Identifying the Structure and Fate of Wastewater Derived Organic Micropollutants by High-resolution Mass Spectrometry

Human activities represent a significant burden on the global water cycle, with large and increasing demands placed on limited water resources by manufacturing, energy production and domestic water use. In addition to changing the quantity of available water resources, human activities lead to changes in water quality by introducing a large and often poorly-characterized array of chemical pollutants, which may negatively impact biodiversity in aquatic ecosystems, leading to impairment of valuable ecosystem functions and services. Domestic and industrial wastewaters represent a significant source of pollution to the aquatic environment due to inadequate or incomplete removal of chemicals introduced into waters by human activities. Currently, incomplete chemical characterization of treated wastewaters limits comprehensive risk assessment of this ubiquitous impact to water. In particular, a significant fraction of the organic chemical composition of treated industrial and domestic wastewaters remains uncharacterized at the molecular level. Efforts aimed at reducing the impacts of water pollution on aquatic ecosystems critically require knowledge of the composition of wastewaters to develop interventions capable of protecting our precious natural water resources.

The goal of this dissertation was to develop a robust, extensible and high-throughput framework for the comprehensive characterization of organic micropollutants in wastewaters by high-resolution accurate-mass mass spectrometry. High-resolution mass spectrometry provides the most powerful analytical technique available for assessing the occurrence and fate of organic pollutants in the water cycle. However, significant limitations in data processing, analysis and interpretation have limited this technique in achieving comprehensive characterization of organic pollutants occurring in natural and built environments. My work aimed to address these challenges by development of automated workflows for the structural characterization of organic pollutants in wastewater and wastewater impacted environments by high-resolution mass spectrometry, and to apply these methods in combination with novel data handling routines to conduct detailed fate studies of wastewater-derived organic micropollutants in the aquatic environment.

In Chapter 2, chemoinformatic tools were implemented along with novel non-targeted mass spectrometric analytical methods to characterize, map, and explore an environmentally-relevant “chemical space” in municipal wastewater. This was accomplished by characterizing the molecular composition of known wastewater-derived organic pollutants and substances that are prioritized as potential wastewater contaminants, using these databases to evaluate the pollutant-likeness of structures postulated for unknown organic compounds that I detected in wastewater extracts using high-resolution mass spectrometry approaches. Results showed that application of multiple computational mass spectrometric tools to structural elucidation of unknown organic pollutants arising in wastewaters improved the efficiency and veracity of screening approaches based on high-resolution mass spectrometry. Furthermore, structural similarity searching was essential for prioritizing substances sharing structural features with known organic pollutants or industrial and consumer chemicals that could enter the environment through use or disposal.

I then applied this comprehensive methodological and computational non-targeted analysis workflow to micropollutant fate analysis in domestic wastewaters (Chapter 3), surface waters impacted by water reuse activities (Chapter 4) and effluents of wastewater treatment facilities receiving wastewater from oil and gas extraction activities (Chapter 5). In Chapter 3, I showed that application of chemometric tools aided in the prioritization of non-targeted compounds arising at various stages of conventional wastewater treatment by partitioning high dimensional data into rational chemical categories based on knowledge of organic chemical fate processes, resulting in the classification of organic micropollutants based on their occurrence and/or removal during treatment. Similarly, in Chapter 4, high-resolution sampling and broad-spectrum targeted and non-targeted chemical analysis were applied to assess the occurrence and fate of organic micropollutants in a water reuse application, wherein reclaimed wastewater was applied for irrigation of turf grass. Results showed that organic micropollutant composition of surface waters receiving runoff from wastewater irrigated areas appeared to be minimally impacted by wastewater-derived organic micropollutants. Finally, Chapter 5 presents results of the comprehensive organic chemical composition of oil and gas wastewaters treated for surface water discharge. Concurrent analysis of effluent samples by complementary, broad-spectrum analytical techniques, revealed that low-levels of hydrophobic organic contaminants, but elevated concentrations of polymeric surfactants, which may effect the fate and analysis of contaminants of concern in oil and gas wastewaters.

Taken together, my work represents significant progress in the characterization of polar organic chemical pollutants associated with wastewater-impacted environments by high-resolution mass spectrometry. Application of these comprehensive methods to examine micropollutant fate processes in wastewater treatment systems, water reuse environments, and water applications in oil/gas exploration yielded new insights into the factors that influence transport, transformation, and persistence of organic micropollutants in these systems across an unprecedented breadth of chemical space.

Advanced Aerogel Composites for Oil Remediation and Recovery

Oil spills in marine environments often damage marine and coastal life if not remediated rapidly and efficiently. In spite of the strict enforcement of environmental legislations (i.e., Oil Pollution Act 1990) following the Exxon Valdez oil spill (June 1989; the second biggest oil spill in U.S. history), the Macondo well blowout disaster (April 2010) released 18 times more oil. Strikingly, the response methods used to contain and capture spilled oil after both accidents were nearly identical, note that more than two decades separate Exxon Valdez (1989) and Macondo well (2010) accidents.

The goal of this dissertation was to investigate new advanced materials (mechanically strong aerogel composite blankets-Cabot® Thermal Wrap™ (TW) and Aspen Aerogels® Spaceloft® (SL)), and their applications for oil capture and recovery to overcome the current material limitations in oil spill response methods. First, uptake of different solvents and oils were studied to answer the following question: do these blanket aerogel composites have competitive oil uptake compared to state-of-the-art oil sorbents (i.e., polyurethane foam-PUF)? In addition to their competitive mechanical strength (766, 380, 92 kPa for Spaceloft, Thermal Wrap, and PUF, respectively), our results showed that aerogel composites have three critical advantages over PUF: rapid (3-5 min.) and high (more than two times of PUF’s uptake) oil uptake, reusability (over 10 cycles), and oil recoverability (up to 60%) via mechanical extraction. Chemical-specific sorption experiments showed that the dominant uptake mechanism of aerogels is adsorption to the internal surface, with some contribution of absorption into the pore space.

Second, we investigated the potential environmental impacts (energy and chemical burdens) associated with manufacturing, use, and disposal of SL aerogel and PUF to remove the oil (i.e., 1 m3 oil) from a location (i.e., Macondo well). Different use (single and multiple use) and end of life (landfill, incinerator, and waste-to-energy) scenarios were assessed, and our results demonstrated that multiple use, and waste-to-energy choices minimize the energy and material use of SL aerogel. Nevertheless, using SL once and disposing via landfill still offers environmental and cost savings benefits relative to PUF, and so these benefits are preserved irrespective of the oil-spill-response operator choices.

To inform future aerogel manufacture, we investigated the different laboratory-scale aerogel fabrication technologies (rapid supercritical extraction (RSCE), CO2 supercritical extraction (CSCE), alcohol supercritical extraction (ASCE)). Our results from anticipatory LCA for laboratory-scaled aerogel fabrication demonstrated that RSCE method offers lower cumulative energy and ecotoxicity impacts compared to conventional aerogel fabrication methods (CSCE and ASCE).

The final objective of this study was to investigate different surface coating techniques to enhance oil recovery by modifying the existing aerogel surface chemistries to develop chemically responsive materials (switchable hydrophobicity in response to a CO2 stimulus). Our results showed that studied surface coating methods (drop casting, dip coating, and physical vapor deposition) were partially successful to modify surface with CO2 switchable chemical (tributylpentanamidine), likely because of the heterogeneous fiber structure of the aerogel blankets. A possible solution to these non-uniform coatings would be to include switchable chemical as a precursor during the gel preparation to chemically attach the switchable chemical to the pores of the aerogel.

Taken as a whole, the implications of this work are that mechanical deployment and recovery of aerogel composite blankets is a viable oil spill response strategy that can be deployed today. This will ultimately enable better oil uptake without the uptake of water, potential reuse of the collected oil, reduced material and energy burdens compared to competitive sorbents (e.g., PUF), and reduced occupational exposure to oiled sorbents. In addition, sorbent blankets and booms could be deployed in coastal and open-ocean settings, respectively, which was previously impossible.

A social-ecological impact assessment for public lands management: application of a conceptual and methodological framework

According to the U.S. National Environmental Policy Act of 1969 (NEPA), federal action to manipulate habitat for species conservation requires an environmental impact statement, which should integrate natural, physical, economic, and social sciences in planning and decision making. Nonetheless, most impact assessments focus disproportionately on physical or ecological impacts rather than integrating ecological and socioeconomic components. We developed a participatory social-ecological impact assessment (SEIA) that addresses the requirements of NEPA and integrates social and ecological concepts for impact assessments. We cooperated with the Bureau of Land Management in Idaho, USA on a project designed to restore habitat for the Greater Sage-Grouse (Centrocercus urophasianus). We employed questionnaires, workshop dialogue, and participatory mapping exercises with stakeholders to identify potential environmental changes and subsequent impacts expected to result from the removal of western juniper (Juniperus occidentalis). Via questionnaires and workshop dialogue, stakeholders identified 46 environmental changes and associated positive or negative impacts to people and communities in Owyhee County, Idaho. Results of the participatory mapping exercises showed that the spatial distribution of social, economic, and ecological values throughout Owyhee County are highly associated with the two main watersheds, wilderness areas, and the historic town of Silver City. Altogether, the SEIA process revealed that perceptions of project scale varied among participants, highlighting the need for specificity about spatial and temporal scales. Overall, the SEIA generated substantial information concerning potential impacts associated with habitat treatments for Greater Sage-Grouse. The SEIA is transferable to other land management and conservation contexts because it supports holistic understanding and framing of connections between humans and ecosystems. By applying this SEIA framework, land managers and affected people have an opportunity to fulfill NEPA requirements and develop more comprehensive management plans that better reflect the linkages of social-ecological systems.

Adapting the social-ecological system framework for urban stormwater management: the case of green infrastructure adoption

Stormwater management has long been a critical societal and environmental challenge for communities. An increasing number of municipalities are turning to novel approaches such as green infrastructure to develop more sustainable stormwater management systems. However, there is a need to better understand the technological decision-making processes that lead to specific outcomes within urban stormwater governance systems. We used the social-ecological system (SES) framework to build a classification system for identifying significant variables that influence urban stormwater governance decisions related to green infrastructure adoption. To adapt the framework, we relied on findings from observations at national stormwater meetings in combination with a systematic literature review on influential factors related to green infrastructure adoption. We discuss our revisions to the framework that helped us understand the decision by municipal governments to adopt green infrastructure. Remaining research needs and challenges are discussed regarding the development of an urban stormwater SES framework as a classification tool for knowledge accumulation and synthesis.

Auditoria e identificação de propostas de melhoria no SGA da Funfrap

O compromisso das organizações com as obrigações decretadas ao nível do ambiente, segurança e qualidade emancipa a implementação de Sistemas de Gestão e o processo de auditar. Neste trabalho, decorrente do estágio curricular no âmbito do Mestrado em Engenharia do Ambiente, está evidenciada a importância dos Sistemas de Gestão Ambiental e as razões preponderantes para que sejam auditados. O trabalho pretendeu auditar e avaliar a conformidade do sistema de gestão ambiental, de acordo com a NP EN ISO 14001:2004, de uma indústria de fundição de metais, Funfrap -. Fundição Portuguesa SA, a fim de identificar oportunidades de melhoria no desempenho ambiental da organização. No âmbito do estágio foram ainda realizadas outras atividades, incluindo campanhas de sensibilização, inventário de resíduos sólidos, ferramentas da metodologia World Class Manufacturing, formação sobre a separação de resíduos nos postos de trabalho, acompanhamento de um ensaio na estação de tratamento de águas residuais industriais e apoio para o desenvolvimento do relatório ambiental anual. Da auditoria interna identificaram-se e corrigiram-se nove não conformidades menores e cinco observações. Da auditoria externa foram identificadas apenas duas não conformidades, nenhuma delas relacionadas com as detetadas anteriormente. Além deste resultado foram sugeridas algumas medidas para alcançar um melhor desempenho ambiental da organização.

Gestão ambiental na indústria da cortiça

Nas últimas décadas tem-se verificado uma degradação contínua do meio ambiente, intensificada pela produção em massa das indústrias, aliado a um crescente consumismo da sociedade. Atualmente, as organizações e a sociedade civil demonstram uma crescente preocupação com os problemas ambientais, é neste contexto que surgem as questões associadas aos sistemas de gestão ambiental (SGA), como forma de integrar as preocupações das organizações com a proteção do ambiente. O presente projeto, realizado no âmbito do estágio curricular do Mestrado de Engenharia do Ambiente, pretende explorar e servir de apoio na implementação e desenvolvimento de um Sistema de Gestão Ambiental em duas Unidades Industriais da Amorim & Irmãos, S.A. Para o cumprimento dos objetivos do projeto foi realizada uma revisão bibliográfica da temática Sistemas de Gestão Ambiental, que possibilitou alargar o conhecimento sobre o tema do estágio. A segunda fase do trabalho consistiu na integração nos processos e infraestruturas da empresa. A terceira fase incluiu a realização dos trabalhos práticos necessários para a implementação e desenvolvimento dos Sistemas de Gestão Ambiental. Tendo em conta a metodologia seguida conclui-se que a realização este projeto foi muito vantajosa para todas as partes envolvidas, tendo contribuído: para um grande avanço na implementação e desenvolvimento dos Sistemas de Gestão Ambiental nas duas Unidades Industriais, permitindo assim melhorar os seus desempenhos ambientais; para a aquisição e consolidação de conhecimentos na área e proporcionou uma experiencia que será benéfica no envolvimento de um projeto desta natureza.

Mitigation of High Alkalinity in Leachates of Aged Steel Slag

Steel slag, an abundant by-product of the steel-making industry, after it is aged, has a huge potential for use as an aggregate in road construction. However, the high pH of steel slag seepage (pH≥12) is a major impediment in its beneficial use. Analyses on aged steel slag samples demonstrated that the alkalinity producing capacity of aged steel slag samples strongly correlated to Ca(OH)2 dissolution and that prolonged aging periods have marginal effects on overall alkalinity. Treatment methods that included bitumen-coating, bathing in Al(III) solutions and addition of an alum-based drinking water treatment residual (WTR) were evaluated based on reduction in pH levels and leachate alkalinity. 10% (wt./wt.) alum-based drinking water treatment residual (WTR) addition to slag was determined to be the most successful mitigation method, providing 65−70% reduction in alkalinity both in batch-type and column leach tests, but final leachate pH was only 0.5−1 units lower and leachates were contaminated by dissolved Al(+III) (≥3−4 mM). Based on the interpretation of calculated saturation indices and SEM and EDX analyses, formation of calcium sulfoaluminate phases (i.e., ettringite and monosulfate) was suggested as the mechanism behind alkalinity mitigation upon WTR-modification. The residual alkalinity in WTR-amended slag leachates was able to be completely eliminated utilizing a biosolids compost with high base neutralization capacity. In column leach tests, effluent pH levels below 7 were maintained for 58−74 pore volumes worth of WTR-amended slag leachate using 0.13 kg compost (dry wt.) per 1 kg WTR-amended slag on average; also, dissolved Al(+III) was strongly retained on the compost.

PREPARATION OF POLYELECTROLYTE MEMBRANES EMBEDDED WITH ZEOLITE NANOPARTICLES FOR ENHANCED PERFORMANCE IN FORWARD OSMOSIS

Water scarcity is a global issue that has already affected every continent. Membrane technology is considered as one of the most promising candidates for resolving this worsening issue. Among all the membrane processes, the emerging forward osmosis (FO) membrane process is osmotically-driven and has unique advantages compared with other traditional pressure-driven membrane processes. One of the major challenges to advancing the FO membrane process is the lack of a suitable membrane. Polyelectrolyte thin film prepared via layer-by-layer (LbL) technique has demonstrated its excellent performance in many applications including electronics, optics, sensors, etc. Recent studies have revealed the potential of polyelectrolyte thin films in acting as the active separation layer of FO membranes, but significant efforts are still needed to improve the membrane performance and understand the transport mechanisms. This dissertation introduces a novel approach to prepare a zeolite-embedded polyelectrolyte composite membrane for enhanced FO performance. This membrane takes advantages of the versatile LbL process to unprecedentedly incorporate high loading of zeolite nanoparticles, which are anticipated to facilitate water transport due to the uniquely interconnected structure of zeolites. Major topics discussed in this dissertation include: (1) the synthesis and evaluation of the polyelectrolyte-zeolite composite FO membrane, (2) the examination of the fouling resistance to identify its technical limitations, (3) the demonstration of the membrane regenerability as an effective strategy for membrane fouling control, and (4) the investigation of crosslinking effects on the membrane performance to elucidate the transport mechanisms involved in the zeolite-embedded polyelectrolyte membranes. Comparative studies have been made between polyelectrolyte membranes with and without zeolite incorporation. The findings suggest that the zeolite-embedded membrane, although slightly more susceptible to silica scaling, has demonstrated enhanced water flux and separation capability, good resistance to organic fouling, and complete regenerability for fouling control. Additionally, the embedded zeolite nanoparticles are proved to be able to create fast pathways for water transport. Overall, this work provides a novel strategy to create zeolite-polymer composite membranes with enhanced separation performance and unique fouling mitigation properties.

fuzzySim: Fuzzy similarity in species distributions

fuzzySim is an R package for calculating fuzzy similarity in species occurrence patterns. It includes functions for data preparation, such as converting species lists (long format) to presence-absence tables (wide format), obtaining unique abbreviations of species names, or transposing (parts of) complex data frames; and sample data sets for providing practical examples. It can convert binary presence-absence to fuzzy occurrence data, using e.g. trend surface analysis, inverse distance interpolation or prevalence-independent environmental favourability modelling, for multiple species simultaneously. It then calculates fuzzy similarity among (fuzzy) species distributions and/or among (fuzzy) regional species compositions. Currently available similarity indices are Jaccard, Sørensen, Simpson, and Baroni-Urbani & Buser.

Città Metropolitane e Smart Governance Iniziative di successo e nodi critici verso la Smart City

The volume contains the results of the research project "Governance Analysis Project (GAP) for the Smart Energy City. The actualization of Smart Cities in the Metropolitan Areas of Europe and Italy” conducted within the PON “Smart Energy Master for the energy management of the territory” at the University Federico II of Naples (TeMA Lab of the Department of Civil, Architectural and Environmental Engineering). Smart Cities have gained increasing relevance in the scientific debate and in the national and international operational practice, emerging as one of the opportunities to rethink cities and, more generally, the life of urban communities. First reflections, researches and projects on the issue seem to converge towards the idea that a “smart” urban development should not only be a result of the yet necessary and unavoidable infrastructural endowment (physical capital) and of its continuing innovation, but also of the quality of human, social and environmental capital, conceived as strategic factors for development. A “smart” city is, primarily, a city able to effectively satisfy the needs of its citizens respecting the rules imposed by the environmental context. It is in such a debate that the project GAP fits with the aim to address Smart Cities in light of the administrative reorganization of Italian large cities as a consequence of the Law 56/2014. With a scientific approach, the volume provides a comprehensive and updated framework of how Italian and European Metropolitan cities are declining the Smart City issue and this thanks to the collection of a wide-ranging screening represented by more than 1.000 initiatives including researches, projects, interventions, technologies, etc. Furthermore, one original element of this research is that after an analysis conducted through indirect sources, a phase of dialogue with “stakeholders” was carried out (and of this there is a wide picture in the volume in which, by the way, are reported long excerpts of the interviews). This has enabled to give a clearer framework of what is now experimenting in Italian and European cities, avoiding being totally naïve for interventions and projects labelled as “smart”, but often lacking of innovative methods and contents.

Spatial Assessment of Indices for Characterizing the Erosive Force of Rainfall in El Salvador Republic

Soil erosion data in El Salvador Republic are scarce and there is no rainfall erosivity map for this region. Considering that rainfall erosivity is an important guide for planning soil erosion control practices, a spatial assessment of indices for characterizing the erosive force of rainfall in El Salvador Republic was carried out. Using pluviometric records from 25 weather stations, we applied two methods: erosivity index equation and the Fournier index. In all study area, the rainiest period is from May to November. Annual values of erosivity index ranged from 7,196 to 17,856 MJ mm ha(-1) h(-1) year(-1) and the Fournier index ranged from 52.9 to 110.0 mm. The erosivity map showed that the study area can be broadly divided into three major erosion risk zones, and the Fournier index map was divided into four zones. Both methods revealed that the erosive force is severe in all study area and presented significant spatial correlation with each other. The erosive force in the country is concentrated mainly from May to November.

UTILIZING ELECTRONIC NOSE AND GC-MS TO EXAMINE CRITICAL FACTORS INFLUENCING THE FORMATION OF ODOROUS VOC’S IN BIOSOLIDS.

Despite the efforts to better manage biosolids field application programs, biosolids managers still lack of efficient and reliable tools to apply large quantities of material while avoiding odor complaints. Objectives of this research were to determine the capabilities of an electronic nose in supporting process monitoring of biosolids production and, to compare odor characteristics of biosolids produced through thermal-hydrolysis anaerobic digestion (TH-AD) to those of alkaline stabilization in the plant, under storage and in the field. A method to quantify key odorants was developed and full scale sampling and laboratory simulations were performed. The portable electronic nose (PEN3) was tested for its capabilities of distinguishing alkali dosages in the biosolids production process. Frequency of recognition of unknown samples was tested achieving highest accuracy of 81.1%. This work exposed the need for a different and more sensitive electronic nose to assure its applicability at full scale for this process. GC-MS results were consistent with those reported in literature and helped to elucidate the behavior of the pattern recognition of the PEN3. Odor characterization of TH-AD and alkaline stabilized biosolids was achieved using olfactometry measurements and GC-MS. Dilution-to-threshold of TH-AD biosolids increased under storage conditions but no correlation was found with the target compounds. The presence of furan and three methylated homologues in TH-AD biosolids was reported for the first time proposing that these compounds are produced during thermal hydrolysis process however, additional research is needed to fully describe the formation of these compounds and the increase in odors. Alkaline stabilized biosolids reported similar odor concentration but did not increase and the ‘fishy’ odor from trimethylamine emissions resulted in more offensive and unpleasant odors when compared to TH-AD. Alkaline stabilized biosolids showed a spike in sulfur and trimethylamine after 3 days of field application when the alkali addition was not sufficient to meet regulatory standards. Concentrations of target compounds from field application of TH-AD biosolids gradually decreased to below the odor threshold after 3 days. This work increased the scientific understanding on odor characteristics and behavior of two types of biosolids and on the application of electronic noses to the environmental engineering field.

Water Quality Impacts due to the Addition of Biosolids-Derived Compost to Bioretention

Bioretention is a common stormwater control measure (SCM). While compost, combined with other bioretention soil media (BSM), has the potential for increased pollutant and water uptake and storage, it also may leach harmful nutrients. Limited information is available on the use of compost in SCMs. Therefore, this project seeks to analyze the impacts of the addition of biosolids-derived compost to bioretention. To accomplish this, bioretention mesocosm column studies were conducted to determine the leaching effects of 15%, 30%, and 30% tap water-washed compost, mixed with standard BSM. Synthetic storm runoff was applied to the columns and the effluent was analyzed for total nitrogen (N), phosphorus (P), and their speciation. All three columns leached N and P with maximum total N concentrations of 2,200, 2,100, and 300 mg-N/L and total P concentrations of 12, 4.9, and 4.6 mg-P/L for the 30%, 15%, and 30% washed mesocosms, respectively. Therefore, based on this study, it is not recommended that biosolids-derived compost be added to bioretention media.

Understanding Urban Stormwater Denitrification in Bioretention Internal Water Storage Zones

Free-draining bioretention systems commonly demonstrate poor nitrate removal. In this study, column tests verified the necessity of a permanently saturated zone to target nitrate removal via denitrification. Experiments determined a first-order denitrification rate constant of 0.0011 min-1 specific to Willow Oak woodchip media. A 2.6-day retention time reduced 3.0 mgN/L to below 0.05 mg-N/L. During simulated storm events, hydraulic retention time may be used as a predictive measurement of nitrate fate and removal. A minimum 4.0 hour retention time was necessary for in-storm denitrification defined by a minimum 20% nitrate removal. Additional environmental parameters, e.g., pH, temperature, oxidation-reduction potential, and dissolved oxygen, affect denitrification rate and response, but macroscale measurements may not be an accurate depiction of denitrifying biofilm conditions. A simple model was developed to predict annual bioretention nitrate performance. Novel bioretention design should incorporate bowl storage and large subsurface denitrifying zones to maximize treatment volume and contact time.