With years of full-scale experience for precombustion CO(2) capture, amine-based technologies are emerging as the prime contender for postcombustion CO(2) capture. However, concerns for postcombustion applications have focused on the possible contamination of air or drinking water supplies downwind by potentially carcinogenic N-nitrosamines and N-nitramines released following their formation by NO(x) reactions with amines within the capture unit. Analytical methods for N-nitrosamines in drinking waters were adapted to measure specific N-nitrosamines and N-nitramines and total N-nitrosamines in solvent and washwater samples. The high levels of amines, aldehydes, and nitrite in these samples presented a risk for the artifactual formation of N-nitrosamines during sample storage or analysis. Application of a 30-fold molar excess of sulfamic acid to nitrite at pH 2 destroyed nitrite with no significant risk of artifactual nitrosation of amines. Analysis of aqueous morpholine solutions purged with different gas-phase NO and NO(2) concentrations indicated that N-nitrosamine formation generally exceeds N-nitramine formation. The total N-nitrosamine formation rate was at least an order of magnitude higher for the secondary amine piperazine (PZ) than for the primary amines 2-amino-2-methyl-1-propanol (AMP) and monoethanolamine (MEA) and the tertiary amine methyldiethanolamine (MDEA). Analysis of pilot washwater samples indicated a 59 μM total N-nitrosamine concentration for a system operated with a 25% AMP/15% PZ solvent, but only 0.73 μM for a 35% MEA solvent. Unfortunately, a greater fraction of the total N-nitrosamine signal was uncharacterized for the MEA-associated washwater. At a 0.73 μM total N-nitrosamine concentration, a ~25000-fold reduction in concentration is needed between washwater units and downwind drinking water supplies to meet proposed permit limits.

Amine-based technologies are emerging as the prime contender for postcombustion CO2 capture. However, concerns have arisen over the health impacts of amine-based CO2 capture associated with the release of nitrosamines and nitramines, which are byproducts from the reactions between flue gas NOx and solvent amines. In this study, flue gas compositions were systematically varied to evaluate their effects on the formation of nitrosamines and nitramines in a lab-scale CO2 capture reactor with morpholine as a model solvent amine. The accumulation of N-nitrosomorpholine in both the absorber and washwater increased linearly with both NO and NO2 for concentrations up to ∼20 ppmv. These correlations could be extrapolated to estimate N-nitrosomorpholine accumulation at extremely low NOx levels (0.3 ppmv NO2 and 1.5 ppmv NO). NO played a particularly important role in driving N-nitrosomorpholine formation in the washwater, likely following partial oxidation to NO2 by O2. The accumulation of N-nitromorpholine in both the absorber and washwater positively correlated with flue gas NO2 concentration, but not with NO concentration. Both N-nitrosomorpholine and N-nitromorpholine accumulated fastest in the absence of CO2. Flue gas humidity did not affect nitrosamine accumulation in either the absorber or the washwater unit. These results provide a basis for estimating the effects of flue gas composition on nitrosamine and nitramine accumulation in postcombustion CO2 capture systems.

Concerns have arisen for the possible contamination of air or drinking water supplies downwind of amine-based CO2 capture facilities by potentially carcinogenic N-nitrosamines formed from reactions between flue gas NOx and amine solvents. This study evaluated the influence of amine structure on the potential to form total N-nitrosamines within the absorber and washwater units of a laboratory-scale CO2 capture reactor, and in the solvent after a pressure-cooker treatment as a mimic of desorber conditions. Among 16 amines representing 3 amine classes (alkanolamines, straight-chain and cyclic diamines, and amino acids), the order of the amine was the primary determinant of total N-nitrosamine formation in the absorber unit, with total N-nitrosamine formation in the order: secondary amines ≈ tertiary amines ≫ primary amines. Similar results were observed upon pressure-cooker treatment, due to reactions between nitrite and amines at high temperature. For secondary and tertiary amines, total N-nitrosamine formation under these desorber-like conditions appeared to be more important than in the absorber, but for primary amines, significant formation of total N-nitrosamines was only observed in the absorber. For diamines and amino acids, total N-nitrosamine accumulation rates in washwaters were lowest for primary amines. For alkanolamines, however, total N-nitrosamine accumulation in the washwater was similar regardless of alkanolamine order, due to the combined effects of amine reactivity toward nitrosation and amine volatility. While total N-nitrosamine accumulation rates in washwaters were generally 1-2 orders of magnitude lower than in the absorber, they were comparable to absorber rates for several primary amines. Decarboxylation of the amino acid sarcosine resulted in the accumulation of significant concentrations of N-nitrosodimethylamine and N-nitrodimethylamine in the washwater.

A U.S.-wide occurrence survey conducted as part of the Unregulated Contaminant Monitoring Rule 2 found that N-nitrosodimethylamine (NDMA) was present in 34% of chloraminated drinking water samples but was the most prevalent of the six N-nitrosamines evaluated using U.S. Environmental Protection Agency (EPA) Method 521. If the U.S. EPA considers limiting exposures to N-nitrosamines as a group, a critical question is whether NDMA is the most prevalent N-nitrosamine or whether significant concentrations occur for N-nitrosamines other than those captured by EPA Method 521. A total N-nitrosamine assay was developed and applied to 36 drinking water plant effluents or distribution system samples from 11 utilities, including 9 utilities that practiced chloramination for secondary disinfection. Concurrent application of EPA Method 521 indicated that NDMA was the most prevalent of the Method 521 N-nitrosamines yet accounted for ∼5% of the total N-nitrosamine pool on a median basis. Among eight plant influent waters, NDMA was detected once, while total N-nitrosamines were detected in five samples, suggesting the importance of source water protection. Similar to NDMA, total N-nitrosamine concentrations in source waters increased after chloramination. Chloramines were applied to organic precursors serving as models for pristine natural organic matter, algal exudate, wastewater effluent, and polyDADMAC quaternary amine-based coagulation polymers. While high yields of NDMA were restricted to the wastewater effluent and polyDADMAC, high yields of total N-nitrosamines were observed from the algal exudate, the wastewater effluent, and polyDADMAC. The results suggest that N-nitrosamines as a class may be more prevalent than suggested by occurrence surveys conducted using EPA Method 521.

Although amine-based CO(2) absorption is a leading contender for full-scale postcombustion CO(2) capture at power plants, concerns have been raised about the potential release of carcinogenic N-nitrosamines and N-nitramines formed by reaction of exhaust gas NO(x) with the amines. Experiments with a laboratory-scale pilot unit suggested that washwater units meant to scrub contaminants from absorber unit exhaust could potentially serve as a source of N-nitrosamines via reactions of residual NO(x) with amines accumulating in the washwater. Dosage requirements for the continuous treatment of the washwater recycle line with ultraviolet (UV) light for destruction of N-nitrosamines and N-nitramines, and with ozone or hydroxyl radical-based advanced oxidation processes (AOPs) for destruction of amines and aldehydes, were evaluated. Although <1000 mJ/cm(2) UV fluence was generally needed for 90% removal of a series of model N-nitrosamines and N-nitramines, 280-1000 mJ/cm(2) average fluence was needed for 90% removal of total N-nitrosamines in pilot washwaters associated with two different solvents. While AOPs were somewhat more efficient than ozone for acetaldehyde destruction, ozone was more efficient for amine destruction. Ozone achieved 90% amine removal in washwaters at 5-12 molar excess of ozone, indicating transferred dosage levels of ∼100 mg/L for 90% removal in a first-stage washwater unit, but likely only ∼10 mg/L if applied to a second-stage washwater. Accurate dosage and cost estimates would require pilot testing to capture synergies between UV and ozone treatments.

Reduced graphene oxide (r-GO) membranes with narrow channels exhibit salt rejections comparable to conventional nanofiltration (NF) membranes. However, their water permeances are much lower because of the high tortuosity for water permeation. Herein, we report a facile solution-processable approach to create in-plane nanopores on GO nanosheets before reduction, dramatically decreasing the tortuosity and increasing water permeance while retaining the salt rejection. Specifically, holey GO (HGO) nanosheets were prepared via chemical etching using hydrogen peroxide followed by the deposition on a porous support by vacuum filtration and then reduction via exposure to hydriodic acid solutions to generate the reduced HGO (r-HGO) membrane. The generation of nanopores increases the water permeance from 0.4 L m–2 h–1 bar–1 (LMH/bar) to 6.6 LMH/bar with Na2SO4 rejection greater than 98.5%, and the membranes were robust under strong cross-flow shearing force for 36 h. Both water permeance and Na2SO4 rejection of these r-HGO membranes for the first time simultaneously reach the level of the commercial polyamide-based NF membranes. Given their good antibacterial properties and resistance to aggressive chemical washing, the r-HGO membranes show promise as next-generation NF membranes for desalination.

N-Nitrosamines are key contaminants of concern for wastewater reuse. Although research has focused on N-nitrosodimethylamine (NDMA), measurements indicate that NDMA accounts for only ∼9% of total N-nitrosamines in wastewaters, similar to previous findings in drinking and recreational waters. Recognizing the limited time scale for biological transformation during wastewater treatment, we targeted N-nitrosodiethanolamine (NDELA) as a component of total N-nitrosamines based upon the widespread usage of its triethanolamine precursor in consumer products. NDELA accounted for ∼6% of total N-nitrosamines, exceeding NDMA concentrations in some cases, and those of all other specific N-nitrosamines measured. While ozone and chloramines increased NDMA concentrations by up to an order of magnitude, and chloramines increased NDELA concentrations in some cases, other N-nitrosamine concentrations did not increase. Total N-nitrosamine concentrations increased by only 38–89% during ozonation and 23–65% during chloramination, suggesting that, in wastewaters, the occurrence of N-nitrosamines upstream of disinfection may be more significant than their formation as disinfection byproducts. In three advanced treatment trains, reverse osmosis and UV/hydrogen peroxide advanced oxidation reduced the levels of specific N-nitrosamines below their quantification limits, although 13–30 ng/L as NDMA of uncharacterized total N-nitrosamines remained.

Tertiary amines are being considered as absorption solvents for post-ombustion CO 2 capture, but their potential to form harmful byproducts nitrosamines is yet to be evaluated. This study investigated the factors influencing the formation of nitrosamines from tertiary alkanolamines under simulated desorber conditions and the effects of amine structural characteristics. Total nitrosamine formation from tertiary alkanolamine was determined to be first-order with respect to nitrite concentration and the absorbed CO 2 , but was zero-order with respect to amine concentration in the range of 0.5−2.5 M. Tertiary alkanolamines formed less nitrosamine than their secondary amine analogues. For tertiary alkanolamines with the same number of 2-hydroxyethyl groups, smaller steric hindrance resulted in more nitrosamine formation and higher yields based on nitrite consumption. The analysis of specific nitrosamines revealed that the cleavage of 2-hydroxyethyl group was preferred over demethylation, but comparable to de-ethylation. Reaction pathways were proposed to account for the experimental observations.