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.

Stakeholder perceptions of ecosystem services of the Wami River and Estuary

Management of riverine and coastal ecosystems warrants enhanced understanding of how different stakeholders perceive and depend upon different kinds of ecosystem services. Employing a mixed methods approach, this study compares and contrasts the use and perceptions of upstream residents, downstream residents, tourism officials, and conservation organizations regarding the value of 30 ecosystem services provided by the Wami River and its estuary in Tanzania, and investigates their perceptions of the main threats to this system. Our findings reveal that all of the stakeholder groups place a high value on the provision of domestic water, habitat for wild plants and animals, tourism, and erosion control, and a relatively low value on the prevention of saltwater intrusion, refuge from predators, spiritual fulfillment, nonrecreational hunting, and the provision of traditional medications and inorganic materials for construction. Differences emerge, however, between the groups in the value assigned to the conservation of riverine and estuarine fauna and the provision of raw materials for building and handicrafts. Declining fish populations and an increasing human population are identified by the residents and conservation employees, respectively, as their prime concerns regarding the future conditions of the Wami River and its estuary. These groups also acknowledge increasing salinity levels and the loss of mangroves as other key concerns. The identification of these mutual interests and shared concerns can help build common ground among stakeholders while the recognition of potential tensions can assist managers in balancing and reconciling the multiple needs and values of these different groups.

A Bayesian network dealing with measurements and residuals for system monitoring

International audience

Specific methanogenic activity in an anaerobic-aerobic reactor applied to the treatment of domestic residual water

The specific methanogenic activity (SMA) test is an important tool for the monitoring of anaerobic digestion. This paper presents the behavior of the methanogenic archaea of an anaerobic sludge under different conditions of oxygenation in a fixed-bed anaerobic-aerobic reactor treating domestic sewage. The reactor was operated in a continuous manner under different liquid recycle ratios from aerobic to anaerobic zones in order to remove carbon and nitrogen. The application of the SMA test was adapted from several authors and the measurement of the accumulated methane in the reactor was carried out by means of gas chromatography. Methanogenic organisms were not inhibited by the presence of oxygen. In contrast, the values of CH, production rate by sludge exposed to oxygen were greater than those obtained for strictly anaerobic sludge.

Numerical analysis of including phase change material in a domestic hot water cylinder

The domestic hot water cylinder incorporates encapsulated pcm placed in 57 vertical pipes. The use of PCM increases the thermal energy storage capacity of the cylinder and allows the use of low cost electricity during low peak periods. After experimental validation the numerical model developed in the project will be used to optimize the distribution of the pcm inside the water tank.

Domestic hot water consumption vs. solar thermal energy storage: the optimum size of the storage tank

Many efforts have been made in order to adequate the production of a solar thermal collector field to the consumption of domestic hot water of the inhabitants of a building. In that sense, much has been achieved in different domains: research agencies, government policies and manufacturers. However, most of the design rules of the solar plants are based on steady state models, whereas solar irradiance, consumption and thermal accumulation are inherently transient processes. As a result of this lack of physical accuracy, thermal storage tanks are sometimes left to be as large as the designer decides without any aforementioned precise recommendation. This can be a problem if solar thermal systems are meant to be implemented in nowadays buildings, where there is a shortage of space. In addition to that, an excessive storage volume could not result more efficient in many residential applications, but costly, extreme in space consumption and in some cases too heavy. A proprietary transient simulation program has been developed and validated with a detailed measurement campaign in an experimental facility. In situ environmental data have been obtained through a whole year of operation. They have been gathered at intervals of 10 min for a solar plant of 50 m2 with a storage tank of 3 m3, including the equipment for domestic hot water production of a typical apartment building. This program has been used to obtain the design and dimensioning criteria of DHW solar plants under daily transient conditions throughout a year and more specifically the size of the storage tank for a multi storey apartment building. Comparison of the simulation results with the current Spanish regulation applicable, “Código Técnico de la Edificación” (CTE 2006), offers fruitful details and establishes solar facilities dimensioning criteria.

The Modelling of Photovoltaic, Solar Thermal, and Photovoltaic/Thermal Domestic Hot Water Systems

Solar heating of potable water has traditionally been accomplished through the use of solar thermal (ST) collectors. With the recent increases in availability and lower cost of photovoltaic (PV) panels, the potential of coupling PV solar arrays to electrically heated domestic hot water (DHW) tanks has been considered. Additionally, innovations in the SDHW industry have led to the creation of photovoltaic/thermal (PV/T) collectors, which heat water using both electrical and thermal energy. The current work compared the performance and cost-effectiveness of a traditional solar thermal (ST) DHW system to PV-solar-electric DHW systems and a PV/T DHW system. To accomplish this, a detailed TRNSYS model of the solar hot water systems was created and annual simulations were performed for 250 L/day and 325 L/day loads in Toronto, Vancouver, Montreal, Halifax, and Calgary. It was shown that when considering thermal performance, PV-DHW systems were not competitive when compared to ST-DHW and PVT-DHW systems. As an example, for Toronto the simulated annual solar fractions of PV-DHW systems were approximately 30%, while the ST-DHW and PVT-DHW systems achieved 65% and 71% respectively. With current manufacturing and system costs, the PV-DHW system was the most cost-effective system for domestic purposes. The capital cost of the PV-DHW systems were approximately $1,923-$2,178 depending on the system configuration, and the ST-DHW and PVT system were estimated to have a capital cost of $2,288 and $2,373 respectively. Although the capital cost of the PVT-DHW system was higher than the other systems, a Present Worth analysis for a 20-year period showed that for a 250 L/day load in Toronto the Present Worth of the PV/T system was approximately $4,597, with PV-DHW systems costing approximately $7,683-$7,816 and the ST-DHW system costing $5,238.

Rural architecture : being a complete description of farm houses, cottages, and out buildings, comprising wood houses, workshops, tool houses, carriage and wagon houses, stables, smoke and ash houses, ice houses, apiary or bee house, poultry houses, rabbitry, dovecote, piggery, barns and sheds for cattle, &c, &c., &c. : Together with lawns, pleasure grounds and parks; the flower, fruit, and vegetable garden. Also, useful and ornamental domestic animals for the country resident &c.,&c., &c. Also, the best method of conducting water into cattle yards and houses /

Mode of access: Internet.

Inquiry into the best mode of supplying the city of Boston with water for domestic purposes : in reply to the pamphlets of Mr. Wilkins and Mr. Shattuck and also to some of the representations to the committee of the legislature, on the hearing of the petition of the city /

Mode of access: Internet.

Water supply; a treatise on the sources, distribution, and consumption of water for commercial and domestic uses,

Mode of access: Internet.

Domestic and service water active solar energy preheat systems.

"February 1992."

Organizational maintenance repair parts and special tool lists : heater, water, liquid fuel, skid-mounted, 600 GPH, M2, FSN 4410-542-5656.

Includes index.

Operator and organizational maintenance manual : heater, water, liquid fuel, skid-mounted, 600 GPH, M2.

"January 1969."

Organizational direct support, and general support maintenance repair parts and special tools lists : heater, bituminous, trailer mounted, 3 tank car heating capacity, oil-fired steam boiler, gasoline engine, driven feed water pump, NSN 3895-00-062-7912, Cleaver Brooks model PSM 50M.

Includes index.

To authorize the Secretary of the Interior to construct facilities to provide water for irrigation, municipal, domestic, military, and other uses from the Santa Margarita River, California, and for other purposes : report (to accompany H.R. 125) (including cost estimate of the Congressional Budget Office).

"November 16, 2005"--Pt. 1.