skip to main content

Title: Acetaminophen and caffeine removal by MnO x(s) and GAC media in column experiments
The objective of this study was to investigate the application of manganese oxide [MnO x(s) ] and granular activated carbon (GAC) media for the removal of caffeine and acetaminophen from water. Organic contaminants of emerging concern represent a developing issue due to their effects on human health and the environment. Manganese oxides are effective for water treatment because of their ability to mediate adsorption and oxidation–reduction reactions for many organic and inorganic constituents. Laboratory scale column experiments were performed using different combinations of commercial MnO x(s) and GAC for assessing the removal of caffeine and acetaminophen, and the subsequent release of soluble Mn due to the reductive dissolution of MnO x(s) . The removal of acetaminophen was detected for all media combinations investigated. However, the removal of caffeine by adsorption only occurred in columns containing GAC media. There was no removal of caffeine in columns containing only MnO x(s) media. Manganese release occurred in columns containing MnO x(s) media, but concentrations were below the secondary drinking water standard of 50 μg L −1 set by the US Environmental Protection Agency. Soluble Mn released from a first process by MnO x(s) media column was removed through adsorption into the GAC media used in a second process. The results of this investigation are relevant for implementation of MnO x(s) and GAC media combinations as an effective treatment process to remove organic contaminants from water.  more » « less
Award ID(s):
Author(s) / Creator(s):
; ; ; ; ; ; ;
Date Published:
Journal Name:
Environmental Science: Water Research & Technology
Page Range / eLocation ID:
134 to 143
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Advanced treated municipal wastewater is an important alternative water source for agricultural irrigation. However, the possible persistence of chemical and microbiological contaminants in these waters raise potential safety concerns with regard to reusing treated wastewater for food crop irrigation. Two low-cost and environmentally-friendly filter media, biochar (BC) and zero-valent iron (ZVI), have attracted great interest in terms of treating reused water. Here, we evaluated the efficacy of BC-, nanosilver-amended biochar- (Ag-BC) and ZVI-sand filters, in reducing contaminants of emerging concern (CECs),Escherichia coli (E. coli)and total bacterial diversity from wastewater effluent. Six experiments were conducted with control quartz sand and sand columns containing BC, Ag-BC, ZVI, BC with ZVI, or Ag-BC with ZVI. After filtration, Ag-BC, ZVI, BC with ZVI and Ag-BC with ZVI demonstrated more than 90% (> 1 log) removal ofE. colifrom wastewater samples, while BC, Ag-BC, BC with ZVI and Ag-BC with ZVI also demonstrated efficient removal of tested CECs. Lower bacterial diversity was also observed after filtration; however, differences were marginally significant. In addition, significantly (p < 0.05) higher bacterial diversity was observed in wastewater samples collected during warmer versus colder months. Leaching of silver ions occurred from Ag-BC columns; however, this was prevented through the addition of ZVI. In conclusion, our data suggest that the BC with ZVI and Ag-BC with ZVI sand filters, which demonstrated more than 99% removal of both CECs andE. coliwithout silver ion release, may be effective, low-cost options for decentralized treatment of reused wastewater.

    Graphical Abstract

    more » « less
  2. Abstract

    Comprehensive treatment of indoor contaminants such as volatile organic compounds (VOCs) and fine particulate matter (PM2.5) using transition metal oxide catalysts or functional fibrous filters has gained substantial attention recently. However, coupling VOC oxidation catalysts into high‐performance filter systems remains a challenge. Herein, an overall solution to strongly bind manganese dioxide (MnO2) nanocrystals onto polypropylene (PP) nonwoven fabrics is provided. For the first time, uniform heterogeneous nucleation and growth of MnO2onto PP nonwoven fabrics using intermediate inorganic nucleation films, including Al2O3, TiO2, and ZnO, formed conformally on the fabrics via atomic layer deposition (ALD) are demonstrated. How different ALD thin films influence the crystallinity, morphology, surface area, and surface oxygen species of the MnO2grown ALD‐coated PP fibers is further investigated. In addition to uniformity and integrity, ZnO thin films give rise to MnO2crystals with the largest fraction of available surface oxygen, enabling 99.5% catalytic oxidation of formaldehyde within 60 min. Moreover, the metal oxide filters provide excellent PM removal efficiencies (ePM), achievingePM2.590% andePM1098%, respectively, making the approach an outstanding method to produce fully dual‐functional filtration media.

    more » « less
  3. Hybrid capacitive deionization (HCDI), which combines a capacitive carbon electrode and a redox active electrode in a single device, has emerged as a promising method for water desalination, enabling higher ion removal capacity than devices containing two carbon electrodes. However, to date, the desalination performance of few redox active materials has been reported. For the first time, we present the electrochemical behavior of manganese oxide nanowires with four different tunnel crystal structures as faradaic electrodes in HCDI cells. Two of these phases are square tunnel structured manganese oxides, α-MnO2 and todorokite-MnO2. The other two phases have novel structures that cross-sectional scanning transmission electron microscopy analysis revealed to have ordered and disordered combinations of structural tunnels with different dimensions. The ion removal performance of the nanowires was evaluated not only in NaCl solution, which is traditionally used in laboratory experiments, but also in KCl and MgCl2 solutions, providing better understanding of the behavior of these materials for desalination of brackish water that contains multiple cation species. High ion removal capacities (as large as 27.8 mg g−1, 44.4 mg g−1, and 43.1 mg g−1 in NaCl, KCl, and MgCl2 solutions, respectively) and high ion removal rates (as large as 0.112 mg g−1 s−1, 0.165 mg g−1 s−1, and 0.164 mg g−1 s−1 in NaCl, KCl, and MgCl2 solutions, respectively) were achieved. By comparing ion removal capacity to structural tunnel size, it was found that smaller tunnels do not favor the removal of cations with larger hydrated radii, and more efficient removal of larger hydrated cations can be achieved by utilizing manganese oxides with larger structural tunnels. Extended HCDI cycling and ex situ X-ray diffraction analysis revealed the excellent stability of the manganese oxide electrodes in repeated ion removal/ion release cycles, and compositional analysis of the electrodes indicated that ion removal is achieved through both surface redox reactions and intercalation of ions into the structural tunnels. This work contributes to the understanding of the behavior of faradaic materials in electrochemical water desalination and elucidates the relationship between the electrode material crystal structure and the ion removal capacity/ion removal rate in various salt solutions. 
    more » « less
  4. null (Ed.)
    The recalcitrance of some emerging organic contaminants through conventional water treatment systems may necessitate advanced technologies that use highly reactive, non-specific hydroxyl radicals. Here, polyacrylonitrile (PAN) nanofibers with embedded titanium dioxide (TiO 2 ) nanoparticles were synthesized via electrospinning and subsequently carbonized to produce mechanically stable carbon/TiO 2 (C/TiO 2 ) nanofiber composite filters. Nanofiber composites were optimized for reactivity in flow through treatment systems by varying their mass loading of TiO 2 , adding phthalic acid (PTA) as a dispersing agent for nanoparticles in electrospinning sol gels, comparing different types of commercially available TiO 2 nanoparticles (Aeroxide® P25 and 5 nm anatase nanoparticles) and through functionalization with gold (Au/TiO 2 ) as a co-catalyst. High bulk and surface TiO 2 concentrations correspond with enhanced nanofiber reactivity, while PTA as a dispersant makes it possible to fabricate materials at very high P25 loadings (∼80% wt%). The optimal composite formulation (50 wt% P25 with 2.5 wt% PTA) combining high reactivity and material stability was then tested across a range of variables relevant to filtration applications including filter thickness (300–1800 μm), permeate flux (from 540–2700 L m −2 h), incident light energy (UV-254 and simulated sunlight), flow configuration (dead-end and cross-flow filtration), presence of potentially interfering co-solutes (dissolved organic matter and carbonate alkalinity), and across a suite of eight organic micropollutants (atrazine, benzotriazole, caffeine, carbamazepine, DEET, metoprolol, naproxen, and sulfamethoxazole). During cross-flow recirculation under UV-irradiation, 300 μm thick filters (30 mg total mass) produced micropollutant half-lives ∼45 min, with 40–90% removal (from an initial 0.5 μM concentration) in a single pass through the filter. The initial reaction rate coefficients of micropollutant transformation did not clearly correlate with reported second order rate coefficients for reaction with hydroxyl radical ( k OH ), implying that processes other than reaction with photogenerated hydroxyl radical ( e.g. , surface sorption) may control the overall rate of transformation. The materials developed herein represent a promising next-generation filtration technology that integrates photocatalytic activity in a robust platform for nanomaterial-enabled water treatment. 
    more » « less
  5. Brominated disinfection byproducts (DBPs) are a concern to drinking water utilities due to their toxicity and increasing prevalence in water systems. Haloacetic acids (HAAs) are a class of DBPs that are partially regulated by the United States Environmental Protection Agency (USEPA), but regulations are likely to increase as evidenced by the brominated HAAs listed on the USEPA Fourth Unregulated Contaminant Monitoring Rule and Fifth Contaminant Candidate List. Utilities often use a pre-oxidant to assist in their treatment training, but this can lead to increased HAA formation during treatment. In this study, tap water was spiked with bromine (Br2) at varying concentrations to simulate bromine-to-chlorine ratios found in the natural environment and the DBPs that may be formed from those waters. The water was fed through a bench-scale biological filter (biofilter) with a small layer of fresh granular activated carbon (GAC) media followed by acclimated anthracite media. The HAA species studied were found to be removable by an average of 89.5% through combined GAC filtration and biofiltration. Biodegradation occurred predominantly in the first five minutes for the acclimated anthracite, with minimal additional removal observed at longer empty bed contact times (15 and 30 min EBCT). This study provides recommendations on biofilter parameters for utilities to reduce the formation of both regulated and unregulated HAAs during the drinking water treatment process. 
    more » « less