport time. Mean effective diameter (Deff) for supermicron SAL dust (d = 1–20 µm) was found to be 5–6 µm regardless of dust age, whereas submicron Deff (d = 0.1–1 µm) showed a decreasing trend with longer transport. For the first time, an airborne laser-induced incandescence instrument (the single particle soot photometer – SP2) was deployed to measure the hematite content of dust. For the Sahel-influenced dust in the SAL, the observed hematite mass fraction of dust (FHm) was found to be anti-correlated with the single scattering albedo (SSA, λ = 550 nm, for particles d &lt; 2.5 µm); as potential dust age increased from 2 to 7 days, FHm increased from 2.5 to 4.5 %, SSA decreased from 0.97 to 0.93 and the derived imaginary part (k) of the refractive index at 550 nm increased from 0.0015 to 0.0035. However, the optical properties of Sahara-influenced plumes (not influenced by the Sahel) were independent of dust age and hematite content with SSA ∼ 0.95 and k ∼ 0.0028. This indicates that the absorbing component of dust may be source dependent, or that gravitational settling of larger particles may lead to a higher fraction of more absorbing clay–iron aggregates at smaller sizes. Mie calculation using the measured size distribution and size-resolved refractive indices of the absorbing components (black carbon and hematite) reproduces the measured SSA to within ±0.02 for SAL dust by assuming a goethite ∕ hematite mass ratio of 2. Overall, hematite and goethite constituted 40–80 % of the absorption for particles d &lt; 2.5 µm, and black carbon (BC) contributed 10–37 %. This highlights the importance of size-dependent composition in determining the optical properties of dust and also the contribution from BC within dust plumes.

Size-Dependent Oxidation State and CO Oxidation Activity of Tin Oxide Clusters

The CO oxidation reaction is an industrially important reaction; however, the practical catalysts are limited to noble metals. In this paper, we report a systematic study of the CO oxidation ability on cheap and less noble tin oxide clusters with the aim of quantitatively understanding the active sites. We synthesized size-controlled tin oxide clusters in mesoporous silica using the dendrimer templating method, employing dendritic phenylazomethine with a tetraphenylmethane core (TPMG4) as the template molecule. The clusters had different sizes depending on the added amount of SnCl2 as a precursor to TPMG4. The synthesized tin oxide clusters contained not only stable tetravalent Sn(IV) but also metastable divalent Sn(II) due to the structural stability and had a size-dependent composition. The CO oxidation activity of the tin oxide clusters increased with decreasing cluster size depending on the Sn(II)/Sn(IV) ratio. We also found the correlation between the Sn(II) fraction and the CO oxidation activity, cl...

Unexpectedly acidic nanoparticles formed in dimethylamine–ammonia–sulfuric-acid nucleation experiments at CLOUD

Abstract. New particle formation driven by acid–base chemistry was initiated in the CLOUD chamber at CERN by introducing atmospherically relevant levels of gas-phase sulfuric acid and dimethylamine (DMA). Ammonia was also present in the chamber as a gas-phase contaminant from earlier experiments. The composition of particles with volume median diameters (VMDs) as small as 10 nm was measured by the Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS). Particulate ammonium-to-dimethylaminium ratios were higher than the gas-phase ammonia-to-DMA ratios, suggesting preferential uptake of ammonia over DMA for the collected 10–30 nm VMD particles. This behavior is not consistent with present nanoparticle physicochemical models, which predict a higher dimethylaminium fraction when NH3 and DMA are present at similar gas-phase concentrations. Despite the presence in the gas phase of at least 100 times higher base concentrations than sulfuric acid, the recently formed particles always had measured base : acid ratios lower than 1 : 1. The lowest base fractions were found in particles below 15 nm VMD, with a strong size-dependent composition gradient. The reasons for the very acidic composition remain uncertain, but a plausible explanation is that the particles did not reach thermodynamic equilibrium with respect to the bases due to rapid heterogeneous conversion of SO2 to sulfate. These results indicate that sulfuric acid does not require stabilization by ammonium or dimethylaminium as acid–base pairs in particles as small as 10 nm.

Agglomeration in counter-current spray drying towers. Part A: Particle growth and the effect of nozzle height

Agglomeration of particles and droplets is critical to the operation of spray dryers, however it remains relatively unexplored. This paper studies the effect of the nozzle height on product properties, wall deposits and dryer conditions in a counter-current spray drying tower of detergent with a swirling air flow. The process efficiency is driven by changes in particle agglomeration. To interpret the results and facilitate the study of swirl towers, it is useful to subdivide these units according to the sources of growth in (a) spray region(s), (b) concentrated near-wall region(s) and (c) wall deposits. The particles formed are very heterogeneous and show a size-dependent composition. In this case, particle properties are driven by the separation of solid and liquid phases during atomization and the formation of a heterogeneous set of droplets. Agglomeration serves to homogenise the product and create a distinct source of porosity. The capacity and energy consumption of the dryer are also determined by the evolution of the particle size, as fine powder is elutriated from the tower top and coarse particles are removed from the product. When the nozzle is moved to lower positions in the tower the increased temperature near the spray suppresses agglomeration, however the residence time is shortened and ultimately it leads to creation of wet, coarse granules. An optimum location is found high enough to maintain the drying efficiency but sufficiently far from the top exit to minimise the loss of fine particles. In this way, a capacity ratio (i.e. product vs spray dried powder) C>90% can be obtained and energy efficiency maximised.

Uptake of Semivolatile Secondary Organic Aerosol Formed from α-Pinene into Nonvolatile Polyethylene Glycol Probe Particles.

Semivolatile organic compounds (SVOCs) play an essential role in secondary organic aerosol (SOA) formation, chemical aging, and mixing of organic aerosol (OA) from different sources. Polyethylene glycol (PEG400) particles are liquid, polar, and nearly nonvolatile; they provide a new vehicle to study the interaction between SVOCs with OA. With a unique fragment ion C4H9O2(+) (m/z 89), PEG400 can be easily separated from α-pinene SOA in aerosol mass spectra. By injecting separately prepared PEG probe particles into a chamber containing SOA coated on ammonium sulfate seeds, we show that a substantial pool of SVOCs exists in equilibrium with the original SOA particles. Quantitative findings are based on bulk mass spectra, size-dependent composition, and the evolution of individual particle mass spectra, which we use to separate the two particle populations. We observed a larger fraction of SVOC vapors with increased amounts of reacted α-pinene. For the same amount of reacted α-pinene, the SOA formed from α-pinene oxidized by OH radicals had a higher fraction of SOA vapors than SOA formed by α-pinene ozonolysis. Compared to the PEG400 probe particles, we observed a lower mass fraction of SVOCs in poly(ethylene glycol) dimethyl ether (MePEG500) probe particles under otherwise identical conditions; this may be due to the lower polarity of the MePEG500 or caused by esterification reactions between the PEG400 and organic acids in the SOA.

A theoretical investigation of size-dependent composition and stresses in nanowires and nanotubes of ceria

In the past few decades, nanostructures of ceria have received significant attention for potential applications in a variety of technologies. Experiments have frequently shown that physical properties of ceria nanomaterials are strongly size-dependent. Here, by accounting for the highly non-linear coupling between electrical, chemical and mechanical driving forces, we develop a continuum model which allows us to investigate equilibrium distribution of defects in nanowires and nanotubes of ceria. It is shown that the model predicts strongly size-dependent non-stoichiometric composition, lattice constant and surface stresses in ceria nanostructures whose diameter is comparable with the Debye's length scale of the problem.

On the link between hygroscopicity, volatility, and oxidation state of ambient and water-soluble aerosols in the southeastern United States

Abstract. The formation of secondary organic aerosols (SOAs) combined with the partitioning of semivolatile organic components can impact numerous aerosol properties including cloud condensation nuclei (CCN) activity, hygroscopicity, and volatility. During the summer 2013 Southern Oxidant and Aerosol Study (SOAS) field campaign in a rural site in the southeastern United States, a suite of instruments including a CCN counter, a thermodenuder (TD), and a high-resolution time-of-flight aerosol mass spectrometer (AMS) were used to measure CCN activity, aerosol volatility, composition, and oxidation state. Particles were either sampled directly from ambient or through a particle-into-liquid sampler (PILS), allowing the investigation of the water-soluble aerosol component. Ambient aerosols exhibited size-dependent composition with larger particles being more hygroscopic. The hygroscopicity of thermally denuded aerosols was similar between ambient and PILS-generated aerosols and showed limited dependence on volatilization. Results of AMS three-factor positive matrix factorization (PMF) analysis for the PILS-generated aerosols showed that the most hygroscopic components are most likely the most and the least volatile features of the aerosols. No clear relationship was found between organic hygroscopicity and the oxygen-to-carbon ratio; in fact, isoprene-derived organic aerosols (isoprene-OAs) were found to be the most hygroscopic factor, while at the same time being the least oxidized and likely most volatile of all PMF factors. Considering the diurnal variation of each PMF factor and its associated hygroscopicity, isoprene-OA and more-oxidized oxygenated organic aerosols are the prime contributors to hygroscopicity and co-vary with less-oxidized oxygenated organic aerosols in a way that induces the observed diurnal invariance in total organic hygroscopicity. Biomass burning organic aerosols contributed little to aerosol hygroscopicity, which is expected since there was little biomass burning activity during the sampling period examined.

Measurement of size-dependent composition variations for gamma prime (γ') precipitates in an advanced nickel-based superalloy.

Energy-dispersive X-ray (EDX) spectroscopy in the scanning transmission electron microscope (STEM) has been used to demonstrate the presence of size-dependent compositional variation for L12-structured Ni3Al-type gamma-prime (γ') precipitates within a commercial RR1000 Ni-based superalloy. This semi-quantitative elemental analysis has been achieved using electrochemical extraction of the γ' precipitates from the γ matrix. The applicability of this approach to size-dependent compositional analysis of precipitates was confirmed by a comparison of the size distribution for the extracted precipitates with those present in traditional electropolished foil specimens in the size range 20-250nm. By applying suitable thickness-dependent absorption-corrections we have demonstrated that the composition of γ' precipitates in our material depends on the size of the precipitate in the range of 5nm to 3μm. In particular, the Al content was observed to increase in smaller γ' precipitates while Ti and Ta contents are constant for all sizes of precipitate. Hf was observed to be present only in the largest precipitates. This type of local compositional information provides invaluable input to assess the accuracy of microstructural modelling for these complex alloys and provides new evidence supporting the importance of anti-site diffusion.

Analysis of CCN activity of Arctic aerosol and Canadian biomass burning during summer 2008

Abstract. The NASA DC-8 aircraft characterized the aerosol properties, chemical composition, and cloud condensation nuclei (CCN) concentrations of the summertime Arctic during the 2008 NASA Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) campaign. Air masses characteristic of fresh and aged biomass burning, boreal forest, Arctic background, and anthropogenic industrial pollution were sampled. Observations were spatially extensive (50–85° N and 40–130° W) and exhibit significant variability in aerosol and CCN concentrations. The chemical composition was dominated by highly oxidized organics (66–94% by volume), with a water-soluble mass fraction of more than 50%. The aerosol hygroscopicity parameter, κ, ranged between κ = 0.08–0.32 for all air mass types. Industrial pollution had the lowest κ of 0.08 ± 0.01, while the Arctic background had the highest and most variable κ of 0.32 ± 0.21, resulting from a lower and more variable organic fraction. Both fresh and aged (long-range transported) biomass burning air masses exhibited remarkably similar κ (0.18 ± 0.13), consistent with observed rapid chemical and physical aging of smoke emissions in the atmosphere, even in the vicinity of fresh fires. The organic hygroscopicity (κorg) was parameterized by the volume fraction of water-soluble organic matter (εWSOM), with a κ = 0.12, such that κorg = 0.12εWSOM. Assuming bulk (size-independent) composition and including the κorg parameterization enabled CCN predictions to within 30% accuracy for nearly all environments sampled. The only exception was for industrial pollution from Canadian oil sands exploration, where an external mixture and size-dependent composition was required. Aerosol mixing state assumptions (internal vs. external) in all other environments did not significantly affect CCN predictions; however, the external mixing assumption provided the best results, even though the available observations could not determine the true degree of external mixing and therefore may not always be representative of the environments sampled. No correlation was observed between κorg and O : C. A novel correction of the CCN instrument supersaturation for water vapor depletion, resulting from high concentrations of CCN, was also employed. This correction was especially important for fresh biomass burning plumes where concentrations exceeded 1.5×104 cm−3 and introduced supersaturation depletions of &amp;amp;geq;25%. Not accounting for supersaturation depletion in these high concentration environments would therefore bias CCN closure up to 25% and inferred κ by up to 50%.

Particle capture models: Comparison with experimental data

Sand filtration is a becoming a widely used technique for the treatment of urban run off water, particularly for the capture of particulate metal pollutants. Currently the design rules for such systems are focussed on the civil engineering and hydrological aspects, whilst metal removals are typical quoted as broad percentages. The present study is the first step in developing a new design method for such systems, by comparing an established particle capture model consisting of two partial differential equations, one for particle capture and one for loading. The particle capture model was fitted to the outlet concentrations of several metal species, assuming that all particles of a particular metal are identical and have the same probability of capture. Particle loading through the column was then used as a check on the model. Whilst the particle loading results near the surface of the sand filter are typically of the right order of magnitude, the model tended to over predict loading of the particles in the mid section of the sand filter. Modelling is presented showing that the assumption of particle uniformity may be the cause of this over prediction. An example is presented where the model fails to predict the loading, highlighting the need to include dissolution and washing in future models. References arc Design Guideline Manual Stormwater Treatment Devices {Auckland: Auckland Regional Council 2003} http://www.arc.govt.nz/plans/technicalpublications/technical-publications-1-50.cfm [Accessed 30/05/2010]. G. Birch and S. Taylor Source of heavy metals in sediments of the Port Jackson estuary, Australia Science of The Total Environment, 227, Issues 2--3, Pages 123--138, 9 March 1999, doi:10.1016/S0048-9697(99)00007-8 G. F. Birch and S. McCready and E. R. Long and S. S. Taylor and G. Spyrakis Contaminant chemistry and toxicity of sediments in Sydney Harbour Australia: spatial extent and chemistry---toxicity relationships Marine Ecology Progress Series, 363 71--87, 2008 doi:10.3354/meps07445 G. F. Birch, and S. McCready Catchment sources of heavy metal contamination and influence on the quality of receiving basin sediments in Port Jackson, Australia The Science of the Total Environment 407 2820--283, 2009 G. F. Birch, Contaminated soil and sediments in a highly-developed catchment-estuary system (Sydney estuary, Australia), an innovative stormwater remediation strategy Journal of Soils and Sediments, 11, 194--208, 2011. C. Carrasco. Experimental Studies of Sand Infiltration MPhil thesis, The University of Sydney, 2012. ccsmpc Georgia Stormwater Management Manual Technical Handbook 2, 2002 http://www.georgiastormwater.com/ [Accessed 18/5/2010]. R. A. Claytor and T. R. Schueler Design of Stormwater Filtering Systems, Ellicot City {Chesapeake Research Consortium}, 1996 T. N. Debo and A. J. Reese. Municipal Storm Water Management {Lewis Publishers, New York}, 2002 V. Gitis and E. Rubinstein and M. Livshits and G. Ziskindc Deep-bed filtration model with multistage deposition kinetics Chemical Engineering Journal, 163 78--85, 2010 M. Jartuna and R. T.Ottesen and E. Steinnesb and T. Voldena. Runoff of particle bound pollutants from urban impervious surfaces studied by analysis of sediments from stormwater traps Science of the Total Environment 396, 147--163, 2008 E. McKenzie and C. Wong and P. Green and M. Kayhanian and T. Young. Size dependent elemental composition of road-associated particles Science of the Total Environment, 398 145--153, 2008 mde. Maryland Stormwater Design Manual [Online]. Maryland: Maryland Department of the Environment, 2006 uprct. Water Sensitive Urban Design: Technical Guidelines for Western Sydney. Sydney: Upper Parramatta River Catchment Trust, 2004 A. Zamani and B. Maini. Flow of dispersed particles through porous media---Deep bed filtration Journal of Petroleum Science and Engineering, 69, 71-88, 2009 J. P. Herzig, D. M. Leclerc, P. Le. Goff. Flow of Suspensions through Porous Media—Application to Deep Filtration Journal of Industrial and Engineering Chemistry , 62 5, 8--35, 1970 doi:10.1021/ie50725a003

Aerosol chemical composition at Cabauw, The Netherlands as observed in two intensive periods in May 2008 and March 2009

Abstract. Observations of aerosol chemical composition in Cabauw, the Netherlands, are presented for two intensive measurement periods in May 2008 and March 2009. Sub-micron aerosol chemical composition was measured by an Aerodyne Aerosol Mass Spectrometer (AMS) and is compared to observations from aerosol size distribution measurements as well as composition measurements with a Monitor for AeRosol and GAses (MARGA) based instrument and a Thermal-Desorption Proton-Transfer-Reaction Mass-Spectrometer (TD-PTR-MS). An overview of the data is presented and the data quality is discussed. In May 2008 enhanced pollution was observed with organics contributing 40% to the PM1 mass. In contrast the observed average mass loading was lower in March 2009 and a dominance of ammonium nitrate (42%) was observed. The semi-volatile nature of ammonium nitrate is evident in the diurnal cycles with maximum concentrations observed in the morning hours in May 2008 and little diurnal variation observed in March 2009. Size dependent composition data from AMS measurements are presented and show a dominance of organics in the size range below 200 nm. A higher O:C ratio of the organics is observed for May 2008 than for March 2009. Together with the time series of individual tracer ions this shows the dominance of OOA over HOA in May 2008.

CCN Spectra, Hygroscopicity, and Droplet Activation Kinetics of Secondary Organic Aerosol Resulting from the 2010 Deepwater Horizon Oil Spill

Secondary organic aerosol (SOA) resulting from the oxidation of organic species emitted by the Deepwater Horizon oil spill were sampled during two survey flights conducted by a National Oceanic and Atmospheric Administration WP-3D aircraft in June 2010. A new technique for fast measurements of cloud condensation nuclei (CCN) supersaturation spectra called Scanning Flow CCN Analysis was deployed for the first time on an airborne platform. Retrieved CCN spectra show that most particles act as CCN above (0.3 ± 0.05)% supersaturation, which increased to (0.4 ± 0.1)% supersaturation for the most organic-rich aerosol sampled. The aerosol hygroscopicity parameter, κ, was inferred from both measurements of CCN activity and from humidified-particle light extinction, and varied from 0.05 to 0.10 within the emissions plumes. However, κ values were lower than expected from chemical composition measurements, indicating a degree of external mixing or size-dependent chemistry, which was reconciled assuming bimodal, size-dependent composition. The CCN droplet effective water uptake coefficient, γ(cond), was inferred from the data using a comprehensive instrument model, and no significant delay in droplet activation kinetics from the presence of organics was observed, despite a large fraction of hydrocarbon-like SOA present in the aerosol.

Improved sample preparation and quality control for the characterisation of titanium dioxide nanoparticles in sunscreens using flow field flow fractionation on-line with inductively coupled plasma mass spectrometry

Titanium dioxide in nanoparticulate form is used in large scale in a variety of consumer products including sunscreens. There is an increasing need for methodology for the reliable characterisation of the particle size and size dependent elemental composition in these complex matrices. Such measurement capability is essential for underpinning safety assessments, for quality control of existing products and for correlation of nanoparticle characteristics with biological effects observed in toxicity tests. This work describes the first systematic comparison and optimisation of extraction methods for titanium dioxide nanoparticles in sunscreen samples. Sunscreens were selected because of their wide use, high fat content and matrix of high complexity. Defatting of the sample with hexane followed by bath sonication with an aqueous extractant was found to provide stable suspensions of secondary titanium dioxide particles for their size characterisation by flow field flow fractionation on-line with element selective detection by inductively coupled plasma mass spectrometry. Further addition of a small amount of hexane to the aqueous extractant resulted in particle disaggregation and thus allowed for characterisation of the primary particle size. A novel approach based on sample spiking with aluminium-labelled titanium dioxide reference particles of known size was used to study the effect of extraction and separation conditions on particle size distribution in the presence of the real sample matrix. The developed methodology was applied to analysis of commercial sunscreens with various sun protection factors. Titanium extraction efficiency, particle size distribution and titanium dioxide recovery from the FFF channel were determined for each product.

Airborne observations of the Eyjafjalla volcano ash cloud over Europe during air space closure in April and May 2010

Abstract. Airborne lidar and in-situ measurements of aerosols and trace gases were performed in volcanic ash plumes over Europe between Southern Germany and Iceland with the Falcon aircraft during the eruption period of the Eyjafjalla volcano between 19 April and 18 May 2010. Flight planning and measurement analyses were supported by a refined Meteosat ash product and trajectory model analysis. The volcanic ash plume was observed with lidar directly over the volcano and up to a distance of 2700 km downwind, and up to 120 h plume ages. Aged ash layers were between a few 100 m to 3 km deep, occurred between 1 and 7 km altitude, and were typically 100 to 300 km wide. Particles collected by impactors had diameters up to 20 μm diameter, with size and age dependent composition. Ash mass concentrations were derived from optical particle spectrometers for a particle density of 2.6 g cm−3 and various values of the refractive index (RI, real part: 1.59; 3 values for the imaginary part: 0, 0.004 and 0.008). The mass concentrations, effective diameters and related optical properties were compared with ground-based lidar observations. Theoretical considerations of particle sedimentation constrain the particle diameters to those obtained for the lower RI values. The ash mass concentration results have an uncertainty of a factor of two. The maximum ash mass concentration encountered during the 17 flights with 34 ash plume penetrations was below 1 mg m−3. The Falcon flew in ash clouds up to about 0.8 mg m−3 for a few minutes and in an ash cloud with approximately 0.2 mg m−3 mean-concentration for about one hour without engine damage. The ash plumes were rather dry and correlated with considerable CO and SO2 increases and O3 decreases. To first order, ash concentration and SO2 mixing ratio in the plumes decreased by a factor of two within less than a day. In fresh plumes, the SO2 and CO concentration increases were correlated with the ash mass concentration. The ash plumes were often visible slantwise as faint dark layers, even for concentrations below 0.1 mg m−3. The large abundance of volatile Aitken mode particles suggests previous nucleation of sulfuric acid droplets. The effective diameters range between 0.2 and 3 μm with considerable surface and volume contributions from the Aitken and coarse mode aerosol, respectively. The distal ash mass flux on 2 May was of the order of 500 (240–1600) kg s−1. The volcano induced about 10 (2.5–50) Tg of distal ash mass and about 3 (0.6–23) Tg of SO2 during the whole eruption period. The results of the Falcon flights were used to support the responsible agencies in their decisions concerning air traffic in the presence of volcanic ash.

Size-resolved analysis of fine and ultrafine particulate matter by laser-induced breakdown spectroscopy

In emissions originating from industrial processes, elemental concentration characteristically depends on particle size. Therefore, not only is the average chemical composition of the particles in the focus of interest but also their size-dependent composition. For industrial applications such as on-line process control, a system using laser-induced breakdown spectroscopy (LIBS) is developed providing the analysis of particulate matter directly in an air stream with a short response time to changes in elemental composition. By using a co-flow in addition to the aersosol flow the time resolution of the system can be enhanced. Investigations are undertaken concerning properties of the laser plasma, the analysis of monodisperse and polydisperse aerosols with regard to the relative elemental concentration and the mass concentration of the particles. The system can be calibrated to either total elemental concentrations or relative compositions. The signal response to a variation of elemental concentration as well as to the particle mass concentration show kinds of saturation effects. Temporal plasma evolution for CaCl2 particles and pure argon are investigated. Different decay times for argon and the particle matter depending on the origin of lines within the plasma are observed. Electron density and temperature are determined using Ca emission lines to describe the temporal evolution of the plasma state for the particle analysis. It has been observed that the electron density increases rapidly for plasma temperatures above 10 000 K. Size-resolved analyses of particles in the size range from 20 nm up to 800 nm are carried out. It has been found that the signal response correlates with the mass distribution of the particles.

On the observability of chemical and physical aerosol properties by optical observations: Inverse modelling with variational data assimilation

Determining size-resolved chemical composition of aerosols is important for modelling the aerosols’ direct and indirect climate impact, for source–receptor modelling, and for understanding adverse health effects of particulate pollutants. Obtaining this kind of information from optical remote sensing observations is an ill-posed inverse problem. It can be solved by variational data assimilation in conjunction with an aerosol transport model. One important question is how much information about the particles’ physical and chemical properties is contained in the observations. We perform a numerical experiment to test the observability of size-dependent aerosol composition by remote sensing observations. An aerosol transport model is employed to produce a reference and a perturbed aerosol field. The perturbed field is taken as a proxy for a background estimate subject to uncertainties. The reference result represents the ‘true’ state of the system. Optical properties are computed from the reference results and are assimilated into the perturbed model. The assimilation results reveal that inverse modelling of optical observations significantly improves the background estimate. However, the optical observations alone do not contain sufficient information for producing a faithful retrieval of the size-resolved aerosol composition. The total mass mixing ratios, on the other hand, are retrieved with remarkable accuracy.

Analysis of size-classified fine and ultrafine particulate matter on substrates with laser-induced breakdown spectroscopy

Airborne particulate matter in the fine (0.1 µm–2.5 µm) and ultrafine (≤ 0.1 µm) size range is supposed to affect human health significantly. Smaller particles intrude more deeply into the lungs, so that an organism directly absorbs toxic compounds. Therefore, knowledge of the size-dependent composition of airborne particles is required to determine their health hazard. In this paper, we demonstrate the application of laser-induced breakdown spectroscopy to directly analyze size-classified particulate matter samples without any sample preparation. Samples analyzed are collected on filter substrates using a cascade impactor. Greased aluminum foils are used as filter substrate. To reduce ablation of the substrate material, low pulse energies of 0.6 mJ are used for plasma excitation. The plasma light is observed using an Echelle spectrometer. The effect of ambient gas and pressure on the line intensities is studied. Calibration samples for 14 elements relevant for human health were produced, and the system was calibrated for concentration ranges up to four orders of magnitude. Finally, the collected samples of particulate originating from steel-making processes were analyzed. The measurements show that the composition of these particles depends strongly on their size. For example, the elements lead, cadmium and copper are enriched within particles of about 200 nm diameter.