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.
Swimming pool water (collected in June 2014 in Phoenix) and model contaminants (Pharmaceuticals and Personal Care Products (PPCPs), Endocrine Disrupting Compounds (EDCs), artificial sweeteners, and artificial human waste products) were chlorinated in controlled laboratory experiments. The CHCl3 production during chlorination was determined using Gas Chromatography-Mass Spectrometry (GC-MS) following solid-phase microextraction (SPME). Upon chlorination, all swimming pool water samples and contaminants produced measureable amounts of chloroform. Chlorination of swimming pool water produced 0.005-0.134 mol CHCl3/mol C and 0.004-0.062 mol CHCl3/mol Cl2 consumed. Chlorination of model contaminants produced 0.004-0.323 mol CHCl3/mol C and 0.001-0.247 mol CHCl3/mol Cl2 consumed. These numbers are comparable and indicate that the model contaminants react similarly to swimming pool water during chlorination. The CHCl3 flux from swimming pools in Phoenix was estimated at approximately 3.9-4.3 Gg/yr and was found to be largely dependent on water temperature and wind speed while air temperature had little effect. This preliminary estimate is orders of magnitude larger than previous estimates of anthropogenic emissions in Phoenix suggesting that swimming pools might be a significant source of atmospheric CHCl3 locally.
Anticipatory LCA seeks to overcome the paucity of data through scenario development and thermodynamic bounding analyses. Critical components of anticipatory LCA include:
1) Laboratory-scale inventory data collection for nano-manufacturing processes and
preliminary performance evaluation.
2) Thermodynamic modeling of manufacturing processes and developing scenarios of
efficiency gains informed by analogous material processing industries.
3) Use-phase bounding to report inventory data in a functional unit descriptive of
performance.
Together, these analyses may call attention to environmentally problematic processes or nanotechnologies before significant investments in R&D and infrastructure contribute to technology lock in. The following case study applies these components of anticipatory LCA to single wall carbon nanotube (SWCNT) manufacturing processes, compares the rapid improvements in SWCNT manufacturing to historic reductions in the embodied energy of aluminum, and discusses the use of SWCNTs as free-standing anodes in advanced lithium ion batteries.
Alternative VI pathways, involving vapor transport along sewer lines and other subsurface infrastructure, have recently been found to be significant contributors to VI impacts at some sites. This study evaluated approaches for identifying and characterizing the significance of alternative VI pathways and assessed the effectiveness of conventional mitigation at a site with an alternative VI pathway that can be manipulated to be on or off. The alternative pathway could not be identified using conventional pathway assessment procedures and can only be discovered under controlled pressure method (CPM) conditions. Measured emission rates were two orders of magnitude greater than screening model estimates and sub-foundation vertical soil gas profiles changed and were no longer consistent with the conventional VI conceptual model when the CPM test was conducted. The pipe flow VI pathway reduced the vacuum performance of the sub-slab depressurization (SSD) VI mitigation system, but the SSD system still provided sufficient protection to the house.
The relationship between groundwater table fluctuations and subsurface vapor emissions and transport is examined using multi-year data from the field site, and is studied in the laboratory. In addition, a broader range of conditions is examined through use of modeling validated with the experimental data. The results indicate that fluctuating groundwater tables will lead to amplified volatile organic chemical (VOC) emissions from groundwater to soil surface relative to steady water table elevation, however, the magnitude of this amplification is less concerned when long-term water fluctuation present. No clear correlations were found between VOC emissions and water table changes at the study site where annual water table fluctuations of about 0.3 m existed. Significant VOC emission amplifications by water table fluctuation would be expected under shallow groundwater conditions according to model analysis results.
In order to better constrain the importance of biomass versus entrained soil as a source of trace metals in burn aerosols, small-scale burn experiments were conducted using soil-free foliage representative of a variety of fire-impacted ecosystems. The resulting burn aerosols were collected in two stages (PM > 2.5 μm and PM < 2.5 μm) on cellulose filters using a high-volume air sampler equipped with an all-Teflon impactor. Unburned foliage and burn aerosols were analyzed for Fe and other trace metals using inductively coupled plasma mass spectrometry (ICP-MS).
Results of this analysis show that less than 2% of Fe in plant biomass is likely mobilized as atmospheric aerosols during biomass burning events. The results of this study and estimates of annual global wildfire area were used to estimate the impact of biomass burning aerosols on total atmospheric Fe flux to the ocean. I estimate that foliage-derived Fe contributes 114 ± 57 Gg annually. Prior studies, which implicitly include both biomass and soil-derived Fe, concluded that biomass burning contributes approximately 690 Gg of Fe. Together, these studies suggest that fire-entrained soil particles contribute 83% (576 Gg) of Fe in biomass burning emissions, while plant derived iron only accounts for at most 17%.