Changes In Particle Composition Research Articles

Substantially positive contributions of new particle formation to cloud condensation nuclei under low supersaturation in China based on numerical model improvements

Abstract. New particle formation (NPF) and subsequent particle growth are important sources of condensation nuclei (CN) and cloud condensation nuclei (CCN). While many observations have shown positive contributions of NPF to CCN at low supersaturation, negative NPF contributions were often simulated in polluted environments. Using the observations in a coastal city of Qingdao, Beijing, and Gucheng in north China, we thoroughly evaluate the simulated number concentrations of CN and CCN using an NPF-explicit parameterization embedded in the WRF-Chem model. For CN, the initial simulation shows large biases of particle number concentrations at 10–40 and 40–100 nm. By adjusting the process of gas–particle partitioning, including the mass accommodation coefficient (MAC) of sulfuric acid, the phase changes in primary organic aerosol emissions, and the condensational amount of nitric acid, the improvement of the particle growth process yields substantially reduced overestimation of CN. Regarding CCN, secondary organic aerosol (SOA) formed from the oxidation of semi-volatile and intermediate-volatility organic compounds (S/IVOCs) is called SI-SOA, the yield of which is an important contributor. At default settings, the SI-SOA yield is too high without considering the differences in precursor oxidation rates. Lowering the SI-SOA yield under linear H2SO4 nucleation scheme results in much-improved CCN simulations compared to observations. On the basis of the bias-corrected model, we find substantially positive contributions of NPF to CCN at low supersaturation (∼ 0.2 %) over broad areas of China, primarily due to competing effects of increasing particle hygroscopicity, a result of reductions in SI-SOA amount, surpassing that of particle size decreases. The bias-corrected model is robustly applicable to other schemes, such as the quadratic H2SO4 nucleation scheme, in terms of CN and CCN, though the dependence of CCN on SI-SOA yield is diminished likely due to changes in particle composition. This study highlights potentially much larger NPF contributions to CCN on a regional and even global basis.

Combination seepage test study of sandy soil and the filter

Abstract Dams are important structures for the development and utilization of water resources, and dam stability is significantly affected by the filter layer. In this paper, eight groups of combination seepage tests of impermeable materials and filter were conducted. The effects of variations in grade, relative density, and thickness of impermeable materials and filter on the combination seepage resistance performance were assessed. The test results showed that: impermeable material and filter grade significantly affect combination seepage resistance. The critical hydraulic gradient and permeability coefficient decrease by 34% with increasing soil coarseness within the design envelope. The critical hydraulic gradient and failure gradient of specimen decreased by 17 and 20%, when the relative density of the filter material decreased from 0.7 to 0.5, respectively. Therefore, in actual engineering applications, the dry density or relative density of the filter material should be strictly controlled during filling. Increasing the thickness of the filter benefits combination seepage. The effect of changes in particle composition and relative density on the combination seepage characteristics can be expressed by controlling constriction size.

Modelling the formation, growth and coagulation of soot in a combustion system using a 2-D population balance model

A 2-D population balance model utilizing carbon mass and surface sites as internal variables was developed for soot formation during hydrocarbon decomposition reactions. The model provides particle properties such as composition and mean polyaromatic hydrocarbon size, enabling the incorporation of cyclization reactions, soot maturation, and a dynamic model of surface reactions. Accompanied by a reduced kinetic model for gas-phase species, this population balance model was then discretized using the fixed-pivot method, to provide predictions of the soot distribution as a function of position within a plug flow reactor. The model predictions of the particle size distribution functions resulting from high-temperature hydrocarbon pyrolysis within a PFTR system provide good comparison with experimental measurements under a variety of conditions. In addition to this, by tracking the changes in particle composition occurring through cyclization reactions, the point of carbon particle maturity could be determined, allowing subsequent predictions of the size distributions of the primary particles comprising soot aggregates. Through comparison with TEM and SEM imaging, these primary particle distributions were found to be accurate for the experimental conditions examined. While the implementation of the second internal variable describing particle composition was not found to provide substantial improvements to the prediction of the overall aggregate distribution from existing models, the additional computational cost that accompanies additional variables is justified in applications where morphological predictions of particle aggregates are of interest, in addition to their size distribution.

Seasonal particle responses to near‐bed shear stress in a shallow, wave‐ and current‐driven environment

AbstractNovel analysis of in situ acoustic and optical data collected in a shallow, wave‐ and current‐driven environment enabled determination of (1) particle characteristics that were most affected by near‐bed physical forcing over seasonal scales and (2) characteristic shear stress, τchar, at which the rate of change to particle characteristics was most pronounced. Near‐bed forcing and particle responses varied by season. Results indicated that moderate τchar values of 0.125 Pa drove changes in particle composition during summer. In winter, particle concentration effects were most affected at τchar of 0.05 Pa, suggesting dominance of fluff layer resuspension. Changes to particle size were most relevant during a biologically productive springtime period, with initiation of particle disaggregation occurring most commonly at τchar of 0.25 Pa. These results suggest that it may be more important to parameterize τchar, as opposed to critical shear stress for erosion, for sediment transport models.

The quantification of entropy for multicomponent systems: Application to microwave-assisted comminution

The second law of thermodynamics, through exergy analysis, is commonly applied to quantify process inefficiencies in metallurgical reactors, however, it has not yet been used to understand physical processes and changes in particle-based systems. Correlating the state of mixing of particle texture and homogeneous liquid mixtures is of importance. This paper applies the exergy analysis and excess entropy method to two sets of experiments highlighting the differential breakage as microwave pre-treatment is applied to a gold-copper ore. Grinding kinetic properties were measured following the top-size fraction method and calculated using the population balance model. The approach combines the mixing entropy on the system level (streams) and the entropy for multicomponent particle systems, using automated mineralogy data to quantify the effects of intergrowth and improvements in grinding performance. This is a first step towards understanding mineral processing not only in terms of energy conservation (first law of thermodynamics) but also in terms of the quality of energy available at multicomponent systems (second law of thermodynamics). When applied to comminution processes, this methodology enables us to understand the change in particle composition (its degree of liberation) as well as changes in particle size, being an important measure of process efficiency and selectivity.

Long-Term Changes of Particle Flux in the Canary Basin Between 1991 and 2009 and Comparison to Sediment Trap Records Off Mauritania

Eastern Boundary Upwelling Ecosystems (EBUEs) are associated with high biological productivity, high fish catch and they highly contribute to marine carbon sequestration. Whether coastal upwelling has intensified or weakened under climate change in the past decades is controversially discussed and different approaches (e.g. time-series of chlorophyll, wind, sea surface temperature, modelling experiments) have been considered. We present a record of almost two decades of particle fluxes (1991-2009) from ca. 600 to 3100 m water depth in the Canary Basin at site ESTOC (European Station for Time series in the Ocean Canary Islands; ca. 29°N, 15°30.W, ca. 3600 m water depth), located in the offshore transition zone of the northern Canary Current-EBUE. We compare these flux records with those measured at a mesotrophic sediment trap site further south off Cape Blanc (Mauretania, ca. 21°N). The deep ocean fluxes at ESTOC in ca. 3 km recorded the evolution of the coastal Cape Ghir filament (30-32°N, 10-12°W) due to lateral advection of particles, whereas the upper water column sediment traps in ca. 1 km reflected the oligotrophic conditions in the overlying waters of ESTOC. We observed an increased emphasis in spring-time fluxes since 2005, associated with a change in particle composition, while satellite chlorophyll biomass did not show this pattern. Due to its northern location in the CC-EBUEs, spring biogenic fluxes at ESTOC provide a better relationship to the forcing of the North Atlantic Oscillation than those recorded further south off Cape Blanc. Off Cape Blanc, deep fluxes showed the best overlap with the deep ESTOC fluxes during the spring season before 2005. On the long-term, both chlorophyll and particle fluxes showed an increasing trend at ESTOC which was not observed further south at the mesotrophic Cape Blanc site. This might indicate that, depending on their location along the NW African margin, coastal upwelling systems react differently to global change.

Significantly Enhanced Aerosol CCN Activity and Number Concentrations by Nucleation‐Initiated Haze Events: A Case Study in Urban Beijing

AbstractThe evolution of haze, involving multiple processes such as nucleation, coagulation, and condensation, may exert complex effects on aerosols' cloud condensation nuclei (CCN) activity and number concentration (NCCN). Based on field campaigns carried out in the winters of 2014 and 2016 in Beijing, we show that NCCN was significantly enhanced by the evolution of haze, substantially driven by the nucleation process (or new particle formation). The enhancement factor of NCCN by such nucleation‐initiated haze episodes, E_NCCN, defined as the ratio of NCCN after haze events to NCCN prior to haze events, ranged from 2.2 to 6.5 at a supersaturation (S) = 0.76% and from 4.2 to 17.3 at S = 0.23%, the magnitude of which partially depends on the severity of the haze event. The enhancements are much greater than those previously observed and those from model simulations of contribution from new particle formation. This suggests that CCN sources from new particle formation may be underestimated, needing reevaluation in polluted environments where the subsequent growth of newly formed particles can last 2–3 days, yielding more CCN‐sized particles. We further quantified that the changes in particle size and composition during the nucleation‐initiated evolution of haze are responsible for > 80% and 12–20%, respectively, of the enhancement in CCN activity. The changes in particle composition had a limited impact because most of the ambient particles were already hydrophilic, with hygroscopic parameters of 0.2–0.65.

Probing soot structure and electronic properties by optical spectroscopy

In this work, the physicochemical transformation of soot particles during the initial stages of formation and growth was investigated in a laminar premixed flame of ethylene and air. The selected flame condition allowed producing two classes of carbon nanoparticles, namely incipient and primary soot particles, on the basis of their size distribution. The two classes of particles have been selectively collected in well distinct flame zones for further chemico-physical characterization. The optical band gap decreases as particle size grows up. Particle medium range order and structure at molecular level have been investigated by Raman and fluorescence spectroscopy. Slight changes in particle composition were observed for incipient and primary soot. Both kinds of particles are made of a similar ensemble of fluorescence centers, which produce excitation dependent emission irrespective of particle sizes. In agreement with the Raman spectra, the molecular constituents of the particles are polyaromatic compounds with an average size of the order of ovalene molecules that only slightly increase from incipient to primary soot particles. These results suggest that the observed decrease of the optical band gap, as particle size increases, typical of a quantum-dot behavior, is not due to changes in particle composition at molecular level. Further investigations are needed to investigate possible evolution in supramolecular organization of the particles as they grow in flame and its effect on the optical band gap.

VIRTIS-H observations of the dust coma of comet 67P/Churyumov-Gerasimenko: spectral properties and color temperature variability with phase and elevation

We analyze 2–5μm spectroscopic observations of the dust coma of comet 67P/Churyumov-Gerasimenko obtained with the Visible InfraRed Thermal Imaging Spectrometer (VIRTIS-H) instrument on board Rosetta from 3 June to 29 October 2015 at heliocentric distancesrh= 1.24–1.55 AU. The 2–2.5μm color, bolometric albedo, and color temperature were measured using spectral fitting. Data obtained atα= 90° solar phase angle show an increase in bolometric albedo (0.05–0.14) with increasing altitude (0.5–8 km), accompanied by a possible marginal decrease in color and color temperature. Possible explanations include dark particles on ballistic trajectories in the inner coma and radial changes in particle composition. In the phase angle range 50°–120°, phase reddening is significant (0.031%/100 nm deg−1) for a mean color of 2%/100 nm atα= 90°, which might be related to the roughness of the dust particles. Moreover, a decrease in color temperature with decreasing phase angle is also observed at a rate of ~0.3 K deg−1, consistent with the presence of large porous particles, with low thermal inertia, and showing a significant day-to-night temperature contrast. Comparing data acquired at fixed phase angle (α= 90°), a 20% increase in bolometric albedo is observed near perihelion. Heliocentric variations in dust color are not significant in the time period we analyzed. The measured color temperatures vary from 260 to 320 K, and follow arh−0.6variation in therh= 1.24–1.5 AU range, which is close to the expectedrh−0.5value.

Impact of aggressive drive cycles on motor vehicle exhaust PM emissions

Aggressive drive cycles can cause substantial discrepancies between particulate matter (PM) measurement methods and increased emissions variability. Previous work demonstrated good agreement, within ~10%, between aerosol instruments and gravimetric determinations of PM mass emissions from gasoline direct injection engine (GDI) vehicles run over the Federal Test Procedure (FTP). In contrast, the present study reveals discrepancies of a factor of three or more for these vehicles run over the US06 portion of the supplemental FTP test. Two aspects of this are examined: 1) Changes in particle composition and morphology and 2) variability associated with vehicle history and test preparation. PM emissions during the US06 cycle are often accompanied by a strong nucleation mode. The organic to elemental carbon ratio increases relative to the FTP cycle. Also, the black carbon to elemental carbon ratio decreases, suggesting the formation of brown soot. The origins of these changes are not entirely clear, but are likely associated with the high engine exhaust temperatures during the US06 cycle. This also contributes to the higher test to test variability observed for the US06 versus FTP cycle. High temperatures can thermally desorb and pyrolyze various materials, including heavy hydrocarbons, ash, and inorganic salts deposited in the exhaust pipe, catalytic converter, and muffler that provide an additional PM source not present during FTP driving. The first day’s PM mass emissions are often substantially higher than on following days for the US06 cycle, but not the FTP. There is also a distinct drop in PM emissions between first and subsequent US06 cycles run in series.

Maximum sinking velocities of suspended particulate matter in a coastal transition zone

Abstract. Marine coastal ecosystem functioning is crucially linked to the transport and fate of suspended particulate matter (SPM). Transport of SPM is controlled by, amongst other factors, sinking velocity ws. Since the ws of cohesive SPM aggregates varies significantly with size and composition of the mineral and organic origin, ws exhibits large spatial variability along gradients of turbulence, SPM concentration (SPMC) and SPM composition. In this study, we retrieved ws for the German Bight, North Sea, by combining measured vertical turbidity profiles with simulation results for turbulent eddy diffusivity. We analyzed ws with respect to modeled prevailing dissipation rates ϵ and found that mean ws were significantly enhanced around log10(ϵ (m2 s−3)) ≈ −5.5. This ϵ region is typically found at water depths of approximately 15 to 20 m along cross-shore transects. Across this zone, SPMC declines towards the offshore waters and a change in particle composition occurs. This characterizes a transition zone with potentially enhanced vertical fluxes. Our findings contribute to the conceptual understanding of nutrient cycling in the coastal region which is as follows. Previous studies identified an estuarine circulation. Its residual landward-oriented bottom currents are loaded with SPM, particularly within the transition zone. This retains and traps fine sediments and particulate-bound nutrients in coastal waters where organic components of SPM become remineralized. Residual surface currents transport dissolved nutrients offshore, where they are again consumed by phytoplankton. Algae excrete extracellular polymeric substances which are known to mediate mineral aggregation and thus sedimentation. This probably takes place particularly in the transition zone and completes the coastal nutrient cycle. The efficiency of the transition zone for retention is thus suggested as an important mechanism that underlies the often observed nutrient gradients towards the coast.

Hygroscopic Behavior of Multicomponent Aerosols Involving NaCl and Dicarboxylic Acids

Atmospheric aerosols are usually complex mixtures of inorganic and organic compounds. The hygroscopicity of mixed particles is closely related to their chemical composition and interactions between components, which is still poorly understood. In this study, the hygroscopic properties of submicron particles composed of NaCl and dicarboxylic acids including oxalic acid (OA), malonic acid (MA), and succinic acid (SA) with various mass ratios are investigated with a hygroscopicity tandem differential mobility analyzer (HTDMA) system. Both the Zdanovskii-Stokes-Robinson (ZSR) method and extended aerosol inorganics model (E-AIM) are applied to predict the water uptake behaviors of sodium chloride/dicarboxylic acid mixtures. For NaCl/OA mixed particles, the measured growth factors were significantly lower than predictions from the model methods, indicating a change in particle composition caused by chloride depletion. The hygroscopic growth of NaCl/MA particles was well described by E-AIM, and that of NaCl/SA particles was dependent upon mixing ratio. Compared with model predictions, it was determined that water uptake of the NaCl/OA mixture could be enhanced and could be closer to the predictions by addition of levoglucosan or malonic acid, which retained water even at low relative humidity (RH), leading to inhibition of HCl evaporation during dehydration. These results demonstrate that the coexisting hygroscopic species have a strong influence on the phase state of particles, thus affecting chemical interactions between inorganic and organic compounds as well as the overall hygroscopicity of mixed particles.

Raman Spectroscopy of Optically Trapped Single Biological Micro-Particles.

The combination of optical trapping with Raman spectroscopy provides a powerful method for the study, characterization, and identification of biological micro-particles. In essence, optical trapping helps to overcome the limitation imposed by the relative inefficiency of the Raman scattering process. This allows Raman spectroscopy to be applied to individual biological particles in air and in liquid, providing the potential for particle identification with high specificity, longitudinal studies of changes in particle composition, and characterization of the heterogeneity of individual particles in a population. In this review, we introduce the techniques used to integrate Raman spectroscopy with optical trapping in order to study individual biological particles in liquid and air. We then provide an overview of some of the most promising applications of this technique, highlighting the unique types of measurements enabled by the combination of Raman spectroscopy with optical trapping. Finally, we present a brief discussion of future research directions in the field.

Evaluating exposure of pedestrians to airborne contaminants associated with non-potable water use for pavement cleaning.

Climate change and increasing demography press local authorities to look after affordable water resources and replacement of drinking water for city necessities like street and pavement cleaning by more available raw water. Though, the substitution of drinking by non-drinking resources demands the evaluation of sanitary hazards. This article aims therefore to evaluate the contribution of cleaning water to the overall exposure of city dwellers in case of wet pavement cleaning using crossed physical, chemical and biological approaches. The result of tracer experiments with fluorescein show that liquid water content of the cleaning aerosol produced is about 0.24 g m(-3), rending possible a fast estimation of exposure levels. In situ analysis of the aerosol particles indicates a significant increase in particle number concentration and particle diameter, though without change in particle composition. The conventional bacterial analysis using total coliforms as tracer suggests that an important part of the contamination is issued from the pavement. The qPCR results show a more than 20-fold increase of background genome concentration for Escherichia coli and 10-fold increase for Enterococcus but a negligible contribution of the cleaning water. The fluorescence analysis of the cleaning aerosol confirms the above findings identifying pavement surface as the major contributor to aerosol organic load. The physical, chemical and microbiological approaches used make it possible to describe accurately the cleaning bioaerosol and to identify the existence of significantly higher levels of all parameters studied during the wet pavement cleaning. Though, the low level of contamination and the very short time of passage of pedestrian in the zone do not suggest a significant risk for the city dwellers. As the cleaning workers remain much longer in the impacted area, more attention should be paid to their chronic exposure.

Aerosol hygroscopicity and cloud condensation nuclei activity during the AC<sup>3</sup>Exp campaign: implications for cloud condensation nuclei parameterization

Abstract. Aerosol hygroscopicity and cloud condensation nuclei (CCN) activity under background conditions and during pollution events are investigated during the Aerosol-CCN-Cloud Closure Experiment (AC3Exp) campaign conducted at Xianghe, China in summer 2013. A gradual increase in size-resolved activation ratio (AR) with particle diameter (Dp) suggests that aerosol particles have different hygroscopicities. During pollution events, the activation diameter (Da) measured at low supersaturation (SS) was significantly increased compared to background conditions. An increase was not observed when SS was > 0.4%. The hygroscopicity parameter (κ) was ~ 0.31–0.38 for particles in accumulation mode under background conditions. This range in magnitude of κ was ~ 20%, higher than κ derived under polluted conditions. For particles in nucleation or Aitken mode, κ ranged from 0.20–0.34 for background and polluted cases. Larger particles were on average more hygroscopic than smaller particles. The situation was more complex for heavy pollution particles because of the diversity in particle composition and mixing state. A non-parallel observation CCN closure test showed that uncertainties in CCN number concentration estimates ranged from 30–40%, which are associated with changes in particle composition as well as measurement uncertainties associated with bulk and size-resolved CCN methods. A case study showed that bulk CCN activation ratios increased as total condensation nuclei (CN) number concentrations (NCN) increased on background days. The background case also showed that bulk AR correlated well with the hygroscopicity parameter calculated from chemical volume fractions. On the contrary, bulk AR decreased with increasing total NCN during pollution events, but was closely related to the fraction of the total organic mass signal at m/z 44 (f44), which is usually associated with the particle's organic oxidation level. Our study highlights the importance of chemical composition in determining particle activation properties and underlines the significance of long-term observations of CCN under different atmospheric environments, especially regions with heavy pollution.

Reactive Uptake and Photo-Fenton Oxidation of Glycolaldehyde in Aerosol Liquid Water

The reactive uptake and aqueous oxidation of glycolaldehyde were examined in a photochemical flow reactor using hydrated ammonium sulfate (AS) seed aerosols at RH = 80%. The glycolaldehyde that partitioned into the aerosol liquid water was oxidized via two mechanisms that may produce aqueous OH: hydrogen peroxide photolysis (H2O2 + hν) and the photo-Fenton reaction (Fe (II) + H2O2 + hν). The uptake of 80 (±10) ppb glycolaldehyde produced 2-4 wt % organic aerosol mass in the dark (kH* = (2.09-4.17) × 10(6) M atm(-1)), and the presence of an OH source increased the aqueous uptake by a factor of 4. Although the uptake was similar in both OH-aging mechanisms, photo-Fenton significantly increased the degree of oxidation (O/C = 0.9) of the aerosols compared to H2O2 photolysis (O/C = 0.5). Aerosol organics oxidized by photo-Fenton and H2O2 photolysis resemble ambient "aged" and "fresh" OA, respectively, after the equivalent of 2 h atmospheric aging. No uptake or changes in particle composition occurred on dry seed aerosol. This work illustrates that photo-Fenton chemistry efficiently forms highly oxidized organic mass in aerosol liquid water, providing a possible mechanism to bridge the gap between bulk-phase experiments and ambient particles.

Nanoparticle Chemical Composition During New Particle Formation

The nano aerosol mass spectrometer (NAMS) was deployed at a coastal site in Lewes, Delaware, to measure the composition of 21 nm mass normalized (18 nm mobility) diameter nanoparticles during new particle formation (NPF) events. NAMS provides a quantitative measure of the atomic composition of individual nanoparticles. NAMS analysis of ambient particles showed only a small change in particle composition during NPF events in Lewes compared with off-event (before and/or after the event). The N mole fraction increased 15% on-event, whereas the C mole fraction decreased 25%, suggesting an enhanced inorganic component to the aerosol during NPF. The measured changes in atomic composition constrain the possible changes in molecular composition. To explore these constraints, an apportionment algorithm was applied to the atomic composition data. This algorithm partitions the atomic composition into sulfate, nitrate, and ammonium on the basis of the atomic abundance of S, N, and O and into organic matter on the basis of C and residual O after removing contributions to inorganic species. Particles were fully neutralized both on- and off-event. The nitrate to sulfate ratio during NPF ranged from 0.7 to 1.4, suggesting that ammonium nitrate is important to particle growth in this environment. Nonetheless, nanoparticles had a significant organic fraction, and upper limits for cationic amine content were determined. The relatively small changes in total particle composition on-event versus off-event suggest that observed changes in particle hygroscopicity and volatility during NPF at other locations may be linked to subtle changes in particle composition or to shifts in the character of the organic content.

Approach for Measuring the Chemistry of Individual Particles in the Size Range Critical for Cloud Formation

Aerosol particles, especially those ranging from 50 to 200 nm, strongly impact climate by serving as nuclei upon which water condenses and cloud droplets form. However, the small number of analytical methods capable of measuring the composition of particles in this size range, particularly at the individual particle level, has limited our knowledge of cloud condensation nuclei (CCN) composition and hence our understanding of aerosols effect on climate. To obtain more insight into particles in this size range, we developed a method which couples a growth tube (GT) to an ultrafine aerosol time-of-flight mass spectrometer (UF-ATOFMS), a combination that allows in situ measurements of the composition of individual particles as small as 38 nm. The growth tube uses water to grow particles to larger sizes so they can be optically detected by the UF-ATOFMS, extending the size range to below 100 nm with no discernible changes in particle composition. To gain further insight into the temporal variability of aerosol chemistry and sources, the GT-UF-ATOFMS was used for online continuous measurements over a period of 3 days.

Identification of chemistry-dependent artifacts on gravimetric PM fine readings at the T1 site during the MILAGRO field campaign

As part of the MIRAGE (MILAGRO) study conducted 7–30 March 2006 in Mexico City and its Metropolitan Area (MCMA), fine particulate matter (PM2.5) was collected using two Tapered Element Oscillating Microbalance (TEOM) systems, and a Partisol instrument at the T1 super-site (Tecamac, State of Mexico). Inorganic analysis was performed on filter-based (PM1, PM2.5-URG) measurements also collected at this site. Measurements from the gravimetric (TEOMs, Partisol) and URG systems were inter-compared with chemical speciation measurements using a Particle Into Liquid Sampler (PILS) and Thermal Optical methods. Mass and chemical balances applied over the first part of the study (11–22 March) showed that a TEOM using a device (SES) which reduces particle-bound water and retains a fraction of semi-volatile compounds (SVM) gives readings ∼30% larger than a conventional TEOM. In the second part of the study (26–30 March), the loss of SVM during TEOM-heated filter collection (both systems) represented a significant fraction of PM2.5 mass due to changes in particle composition. Overall, when nonvolatile nitrate dominated (i.e., when associated with crustal species and not NH4+) and/or sulfate dominates (SO42−/NO3− molar ratio is >1), PM2.5 mass readings are in agreement with those reported for the T1 site if TEOM is using a SES device. However, when volatile nitrate dominates (i.e., NH4NO3) or SO42−/NO3− molar ratio is <1, a larger fraction is lost from both TEOMs (with or without the SES device). Under the latter regime, uncertainties are large and gravimetric losses may reach 30%–50%. The gravimetric PARTISOL instrument recorded lower readings under all of the aforementioned conditions with differences versus TEOMs decreasing with increasing RH. These findings call for a careful characterization of such volatilization biases to improve current PM (PM10, PM2.5) measurements/networks, especially in alkaline-rich environments that can favor such biases. With regards to PM1 and PM2.5 filter-based measurements, findings are: 1) crustal-related elements are important features in the PM2.5–1 size fraction; 2) a factor of ∼2 overestimation of SO42− concentrations is recorded on substrates during PM collection and 3) main elements of a typical urban aerosol size distribution are concentrated in the 1 μm (versus 2.5 μm) size fraction.

Optical Characterization of an Eddy-induced Diatom Bloom West of the Island of Hawaii

Abstract. Optical properties were collected along a transect across cyclonic eddy Opal in the lee of Hawaii during the E-Flux III field experiment (10–27 March 2005). The eddy was characterized by an intense doming of isopycnal surfaces, and by an enhanced Deep Chlorophyll Maximum Layer (DCML) within its core. The phytoplankton bloom was diatom dominated, evidencing an eddy-induced shift in ecological community. Four distinct regions were identified throughout the water column at Opal's core: a surface mixed layer dominated by small phytoplankton; a layer dominated by "senescent" diatoms between the bottom of the upper mixed layer and the DCML; the DCML; and a deep layer characterized by decreasing phytoplankton activity. We focused on two parameters, the ratio of chlorophyll concentration to particulate beam attenuation coefficient, [chl]/cp, and the backscattering ratio (the particle backscattering to particle scattering ratio), b~bp, and tested their sensitivity to the changes in particle composition observed through the water column at the eddy center. Our results show that [chl]/cp is not a good indicator. Despite the shift in ecological community, the ratio remains controlled primarily by the variation in chlorophyll concentration per cell with depth (photoadaptation), so that its values increase throughout the DCML. Steeper increase of [chl]/cp below the DCML suggest that remineralization might be another important controlling factor. On the other hand, b~bp clearly indicates a shift from a small phytoplankton to a diatom dominated community. Below an upper layer characterized by constant values, the b~bp showed a rapid decrease to a broad minimum within the DCML. The higher values below the DCML are consistent with enhanced remineralization below the eddy-induced bloom. Both the "senescent" and the "healthy" diatom layers are characterized by similar optical properties, indicating some possible limitations in using optical measurements to fully characterize the composition of suspended material in the water column. The inverse relationship between b~bp, reported by others for Case II waters, is observed neither for the background conditions, nor in the presence of the eddy-induced diatom bloom. Between the two parameters, only the backscattering ratio showed the potential to be a successful indicator for changes in particle composition in Case I waters.