Attitudes toward Social Issues Related to Opioid Use among Palliative Care Physicians.

Purpose: This study investigated palliative care physicians' attitudes regarding social issues related to opioid use. Methods: An email survey was sent to 674 physicians who were members of the Korean Society for Hospice and Palliative Care (KSHPC). Results: Data from 66 physicians were analyzed (response rate, 9.8%). About 70% of participants stated that their prescribing patterns were not influenced by social issues related to opioid use, and 90% of participants thought that additional regulations should be limited to non-cancer pain. Under the current circumstances, pain education for physicians is urgently needed, as well as increased awareness among the public. Half of the respondents identified the KSHPC as the primary organization responsible for providing pain education. Conclusion: Palliative care physicians' prescribing patterns were not influenced by social issues related to opioid use, and these issues also should not affect cancer pain control.

Characteristics and Stability of Ozone Nanobubbles in Freshwater Conditions.

The characteristics and stability of ozone nanobubbles (NBs) were investigated for the first time under different preparation conditions and freshwater conditions (i.e., pH, natural organic matter [NOM], carbonate, calcium, and temperature) for an extended period. Two oxygen gas flow rates (4 and 1 L/min) used in ozone NB generation affected the characteristics and stability of ozone NBs. The ozone NBs generated at a high initial dissolved ozone (12.5 mg/L) concentration showed a much higher brightness during measurements than the ozone NBs generated at a low initial dissolved ozone concentration (1 mg/L). The former also exhibited a higher negative surface charge and higher stability in comparison to the latter. The stability and half-lives of ozone NBs followed the order of 3 mM Ca2+ < pH 3 < NOM with high specific ultraviolet absorbance at 254 nm (SUVA254 = 4.1 L/mg·m) < pH 7 < pH 9, while the effects of carbonate and temperature were insignificant. Ozone NBs were relatively stable in waters for a long period (e.g., ≥ 60 days) except for high hardness or low pH conditions. Higher levels of hydroxyl radicals were produced from ozone NB solutions as compared to conventional ozonation.

Primary Malignant Lymphoma Presenting as an Isolated Epidural Mass.

Primary central nervous system lymphoma is a rare form of extranodal non-Hodgkin's lymphoma that occurs in the brain, spinal cord, leptomeninges, or eyes and typically remains confined to the central nervous system. Among them, malignant lymphoma presenting as a primary tumor of the spinal cord is extremely uncommon, and epidural mass formation is known to occur in only 0.8-2.8% of cases of malignant lymphomas. Furthermore, primary malignant lymphoma presenting as an isolated epidural mass is much rarer. Here, we report a case of primary malignant lymphoma of the thoracic spine presenting as an isolated epidural mass that did not involve the vertebral body or posterior element. Surgical decompression is essential to prevent further neurological deterioration. Here, we present a successful treatment strategy for this rare case.

Effect of activated sludge treatment on the formation of Nnitrosamines under different chloramination conditions.

Municipal wastewater discharge is considered as one of the main sources of N-nitrosamine precursors which can impact the qualities of downstream source waters and reclaimed wastewaters for potable reuse. NNitrosamine precursors can be removed to various degrees during biological wastewater treatment (e.g., the activated sludge (AS) process). So far, little is known about the impact of the AS process on N-nitrosamine formation under practical disinfection condition (e.g., uniform formation condition (UFC)). In this study, N-nitrosamine UFC from selected model compounds, sewage components (i.e., blackwaters and greywaters) and sewage samples were comprehensively investigated during batch AS treatment tests. NNitrosodimethylamine (NDMA) formation from the tested precursor compounds (i.e., trimethylamine (TMA) and sumatriptan (SMTR)) under UFC chloramination decreased mostly after 6 or 24 hr treatment with different types of AS (i.e., domestic rural AS, domestic urban AS, and textile AS), and the reductions in NDMA UFC were comparable to their NDMA formation potential (FP) reductions. In urine and feces blackwaters, NDMA UFC increased after 6 or 24 hr treatment with the domestic (i.e., rural and urban) AS, while NDMA FP decreased substantially. The increases in NDMA UFC after AS treatment was presumably attributed to the removal of bulk organic matters (e.g., dissolved organic carbon (DOC)) which favored NDMA formation under UFC. On the other hand, in laundry greywaters having relatively abundant DOC, N-nitrosamine UFC was less affected by DOC removal before or after AS treatment, but decreased to similar degrees with N-nitrosamine FP. In sewage samples collected from wastewater treatment plants, N-nitrosamines UFC tended to increase or remain constant during AS treatment, despite the decreases in their FPs. These results suggest that biological wastewater treatment (e.g., the AS process) may not effectively reduce N-nitrosamine formation (e.g., measured under UFC) partially because the concurrent removal of bulk organic matters (e.g., DOC) favored N-nitrosamine formation in s econdary effluents.

Inputs of disinfection by-products to the marine environment from various industrial activities: Comparison to natural production.

Oxidative treatment of seawater in coastal and shipboard installations is applied to control biofouling and/or minimize the input of noxious or invasive species into the marine environment. This treatment allows a safe and efficient operation of industrial installations and helps to protect human health from infectious diseases and to maintain the biodiversity in the marine environment. On the downside, the application of chemical oxidants generates undesired organic compounds, so-called disinfection by-products (DBPs), which are discharged into the marine environment. This article provides an overview on sources and quantities of DBP inputs, which could serve as basis for hazard analysis for the marine environment, human health and the atmosphere. During oxidation of marine water, mainly brominated DBPs are generated with bromoform (CHBr3) being the major DBP. CHBr3 has been used as an indicator to compare inputs from different sources. Total global annual volumes of treated seawater inputs resulting from cooling processes of coastal power stations, from desalination plants and from ballast water treatment in ships are estimated to be 470-800 × 109 m3, 46 × 109 m3 and 3.5 × 109 m3, respectively. Overall, the total estimated anthropogenic bromoform production and discharge adds up to 13.5-21.8 × 106 kg/a (kg per year) with contributions of 11.8-20.1 × 106 kg/a from cooling water treatment, 0.89 × 106 kg/a from desalination and 0.86 × 106 kg/a from ballast water treatment. This equals approximately 2-6% of the natural bromoform emissions from marine water, which is estimated to be 385-870 × 106 kg/a.

Patient Factors Associated with Different Hospice Programs in Korea: Analyzing Healthcare Big Data.

The Korean government has implemented a pilot project that introduces a new type of hospice care program called "Consultative Hospice Care" (COHC) since August 2017. The COHC is a new type of hospice program for terminally ill patients in acute care wards, which is different from the Independent Hospice Unit (IHU) care. This study aimed to compare the characteristics of two groups of hospice patients: COHC care only and both IHU care and COHC groups. Healthcare claim data from 1 April 2018 to 31 March 2020 were retrieved from the HIRA data warehouse system. The main outcome variable was patients receiving COHC only or both COHC and IHU care. The total number of hospice patients was 6482. A multivariate logistic regression analysis was used. Of 6482 hospice care recipients, 3789 (58.5%) received both COHC and IHU care. Those who received both COHC and IHU care were significantly associated with several factors: period from the first evaluation to death (adjusted odds ratio (aOR), 1.026; 95% confidence internal (CI), 1.024-1.029; p < 0.0001), disease severity measured by the Charlson Comorbidity Index (aOR, 1.032; CI, 1.017-1.047; p < 0.0001), consciousness (aOR, 3.654; CI, 3.269-4.085; p < 0.0001), and awareness of end-stage disease (aOR, 1.422; CI, 1.226-1.650; p < 0.0001). The COHC program had a critical role in hospice delivery to terminally ill patients. Policymakers on hospice care need to establish plans that promote efficient hospice care delivery systems.

Beliefs and Attitudes toward Physician-assisted Suicide among Korean Adults.

Purpose: To grasp public opinion accurately, we conducted an opinion poll on beliefs and attitudes toward physician-assisted suicide (PAS). Methods: A randomized telephone survey ensuring a representative sample was conducted, 1,007 participants aged 18 years or older (response rate, 9.5%). Results: The main results are as follows i) 61.1% of participants thought that the current social support system for terminally ill patients and their families is insufficient; ii) 60% of participants did not recognize the term "hospice and palliative care"; iii) 81.7% of participants would not like to receive life-sustaining treatment if there is no possibility of recovery; iv) 58.4% of participants would like to receive hospice and palliative care if they are diagnosed with a terminal illness; v) the priorities for dignified dying were preparing a support system to reduce the burden of care (28.6%), economic support including reduction of medical expenses (26.7%), expansion of hospice and palliative care services (25.4%), and legalization of PAS (13.6%); and vi) 58.3% of participants agreed that the expansion of hospice and palliative care should precede the legalization of PAS. Conclusion: Koreans currently want other efforts, including expansion of hospice and palliative care services, instead of the legalization of PAS.

Stability of Oxygen Nanobubbles under Freshwater Conditions.

The use of nanobubbles (NBs) has gained significant attention in various applications (e.g., aeration in biological water treatment, water disinfection, membrane defouling, and ground water and sediment remediation) in recent decades because of their superior characteristics such as the improved mass transfer at the gas-liquid interfaces, their lifetime up to a couple of weeks, the formation of reactive oxygen species (ROS) with high oxidative potential. However, there is a lack of information about the effect of various factors on the stability of NBs for a long storage period under freshwater conditions. In this study, a comprehensive investigation was conducted to systematically examine the stability of oxygen NBs in water under various conditions which are closely related to a typical freshwater or the drinking water treatment. The oxygen NB stability in water was evaluated by monitoring the change in the bubble concentrations, size distribution, average diameter, and zeta potential for 60 days of storage time under different pH, hardness, ionic strength, natural organic matter (NOM), chlorine, and temperature conditions. In addition, the formation of hydroxyl radical (•OH) was investigated using disodium terephthalate which form fluorescent adducts with •OH in the presence of oxygen NBs. Among the parameters investigated, the impacts of cations, low pH, and high SUVA254 NOM on the stability of oxygen NBs were more significant than other conditions. The half-lives of oxygen NBs under various conditions follow the order Ca2+ < Na+ < pH 3 < high SUVA254 NOM < pH 5 < 30 °C. Oxygen NBs were more stable in softwater than hardwater. Oxygen NBs were relatively stable for 3 days regardless of pH. For a longer storage period, oxygen NBs disappeared faster at pH 3 than at high pH. High SUVA254 NOM destabilized NBs more than low SUVA254 NOM, indicating the impact of hydrophobicity on the NB stability. The temperature effect on the NB stability was negligible for a short storage time, while higher temperature destabilized oxygen NBs for a longer storage time. One of the main disappearance pathway of oxygen NBs in water was found to be coalescing, rising, and leaving the container, which would be promoted greatly by cations, low pH and NOM with high aromaticity. The formation of hydroxyl radical in NB solutions was detected at pH 3 by a florescent probe molecule. When oxygen NBs are released in water bodies, high calcium, high SUVA254 NOM, and low pH would significantly reduce the availability of NBs and their residence time in freshwater.

Impact of biological wastewater treatment on the reactivity of N-Nitrosodimethylamine precursors.

N-Nitrosodimethylamine (NDMA) is a probable human carcinogen which forms during chloramination of wastewater-impacted drinking waters. Municipal wastewater effluents are considered as major sources of NDMA precursors affecting downstream water quality. To evaluate the deactivation mechanisms and efficiencies of NDMA precursors during secondary treatment with the activated sludge (AS) process, NDMA formation potentials (FPs) of selected model precursor compounds and sewage components (i.e., blackwaters and greywaters) were monitored in batch AS treatment tests. After 24-h incubation with four different types of AS (i.e., domestic rural, domestic urban, textile and lab-grown AS), NDMA FP of trimethylamine (TMA) and minocycline (MNCL) decreased by 77-100%, while there was only 29-46% reduction in NDMA FP of sumatriptan (SMTR). The reduction in NDMA FP associated with ranitidine (RNTD) varied between 34% and 87%. The decrease in NDMA FP of RNTD depended on the AS type, hydraulic retention time (HRT) and solids retention time (SRT). The domestic AS (rural and urban) achieved higher decreases in NDMA FPs of the tested model precursors than the textile AS or lab-grown AS. Increasing the HRT or SRT enhanced NDMA FP decrease for RNTD. Among different processes tested (i.e., biodegradation, biosorption and volatilization), biosorption was the major mechanism responsible for the NDMA FP decrease of RNTD, MNCL and SMTR, while biodegradation was the major NDMA FP reduction mechanism for TMA. The reduction in NDMA FP of RNTD via biodegradation depended on the AS activity which may vary with sampling seasons and SRT. NDMA FPs in all tested sewage components (i.e., blackwaters and greywaters) decreased after 24-h AS treatment. Urine in blackwater was the predominant (i.e., >90%) contributor to NDMA FP in domestic sewage and AS-treated effluents.

Removal of wastewater and polymer derived N-nitrosodimethylamine precursors with integrated use of chlorine and chlorine dioxide.

In this study, the effects of five different pre-oxidation scenarios (i.e., individual, simultaneous, and sequential applications of chlorine dioxide [ClO2] and chlorine [Cl2]) on the removal of N-nitrosodimethylamine (NDMA) formation potential (FP) from different water matrices (i.e., non-impacted natural waters, wastewater [WW]-impacted, and polymer-impacted waters) with subsequent chloramination were investigated. Practically relevant doses of ClO2 and Cl2 were applied for all scenarios to avoid the formation of disinfection by-products (DBPs) at regulatory levels. The removal efficiency of NDMA FP for all the oxidation scenarios (individual or simultaneous) was <20% in non-impacted natural water samples. In 20% WW-impacted waters, pre-oxidation with ClO2 at pH 7.8 resulted in a significant reduction in NDMA FP (56-73%), whereas pre-oxidation with Cl2 showed less removals (40-50%). For the integrated oxidation scenarios (i.e., simultaneous or sequential application), NDMA FP removals further increased (20-45%), especially, at pH 6.0 compared to individual application of oxidants in WW-impacted waters. The formation of NDMA in pre-oxidized water samples also decreased significantly under uniform formation condition (UFC). In polymer-impacted waters, integrated applications of Cl2 and ClO2 significantly improved the deactivation of polymer-derived NDMA precursors independent of oxidation time (10 vs. 60 min) and pH (6.0 vs. 7.8) compared to individual application of these oxidants. In addition, chlorite (ClO2-) formation was low and maintained well below 1 mg/L for integrated applications of Cl2 and ClO2, while chlorate (ClO3-) formation increased significantly as compared to application of ClO2 only.

Removal of N-nitrosodimethylamine precursors by cation exchange resin: The effects of pH and calcium.

Cation exchange resins have proved to be efficient in removing precursors of N-nitrosodimethylamine (NDMA). NDMA is a probable human carcinogen with a calculated lifetime cancer risk of 10-6 at 0.7 ng/L in drinking water. This paper investigated the effect of pH and calcium levels on the removal of NDMA precursors using a cation exchange resin. At pH 5 and 7, 30-50% of NDMA precursors, measured by formation potentials (FPs) changes before and after the treatment, were removed by Plus resin. However, increases in NDMA FPs were observed after the treatment at pH 10 indicating that NDMA precursors were released from the resin. NDMA FPs removals in samples containing 15 and 115 mg/L Ca2+ were 40% and -10% after the ion exchange treatments at pH 7, respectively. It was found that in the presence of high concentration of calcium only one out of four cation exchange resins released NDMA precursors (probably due to manufacturing impurities). Also, the release of NDMA precursors depended on the calcium concentration and the contact time of the resin with the solution containing calcium. Nonetheless, NDMA precursors release from the resin subsided significantly with increasing the number of regeneration cycles of the resin.

Deactivation of wastewater-derived N-nitrosodimethylamine precursors with chlorine dioxide oxidation and the effect of pH.

In this study, the effect of chlorine dioxide (ClO2) oxidation on the deactivation of wastewater (WW)-derived N-nitrosodimethylamine (NDMA) precursors was investigated under various conditions (i.e., ClO2 application pH, dose and contact time). At pH 6.0, decreases in NDMA formation potentials (FPs) or occurrences (under uniform formation conditions [UFC]) were relatively low (<25%) with ClO2 oxidation regardless of WW-impact. A negative removal was also observed after ClO2 oxidation in some of the non-impacted waters. However, NDMA FP removals were significant (up to ~85%) under the same oxidation conditions in WW-impacted waters at pH 7.8. This indicates that the majority of WW-derived NDMA precursors can be deactivated with ClO2 oxidation above neutral pH. This was attributed to the better oxidative reaction of ClO2 with amines that have lone pair electrons to be shared at higher oxidation pH conditions. In addition, relatively short oxidation periods with ClO2 (i.e., ≤10 min) or low Ct (concentration × time, ~10 mg ∗ min/L) values were sufficient for the deactivation of WW-derived NDMA precursors. ClO2 oxidation was effective in freshly WW-impacted waters. Natural attenuation processes (e.g., sorption, biodegradation, etc.) can change the reactivity of WW-derived NDMA precursors for oxidation with ClO2. The effect of ClO2 on the removal of THM precursors was low (<25%) and independent of oxidation conditions. Given the low formation of regulated THMs and HAAs, ClO2 oxidation presents a viable option for the simultaneous control of NDMA and regulated DBP formation during water treatment, especially for utilities treating WW-impacted water sources.

The role of chloramine species in NDMA formation.

N-nitrosodimethylamine (NDMA), a probable human carcinogen disinfection by-product, has been detected in chloraminated drinking water systems. Understanding its formation over time is important to control NDMA levels in distribution systems. The main objectives of this study were to investigate the role of chloramine species (i.e., monochloramine and dichloramine); and the factors such as pH, sulfate, and natural organic matter (NOM) influencing the formation of NDMA. Five NDMA precursors (i.e., dimethylamine (DMA), trimethylamine (TMA), N,N-dimethylisopropylamine (DMiPA), N,N-dimethylbenzylamine (DMBzA), and ranitidine (RNTD)) were carefully selected based on their chemical structures and exposed to varying ratios of monochloramine and dichloramine. All amine precursors reacted relatively fast to form NDMA and reached their maximum NDMA yields within 24 h in the presence of excess levels of chloramines (both mono- and dichloramine) or excess levels of dichloramine conditions (with limited monochloramine). When the formation of dichloramine was suppressed (i.e., only monochloramine existed in the system) over the 5 day contact time, NDMA formation from DMA, TMA, and DMiPA was drastically reduced (∼0%). Under monochloramine abundant conditions, however, DMBzA and RNTD showed 40% and 90% NDMA conversions at the end of 5 day contact time, respectively, with slow formation rates, indicating that while these amine precursors react preferentially with dichloramine to form NDMA, they can also react with monochloramine in the absence of dichloramine. NOM and pH influenced dichloramine levels that affected NDMA yields. NOM had an adverse effect on NDMA formation as it created a competition with NDMA precursors for dichloramine. Sulfate did not increase the NDMA formation from the two selected NDMA precursors. pH played a key role as it influenced both chloramine speciation and protonation state of amine precursors and the highest NDMA formation was observed at the pH range where dichloramine and deprotonated amines coexisted. In selected natural water and wastewater samples, dichloramine led to the formation of more NDMA than monochloramine.

Impact of combining chlorine dioxide and chlorine on DBP formation in simulated indoor swimming pools.

The main objective of this study was to assess the combined use of chlorine dioxide (ClO2) and chlorine (Cl2) on the speciation and kinetics of disinfection by-product (DBP) formation in swimming pools using synthetic pool waters prepared with a body fluid analog (BFA) and/or fresh natural water. At 1:25 (mass ratio) of ClO2 to Cl2, there was no significant reduction in the formation of trihalomethanes (THMs) and haloacetic acids (HAAs) for both BFA solution and natural water compared to the application of Cl2 alone. When the mass ratio of ClO2 to Cl2 increased to 1:1, substantial decreases in both THMs and HAAs were observed in the natural water, while there was almost no change of DBP formations in the BFA solution. Haloacetonitriles and halonitromethanes levels in both water matrices remained similar. In the presence of bromide, the overall DBP formation increased in both BFA solution and natural water. For the DBP formation kinetics, after 72hr of contact time, very low formation of THMs and HAAs was observed for the use of ClO2 only. Compared to Cl2 control, however, applying the 1:1 mixture of ClO2/Cl2 reduced THMs by >60% and HAAs by >50%. Chlorite was maintained below 1.0mg/L, while the formation of chlorate significantly increased over the reaction time. Finally, in a bench-scale indoor pool experiment, applying ClO2 and Cl2 simultaneously produced less THMs compared to Cl2 control and kept chlorite at <0.4mg/L, while HAAs and chlorate accumulated over 4-week operation period.

Disinfection by-product formation during seawater desalination: A review.

Due to increased freshwater demand across the globe, seawater desalination has become the technology of choice in augmenting water supplies in many parts of the world. The use of chemical disinfection is necessary in desalination plants for pre-treatment to control both biofouling as well as the post-disinfection of desalinated water. Although chlorine is the most commonly used disinfectant in desalination plants, its reaction with organic matter produces various disinfection by-products (DBPs) (e.g., trihalomethanes [THMs], haloacetic acids [HAAs], and haloacetonitriles [HANs]), and some DBPs are regulated in many countries due to their potential risks to public health. To reduce the formation of chlorinated DBPs, alternative oxidants (disinfectants) such as chloramines, chlorine dioxide, and ozone can be considered, but they also produce other types of DBPs. In addition, due to high levels of bromide and iodide concentrations in seawater, highly cytotoxic and genotoxic DBP species (i.e., brominated and iodinated DBPs) may form in distribution systems, especially when desalinated water is blended with other source waters having higher levels of organic matter. This article reviews the knowledge accumulated in the last few decades on DBP formation during seawater desalination, and summarizes in detail, the occurrence of DBPs in various thermal and membrane plants involving different desalination processes. The review also identifies the current challenges and future research needs for controlling DBP formation in seawater desalination plants and to reduce the potential toxicity of desalinated water.

Seasonal and temporal patterns of NDMA formation potentials in surface waters.

The seasonal and temporal patterns of N-nitrosodimethylamine (NDMA) formation potentials (FPs) were examined with water samples collected monthly for 21 month period in 12 surface waters. This long term study allowed monitoring the patterns of NDMA FPs under dynamic weather conditions (e.g., rainy and dry periods) covering several seasons. Anthropogenically impacted waters which were determined by high sucralose levels (>100 ng/L) had higher NDMA FPs than limited impacted sources (<100 ng/L). In most sources, NDMA FP showed more variability in spring months, while seasonal mean values remained relatively consistent. The study also showed that watershed characteristics played an important role in the seasonal and temporal patterns. In the two dam-controlled river systems (SW A and G), the NDMA FP levels at the downstream sampling locations were controlled by the NDMA levels in the dams independent of either the increases in discharge rates due to water releases from the dams prior to or during the heavy rain events or intermittent high NDMA FP levels observed at the upstream of dams. The large reservoirs and impoundments on rivers examined in this study appeared serving as an equalization basin for NDMA precursors. On the other hand, in a river without an upstream reservoir (SW E), the NDMA levels were influenced by the ratio of an upstream wastewater treatment plant (WWTP) effluent discharge to the river discharge rate. The impact of WWTP effluent decreased during the high river flow periods due to rain events. Linear regression with independent variables DOC, DON, and sucralose yielded poor correlations with NDMA FP (R(2) < 0.27). Multiple linear regression analysis using DOC and log [sucralose] yielded a better correlation with NDMA FP (R(2) = 0.53).

Assessing trihalomethanes (THMs) and N-nitrosodimethylamine (NDMA) formation potentials in drinking water treatment plants using fluorescence spectroscopy and parallel factor analysis.

The formation of disinfection byproducts (DBPs) is a major challenge in drinking water treatments. This study explored the applicability of fluorescence excitation-emission matrices and parallel factor analysis (EEM-PARAFAC) for assessing the formation potentials (FPs) of trihalomethanes (THMs) and N-nitrosodimethylamine (NDMA), and the treatability of THM and NDMA precursors in nine drinking water treatment plants. Two humic-like and one tryptophan-like components were identified for the samples using PARAFAC. The total THM FP (TTHM FP) correlated strongly with humic-like component C2 (r=0.874), while NDMA FP showed a moderate and significant correlation with the tryptophan-like component C3 (r=0.628). The reduction by conventional treatment was more effective for C2 than C3, and for TTHM FP than NDMA FP. The treatability of DOM and TTHM FP correlated negatively with the absorption spectral slope (S275-295) and biological index (BIX) of the raw water, but it correlated positively with humification index (HIX). Our results demonstrated that PARAFAC components were valuable for assessing DBPs FP in drinking water treatments, and also that the raw water quality could affect the treatment efficiency.

The effect of pre-oxidation on NDMA formation and the influence of pH.

N-nitrosodimethylamine (NDMA), a probable human carcinogen, is a disinfection by-product that has been detected in chloraminated drinking water systems. Pre-oxidation of the NDMA precursors prior to chloramination can be a viable approach for water utilities to control the NDMA levels. This study examined the effects of (i) commonly used oxidants (i.e., chlorine, chlorine dioxide and ozone) in water treatment, (ii) oxidant concentration and contact time (CT), and (iii) pre-oxidation pH on the formation of NDMA from subsequent chloramination. Fifteen model precursors with NDMA molar yields ranging from approximately 0.1%-90% were examined. Pre-chlorination reduced NDMA formation from most precursors by 10%-50% except quaternary amine polymers (i.e., PolyDADMAC, PolyACRYL, PolyAMINE). Pre-oxidation with chlorine dioxide and ozone achieved the same or higher deactivation of NDMA precursors (e.g., ranitidine) while increasing NDMA formation for some other precursors (e.g., daminozid). The increases with chlorine dioxide exposure were attributed to the release of oxidation products with dimethylamine (DMA) moiety, which may form more NDMA upon chloramination than the unoxidizied parent compound. On the other hand, chlorine dioxide was effective, if a precursors NDMA yield were higher than DMA. The ozone-triggered increases could be related to direct NDMA formation from DMA which are released by ozonation of amines with DMA moiety, amides or hydrazines. However, hydroxyl radicals formed from the decomposition of ozone would be also involved in decomposition of formed NDMA, reducing the overall NDMA levels at longer contact times. pH conditions influenced significantly the effectiveness of deactivation of precursors depending on the type of precursor and oxidant used.

The roles of tertiary amine structure, background organic matter and chloramine species on NDMA formation.

N-nitrosodimethylamine (NDMA), a probable human carcinogen, is a disinfection by-product that has been detected in chloraminated and chlorinated drinking waters and wastewaters. Formation mechanisms and precursors of NDMA are still not well understood. The main objectives of this study were to systematically investigate (i) the effect of tertiary amine structure, (ii) the effect of background natural organic matter (NOM), and (iii) the roles of mono vs. dichloramine species on the NDMA formation. Dimethylamine (DMA) and 20 different tertiary aliphatic and aromatic amines were carefully examined based on their functional groups attached to the basic DMA structure. The wide range (0.02-83.9%) of observed NDMA yields indicated the importance of the structure of tertiary amines, and both stability and electron distribution of the leaving group of tertiary amines on NDMA formation. DMA associated with branched alkyl groups or benzyl like structures having only one carbon between the ring and DMA structure consistently gave higher NDMA yields. Compounds with electron withdrawing groups (EWG) reacted preferentially with monochloramine, whereas compounds with electron donating group (EDG) showed tendency to react with dichloramine to form NDMA. When the selected amines were present in NOM solutions, NDMA formation increased for compounds with EWG while decreased for compounds with EDG. This impact was attributed to the competitions between NOM and amines for chloramine species. The results provided additional information to the commonly accepted mechanism for NDMA formation including chloramine species reacting with tertiary amines and the role of the leaving group on overall NDMA conversion.