The treatment of potable water in Vars, ON is accomplished by filtering the colored, iron-laden groundwater through granular activated carbon (GAC) filters. When first installed, these filters unexpectedly experienced chromatographic displacements of iron into the produced water which resulted in orange-brown water at consumers’ taps. The treatment plant was later modified by adding potassium permanganate oxidation and a greensand filter prior to the GAC adsorption columns. Consequently, iron was almost completely removed and no longer caused operational problems. The main objective of this dissertation is to study the interactions between natural organic matter (NOM) and iron that caused the observed chromatographic effect. This study was divided into three main stages: a) characterization study on Vars groundwater and its treatment system; b) study of the competitive adsorption of iron with NOM in Vars groundwater; and c) evaluation of the rapid small-scale column test (RSSCT) for predicting the full-scale GAC column breakthroughs. The characterization of Vars groundwater showed that ferrous iron was found to be the dominant iron species, representing 90% of the total iron, and that 15 - 35% of the iron was complexed with NOM. It was hypothesized that the chromatographic displacement of iron from the GAC columns was caused by NOM-iron complexes; however, field mini-column experiments showed this was not the case. Thus, competitive adsorption between iron and NOM was seen as the more likely cause of the chromatographic effect. The adsorption capacity of ferrous iron in Vars raw water was less than that in organic-free water by a factor of 7 due to the competition with NOM over the GAC adsorbing sites. However, the NOM adsorption capacity was not reduced due to the presence of ferrous iron. It was hypothesized that ideal adsorption solution theory (IAST) models, which have been successful in describing competitive adsorption between target organic compounds and NOM, could model the competition between an inorganic compound such as ferrous iron and NOM. The hypothesis was proved to be correct, and the adsorption isotherm of iron in competition with NOM in Vars groundwater was simulated very well by several versions of the IAST model. However, none of the models were capable of simulating the competitive adsorption of NOM and ferrous iron simultaneously. Since the presence of iron did not significantly reduce the adsorption capacity of NOM, a simplified approach of using the single-solute NOM isotherm to represent the competitive NOM isotherm was recommended. The performance of the rapid small-scale column test (RSSCT) was evaluated in order to simulate the iron chromatographic effect observed at Vars’ full-scale GAC column. The RSSCT was not capable of predicting the iron phenomenon and the test proved to be problematic due to the oxidation and precipitation of iron within the small voids between the small-scale column’s GAC particles. The RSSCT, using constant and linear diffusivities, were applied to simulate the NOM adsorption after greensand treatment. Integrating both diffusivities, the tests predicted the onset and slope of the NOM breakthrough up to 10-L water treated/g GAC, which is equivalent to 250 days of operation time for the full-scale column. However, the NOM breakthroughs deviated beyond that point and the RSSCT using constant diffusivity underestimated the column performance greatly. On the other hand, the linear diffusivity RSSCT underestimated the performance to a lesser degree and its NOM breakthrough was quite parallel to the full-scale performance with lower NOM removals of 15%. The higher long-term NOM removal in the full-scale system may be explained by biodegradation, a phenomenon that was not considered by the short duration of RSSCT.

The treatment of potable water in Vars, ON is accomplished by filtering the colored, iron-laden groundwater through granular activated carbon (GAC) filters. When first installed, these filters unexpectedly experienced chromatographic displacements of iron into the produced water which resulted in orange-brown water at consumers’ taps. The treatment plant was later modified by adding potassium permanganate oxidation and a greensand filter prior to the GAC adsorption columns. Consequently, iron was almost completely removed and no longer caused operational problems. The main objective of this dissertation is to study the interactions between natural organic matter (NOM) and iron that caused the observed chromatographic effect. This study was divided into three main stages: a) characterization study on Vars groundwater and its treatment system; b) study of the competitive adsorption of iron with NOM in Vars groundwater; and c) evaluation of the rapid small-scale column test (RSSCT) for predicting the full-scale GAC column breakthroughs. The characterization of Vars groundwater showed that ferrous iron was found to be the dominant iron species, representing 90% of the total iron, and that 15 - 35% of the iron was complexed with NOM. It was hypothesized that the chromatographic displacement of iron from the GAC columns was caused by NOM-iron complexes; however, field mini-column experiments showed this was not the case. Thus, competitive adsorption between iron and NOM was seen as the more likely cause of the chromatographic effect. The adsorption capacity of ferrous iron in Vars raw water was less than that in organic-free water by a factor of 7 due to the competition with NOM over the GAC adsorbing sites. However, the NOM adsorption capacity was not reduced due to the presence of ferrous iron. It was hypothesized that ideal adsorption solution theory (IAST) models, which have been successful in describing competitive adsorption between target organic compounds and NOM, could model the competition between an inorganic compound such as ferrous iron and NOM. The hypothesis was proved to be correct, and the adsorption isotherm of iron in competition with NOM in Vars groundwater was simulated very well by several versions of the IAST model. However, none of the models were capable of simulating the competitive adsorption of NOM and ferrous iron simultaneously. Since the presence of iron did not significantly reduce the adsorption capacity of NOM, a simplified approach of using the single-solute NOM isotherm to represent the competitive NOM isotherm was recommended. The performance of the rapid small-scale column test (RSSCT) was evaluated in order to simulate the iron chromatographic effect observed at Vars’ full-scale GAC column. The RSSCT was not capable of predicting the iron phenomenon and the test proved to be problematic due to the oxidation and precipitation of iron within the small voids between the small-scale column’s GAC particles. The RSSCT, using constant and linear diffusivities, were applied to simulate the NOM adsorption after greensand treatment. Integrating both diffusivities, the tests predicted the onset and slope of the NOM breakthrough up to 10-L water treated/g GAC, which is equivalent to 250 days of operation time for the full-scale column. However, the NOM breakthroughs deviated beyond that point and the RSSCT using constant diffusivity underestimated the column performance greatly. On the other hand, the linear diffusivity RSSCT underestimated the performance to a lesser degree and its NOM breakthrough was quite parallel to the full-scale performance with lower NOM removals of 15%. The higher long-term NOM removal in the full-scale system may be explained by biodegradation, a phenomenon that was not considered by the short duration of RSSCT.

The treatment of potable water in Vars, ON is accomplished by filtering the colored, iron-laden groundwater through granular activated carbon (GAC) filters. When first installed, these filters unexpectedly experienced chromatographic displacements of iron into the produced water which resulted in orange-brown water at consumers’ taps. The treatment plant was later modified by adding potassium permanganate oxidation and a greensand filter prior to the GAC adsorption columns. Consequently, iron was almost completely removed and no longer caused operational problems. The main objective of this dissertation is to study the interactions between natural organic matter (NOM) and iron that caused the observed chromatographic effect. This study was divided into three main stages: a) characterization study on Vars groundwater and its treatment system; b) study of the competitive adsorption of iron with NOM in Vars groundwater; and c) evaluation of the rapid small-scale column test (RSSCT) for predicting the full-scale GAC column breakthroughs. The characterization of Vars groundwater showed that ferrous iron was found to be the dominant iron species, representing 90% of the total iron, and that 15 - 35% of the iron was complexed with NOM. It was hypothesized that the chromatographic displacement of iron from the GAC columns was caused by NOM-iron complexes; however, field mini-column experiments showed this was not the case. Thus, competitive adsorption between iron and NOM was seen as the more likely cause of the chromatographic effect. The adsorption capacity of ferrous iron in Vars raw water was less than that in organic-free water by a factor of 7 due to the competition with NOM over the GAC adsorbing sites. However, the NOM adsorption capacity was not reduced due to the presence of ferrous iron. It was hypothesized that ideal adsorption solution theory (IAST) models, which have been successful in describing competitive adsorption between target organic compounds and NOM, could model the competition between an inorganic compound such as ferrous iron and NOM. The hypothesis was proved to be correct, and the adsorption isotherm of iron in competition with NOM in Vars groundwater was simulated very well by several versions of the IAST model. However, none of the models were capable of simulating the competitive adsorption of NOM and ferrous iron simultaneously. Since the presence of iron did not significantly reduce the adsorption capacity of NOM, a simplified approach of using the single-solute NOM isotherm to represent the competitive NOM isotherm was recommended. The performance of the rapid small-scale column test (RSSCT) was evaluated in order to simulate the iron chromatographic effect observed at Vars’ full-scale GAC column. The RSSCT was not capable of predicting the iron phenomenon and the test proved to be problematic due to the oxidation and precipitation of iron within the small voids between the small-scale column’s GAC particles. The RSSCT, using constant and linear diffusivities, were applied to simulate the NOM adsorption after greensand treatment. Integrating both diffusivities, the tests predicted the onset and slope of the NOM breakthrough up to 10-L water treated/g GAC, which is equivalent to 250 days of operation time for the full-scale column. However, the NOM breakthroughs deviated beyond that point and the RSSCT using constant diffusivity underestimated the column performance greatly. On the other hand, the linear diffusivity RSSCT underestimated the performance to a lesser degree and its NOM breakthrough was quite parallel to the full-scale performance with lower NOM removals of 15%. The higher long-term NOM removal in the full-scale system may be explained by biodegradation, a phenomenon that was not considered by the short duration of RSSCT.

This research ranked the adsorbability of 115 emerging contaminants by granular activated carbon (GAC) from drinking water, mainly the organic chemicals identified on the Contaminant Candidate List 3 (CCL3), using classical and quantum quantitative structure activity relationships (QSAR). 80% of the investigated contaminants were classified as cost effectively treatable by GAC based on the models. A rapid small-scale column test (RSSCT) conducted with Lake Ontario water spiked with 8 selected emerging contaminants showed the modeling results were accurate. This research also tested the hypothesis that GAC exhaustion for geosmin and 2-methylisoborneol would be due entirely to natural organic matter, and would occur independently of the presence of these two compounds. RSSCT results confirmed this hypothesis. Mathematical modeling supported this observation by demonstrating that the ratio of the effluent concentration to the influent concentration of a trace organic contaminant is only dependent on the NOM loading state at any bed depth.

This research ranked the adsorbability of 115 emerging contaminants by granular activated carbon (GAC) from drinking water, mainly the organic chemicals identified on the Contaminant Candidate List 3 (CCL3), using classical and quantum quantitative structure activity relationships (QSAR). 80% of the investigated contaminants were classified as cost effectively treatable by GAC based on the models. A rapid small-scale column test (RSSCT) conducted with Lake Ontario water spiked with 8 selected emerging contaminants showed the modeling results were accurate. This research also tested the hypothesis that GAC exhaustion for geosmin and 2-methylisoborneol would be due entirely to natural organic matter, and would occur independently of the presence of these two compounds. RSSCT results confirmed this hypothesis. Mathematical modeling supported this observation by demonstrating that the ratio of the effluent concentration to the influent concentration of a trace organic contaminant is only dependent on the NOM loading state at any bed depth.

No description available.

abstract: Activated Carbon has been used for decades to remove organics from water at large scale in municipal water treatment as well as at small scale in Point of Use (POU) and Point of Entry (POE) water treatment. This study focused on Granular Activated Carbon (GAC) and also activated Carbon Block (CB) were studied. This thesis has three related elements for organics control in drinking water. First, coagulation chemistry for Alum and Aluminum Chlorohydrate (ACH) was optimized for significant organics removal to address membrane fouling issue at a local municipal water treatment plant in Arizona. Second, Rapid Small Scale Column Tests were conducted for removal of Perfluorinated compounds (PFC), PFC were present in groundwater at a local site in Arizona at trace levels with combined concentration of Perfluorooctaneoic Acid (PFOA) and Perfloorooctanesulfonic Acid (PFOS) up to 245 ng/L. Groundwater from the concerned site is used as drinking water source by a private utility. PFC Removal was evaluated for different GAC, influent concentrations and particle sizes. Third, a new testing protocol (Mini Carbon Block (MCB)) for bench scale study of POU water treatment device, specifically carbon block filter was developed and evaluated. The new bench scale decreased the hydraulic requirements by 60 times approximately, which increases the feasibility to test POU at a lab scale. It was evaluated for a common POU organic contaminant: Chloroform, and other model contaminants. 10 mg/L of ACH and 30 mg/L of Alum with pH adjustment were determined as optimal coagulant doses. Bituminous coal based GAC was almost three times better than coconut shell based GAC for removing PFC. Multiple tests with MCB suggested no short circuiting and consistent performance for methylene blue though chloroform removal tests underestimated full scale carbon block performance but all these tests creates a good theoretical and practical fundament for this new approach and provides directions for future researchers. / Dissertation/Thesis / Masters Thesis Civil, Environmental and Sustainable Engineering 2017

abstract: Per- and polyfluoroalkyl substances (PFAS) are a group of man-made chemicals that are detected ubiquitously in the aquatic environment, biota, and humans. Human exposure and adverse health of PFAS through consuming impacted drinking water is getting regulatory attention. Adsorption using granular activated carbon (GAC) and ion exchange resin (IX) has proved to be efficient in removing PFAS from water. There is a need to study the effectiveness of commercially available sorbents in PFAS removal at the pilot-scale with real PFAS contaminated water, which would aid in efficient full-scale plant design. Additionally, there is also a need to have validated bench-scale testing techniques to aid municipalities and researchers in selecting or comparing adsorbents to remove PFAS. Rapid Small-Scale Column Tests (RSSCTs) are bench-scale testing to assess media performance and operational life to remove trace organics but have not been validated for PFAS. Different design considerations exist for RSSCTs, which rely upon either proportional diffusivity (PD) or constant diffusivity (CD) dimensionless scaling relationships. This thesis aims to validate the use of RSSCTs to simulate PFAS breakthrough in pilot columns. First, a pilot-scale study using two GACs and an IX was conducted for five months at a wellsite in central Arizona. PFAS adsorption capacity was greatest for a commercial IX, and then two GAC sources exhibited similar performance. Second, RSSCTs scaled using PD or CD relationships, simulated the pilot columns, were designed and performed. For IX and the two types of GAC, the CD–RSSCTs simulated the PFAS breakthrough concentration, shape, and order of C8 to C4 compounds observed pilot columns better than the PD-RSSCTs. Finally, PFAS breakthrough and adsorption capacities for PD- and CD-RSSCTs were performed on multiple groundwaters (GWs) from across Arizona to assess the treatability of PFAS chain length and functional head-group moieties. PFAS breakthrough in GAC and IX was dictated by chain length (C4>C6>C8) and functional group (PFCAs>PFSAs) of the compound. Shorter-chain PFAS broke through earlier than the longer chain, and removal trends were related to the hydrophobicity of PFAS. Overall, single-use IX performed superior to any of the evaluated GACs across a range of water chemistries in Arizona GWs. / Dissertation/Thesis / Masters Thesis Chemical Engineering 2020

No description available.

Zur Entfernung von anthropogenen organischen Spurenstoffen werden bei der Wasseraufbereitung sehr oft Aktivkohle-Festbettadsorber eingesetzt. Dabei konkurrieren die organischen Einzelstoffe während des Adsorptionsprozesses mit dem adsorbierbaren Anteil der natürlichen Wasserinhaltsstoffe um die aktiven Zentren der Aktivkohle. Durch dieses Konkurrenzverhalten ist es sehr schwierig, für einen zu untersuchenden organischen Einzelstoff seine Entfernbarkeit mittels Aktivkohle abzuschätzen. Gleichzeitig werden der Liste der aus dem Wasser zu entfernenden Substanzen ständig neue Stoffe hinzugefügt. Deshalb wäre es wünschenswert, eine schnelle, einfache und kostengünstige Methode zu haben, mit der unter wasserwerksnahen Bedingungen die Entfernbarkeit eines organischen Einzelstoffs bei der Aktivkohlefiltration in einem Großfilter bestimmt werden kann. Da die bisher entwickelten Methoden nicht in der Lage sind, all diese Vorgaben zu erfüllen, sollte im Rahmen dieser Arbeit eine neue Methode zur Beurteilung der Entfernbarkeit organischer Einzelstoffe mittels Aktivkohlefiltration entwickelt werden. Es wurde ein Aktivkohle-Kleinfiltertest konzipiert und aufgebaut, der eine Einstufung von organischen Substanzen, die auf den Rückhaltepotenzialen von Aktivkohlefiltern basiert, ermöglichen soll. Um die Einstufung nach Sontheimer in trinkwasserrelevante und nicht-trinkwasserrelevante Substanzen vornehmen zu können, wurde ein spezielles Bewertungskonzept entwickelt, das auf die Aktivkohle-Kleinfiltertest-Durchbruchskurven der verschiedenen organischen Einzelstoffe angewendet werden kann. Da der Kleinfiltertest einfach und kostengünstig durchzuführen sein sollte, wurde bei der Auslegung des gesamten Versuchaufbaus darauf geachtet, dass nur Zukaufteile oder Teile verwendet wurden, die sich aus Glas fertigen ließen. Die Versuchsparameter wurden so gewählt, dass die Versuchsvorbereitung und -durchführung nicht zu zeit- und arbeitsintensiv ist. Als Standard für die Versuchsdurchführung wurde eine handelsübliche und in der Wasseraufbereitung weitverbreitete Kohlesorte (F 300) und als Matrix Leitungswasser verwendet. Die Filterzulaufkonzentration des organischen Einzelstoffs wurde auf 500 µg/l festgelegt. Durch verschiedene Vorversuche konnte gezeigt werden, dass der Aktivkohle-Kleinfilter die kinetischen Vorgaben erfüllt und es zu keinen unerwünschten Effekten wie Kanalbildung oder Randeinflüssen kommt. Die Validierung der neu entwickelten Versuchsmethode ergab, dass die Kleinfilter-Durchbruchskurven von Substanzen, deren Entfernbarkeit in Aktivkohlefiltern von Wasserwerken bekannt ist (1,1,1-Trichlorethan, EDTA, Trichlorethen, Atrazin, Isoproturon), plausibel sind. Die Durchbruchsreihenfolge und der Durchbruchsbeginn der einzelnen Substanzen im Kleinfilter waren identisch mit denen in einem Großfilter. Zudem war die Trennschärfe des Kleinfilters für die schlecht (1,1,1-Trichlorethan und EDTA), mäßig (Trichlorethen) und gut (Atrazin und Isoproturon) zu entfernenden Substanzen ausreichend, so dass eine Einstufung in Entfernbarkeitsklassen ohne Probleme vorgenommen werden konnte. Um die organischen Einzelstoffe aufgrund der mit dem Kleinfiltertest aufgenommenen Durchbruchskurven einstufen zu können, musste ein Kriterium für die Trinkwasserrelevanz nach Sontheimer gefunden werden, das sich direkt aus den Durchbruchskurven ableiten lässt. Es bot sich an, eine bestimmte Ablaufkonzentration, die nach einer bestimmten Versuchslaufzeit erreicht wird, als Kriterium festzulegen. Durch die Durchbruchskurven der Stoffe, die bei der Validierung des Kleinfiltertests zum Einsatz kamen, wurde das Kriterium bei einem 10%igen Durchbruch nach 15000 BVT festgelegt. Mit Hilfe des Bewertungskonzepts wurden verschiedene organische Einzelstoffe, deren Entfernbarkeit in einem Wasserwerks-Aktivkohleadsorber nicht oder nur unzureichend bekannt war, anhand der jeweiligen Kleinfilter-Durchbruchskurven eingestuft (MTBE, ETBE, Amidotrizoesäure, Iopamidol).