Processing-Structure-Performance Relationships of Microporous Metal-Organic Polymers for Size-Selective Separations.

Small-molecule impurities, such as N-nitrosodimethylamine (NDMA), have infiltrated the generic drug industry, leading to recalls in commonly prescribed blood pressure and stomach drugs in over 43 countries since 2018 and directly affecting tens of millions of patients. One promising strategy to remove small-molecule impurities like NDMA from drug molecules is by size exclusion, in which the contaminant is removed by selective adsorption onto a (micro)porous material due to its smaller size. However, current solution-phase size-exclusion separations are primarily limited by the throughput-selectivity trade-off. Here, we report a bioinspired solution to conquer these critical challenges by leveraging the assembly of atomically precise building blocks into hierarchically porous structures. We introduce a bottom-up approach to form micropores, mesopores, and macroscopic superstructures simultaneously using functionalized oxozirconium clusters as building blocks. Further, we leverage recent advances in photopolymerization to design macroscopic flow structures to mitigate backpressure. Based on these multiscale design principles, we engineer simple, inexpensive devices that are able to separate NDMA from contaminated drugs. Beyond this urgent model system, we expect this design strategy to open up hitherto unexplored avenues of nanomaterial superstructure fabrication for a range of size-exclusion purification strategies.

Reversible photochromic photocatalyst Bi2O3/TiO2/Al2O3 with enhanced visible photoactivity: application toward UDMH degradation in wastewater.

1,1-Dimethylhydrazine (UDMH) and its by-products were considered carcinogenic toxins and represent a serious health hazard to the population once present in water under natural conditions without treatment. The conventional degradation method suffers from incomplete removal of intermediate products (especially N-nitrosodimethylamine (NDMA)), the powdery catalysis being difficult to recover and results in high energy consumption. In this study, a series of Bi2O3/TiO2/Al2O3 (BTA) photocatalysts have been successfully synthesized by a simple dry mixing method with powder material followed by their immobilization. It was evaluated by the photocatalytic degradation of UDMH present in wastewater, which can be recovered by rapid filtration and utilizes only solar energy. The catalyst exhibited markedly enhanced photocatalytic activity for the degradation of UDMH wastewater compared with conventional TiO2/Al2O3 (TA) catalysts under UV, visible and solar irradiation. Besides, the intermediate NDMA was gradually completely degraded. The photocatalysts were extensively characterized using scanning electron microscopy, energy dispersive spectrometry, specific surface area (BET), X-ray diffraction, X-ray photoelectron spectroscopy, UV-visible diffuse reflectance spectroscopy and photo-electrochemical I-t curves evaluation. The results revealed that all the BTA composites exhibited high stability and stronger absorbance in visible light. In addition, the BTA exhibited a reversible photochromic property that can effectively expand the range of light absorption and enhance the photocatalytic activity. The reversible photochromic properties of BTA explained in the proposed mechanism model are expected to be useful for detecting and sensing UDMH or other organic contaminants.

Influence of reverse osmosis membrane age on rejection of NDMA precursors and formation of NDMA in finished water after full advanced treatment for potable reuse.

The influence of reverse osmosis (RO) membrane age on rejection of N-nitrosodimethylamine (NDMA) precursors was evaluated for a full-scale potable water reuse facility. The rejection of NDMA precursors decreased slightly with increased membrane age in most RO membrane products evaluated, but remained high overall (91% average). Chloride rejection was well-correlated with rejection of NDMA precursors. Precursor removal varied (75-98%) by membrane product, with certain membrane products maintaining better precursor rejection over time. NDMA rejection, however, did not decline significantly over time, while passage of other low molecular weight organics (LMWOs) increased with membrane age. Thus, rejection of NDMA was not highly correlated with rejection of these LMWOs, suggesting that NDMA is not a good surrogate for these compounds. Incomplete removal of NDMA precursors by RO and a UV/advanced oxidation process (UV/AOP) led to NDMA formation in the finished water and miles downstream in the transmission pipelines. An average NDMA formation rate of 0.7 ng/L/hr in the transmission lines was observed, despite typical removal of NDMA by UV/AOP to non-detect levels. The study indicates that RO membranes throughout their lifetime are not an absolute barrier to NDMA precursors, and that while older membranes continue to sufficiently remove NDMA precursors to a high degree, NDMA precursor rejection may decrease slightly as membranes age. Thus, the potential exists for NDMA to form from these precursors in purified, potable reuse water after treatment despite the effective removal of NDMA by UV/AOP.

Removal of chlorpheniramine and variations of nitrosamine formation potentials in municipal wastewaters by adsorption onto the GO-Fe3O4.

Chlorpheniramine is a pharmaceutical pollutant and a precursor of carcinogenic nitrosamines during disinfection/oxidation. In our previous study, graphene oxide coated with magnetite (GO-Fe3O4) was capable of removing chlorpheniramine in deionized water by adsorption. This study investigated the removal of chlorpheniramine and its nitrosamine formation potentials (FPs) by adsorption onto magnetic GO-Fe3O4, with respect to the influence by using real municipal wastewaters as the background. In the results, the adsorption performances of chlorpheniramine in wastewaters decreased in the order: GO-Fe3O4 suspension > GO-Fe3O4 particles > activated carbon. Chlorpheniramine adsorptions on GO-Fe3O4 particles and activated carbon were reduced by using real wastewaters as the background, whereas chlorpheniramine adsorption on GO-Fe3O4 suspension was enhanced due to the effects of surface charge on GO-Fe3O4 and ionic strength variation in water. The fittings of adsorption isotherms indicated that the wastewater background reduced the surface heterogeneity of GO-Fe3O4 suspension and improved the adsorption performance. Appreciable removal efficiencies of NDMA and other nitrosamine FPs were observed when GO-Fe3O4 particles were added in real wastewaters. However, when chlorpheniramine was present in wastewaters, chlorpheniramine adsorption and degradation reaction simultaneously occurred on the surface of GO-Fe3O4, increasing NDMA and other nitrosamine FPs in wastewaters after GO-Fe3O4 addition for chlorpheniramine adsorption. The assumption was further demonstrated by observing the NDMA-FP increase during chlorpheniramine adsorption on GO-Fe3O4 in deionized water. GO-Fe3O4 is a potential adsorbent for chlorpheniramine removal. Nevertheless, the low treatment efficiencies at high doses limit its application for nitrosamine FP adsorptions in real wastewaters.

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.

Contributions of volatilization, photolysis, and biodegradation to N­nitrosodimethylamine removal in conventional drinking water treatment plants.

N­nitrosodimethylamine (NDMA) was detected in the source water of some Chinese drinking water treatment plants (DWTPs), which decreased in concentration along the treatment train. Volatilization, photolysis, and/or biodegradation were suspected of being capable of attenuating NDMA. In this study, the contribution of these mechanisms to NDMA removal was investigated by a field study in a conventional DWTP with aerated bio-pretreatment, as well as in laboratory-based experiments. The effluent of each unit process (i.e., aerated bio-pretreatment tank, horizontal sedimentation tank, sand filter) of this DWTP was sampled in the winter and summer, and the concentration of NDMA, its formation potential, and other water quality parameters were measured. NDMA removal by volatilization and biodegradation was simulated in batch experiments, and that by photolysis was calculated with parameters reported in the literature. The sampling results indicated that the aerated biofilm reactor of this DWTP removed 48% of the NDMA in August and 22% in December. According to modeling results, it could be well explained by photolysis (NDMA removal of 51% in summer and 25% in winter) and biotreatment (NDMA removal of 0.2-12% in summer and 0.1-6.1% in winter), with little contribution from aeration (NDMA removal of 0.8%). The sampling results indicated that the sedimentation tank removed 19% of NDMA in August and 9.2% in December. According to modeling results, it could be well explained by photolysis (NDMA removal of 16% in August and 9.4% in December), but little by volatilization. Thus, photolysis was shown to be the most important process for NDMA removal in this DWTP. Further investigation is needed to better understand NDMA removal during biotreatment.

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.

A four-year simulation of soil aquifer treatment using columns filled with San Gabriel Valley sand.

Two column pairs filled with 3.05-m of a sandy soil from the Upper San Gabriel Valley were operated for a period of four and ½ years on municipal effluent from the San Jose Creek Water Reclamation Plant operated by the Sanitation Districts of Los Angeles County (LACSD). One column pair was fed filtered, chlorinated effluent (tertiary effluent) for the entire period. The other pair was fed ozonated secondary effluent for 8-mo, ozonated secondary effluent filtered through biological activated carbon (O3/BAC) for 7-mo and tertiary effluent for 38-mo. Each column pair was operated in series, where the first column was operated for a shorter residence time and the second column for a longer residence time. Residence times tested were 5-d, 28-d, 30-d, 58-d, 60-d, 150-d and 180-d. For the last 38-mo, both pairs of columns had a residence time of 30-d in the first column and the total residence time of the two pairs was 150 and 180-d, respectively. Testing showed both of these pairs had the same long-term performance. The column pairs with a 150 to 180-d residence time, which were both fed tertiary effluent, reached an effluent total organic carbon (TOC) of 1.8 mg/L. Column pairs with a 28 to 30-d residence time, which were fed tertiary, ozonated, and O3/BAC effluent, reached effluent TOCs of 2.3, 2.1 and 1.8 mg/L respectively. In the latter, some TOC removal was shifted from the soil columns to the BAC. During the last 38 months of testing, using tertiary effluent as the source water, a series of sampling events was performed throughout the soil column system for N-nitrosodimethylamine (NDMA) and chemicals of emerging concern (CECs). NDMA was substantially reduced in all the columns, with a median value of 3 ng/L after 30-d and <2 ng/L after both 150 and 180-d. Twenty-one CECs were found in the majority of tertiary effluent samples, twelve of which were attenuated by the soil columns and the remaining were not. Chemicals found to be recalcitrant were 4-nonylphenol, acesulfame-k, carbamazepine, lidocaine, primidone, simazine, sucralose, sulfamethoxazole, and TCEP. Using excitation-emission matrix (EEM) techniques, soluble microbial products (SMP) peak characteristic of effluent organic matter (EfOM) is nearly eliminated after a 30-d hydraulic retention time (HRT) and completely eliminated in the 150/180-d samples. The intensity of the other peaks is significantly reduced as well, resulting in an EEM much like that of natural groundwater.

A pilot-scale investigation of disinfection by-product precursors and trace organic removal mechanisms in ozone-biologically activated carbon treatment for potable reuse.

Although granular activated carbon (GAC) has been broadly applied in ozone-biologically activated carbon filtration (O3/BAC) systems for potable reuse of municipal wastewater, the mechanisms of various pollutant removal remain largely unknown as the regenerated GAC develops microbial populations resulting in biofiltration but loses significant adsorption capacity as it becomes spent GAC. Therefore, pilot-scale parallel performance comparisons of spent and regenerated GAC, along with a range of pre-oxidant ozone doses, were used to shed light on the mechanisms responsible for the removal of various types of treatment byproduct precursors and trace organic compounds. It was confirmed from this pilot-study that ozone alone can effectively degrade chlorinated trihalomethane (THM) and haloacetic acid (HAA) precursors, chloramine-reactive N-nitrosodimethylamine (NDMA) precursors, and 29 PPCPs. In contrast, biodegradation by microbial population on spent or regenerated GAC can remove NDMA and 22 PPCPs, while the adsorption by regenerated GAC can remove chlorinated THM and HAA precursors, PFAS, flame retardants, and 27 PPCPs. The results of this pilot study are intended to provide those interested in potable reuse with an example of the simultaneous removal capabilities and mechanisms that can be anticipated for treating a complex mixture of organics present in real municipal wastewater effluent.

Online monitoring of N-nitrosodimethylamine rejection as a performance indicator of trace organic chemical removal by reverse osmosis.

The security of recycled water quality in potable reuse can be enhanced by improving the credibility of reverse osmosis (RO) treatment for the removal of trace organic chemicals (TOrCs). This study evaluated the potential of online monitoring of N-nitrosodimethylamine (NDMA) before and after RO treatment as a surrogate indicator for TOrC removal by RO. This pilot-scale study monitored NDMA concentrations in RO feedwater (ultrafiltration-treated wastewater) and RO permeate every 22 min using novel online NDMA analyzers-high-performance liquid chromatography followed by photochemical reaction and chemiluminescence detection. NDMA rejection by RO varied considerably in response to changes in operating conditions (permeate flux and feedwater temperature). A high linear correlation between NDMA rejection and the rejection of six other TOrCs was observed. The linear correlation was also identified for an RO membrane damaged with chlorine. The correlation between another potential surrogate indicator (conductivity rejection) and TOrC rejection was relatively low. NDMA, which is the smallest compound among regulated TOrCs, revealed rejections lower than the other TOrCs, indicating that NDMA rejection can be a conservative surrogate indicator capable of predicting changes in TOrC removal.

High rejection reverse osmosis membrane for removal of N-nitrosamines and their precursors.

Direct potable reuse is becoming a feasible option to cope with water shortages. It requires more stringent water quality assurance than indirect potable reuse. Thus, the development of a high-rejection reverse osmosis (RO) membrane for the removal of one of the most challenging chemicals in potable reuse - N-nitrosodimethylamine (NDMA) - ensures further system confidence in reclaimed water quality. This study aimed to achieve over 90% removal of NDMA by modifying three commercial and one prototype RO membrane using heat treatment. Application of heat treatment to a prototype membrane resulted in a record high removal of 92% (1.1-log) of NDMA. Heat treatment reduced conductivity rejection and permeability, while secondary amines, selected as N-nitrosamine precursors, were still well rejected (>98%) regardless of RO membrane type. This study also demonstrated the highly stable separation performance of the heat-treated prototype membrane under conditions of varying feed temperature and permeate flux. Fouling propensity of the prototype membrane was lower than a commercial RO membrane. This study identified a need to develop highly selective RO membranes with high permeability to ensure the feasibility of using these membranes at full scale.

Rapid method for monitoring N-nitrosodimethylamine in drinking water at the ng/L level without pre-concentration using high-performance liquid chromatography-chemiluminescence detection.

As a contaminant in drinking water, N-nitrosodimethylamine (NDMA) is of great concern because of its carcinogenicity; it has been limited to levels of ng/L by regulatory bodies worldwide. Consequently, a rapid and sensitive method for monitoring NDMA in drinking water is urgently required. In this study, we report an improvement of our previously proposed HPLC-based system for NDMA determination. The approach consists of the HPLC separation of NDMA, followed by NDMA photolysis to form peroxynitrite and detection with a luminol chemiluminescence reaction. The detection limit for the improved HPLC method was 0.2ng/L, which is 10 times more sensitive than our previously reported system. For tap water measurements, only the addition of an ascorbic acid solution to eliminate residual chlorine and passage through an Oasis MAX solid-phase extraction cartridge are needed. The proposed NDMA determination method requires a sample volume of less than 2mL and a complete analysis time of less than 15min per sample. The method was utilized for the long-term monitoring of NDMA in tap water. The NDMA level measured in the municipal water survey was 4.9ng/L, and a seasonal change of the NDMA concentration in tap water was confirmed. The proposed method should constitute a useful NDMA monitoring method for protecting drinking water quality.

Rejection of pharmaceutically-based N-nitrosodimethylamine precursors using nanofiltration.

N-Nitrosodimethylamine (NDMA) is a disinfection by-product (DBP) with many known precursors such as amine-containing pharmaceuticals that can enter the environment via treated wastewater. Reverse osmosis and tight nanofiltration membranes (MW cutoff < 200 Da) are treatment technologies that demonstrate high removal of many compounds, but at relatively high energy costs. Looser membranes (>200 Da) may provide sufficient removal of a wide range of contaminants with lower energy costs. This study examined the rejection of pharmaceuticals that are known NDMA precursors (∼300 Da) using nanofiltration (MW cutoff ∼350 Da). MQ water was compared to two raw water sources, and results illustrated that NDMA precursors (as estimated by formation potential testing) were effectively rejected in all water matrices (>84%). Mixtures of pharmaceuticals vs. single-spiked compounds were found to have no impact on rejection from the membranes used. The use of MQ water vs. surface waters illustrated that natural organic matter, colloids, and inorganic ions present did not significantly impact the rejection of the amine-containing pharmaceuticals. This study illustrates that NDMA formation potential testing can be effectively used for assessing NDMA precursor rejection from more complex samples with multiple and/or unknown NDMA precursors present, such as wastewater matrices.

Determination of a N-Nitrosodimethylamine Precursor in Water Using Ultra-high Performance Liquid Chromatography-Tandem Mass Spectrometry.

1,1,5,5-Tetramethylcarbohydrazide (TMCH) is the main precursor of N-nitrosodimethylamine upon ozonation in the Yodo River basin, Japan. This study was performed to develop an analytical method for TMCH using solid-phase extraction with ultra-high performance liquid chromatography-tandem mass spectrometry. TMCH is hydrophilic and a tertiary amine derivative, so Oasis(®) MCX cartridges were used as solid-phase cartridges. The recoveries of TMCH in tap and river waters as well as secondary effluent from a sewage treatment plant ranged from 75 to 94%. The limit of quantification of TMCH was 4 ng L(-1). The source of TMCH in the Yodo River basin was found to be effluent from one sewage treatment plant. The concentrations were < 4 ng L(-1) in raw water from water purification plants in regions other than the Yodo River basin, indicating that TMCH was used specifically in the basin.

Sorption characteristics of N-nitrosodimethylamine onto biochar from aqueous solution.

N-nitrosodimethylamine (NDMA) is an emerging carcinogenic disinfection by-product in water environment. Biochars utilized as sorbents for the removal of NDMA from aqueous solution, and the sorption characteristics and mechanism were investigate. Biochars were prepared from bamboo, rice straw and wood sawdust at 300-700°C. The pseudo-second-order model provided the best fit for the sorption kinetics of NDMA onto biochar and the sorption isotherms were described best with the Slips model. Biochar produced at 500°C removed NDMA from aqueous solution relatively efficiently, and the bamboo char demonstrated the best sorption potential among the three types of biochars. Solution chemistry such as pH and metal ions did not show obvious effect on NDMA removal. Three sorption mechanisms are suggested for NDMA sorption onto biochars, H-bond attraction between -N=O and the O-containing moieties, hydrophobic force between -CH3 and the ordered graphitic structure, and partition process of NDMA into the non-carbonization part of biochar.

Formation of N-nitrosamines from chlorination and chloramination of molecular weight fractions of natural organic matter.

N-Nitrosamines are a class of disinfection by-products (DBPs) that have been reported to be more toxic than the most commonly detected and regulated DBPs. Only a few studies investigating the formation of N-nitrosamines from disinfection of natural waters have been reported, and little is known about the role of natural organic matter (NOM) and the effects of its nature and reactivity on the formation of N-nitrosamines. This study investigated the influence of the molecular weight (MW) characteristics of NOM on the formation of eight species of N-nitrosamines from chlorination and chloramination, and is the first to report on the formation of eight N-nitrosamines from chlorination and chloramination of MW fractions of NOM. Isolated NOM from three different source waters in Western Australia was fractionated into several apparent MW (AMW) fractions using preparative-scale high performance size exclusion chromatography. These AMW fractions of NOM were then treated with chlorine or chloramine, and analysed for eight species of N-nitrosamines. Among these N-nitrosamines, N-nitrosodimethylamine (NDMA) was the most frequently detected. All AMW fractions of NOM produced N-nitrosamines upon chlorination and chloramination. Regardless of AMW characteristics, chloramination demonstrated a higher potential to form N-nitrosamines than chlorination, and a higher frequency of detection of the N-nitrosamines species was also observed in chloramination. The results showed that inorganic nitrogen may play an important role in the formation of N-nitrosamines, while organic nitrogen is not necessarily a good indicator for their formation. Since chlorination has less potential to form N-nitrosamines, chloramination in pre-chlorination mode was recommended to minimise the formation of N-nitrosamines. There was no clear trend in the formation of N-nitrosamines from chlorination of AMW fractions of NOM. However, during chloramination, NOM fractions with AMW <2.5 kDa were found to produce higher concentrations of NDMA and total N-nitrosamines. The precursor materials of N-nitrosamines appeared to be more abundant in the low to medium MW fractions of NOM, which correspond to the fractions that are most difficult to remove using conventional drinking water treatment processes. Alternative or advanced treatment processes that target the removal of low to medium MW NOM including activated carbon adsorption, biofiltration, reverse osmosis, and nanofiltration, can be employed to minimise the formation of N-nitrosamines.

Determination of volatile N-nitrosamines in meat products by microwave-assisted extraction coupled with dispersive micro solid-phase extraction and gas chromatography--chemical ionisation mass spectrometry.

A sensitive procedure, microwave-assisted extraction (MAE) coupled dispersive micro solid-phase extraction (D-µ-SPE), was developed to extract N-nitrosodimethylamine (NDMA) and other six volatile N-nitrosamines (NAms) from meat products. Parameters affecting the efficiency of MAE and D-µ-SPE were systematically investigated. For MAE, 5-g of a homogenised meat sample was extracted with 30 mL of a sodium hydroxide (0.025 M) solution at 100 °C for 10 min. The optimum D-µ-SPE conditions were immersing 100mg of Carboxen™ 1000 adsorbent in the MAE extract. After vigorously shaking for 30 min, the NAms were then desorbed by treatment with 200 µL of dichloromethane. A 10 µL aliquot was determined by gas chromatography with chemical ionisation mass spectrometry (GC-CI-MS) using the selected-ion-storage (SIS) mode. The limits of quantitation (LOQs) were 0.03-0.36 ng/g. Preliminary results revealed that NDMA was present in the highest concentration, ranging from 0.8 to 3.2 ng/g.

Dispersive micro-solid phase extraction combined with gas chromatography-chemical ionization mass spectrometry for the determination of N-nitrosamines in swimming pool water samples.

A simple sample pretreatment technique, dispersive micro-solid phase extraction, was applied for the extraction of N-nitrosodimethylamine (NDMA) and other four N-nitrosamines (NAs) from samples of swimming pool water. The parameters affecting the extraction efficiency were systematically investigated. The best extraction conditions involved immersing 75 mg of carbon molecular sieve, Carboxen™ 1003 (as an adsorbent), in a 50-mL water sample (pH 7.0) containing 5% sodium chloride in a sample tube. After 20 min of extraction by vigorous shaking, the adsorbent was collected on a filter and the NAs desorbed by treatment with 150 µL of dichloromethane. A 10-µL aliquot was then directly determined by large-volume injection gas chromatography with chemical ionization mass spectrometry using the selected ion storage mode. The limits of quantitation were <0.9 ng/L. The precision for these analytes, as indicated by relative standard deviations, were <8% for both intra- and inter-day analyses. Accuracy, expressed as the mean extraction recovery, was between 62% and 109%. A preliminary analysis of swimming pool water samples revealed that NDMA was present in the highest concentration, in the range from n.d. to 100 ng/L.

Occurrence of N-nitrosodimethylamine precursors in wastewater treatment plant effluent and their fate during ultrafiltration-reverse osmosis membrane treatment.

The formation of N-nitrosodimethylamine (NDMA) is of major concern among wastewater recycling utilities practicing disinfection with chloramines. The NDMA formation potential (FP) test is a simple and straightforward method to evaluate NDMA precursor concentrations in waters. In this paper we show the NDMA FP results of a range of tertiary wastewater treatment plants that are also the source for production of recycled water using an Ultrafiltration - Reverse Osmosis (UF-RO) membrane process. The results indicate that the NDMA FP of different source waters range from 350 to 1020±20 ng/L. The fate of these NDMA precursors was also studied across the different stages of two Advanced Water Treatment Plants (AWTP) producing recycled water. These results show that more than 98.5±0.5% of NDMA precursors are effectively removed by the Reverse Osmosis (RO) membranes used at the AWTPs. This drastically reduces any potential for re-formation of NDMA after the RO stage even if chloramines may be present (or added) there.