Eric R.V. Dickenson

The potential role of biochar in the removal of organic and microbial contaminants from potable and reuse water: A review.

In this work, the potential benefits, economics, and challenges of applying biochar in water treatment operations to remove organic and microbial contaminants was reviewed. Minimizing the use of relatively more expensive traditional sorbents in water treatment is a motivating aspect of biochar production, e.g.,

Nitrosamines in pilot-scale and full-scale wastewater treatment plants with ozonation.

246/ton non-activated biochar to

N -nitrosodimethylamine (NDMA) formation from the ozonation of model compounds

1500/ton activated carbon. Biochar can remove organic contaminants in water, such as some pesticides (0.02-23 mg g(-1)), pharmaceutical and personal care products (0.001-59 mg g(-1)), dyes (2-104 mg g(-1)), humic acid (60 mg g(-1)), perfluorooctane sulfonate (164 mg g(-1)), and N-nitrosomodimethylamine (3 mg g(-1)). Including adsorption/filtration applications, biochar can potentially be used to inactivate Escherichia coli via disinfection, and transform 95% of 2-chlorobiphenyl via advanced oxidation processes. However, more sorption data using biochar especially at demonstration-scale, for treating potable and reuse water in adsorption/filtration applications will help establish the potential of biochars to serve as surrogates for activated carbons.

Biotransformation of trace organic compounds by activated sludge from a biological nutrient removal treatment system

Ozone-based treatment trains offer a sustainable option for potable reuse applications, but nitrosamine formation during ozonation poses a challenge for municipalities seeking to avoid reverse osmosis and high-dose ultraviolet (UV) irradiation. Six nitrosamines were monitored in full-scale and pilot-scale wastewater treatment trains. The primary focus was on eight treatment trains employing ozonation of secondary or tertiary wastewater effluents, but two treatment trains with chlorination or UV disinfection of tertiary wastewater effluent and another with full advanced treatment (i.e., reverse osmosis and advanced oxidation) were also included for comparison. N-nitrosodimethylamine (NDMA) and N-nitrosomorpholine (NMOR) were the most prevalent nitrosamines in untreated (up to 89xa0ng/L and 67xa0ng/L, respectively) and treated wastewater. N-nitrosomethylethylamine (NMEA) and N-nitrosodiethylamine (NDEA) were detected at one facility each, while N-nitrosodipropylamine (NDPrA) and N-nitrosodibutylamine (NDBA) were less than their method reporting limits (MRLs) in all samples. Ozone-induced NDMA formation ranging from <10 to 143xa0ng/L was observed at all but one site, but the reasons for the variation in formation remain unclear. Activated sludge, biological activated carbon (BAC), and UV photolysis were effective for NDMA mitigation. NMOR was also removed with activated sludge but did not form during ozonation.

Effects of molecular ozone and hydroxyl radical on formation of N-nitrosamines and perfluoroalkyl acids during ozonation of treated wastewaters

Nitrosamines are a class of toxic disinfection byproducts commonly associated with chloramination, of which several were included on the most recent U.S. EPA Contaminant Candidate List. Nitrosamine formation may be a significant barrier to ozonation in water reuse applications, particularly for direct or indirect potable reuse, since recent studies show direct formation during ozonation of natural water and treated wastewaters. Only a few studies have identified precursors which react with ozone to form N-nitrosodimethylamine (NDMA). In this study, several precursor compound solutions, prepared in ultrapure water and treated wastewater, were subjected to a 10xa0M excess of ozone. In parallel experiments, the precursor solutions in ultrapure water were exposed to gamma radiation to determine NDMA formation as a byproduct of reactions of precursor compounds with hydroxyl radicals. The results show six new NDMA precursor compounds that have not been previously reported in the literature, including compounds with hydrazone and carbamate moieties. Molar yields in deionized water were 61-78% for 3 precursors, 12-23% for 5 precursors and <4% for 2 precursors. Bromide concentration was important for three compounds (1,1-dimethylhydrazine, acetone dimethylhydrazone and dimethylsulfamide), but did not enhance NDMA formation for the other precursors. NDMA formation due to chloramination was minimal compared to formation due to ozonation, suggesting distinct groups of precursor compounds for these two oxidants. Hydroxyl radical reactions with the precursors will produce NDMA, but formation is much greater in the presence of molecular ozone. Also, hydroxyl radical scavenging during ozonation leads to increased NDMA formation. Molar conversion yields were higher for several precursors in wastewater as compared to deionized water, which could be due to catalyzed reactions with constituents found in wastewater or hydroxyl radical scavenging.

Plasma-based water treatment: development of a general mechanistic model to estimate the treatability of different types of contaminants

The removal of trace organic compounds (TOrCs) and their biotransformation rates, kb (LgSS(-)(1)h(-)(1)) was investigated across different redox zones in a biological nutrient removal (BNR) system using an OECD batch test. Biodegradation kinetics of fourteen TOrCs with initial concentration of 1-36μgL(-)(1) in activated sludge were monitored over the course of 24h. Degradation kinetic behavior for the TOrCs fell into four groupings: Group 1 (atenolol) was biotransformed (0.018-0.22LgSS(-)(1)h(-)(1)) under anaerobic, anoxic, and aerobic conditions. Group 2 (meprobamate and trimethoprim) biotransformed (0.01-0.21LgSS(-)(1)h(-)(1)) under anoxic and aerobic conditions, Group 3 (DEET, gemfibrozil and triclosan) only biotransformed (0.034-0.26LgSS(-)(1)h(-)(1)) under aerobic conditions, and Group 4 (carbamazepine, primidone, sucralose and TCEP) exhibited little to no biotransformation (<0.001LgSS(-)(1)h(-)(1)) under any redox conditions. BNR treatment did not provide a barrier against Group 4 compounds.

Natural attenuation of NDMA precursors in an urban, wastewater-dominated wash

N-Nitrosamines—toxic disinfection byproducts commonly associated with chloramination—have recently been shown to increase after ozonation of some surface waters and treated wastewaters. In addition to five nitrosamines, two perfluoroalkyl acids (PFAAs) are included in the most recent U.S. EPA Contaminant Candidate List due to potential public health risks. In this manuscript, the potential roles of molecular ozone (O3) and hydroxyl radical (˙OH) were investigated in the formation of N-nitrosamines and PFAAs in treated wastewaters. The results herein are based on controlled bench-scale experiments designed to isolate the effects of O3 with the use of t-butanol as a ˙OH scavenger. Nitrous oxide gas saturated samples were exposed to gamma radiation to isolate the effects of ˙OH, and para-chlorobenzoic acid was used to assess ˙OH exposure. This study found that the presence of molecular ozone versus the hydroxyl radical promoted N-nitrosodimethylamine (NDMA) formation. Six other N-nitrosamines showed very little or no formation upon the ozonation of six treated wastewaters up to an O3u2006:u2006TOC ratio of 1.0. For PFAAs, perfluorohexanoic acid (PFHxA) formed the highest and most consistently upon ozonation (up to an O3u2006:u2006TOC ratio of 2.0) of the same six treated wastewaters. Presence of molecular ozone (more so than hydroxyl radical), appears to promote the formation of PFHxA and perfluorobutane sulfonic acid (PFBS). The effect of pH in the range of 6–8 upon the formation of NDMA and PFAAs was found to be minimal. These findings provide new understanding of the formation of oxidation byproducts during ozonation of reclaimed wastewaters. Depending on future regulatory determinations, NDMA and a few PFAAs could be of concern for potable reuse treatment systems that employ ozone.

Ozone regeneration of granular activated carbon for trihalomethane control

To determine the types of applications for which plasma-based water treatment (PWT) is best suited, the treatability of 23 environmental contaminants was assessed through treatment in a gas discharge reactor with argon bubbling, termed the enhanced-contact reactor. The contaminants were treated in a mixture to normalize reaction conditions and convective transport limitations. Treatability was compared in terms of the observed removal rate constant (k obs). To characterize the influence of interfacial processes on k obs, a model was developed that accurately predicts k obs for each compound, as well as the contributions to k obs from each of the three general degradation mechanisms thought to occur at or near the gas–liquid interface: sub-surface, surface and above-surface. Sub-surface reactions occur just underneath the gas–liquid interface between the contaminants and dissolved plasma-generated radicals, contributing significantly to the removal of compounds that lack surfactant-like properties and so are not highly concentrated at the interface. Surface reactions occur at the interface between the contaminants and dissolved radicals, contributing significantly to the removal of surfactant-like compounds that have high interfacial concentrations. The contaminants interfacial concentrations were calculated using surface-activity parameters determined through surface tension measurements. Above-surface reactions are proposed to take place in the plasma interior between highly energetic plasma species and exposed portions of compounds that extend out of the interface. This mechanism largely accounts for the degradation of surfactant-like contaminants that contain highly hydrophobic perfluorocarbon groups, which are most likely to protrude from the interface. For a few compounds, the degree of exposure to the plasma interior was supported by new and previously reported molecular dynamics simulations results. By reviewing the predicted contributions from the three general mechanisms, it was determined that surface concentration is the dominant factor determining a compounds treatability. These insights indicate that PWT would be most viable for the treatment of surfactant-like contaminants.

Impacts of solids retention time on trace organic compound attenuation and bacterial resistance to trimethoprim and sulfamethoxazole

N-Nitrosodimethylamine (NDMA) is a disinfection by-product (DBP) that is potentially carcinogenic and has been found to occur in drinking water treatment systems impacted with treated wastewater. A major gap in NDMA research is an understanding of the persistence of wastewater-derived precursors within the natural environment. This research sought to fill this knowledge gap by surveying NDMA precursors across the length of a wastewater effluent-dominated wash. Significant precursor reduction (17%) was found to occur from introduction into the wash to a point 9xa0h downstream. This reduction translates into a half-life of roughly 32xa0h for bulk NDMA precursors. Further laboratory experiments examining rates of photolysis, biodegradation and loss to sediments, illustrated that both photolytic and biological degradation were effective removal mechanisms for NDMA precursors. Loss to sediments that were acquired from the wash did not appear to reduce NDMA precursors in the water column, although a control conducted with DI water provided evidence that significant NDMA precursors could be released from autoclaved sediments (suggesting that sorption does occur). Microbial experiments revealed that microbes associated with sediments were much more effective at degrading precursors than microbes within the water column. Overall, this study demonstrated that natural processes are capable of attenuating NDMA precursors relatively quickly within the environment, and that utilities might benefit from maximizing source water residency time in the environment, prior to introduction into treatment plants.

Microbial Community Characterization Of Ozone-biofiltration Systems In Drinking Water And Potable Reuse Applications

Spatial and temporal variations of trihalomethanes (THMs) in distribution systems have challenged water treatment facilities to comply with disinfection byproduct rules. In this study, granular activated carbon (GAC) and modified GAC (i.e., Ag-GAC and TiO2-GAC) were used to treat chlorinated tap water containing CHCl3 (15-21μg/L), CHBrCl2 (13-16μg/L), CHBr2Cl (13-14μg/L), and CHBr3 (3μg/L). Following breakthrough of dissolved organic carbon (DOC), GAC were regenerated using conventional and novel methods. GAC regeneration efficiency was assessed by measuring adsorptive (DOC, UV absorbance at 254nm, and THMs) and physical (surface area and pore volume) properties. Thermal regeneration resulted in a brief period of additional DOC adsorption (bed volume, BV, ∼6000), while ozone regeneration was ineffective regardless of the GAC type. THM adsorption was restored by either method (e.g., BV for ≥80% breakthrough, CHBr3u2009∼44,000>CHBr2Clu2009∼35,000>CHBrCl2u2009∼31,000>CHCl3u2009∼7000). Cellular and attached adenosine triphosphate measurements illustrated the antimicrobial effects of Ag-GAC, which may have allowed for the extended THM adsorption compared to the other GAC types. The results illustrate that ozone regeneration may be a viable in-situ alternative for the adsorption of THMs during localized treatment in drinking water distribution systems.