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- All Subjects: Atmospheric chemistry
- All Subjects: Nanoparticles
- Creators: Herckes, Pierre
In this work High Performance Size Exclusion Chromatography coupled with inline organic carbon detection (SEC-DOC), Diffusion-Ordered Nuclear Magnetic Resonance spectroscopy (DOSY-NMR) and Fluorescence Excitation-Emission Matrices (EEM) were used to characterize molecular weight distribution, functionality and optical properties of atmospheric organic matter. Fogs, aerosols and clouds were studied in a variety of environments including Central Valley of California (Fresno, Davis), Pennsylvania (Selinsgrove), British Columbia (Whistler) and three locations in Norway. The molecular weight distributions using SEC-DOC showed smaller molecular sizes for atmospheric organic matter compared to surface waters and a smaller material in fogs and clouds compared to aerosol particles, which is consistent with a substantial fraction of small volatile gases that partition into the aqueous phase. Both, cloud and aerosol samples presented a significant fraction (up to 21% of DOC) of biogenic nanoscale material. The results obtained by SEC-DOC were consistent with DOSY-NMR observations.
Cloud processing of organic matter has also been investigated by combining field observations (sample time series) with laboratory experiments under controlled conditions. Observations revealed no significant effect of aqueous phase chemistry on molecular weight distributions overall although during cloud events, substantial differences were apparent between organic material activated into clouds compared to interstitial material. Optical properties on the other hand showed significant changes including photobleaching and an increased humidification of atmospheric material by photochemical aging. Overall any changes to atmospheric organic matter during cloud processing were small in terms of bulk carbon properties, consistent with recent reports suggesting fogs and clouds are too dilute to substantially impact composition.
The size detection limit of single particle inductively coupled plasma spectrometry (spICP-MS) was determined for 40 elements, demonstrating the feasibility of spICP-MS to different NP species in water. The K-means Clustering Algorithm was used to process the spICP-MS signals, and achieved precise particle-noise differentiation and quantitative particle size resolution. A dry powder assay based on NP-catalyzed methylene blue (MB) reduction was developed to rapidly and sensitively detect metallic NPs in water by measuring their catalytic reactivity.
Four different wet-chemical-based NP surface reactivity assays were demonstrated: “borohydride reducing methylene blue (BHMB)”, “ferric reducing ability of nanoparticles (FRAN)”, “electron paramagnetic resonance detection of hydroxyl radical (EPR)”, and “UV-illuminated methylene blue degradation (UVMB)”. They gave different reactivity ranking among five NP species, because they targeted for different surface reactivity types (catalytic, redox and photo reactivity) via different reaction mechanisms. Kinetic modeling frameworks on the assay outcomes revealed two surface electron transfer schemes, namely the “sacrificial reducing” and the “electrode discharging”, and separated interfering side reactions from the intended surface reaction.
The application of NPs in chemical mechanical polishing (CMP) was investigated as an industrial case to understand NP surface transformation via adsorbing ions in water. Simulation of wastewater treatment showed CMP NPs were effectively removed (>90%) by lime softening at high pH and high calcium dosage, but 20-40% of them remained in water after biomass adsorption process. III/V ions (InIII, GaIII, and AsIII/V) derived from semiconductor materials showed adsorption potentials to common CMP NPs (SiO2, CeO2 and Al2O3), and a surface complexation model was developed to determine their intrinsic complexation constants for different NP species. The adsorption of AsIII and AsV ions onto CeO2 NPs mitigated the surface reactivity of CeO2 NPs suggested by the FRAN and EPR assays. The impact of the ion adsorption on the surface reactivity of CeO2 NPs was related to the redox state of Ce and As on the surface, but varied with ion species and surface reaction mechanisms.
A database of ENM removal by biomass was established by analyzing data from published papers, and non-linear solid-liquid distribution functions were built into the database. A conventional activated sludge (CAS) model was built based on a membrane bioreactor (MBR) model from a previous paper. An iterative numeric approach was adapted to the CAS model to calculate the result of non-linear adsorption of ENM by biomass in the CAS process. Kinetic studies of the CAS model showed the model performance changed mostly in the first 10 days after changing influent chemical oxygen demand (COD) concentration, and reached a steady state after 11 days. Over 60% of ENMs which have distribution coefficients in the database reached higher than 50% removal by the CAS model under general operational conditions. This result suggests that traditional WWTP which include the CAS process can remove many known types of ENMs in certain degree.
Polycyclic aromatic hydrocarbon (PAH) redistribution in extreme dust storms and processing in clouds
Dry deposition is compared with the aqueous chemistry of Tempe Town Lake. Water management and other factors may have a stronger impact on Tempe Town Lake chemistry than haboob dry-deposition. Haboobs alter the Polycyclic Aromatic Hydrocarbon (PAH) concentrations and distributions in Tempe, AZ. PAH isomer ratios suggest PM2.5 (particulate matter with aerodynamic diameters less than or equal to 2.5 μm) sources consistent with approximate thunderstorm outflow paths.
The importance of the atmospheric aqueous phase, fogs and clouds, for the processing and removal of PAHs is not well known. A multiphase model was developed to determine the fate and lifetime of PAHs in fogs and clouds. The model employed literature values that describe the partitioning between three phases (aqueous, liquid organic, and gas), in situ PAH measurements, and experimental and estimated (photo)oxidation rates. At 25 °C, PAHs with two, three and four rings were predicted to be primarily gas phase (fraction in the gas phase xg > 90 %) while five- and six-ring PAHs partitioned significantly into droplets (xg < 60 %) with aqueous phase fractions of 1 to 6 % and liquid organic phase fractions of 31 to 91 %. The predicted atmospheric lifetimes of PAHs in the presence of fog or cloud droplets (< 5 hours) were significantly shorter than literature predictions of PAH wet and dry deposition lifetimes (1 to 14 days and 5 to 15 months respectively) and shorter than or equal to predicted PAH gas phase / particle phase atmospheric lifetimes (1 to 300 hours). The aqueous phase cannot be neglected as a PAH sink due to the large aqueous volume (vs. organic volume) and the relatively fast aqueous reactions.
Quantifying halogen presence and speciation in particulate matter is crucial given the role atmospheric particulates play in transport and cycling. While some halogens (fluorine and chlorine) are often included in aerosol studies, iodine and bromine have rarely been examined, especially outside of a marine environment. Focus on this environment is, in part, due to the existence of biogenic marine sources for both halogens. However, examining iodine and bromine in an urban environment has the potential to provide key insights into the transport and processing of these species in the atmosphere. As Tempe is set within a desert environment, bromine concentration is expected to be relatively high due to its presence in Earth’s crust, while iodine is expected to exist in higher concentrations near the coast. To detect presence and concentration, ICP-MS analysis was performed on samples taken in Tempe, AZ as well as sites in Bakersfield, CA and Davis, CA, which yielded preliminary results in line with these expectations. A secondary set of samples were taken in Tempe, AZ during dust storms, haboobs, and winter holidays. CIC was used to determine the organic fraction. In doing so, this study aims to identify species present in an urban environment as well as potential transportation pathways.