Treavor H. Boyer

Behavior of reoccurring PARAFAC components in fluorescent dissolved organic matter in natural and engineered systems: a critical review.

Fluorescence spectroscopy coupled with parallel factor analysis (PARAFAC) has been widely used to characterize dissolved organic matter (DOM). Characterization is based on the intensity and location of independent fluorescent components identified in models constructed from excitation-emission matrices (EEMs). Similar fluorescent components have been identified in PARAFAC studies across a wide range of systems; however, there is a lack of discussion regarding the consistency with which these similar components behave. The overall goal of this critical review is to compare results for PARAFAC studies published since the year 2000 which include one or more of three reoccurring humic-like components. Components are compared and characterized based on EEM location, characteristic ecosystems, and behavior in natural and engineered systems. This synthesis allows PARAFAC users to more confidently infer DOM characteristics based on identified components. Additionally, behavioral inconsistencies between similar components help elucidate DOM properties for which fluorescence spectroscopy with PARAFAC may be a weak predictive tool.

Combined ion exchange treatment for removal of dissolved organic matter and hardness

Dissolved organic matter (DOM) and hardness cations are two common constituents of natural waters that substantially impact water treatment processes. Anion exchange treatment, and in particular magnetic ion exchange (MIEX), has been shown to effectively remove DOM from natural waters. An important advantage of the MIEX process is that it is used as a slurry in a completely mixed flow reactor at the beginning of the treatment train. Hardness ions can be removed with cation exchange resins, although typically using a fixed bed reactor at the end of a treatment train. In this research, the feasibility of combining anion and cation exchange treatment in a single completely mixed reactor for treatment of raw water was investigated. The sequence of anion and cation exchange treatment, the number of regeneration cycles, and the chemistry of the regeneration solution were systematically explored. Simultaneous removal of DOM (70% as dissolved organic carbon) and hardness (>55% as total hardness) was achieved by combined ion exchange treatment. Combined ion exchange is expected to be useful as a pre-treatment for membrane systems because both DOM and divalent cations are major foulants of membranes.

Evaluating nutrient impacts in urban watersheds: Challenges and research opportunities

This literature review focuses on the prevalence of nitrogen and phosphorus in urban environments and the complex relationships between land use and water quality. Extensive research in urban watersheds has broadened our knowledge about point and non-point pollutant sources, but the fate of nutrients is not completely understood. For example, it is not known how long-term nutrient cycling processes in turfgrass landscapes influence nitrogen retention rates or the relative atmospheric contribution to urban nitrogen exports. The effect of prolonged reclaimed water irrigation is also unknown. Stable isotopes have been used to trace pollutants, but distinguishing sources (e.g., fertilizers, wastewater, etc.) can be difficult. Identifying pollutant sources may aid our understanding of harmful algal blooms because the extent of the relationship between urban nutrient sources and algal blooms is unclear. Further research on the delivery and fate of nutrients within urban watersheds is needed to address manageable water quality impacts.

Equilibrium and intra-particle diffusion of stabilized landfill leachate onto micro- and meso-porous activated carbon.

Stabilized landfill leachate has previously been treated with activated carbon (AC); however, information on the selectivity of AC depending upon the pore size is minimal. Isotherm and kinetic experiments were conducted using three commercially available AC products, one micro-porous and two meso-porous. Equilibrium adsorption and intra-particle diffusion of organic matter from stabilized leachate was studied. Isotherm experimental data were fitted to Langmuir, Freundlich, and Redlich-Peterson isotherm models in non-linear forms. Of the three isotherm models, the Redlich-Peterson model provided the best fit to the experimental data and showed a similar organic matter adsorption capacity (approximately 0.2 g total organic carbon (TOC) g(-1) AC) for both micro-porous and meso-porous AC. The organic matter effective intra-particle diffusion coefficients (D(e)) in both AC types were on the order of 10(-10) m(2) s(-1) for AC particle sizes greater than 0.5 mm. Meso-porous ACs showed slightly higher D(e) compared to micro-porous AC. Rapid small-scale tests showed a maximum of 80% TOC removal from leachate by each AC investigated. Fluorescence spectroscopy showed a preferential adsorption of fulvic-type organic matter with an increase in empty bed contact time by each AC.

Total Value of Phosphorus Recovery

Phosphorus (P) is a critical, geographically concentrated, nonrenewable resource necessary to support global food production. In excess (e.g., due to runoff or wastewater discharges), P is also a primary cause of eutrophication. To reconcile the simultaneous shortage and overabundance of P, lost P flows must be recovered and reused, alongside improvements in P-use efficiency. While this motivation is increasingly being recognized, little P recovery is practiced today, as recovered P generally cannot compete with the relatively low cost of mined P. Therefore, P is often captured to prevent its release into the environment without beneficial recovery and reuse. However, additional incentives for P recovery emerge when accounting for the total value of P recovery. This article provides a comprehensive overview of the range of benefits of recovering P from waste streams, i.e., the total value of recovering P. This approach accounts for P products, as well as other assets that are associated with P and can be recovered in parallel, such as energy, nitrogen, metals and minerals, and water. Additionally, P recovery provides valuable services to society and the environment by protecting and improving environmental quality, enhancing efficiency of waste treatment facilities, and improving food security and social equity. The needs to make P recovery a reality are also discussed, including business models, bottlenecks, and policy and education strategies.

Effect of landfill characteristics on leachate organic matter properties and coagulation treatability

This work spans landfill characteristics, leachate organic matter properties, and coagulation chemistry to provide new insights into the physical-chemical treatability of stabilized landfill leachate. Furthermore, leachate organic matter is viewed in terms of dissolved organic matter (DOM) present in the natural environment, and coagulation chemistry is evaluated based on previous leachate and water treatment coagulation studies. Stabilized leachate was collected from four landfills for a total of seven leachate samples, and samples were coagulated using ferric chloride, ferric sulfate, and aluminum sulfate. Landfill characteristics, such as age, leachate recirculation, and cover material, influenced properties of DOM present in the leachate, as measured by specific ultraviolet (UV) absorbance at 254 nm (SUVA254) and fluorescence excitation-emission matrices. The coagulation performance of the metal salts was ferric sulfate>aluminum sulfate>ferric chloride, and DOM removal followed the trend of color>UV254>dissolved organic carbon>chemical oxygen demand (COD). Finally, a strong association was found between increasing SUVA254 and increasing DOM removal for coagulation of both leachate and natural surface water. Thus, SUVA254 is expected to be a better predictor of leachate treatability, in particular DOM removal, than the traditionally used ratio of biochemical oxygen demand to COD.

Phosphate recovery using hybrid anion exchange: Applications to source-separated urine and combined wastewater streams

There is increasing interest in recovering phosphorus (P) from various wastewater streams for beneficial use as fertilizer and to minimize environmental impacts of excess P on receiving waters. One such example is P recovery from human urine, which has a high concentration of phosphate (200-800 mg P/L) and accounts for a small volume (≈ 1%) of total wastewater flow. Accordingly, the goal of this study was to evaluate the potential to recover P from source-separated and combined wastewater streams that included undiluted human urine, urine diluted with tap water, greywater, mixture of urine and greywater, anaerobic digester supernatant, and secondary wastewater effluent. A hybrid anion exchange (HAIX) resin containing hydrous ferric oxide was used to recover P because of its selectivity for phosphate and the option to precipitate P minerals in the waste regeneration solution. The P recovery potential was fresh urine > hydrolyzed urine > greywater > biological wastewater effluent > anaerobic digester supernatant. The maximum loading of P on HAIX resin was fresh urine > hydrolyzed urine > anaerobic digester supernatant ≈ greywater > biological wastewater effluent. Results indicated that the sorption capacity of HAIX resin for phosphate and the total P recovery potential were greater for source-separated urine than the combined wastewater streams of secondary wastewater effluent and anaerobic digester supernatant. Dilution of urine with tap water decreased the phosphate loading on HAIX resin. The results of this work advance the current understanding of nutrient recovery from complex wastewater streams by sorption processes.

Diclofenac removal in urine using strong-base anion exchange polymer resins.

One of the major sources of pharmaceuticals in the environment is wastewater effluent of which human urine contributes the majority of pharmaceuticals. Urine source separation has the potential to isolate pharmaceuticals at a higher concentration for efficient removal as well as produce a nutrient byproduct. This research investigated the efficacy of using strong-base anion exchange polymer resins to remove the widely detected and abundant pharmaceutical, diclofenac, from synthetic human urine under fresh and ureolyzed conditions. The majority of experiments were conducted using a strong-base, macroporous, polystyrene resin (Purolite A520E). Ion-exchange followed a two-step removal rate with rapid removal in 1 h and equilibrium removal in 24 h. Diclofenac removal was >90% at a resin dose of 8 mL/L in both fresh and ureolyzed urine. Sorption of diclofenac onto A520E resin was concurrent with desorption of an equivalent amount of chloride, which indicates the ion-exchange mechanism is occurring. The presence of competing ions such as phosphate and citrate did not significantly impact diclofenac removal. Comparisons of three polystyrene resins (A520E, Dowex 22, Dowex Marathon 11) as well as one polyacrylic resin (IRA958) were conducted to determine the major interactions between anion exchange resin and diclofenac. The results showed that polystyrene resins provide the highest level of diclofenac removal due to electrostatic interactions between quaternary ammonium functional groups of resin and carboxylic acid of diclofenac and non-electrostatic interactions between resin matrix and benzene rings of diclofenac. Diclofenac was effectively desorbed from A520E resin using a regeneration solution that contained 4.5% (m/m) NaCl in an equal-volume mixture of methanol and water. The greater regeneration efficiency of the NaCl/methanol-water mixture over the aqueous NaCl solution supports the importance of non-electrostatic interactions between resin matrix and benzene rings of diclofenac. Experiments with ketoprofen, in addition to diclofenac, suggest that polystyrene anion exchange resins can be used to selectively remove other acidic pharmaceuticals from urine.

Treatment of nanofiltration and reverse osmosis concentrates: comparison of precipitative softening, coagulation, and anion exchange.

Disposal and treatment of concentrate from nanofiltration (NF) and reverse osmosis (RO) are major challenges to implementing membrane treatment processes. Intermediate treatment of membrane concentrate, between primary and secondary membrane stages, has the potential to increase membrane recovery rates and decrease the volume of concentrate produced. To achieve this, however, there is a need to better understand treatment of membrane concentrate. As a result, this work systematically evaluated lime softening, ferric sulfate coagulation, and magnetic ion exchange (MIEX) as individual, intermediate treatment processes for membrane concentrate. Six membrane concentrates, from NF and RO, with varying concentrations of calcium, dissolved organic matter (DOM), and sulfate were chosen for this study. Maximum removal of calcium was achieved by lime softening, whereas maximum removals of DOM and sulfate were achieved by MIEX. The results of this work show that intermediate treatment of NF/RO concentrate is capable of producing treated concentrate with water quality approximately equal to the initial source water.

Long-term performance of bicarbonate-form anion exchange: Removal of dissolved organic matter and bromide from the St. Johns River, FL, USA

The goal of this research was to evaluate the long-term performance of magnetic ion exchange (MIEX) treatment using bicarbonate as the mobile counter ion (i.e., MIEX-HCO(3)) and sodium bicarbonate for regeneration. This work is important because there are many unknowns concerning the affinity and regeneration efficiency of bicarbonate-form anion exchange, whereas chloride-form anion exchange (i.e., MIEX-Cl resin) is well-studied. Raw water samples were collected approximately two times per month for one year from a single location on the St. Johns River (SJR), FL, USA. The SJR is characterized by high concentrations of dissolved organic carbon (DOC; 12-26 mg C/L) and bromide (550-1100 μg/L), and is being considered as an alternative drinking water supply. Jar tests were conducted using MIEX-HCO(3) resin, and MIEX-Cl resin was used as a baseline for comparison. The same batch of MIEX-HCO(3) and MIEX-Cl resin was used for the entire study, which was accomplished by regenerating the resins after each jar test in concentrated solutions of sodium bicarbonate and sodium chloride, respectively, and resulted in 21 regeneration cycles. Maximum removal efficiency was achieved with fresh MIEX-HCO(3) resin and virgin MIEX-Cl resin. Both forms of fresh/virgin MIEX resin also had the same affinity sequence with sulfate ≈ UV-absorbing substance > DOC > bromide. The removal efficiency of both forms of MIEX resin decreased as the number of regeneration cycles increased, with MIEX-HCO(3) resin showing 7-18% lower removals than MIEX-Cl resin after 21 regeneration cycles. The affinity sequence of regenerated MIEX-HCO(3) and MIEX-Cl resins differed from fresh resin with UV-absorbing substances > DOC > sulfate > bromide. Scanning electron microscopy and simulated MIEX-HCO(3) treatment under rapidly changing water quality were also used to improve the understanding of bicarbonate-form anion exchange. The major contribution of this research is a systematic study of the extended use of bicarbonate-form anion exchange resin in the context of affinity, regeneration efficiency, and changing water quality.