N-Nitrosodimethylamine (NDMA), a probable human carcinogen, has been found in clouds and fogs at concentration up to 500 ng/L and in drinking water as disinfection by-product. NDMA exposure to the general public is not well understood because of knowledge gaps in terms of occurrence, formation and fate both in air and water. The goal of this dissertation was to contribute to closing these knowledge gaps on potential human NDMA exposure through contributions to atmospheric measurements and fate as well as aqueous formation processes.

Novel, sensitive methods of measuring NDMA in air were developed based on Solid Phase Extraction (SPE) and Solid Phase Microextraction (SPME) coupled to Gas Chromatography-Mass Spectrometry (GC-MS). The two measuring techniques were evaluated in laboratory experiments. SPE-GC-MS was applicable in ambient air sampling and NDMA in ambient air was found in the 0.1-13.0 ng/m3 range.

NDMA photolysis, the main degradation atmospheric pathway, was studied in the atmospheric aqueous phase. Water soluble organic carbon (WSOC) was found to have more impact than inorganic species on NDMA photolysis by competing with NDMA for photons and therefore could substantially increase the NDMA lifetime in the atmosphere. The optical properties of atmospheric WSOC were investigated in aerosol, fog and cloud samples and showed WSOC from atmospheric aerosols has a higher mass absorption efficiency (MAE) than organic matter in fog and cloud water, resulting from a different composition, especially in regards of volatile species, that are not very absorbing but abundant in fogs and clouds.

NDMA formation kinetics during chloramination were studied in aqueous samples including wastewater, surface water and ground water, at two monochloramine concentrations. A simple second order NDMA formation model was developed using measured NDMA and monochloramine concentrations at select reaction times. The model fitted the NDMA formation well (R2 >0.88) in all water matrices. The proposed model was then optimized and applied to fit the data of NDMA formation from natural organic matter (NOM) and model precursors in previously studies. By determining the rate constants, the model was able to describe the effect of water conditions such as DOC and pH on NDMA formation.

To date, the production of algal biofuels is not economically sustainable due to the cost of production and the low cost of conventional fuels. As a result, interest has been shifting to high value products in the algae community to make up for the low economic potential of algal biofuels. The economic potential of high-value products does not however, eliminate the need to consider the environmental impacts. The majority of the environmental impacts associated with algal biofuels overlap with algal bioproducts in general (high-energy dewatering) due to the similarities in their production pathways. Selecting appropriate product sets is a critical step in the commercialization of algal biorefineries.

This thesis evaluates the potential of algae multiproduct biorefineries for the production of fuel and high-value products to be economically self-sufficient and still contribute to climate change mandates laid out by the government via the Energy Independence and Security Act (EISA) of 2007. This research demonstrates:

1) The environmental impacts of algal omega-3 fatty acid production can be lower than conventional omega-3 fatty acid production, depending on the dewatering strategy.

2) The production of high-value products can support biofuels with both products being sold at prices comparable to 2016 prices.

3) There is a tradeoff between revenue and fuel production

4) There is a tradeoff between the net energy ratio of the algal biorefinery and the economic viability due to the lower fuel production in a multi-product model that produces high-value products and diesel vs. the lower economic potential from a multi-product model that just produces diesel.

This work represents the first efforts to use life cycle assessment and techno-economic analysis to assess the economic and environmental sustainability of an existing pilot-scale biorefinery tasked with the production of high-value products and biofuels. This thesis also identifies improvements for multiproduct algal biorefineries that will achieve environmentally sustainable biofuel and products while maintaining economic viability.

Several prominent research strategy organizations recommend applying life cycle assessment (LCA) early in the development of emerging technologies. For example, the US Environmental Protection Agency, the National Research Council, the Department of Energy, and the National Nanotechnology Initiative identify the potential for LCA to inform research and development (R&D) of photovoltaics and products containing engineered nanomaterials (ENMs). In this capacity, application of LCA to emerging technologies may contribute to the growing movement for responsible research and innovation (RRI). However, existing LCA practices are largely retrospective and ill-suited to support the objectives of RRI. For example, barriers related to data availability, rapid technology change, and isolation of environmental from technical research inhibit application of LCA to developing technologies. This dissertation focuses on development of anticipatory LCA tools that incorporate elements of technology forecasting, provide robust explorations of uncertainty, and engage diverse innovation actors in overcoming retrospective approaches to environmental assessment and improvement of emerging technologies. Chapter one contextualizes current LCA practices within the growing literature articulating RRI and identifies the optimal place in the stage gate innovation model to apply LCA. Chapter one concludes with a call to develop anticipatory LCA – building on the theory of anticipatory governance – as a series of methodological improvements that seek to align LCA practices with the objectives of RRI.

Chapter two provides a framework for anticipatory LCA, identifies where research from multiple disciplines informs LCA practice, and builds off the recommendations presented in the preceding chapter. Chapter two focuses on crystalline and thin film photovoltaics (PV) to illustrate the novel framework, in part because PV is an environmentally motivated technology undergoing extensive R&D efforts and rapid increases in scale of deployment. The chapter concludes with a series of research recommendations that seek to direct PV research agenda towards pathways with the greatest potential for environmental improvement.

Similar to PV, engineered nanomaterials (ENMs) are an emerging technology with numerous potential applications, are the subject of active R&D efforts, and are characterized by high uncertainty regarding potential environmental implications. Chapter three introduces a Monte Carlo impact assessment tool based on the toxicity impact assessment model USEtox and demonstrates stochastic characterization factor (CF) development to prioritize risk research with the greatest potential to improve certainty in CFs. The case study explores a hypothetical decision in which personal care product developers are interested in replacing the conventional antioxidant niacinamide with the novel ENM C60, but face high data uncertainty, are unsure regarding potential ecotoxicity impacts associated with this substitution, and do not know what future risk-relevant experiments to invest in that most efficiently improve certainty in the comparison. Results suggest experiments that elucidate C60 partitioning to suspended solids should be prioritized over parameters with little influence on results. This dissertation demonstrates a novel anticipatory approach to exploration of uncertainty in environmental models that can create new, actionable knowledge with potential to guide future research and development decisions.

Ion exchange sorbents embedded with metal oxide nanoparticles can have high affinity and high capacity to simultaneously remove multiple oxygenated anion contaminants from drinking water. This research pursued answering the question, “Can synthesis methods of nano-composite sorbents be improved to increase sustainability and feasibility to remove hexavalent chromium and arsenic simultaneously from groundwater compared to existing sorbents?” Preliminary nano-composite sorbents outperformed existing sorbents in equilibrium tests, but struggled in packed bed applications and at low influent concentrations. The synthesis process was then tailored for weak base anion exchange (WBAX) while comparing titanium dioxide against iron hydroxide nanoparticles (Ti-WBAX and Fe-WBAX, respectively). Increasing metal precursor concentration increased the metal content of the created sorbents, but pollutant removal performance and usable surface area declined due to pore blockage and nanoparticle agglomeration. An acid-post rinse was required for Fe-WBAX to restore chromium removal capacity. Anticipatory life cycle assessment identified critical design constraints to improve environmental and human health performance like minimizing oven heating time, improving pollutant removal capacity, and efficiently reusing metal precursor solution. The life cycle environmental impact of Ti-WBAX was lower than Fe-WBAX as well as a mixed bed of WBAX and granular ferric hydroxide for all studied categories. A separate life cycle assessment found the total number of cancer and non-cancer cases prevented by drinking safer water outweighed those created by manufacture and use of water treatment materials and energy. However, treatment relocated who bore the health risk, concentrated it in a sub-population, and changed the primary manifestation from cancer to non-cancer disease. This tradeoff was partially mitigated by avoiding use of pH control chemicals. When properly synthesized, Fe-WBAX and Ti-WBAX sorbents maintained chromium removal capacity while significantly increasing arsenic removal capacity compared to the parent resin. The hybrid sorbent performance was demonstrated in packed beds using a challenging water matrix and low pollutant influent conditions. Breakthrough curves hint that the hexavalent chromium is removed by anion exchange and the arsenic is removed by metal oxide sorption. Overall, the hybrid nano-sorbent synthesis methods increased sustainability, improved sorbent characteristics, and increased simultaneous removal of chromium and arsenic for drinking water.

Vapor intrusion (VI), can pose health risks to building occupants. Assessment and mitigation at VI impacted sites have been guided by a site conceptual model (SCM) in which vapors originate from subsurface sources, diffuse through soil matrix and enter into a building by gas flow across foundation cracks. Alternative VI pathways and groundwater table fluctuations are not often considered.

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.

Arsenic (As) is a naturally occurring element that poses a health risk when continually consumed at levels exceeding the Environmental Protection Agencies (EPA) maximum contaminant level (MCL) of 10 ppb. With the Arizona Department of Water Resources considering reliance on other sources of water other than just solely surface water, groundwater proves a reliable, supplemental source. The Salt River Project (SRP) wants to effectively treat their noncompliance groundwater sources to meet EPA compliance. Rapid small-scale column tests (RSSCTs) of two SRP controlled groundwater wells along the Eastern Canal and Consolidated Canal were designed to assist SRP in selection and future design of full-scale packed bed adsorbent media. Main concerns for column choice is effectiveness, design space at groundwater wells, and simplicity. Two adsorbent media types were tested for effective treatment of As to below the MCL: a synthetic iron oxide, Bayoxide E33, and a strong base anion exchange resin, SBG-1. Both media have high affinity toward As and prove effective at treating As from these groundwater sources. Bayoxide E33 RSSCT performance indicated that As treatment lasted to near 60,000 bed volumes (BV) in both water sources and still showed As adsorption extending past this operation ranging from several months to a year. SBG-1 RSSCT performance indicated As, treatment lasted to 500 BV, with the added benefit of being regenerated. At 5%, 13%, and 25% brine regeneration concentrations, regeneration showed that 5% brine is effective, yet would complicate overall design and footprint. Bayoxide E33 was selected as the best adsorbent media for SRP use in full-scale columns at groundwater wells due to its simplistic design and high efficiency.

This dissertation focused on the development and application of state-of-the-art monitoring tools and analysis methods for tracking the fate of trace level contaminants in the natural and built water environments, using fipronil as a model; fipronil and its primary degradates (known collectively as fiproles) are among a group of trace level emerging environmental contaminants that are extremely potent arthropodic neurotoxins. The work further aimed to fill in data gaps regarding the presence and fate of fipronil in engineered water systems, specifically in a wastewater treatment plant (WWTP), and in an engineered wetland. A review of manual and automated “active” water sampling technologies motivated the development of two new automated samplers capable of in situ biphasic extraction of water samples across the bulk water/sediment interface of surface water systems. Combined with an optimized method for the quantification of fiproles, the newly developed In Situ Sampler for Biphasic water monitoring (IS2B) was deployed along with conventional automated water samplers, to study the fate and occurrence of fiproles in engineered water environments; continuous sampling over two days and subsequent analysis yielded average total fiprole concentrations in wetland surface water (9.9 ± 4.6 to 18.1 ± 4.6 ng/L) and wetland sediment pore water (9.1 ± 3.0 to 12.6 ± 2.1 ng/L). A mass balance of the WWTP located immediately upstream demonstrated unattenuated breakthrough of total fiproles through the WWTP with 25 ± 3 % of fipronil conversion to degradates, and only limited removal of total fiproles in the wetland (47 ± 13%). Extrapolation of local emissions (5–7 g/d) suggests nationwide annual fiprole loadings from WWTPs to U.S. surface waters on the order of about one half to three quarters of a metric tonne. The qualitative and quantitative data collected in this work have regulatory implications, and the sampling tools and analysis strategies described in this thesis have broad applicability in the assessment of risks posed by trace level environmental contaminants.

N-nitrosodimethylamine (NDMA) is a probable human carcinogen and drinking water disinfection by-product. NDMA forms as the product of reactions between chloramines and precursor compounds in water. This dissertation aims to provide insight into the removal of NDMA precursors, their nature, and a method to aid in their identification. Watershed-derived precursors accounted for more of and greater variability to NDMA formation upon chloramination than polymer-derived precursors in environmental samples. Coagulation polymers are quaternary amines, which have low NDMA yield but high use rates. Watershed-derived precursors were removed up to 90% by sorption to activated carbon, but activated carbon exhibited much less (<10%) sorption of polymer-derived precursors. Combined with literature NDMA molar yields of model anthropogenic compounds, where anthropogenic chemicals in some cases have NDMA yields >90% and biological compounds always have yields <2%, trace, organic, amine containing, anthropogenic chemicals were implicated as the most likely source of NDMA precursors in the watershed. Although activated carbon removes these precursors well, identification of individual compounds may result in more cost effective mitigation strategies. Therefore, I developed a method to isolate NDMA precursors from other organic matter into methanol to facilitate their identification. Optimization of the method resulted in a median recovery of NDMA precursors of 82% from 10 surface waters and one wastewater. The method produces 1,000X concentrated NDMA precursors and, in collaboration with the University of Colorado Center for Environmental Mass Spectrometry, time of flight mass spectrometry (TOF-MS) was performed on multiple treated wastewater and raw drinking water isolates. During TOF-MS, tertiary amines can cleave to form a neutral loss and an R group ion that is dependent on the original structure and I wrote a software program to “trawl” exported TOF-MS spectra for the diagnostic neutral loss resulting from fragmentation of tertiary amines. Methadone was identified as one new NDMA precursor that occurs at concentrations that form physiologically relevant levels of NDMA in surface water and wastewater. The approach used here to identify NDMA precursors is adaptable to other unknown disinfection by-product precursors given that a functional group is known that can 1)control sorption and 2)produce a predictable diagnostic fragment.

Photosynthesis converts sunlight to biomass at a global scale. Among the photosynthetic organisms, cyanobacteria provide an excellent model to study how photosynthesis can become a practical platform of large-scale biotechnology. One novel approach involves metabolically engineering the cyanobacterium Synechocystis sp. PCC 6803 to excrete laurate, which is harvested directly.

This work begins by defining a working window of light intensity (LI). Wild-type and laurate-excreting Synechocystis required an LI of at least 5 µE/m2-s to sustain themselves, but are photo-inhibited by LI of 346 to 598 µE/m2-s.

Fixing electrons into valuable organic products, e.g., biomass and excreted laurate, is critical to success. Wild-type Synechocystis channeled 75% to 84% of its fixed electrons to biomass; laurate-excreting Synechocystis fixed 64 to 69% as biomass and 6.6% to 10% as laurate. This means that 16 to 30% of the electrons were diverted to non-valuable soluble products, and the trend was accentuated with higher LI.

How the Ci concentration depended on the pH and the nitrogen source was quantified by the proton condition and experimentally validated. Nitrate increased, ammonium decreased, but ammonium nitrate stabilized alkalinity and Ci. This finding provides a mechanistically sound tool to manage Ci and pH independently.

Independent evaluation pH and Ci on the growth kinetics of Synechocystis showed that pH 8.5 supported the fastest maximum specific growth rate (µmax): 2.4/day and 1.7/day, respectively, for the wild type and modified strains with LI of 202 µE/m2-s. Half-maximum-rate concentrations (KCi) were less than 0.1 mM, meaning that Synechocystis should attain its µmax with a modest Ci concentration (≥1.0 mM).

Biomass grown with day-night cycles had a night endogenous decay rate of 0.05-1.0/day, with decay being faster with higher LI and the beginning of dark periods. Supplying light at a fraction of daylight reduced dark decay rate and improved overall biomass productivity.

This dissertation systematically evaluates and synthesizes fundamental growth factors of cyanobacteria: light, inorganic carbon (Ci), and pH. LI remains the most critical growth condition to promote biomass productivity and desired forms of biomass, while Ci and pH now can be managed to support optimal productivity.

Over the past decade, there has been a revival in applied algal research and attempts at commercialization. However, the main limitation in algal commercialization is the process of cultivation, which is one of the main cost and energy burdens in producing biomass that is economically feasible for different products. There are several parameters that must be considered when growing algae, including the type of growth system and operating mode, preferred organism(s), and many other criteria that affect the process of algal cultivation. The purpose of this dissertation was to assess key variables that affect algal productivity and to improve outdoor algal cultivation procedures. The effect of reducing or eliminating aeration of algal cultures at night, in flat panel photobioreactors (panels), was investigated to assess the reduction of energy consumption at night. The lack of aeration at night resulted in anoxic conditions, which significantly reduced lipid accumulation and productivity, but did not affect log phase biomass productivity. In addition, the reduction in aeration resulted in lower pH values, which prevented ammonia volatility and toxicity. Raceways are operated at deeper cultivation depths, which limit culture density and light exposure. Experimentation was accomplished to determine the effects of decreasing cultivation depth, which resulted in increased lipid accumulation and lipid productivity, but did not significantly affect biomass productivity. A comparison of semi-continuous cultivation of algae in raceways and panels in side-by-side experiments showed that panels provided better temperature control and higher levels of mixing, which resulted in higher biomass productivity. In addition, sub-optimal morning temperatures in raceways compared to panels were a significant factor in reducing algae biomass productivity. The results from this research indicate that increasing lipid productivity and biomass productivity cannot be completed simultaneously. Therefore, the desired product will determine if lipid or biomass productivity is more crucial, which also dictates whether the system should be operated in batch mode to either allow lipid accumulation or in semi-continuous mode to allow high biomass productivity. This work is a critical step in improving algal cultivation by understanding key variables that limit biomass and lipid productivity.