N-functionalized carbon nanotubes as a source and precursor of N-nitrosodimethylamine: implications for environmental fate, transport, and toxicity.

Hazardous byproducts may be generated during the environmental processing of engineered nanomaterials. Here, we explore the ability of carbon nanotubes with nitrogen-containing surface groups (N-CNTs) to generate N-nitrosodimethylamine (NDMA) during chemical disinfection. Unexpectedly, we observed that commercial N-CNTs with amine, amide, or N-containing polymer (PABS) surface groups are a source of NDMA. As-received powders can leach up to 50 ng of NDMA per mg of N-CNT in aqueous suspension; presumably NDMA originates as a residue from N-CNT manufacturing. Furthermore, reaction of N-CNTs with free chlorine, monochloramine, and ozone generated byproduct NDMA at yields comparable to those reported for natural organic matter. Chlorination also altered N-CNT surface chemistry, with X-ray photoelectron spectroscopy indicating addition of Cl, loss of N, and an increase in surface O. Although these changes can increase N-CNT suspension stability, they do not enhance their acute toxicity in E. coli bioassays above that observed for as-received powders. Notably, however, dechlorination of reacted N-CNTs with sulfite completely suppresses N-CNT toxicity. Collectively, our work demonstrates that N-CNTs are both a source and precursor of NDMA, a probable human carcinogen, while chemical disinfection can produce CNTs exhibiting surface chemistry and environmental behavior distinct from that of native (i.e., as-received) materials.

Controlling disinfection byproducts from treated wastewater using adsorption with granular activated carbon: Impact of pre-ozonation and pre-chlorination.

This study measured chlorine- and chloramine-reactive precursors using formation potential (FP) tests of nine U.S. Environmental Protection Agency (EPA) regulated and 57 unregulated disinfection byproducts (DBPs) in tertiary-filtered wastewater before and after pilot-scale granular activated carbon (GAC) adsorption. Using breakthrough of precursor concentration and of concentration associated calculated cytotoxicity and genotoxicity (by correlating known lethal concentrations reported elsewhere), the performance of three parallel GAC treatment trains were compared against tertiary-filtered wastewater: ozone/GAC, chlorine/GAC, and GAC alone. Results show GAC alone was the primary process, versus ozone or chlorine alone, to remove the largest fraction of total chlorine- and chloramine-reactive DBP precursors and calculated cytotoxicity and genotoxicity potencies. GAC with pre-ozonation removed the most chlorine- and chloramine-reactive DBP precursors followed by GAC with pre-chlorination and lastly GAC without pre-treatment. GAC with pre-ozonation produced an effluent with cytotoxicity and genotoxicity of DBPs from FP that generally matched that of GAC without pre-oxidation; meanwhile removal of toxicity was greater by GAC with pre-chlorination. The cytotoxicity and genotoxicity of DBPs from FP tests did not scale with DBP concentration; for example, more than 90% of the calculated cytotoxicity resulted from 20% of the DBPs, principally from haloacetaldehydes, haloacetamides, and haloacetonitriles. The calculated cytotoxicity and genotoxicity from DBPs associated with FP-chloramination were at times higher than with FP-chlorination though the concentration of DBPs was five times higher with FP-chlorination. The removal of DBP precursors using GAC based treatment was at least as effective as removal of DOC (except for halonitromethanes for GAC without pre-oxidation and with pre-chlorination), indicating DOC can be used as an indicator for DBP precursor adsorption efficacy. However, the DOC was not a good surrogate for total cytotoxicity and genotoxicity breakthrough behavior, therefore, unregulated DBPs could have negative health implications that are disconnected from general water quality parameters, such as DOC, and regulated classes of DBPs. Instead, cytotoxicity and genotoxicity correlate with the concentration of specific classes of unregulated DBPs.

N-nitrosomorpholine in potable reuse.

As potable reuse guidelines and regulations continue to develop, the presence of N-nitrosamines is a primary concern because of their associated health concerns. In this study, bench-, pilot-, and full-scale tests were conducted to focus on the occurrence and treatment of N-nitrosomorpholine (NMOR) in United States (U.S.) potable reuse systems. Out of twelve U.S. wastewater effluents collected, ambient NMOR was detected in eleven (average = 20 ±â€¯18 ng/L); in contrast, only two of the thirteen surface water and stormwater samples had NMOR. Across all of these samples maximum formation potential by chloramination produced an average increase of 3.6 ±â€¯1.8 ng/L. This result underscores the need to understand the sources of NMOR as it is not likely a disinfection byproduct and it is not known to be commercially produced within the U.S. At the pilot-scale, three potable reuse systems were evaluated for ambient NMOR with oxidation (i.e., chlorination and ozonation), biofiltration, and granular activated carbon (GAC). Both pre-oxidation and biofiltration were ineffective at mitigating NMOR during long-term pilot plant operation (at least eight-months). GAC adsorbers were the only pilot-scale treatment to remove NMOR; however, complete breakthrough occurred rapidly from <2000 to 10,000 bed volumes. For comparison, a full-scale reverse osmosis (RO) potable reuse system was monitored for a year and confirmed that RO effectively removes NMOR. Systematic bench-scale UV-advanced oxidation experiments were undertaken to assess the mitigation potential for NMOR. At a fluence dose of 325 ±â€¯10 mJ/cm2, UV alone degraded 90% of the NMOR present. The addition of 5 mg/L hydrogen peroxide did not significantly decrease the UV dose required for one-log removal. These data illustrate that efficient NMOR removal from potable reuse systems is limited to RO or UV treatment.