Digital synthetic polymers for information storage.

Digital synthetic polymers with uniform chain lengths and defined monomer sequences have recently become intriguing alternatives to traditional silicon-based information devices or natural biomacromolecules for data storage. The structural diversity of information-containing macromolecules endows the digital synthetic polymers with higher stability and storage density but less occupied space. Through subtly designing each unit of coded structure, the information can be readily encoded into digital synthetic polymers in a more economical scheme and more decodable, opening up new avenues for molecular digital data storage with high-level security. This tutorial review summarizes recent advances in salient features of digital synthetic polymers for data storage, including encoding, decoding, editing, erasing, encrypting, and repairing. The current challenges and outlook are finally discussed to offer potential solution guidance and new perspectives for the creation of next-generation digital synthetic polymers and broaden the scope of their applicability.

Antifouling Asymmetric Block Copolymer Nanofilms via Freestanding Interfacial Polymerization for Efficient and Sustainable Water Purification.

Membrane materials that resist nonspecific or specific adsorption are urgently required in widespread applications. In water purification, inevitable membrane fouling not only limits separation performance, but also remarkably increases operation requirements, and augments extra maintenance costs and higher energy consumption. In this work, we report a freestanding interfacial polymerization (IP) fabrication strategy for in-situ creation of asymmetric block copolymer (BCP) nanofilms with antifouling properties, greatly outperforming the conventional surface post-modification approaches. The resultant asymmetric BCP nanofilms with highly-dense, highly-hydrophilic polyethylene glycol (PEG) brushes, can be readily formed via a typical IP process of a double-hydrophilic BCP composed of an antifouling PEG block and a membrane-forming multiamine block. The asymmetric BCP nanofilms have been applied for efficient and sustainable natural water purification, demonstrating extraordinary antifouling capabilities accompanied with superior separation performance far beyond commercial polyamide nanofiltration membranes. The antifouling behaviors of BCP nanofilms derived from the combined effect of the hydration layer, electrostatic repulsion and steric hindrance were further elucidated by water flux and fouling resistance in combination with all-atom molecular dynamics simulation. This work opens up a new avenue for large-scale and low-cost creation of broad-spectrum, asymmetric membrane materials with diverse functional "defect-free" surfaces in real-world applications.

Simultaneous determination of dissolved organic nitrogen, nitrite, nitrate and ammonia using size exclusion chromatography coupled with nitrogen detector.

Accurate quantification of dissolved organic nitrogen (DON) has been a challenge due to the cumulative analytical errors in the conventional method via subtracting dissolved inorganic nitrogen species (DIN) from total dissolved nitrogen (TDN). Size exclusion chromatography coupled with an organic nitrogen detector (SEC-OND) has been developed as a direct method for quantification and characterization of DON. However, the applications of SEC-OND method still subject to poor separations between DON and DIN species and unsatisfied N recoveries of macromolecules. In this study, we packed a series of SEC columns with different lengths and resin materials for separation of different N species and designed an independent vacuum ultraviolet (VUV) oxidation device for complete oxidation converting N species to nitrate. To guarantee sufficient N recoveries, the operation conditions were optimized as oxidation time ≥ 30 min, injection mass (sample concentration × injection volume) < 1000 µL × mg-N/L for macromolecular proteins, and neutral pH mobile eluent. The dissolved O2 concentration in SEC mobile phase determined the upper limit of VUV oxidation at a specific oxidation time. Compared to conventional HW50S column (20 × 250 mm), HW40S column (20 × 350 mm) with mobile phase comprising of 1.5 g/L Na2HPO4·2H2O + 2.5 g/L KH2PO4 (pH = 6.85) could achieve a better separation of DON, nitrite, nitrate, and ammonia. When applied to river water, lake water, wastewater effluent, groundwater, and landfill leachate, the SEC-OND method could quantify DON as well as DIN species accurately and conveniently even the DIN/TDN ratio reached 0.98.

Overlooked Formation of H2O2 during the Hydroxyl Radical-Scavenging Process When Using Alcohols as Scavengers.

Hydroxyl radical (•OH) is an active species widely reported in studies across many scientific fields, and hence, its reliable analysis is vitally important. Currently, alcohols are commonly used as scavengers for •OH determination. However, the impacts of alcohols on the reliability of •OH detection remain unknown. In this study, we found that adding different types and different amounts of alcohols in water samples treated with ultraviolet irradiation undesirably produced substantial amounts of hydrogen peroxide (H2O2), which is a known •OH precursor. This means that the conventional •OH determination method using alcohols is likely unreliable or even misleading. Through careful investigation, we revealed an overlooked reaction pathway during H2O2 and •OH transformations. Varying oxygen concentrations, pHs, alcohol dosages, and types altered H2O2 formation, which can affect •OH determination accuracy. Among alcohols, n-butanol is the best scavenger because it quenches •OH rapidly but re-forms little H2O2.

Platelet-neutrophil hybrid membrane-coated gelatin nanoparticles for enhanced targeting ability and intelligent release in the treatment of non-alcoholic steatohepatitis.

Non-alcoholic steatohepatitis (NASH) is the major form of chronic liver disease in adults; however, there are no approved drugs for NASH. In this study, we designed the PNM-G-PV method, in which gelatin nanoparticles (G) are loaded with pioglitazone and vitamin E (G-PV) and then encapsulated by the surfaces of platelet-neutrophil hybrid membranes (PNM). Inherited from the natural source cells, the PNM show immune evading ability due to the surface marker comprising a number of "do not eat me" signals and has dual inflammatory enrichment capabilities due to specific surface adhesion molecules. By functionalizing the gelatin nanoparticle biomimetic surfaces, PNM-G can enhance the targeting to inflammatory sites and enrich liver tissue. The high expression of matrix metalloproteinase-9 (MMP-9) at the NASH site enables the gelatin nanoparticles to intelligently respond to degradation and then release vitamin E and pioglitazone for drug treatment. We performed an in vivo analysis of these nanoparticles to monitor changes in triacylglycerol metabolism in liver tissues and assessed the therapeutic efficacy of PNM-G-PV in a NASH rat model. The results showed that PNM-G-PV exhibited better therapeutic efficacy than therapies using G-PV or PV alone. This work explores a new biomedical use of PNM-G-PV and a promising NASH treatment protocol based on a new drug delivery system.

Toxicity of 17 Disinfection By-products to Different Trophic Levels of Aquatic Organisms: Ecological Risks and Mechanisms.

Intensified disinfection of wastewater during the COVID-19 pandemic increased the release of toxic disinfection by-products (DBPs). However, studies relating to the ecological impacts of DBPs on the aquatic environment remain insufficient. In this study, we comparatively investigated the toxicities and ecological risks of 17 typical, halogenated DBPs to three trophic levels of organisms in the freshwater ecosystem, including phytoplankton (Scenedesmus sp.), zooplankton (Daphnia magna), and fish (Danio rerio). Toxicity of DBPs was found to be species-specific: Scenedesmus sp. was the most sensitive to haloacetic acids, while D. magna was the most sensitive to haloacetonitriles and trihalomethanes. Specific to each DBP, toxicities were also related to their classes and substituted halogen atoms. Damage to photosystems and oxidative stress served as the potential mechanisms for DBPs toxicity to microalgae. The different sensitivities to DBPs indicate that a battery of bioassays with organisms at different trophic levels is necessary to determine the ecotoxicity of DBPs. Furthermore, the ecological risks of DBPs were assessed by calculating the risk quotients (RQs) based on toxicity data from multiple bioassays. The cumulative RQs of DBPs to all the organisms were greater than 1.0, indicating high ecological risks of DBPs in wastewater effluents.

Formation of Nitrite and Hydrogen Peroxide in Water during the Vacuum Ultraviolet Irradiation Process: Impacts of pH, Dissolved Oxygen, and Nitrate Concentration.

Photolysis via vacuum ultraviolet (VUV) irradiation is a robust technology capable of inactivating pathogens and degrading micropollutants, and therefore, its application has recently attracted great interest. However, VUV irradiation of water may yield nitrite (NO2-, a regulated carcinogenic contaminant) and hydrogen peroxide (H2O2, a compound linked to aging, inflammation, and cancer), thus motivating us to better understand its risks. By applying a novel H2O2 detection method insensitive to coexisting compounds, this study clearly observed concurrent and substantial formations of NO2- and H2O2 during VUV irradiation of various synthetic and real waters. Increasing pH and/or decreasing oxygen promoted the conversion of nitrate (NO3-) into NO2- but suppressed the H2O2 formation, suggesting that there was a transition of radicals from oxidizing species like hydroxyl radicals to reducing species like hydrogen atoms and hydrated electrons. Under low light dose conditions, both NO2- and H2O2 were formed concurrently; however, under high radiation dosage conditions, the patterns conducive to NO2- formation were opposite to those conducive to H2O2 formation. Real water irradiation proved the formation of NO2- and H2O2 at levels near to or greater than current drinking water regulatory limits. Hence, the study reminds of a holistic view of benefits and disbenefits of a VUV process.

Hydrogen peroxide formation in water during the VUV/UV irradiation process: Impacts and mechanisms of selected anions.

Understanding the formation and transformation of radicals generated by a low pressure mercury lamp emitting both 254 nm ultraviolet (UV254) and 185 nm vacuum UV (VUV185) is currently challenging due to the complexity of concurrent redox reactions occurring in this complex system. Because hydrogen peroxide (H2O2) is a common product of both oxidizing and reducing radicals generated during the VUV irradiation process, monitoring the variations in H2O2 levels can help us better understand the presence and relative dominance of different radicals. In this study, we systematically evaluated the effects of several selected anions on the formation of H2O2 under a variety of pH and dissolved oxygen (DO) conditions. Results show that although addition of these anions inhibited the formation of H2O2, their H2O2-inhibition mechanisms are markedly different. At low concentrations (≤1.0 mg/L), chloride reduced the generation of H2O2 primarily by consuming hydroxyl radicals (•OH); however, in high concentrations (11.0 mg/L), its light-screening effect was dominant. In comparison, the presence of bromide (≤1.0 mg/L) inhibited H2O2 formation mainly by reacting rapidly with both •OH and H2O2. Carbonate and phosphorous species exerted influence mainly by consuming •OH. Along with irradiation, increasing pH significantly decreased H2O2 levels, confirming that H2O2 was formed mainly by •OH. In contrast, raising DO did not raise H2O2 maximum yields, confirming that reducing radicals like aqueous electrons (e-aq) and hydrogen atoms (•H) are not the key precursors of H2O2 in this process. Mathematically, the evolutions of H2O2 can be reliably modeled (R2 ≥ 0.80) using a kinetics model incorporating H2O2 formation and decomposition kinetics. The results of this study may contribute to better understanding the use of VUV technology in water/wastewater treatment.

Down-regulation of MARCO associates with tumor progression in hepatocellular carcinoma.

Hepatocellular carcinoma(HCC) is a malignant tumor with high mortality due to lack of early diagnostic methods and effective treatments, and the molecular mechanisms are intricate and remain unclear. In the present study, the role of macrophage receptor with collagenous structure (MARCO) in tumor advancement of HCC was investigated. We examined expression level of MARCO in HCC samples, corresponding adjacent nontumor tissues and six hepatoma cell lines by polymerase chain reaction and immunohistochemistry (IHC). Clinical information of HCC patients was also analyzed. The role of MARCO involved in HCC progression via multiple functional experiments in vitro and in vivo was investigated. Bioinformatics analysis was conducted to further explore biological functions of MARCO. We found MARCO was suggestively down-regulated in HCC and associated with favorable prognosis, and MARCO upregulation oppressed tumor cell migration and invasion. Besides, overexpression of MARCO not only promoted apoptosis of hepatoma cells but also suppressed proliferation in vivo and in vitro. Furthermore, gene set enrichment analysis (GSEA) analysis suggested that MARCO may be related to the P53 signaling pathway, and this prediction was confirmed in this study as well. In sum, our study indicated that MARCO was involved in HCC progression and it can be defined as a novel probable biomarker as well as treatment target for HCC.

Small nucleolar RNA U2_19 promotes hepatocellular carcinoma progression by regulating Wnt/ß-catenin signaling.

Emerging evidence suggests that small nucleolar RNAs (snoRNAs) have malfunctioning roles in oncogenesis. In the present study, we investigated the role of box C/D small nucleolar RNA U2_19 (snoU2_19) in the tumorigenesis of hepatocellular carcinoma (HCC). Recently, we screened snoRNAs differential signatures by performing high-throughput small RNA sequence in HCC tissues and validated that upregulated snoU2_19 was associated with aggressive phenotypes in HCC patients. Aberrant snoU2_19 facilitated HCC cell proliferation, inhibited apoptosis and induced cell cycle progression in vitro analyses. We globally investigated the molecular mechanisms of snoU2_19 in HCC and found that snoU2_19 knockdown inhibited Wnt/ß-catenin signaling pathway through inducing the translocation of ß-catenin in cytoplasm. We concluded that snoU2_19 plays a pathological role in the development and progression of HCC, and is a potential therapeutic target for HCC.

A Facile, Nonreactive Hydrogen Peroxide (H2O2) Detection Method Enabled by Ion Chromatography with UV Detector.

Hydrogen peroxide (H2O2) is ubiquitous in the natural environment, and it is now widely used for pollutant control in water and wastewater treatment processes. However, current analytical methods for H2O2 inevitably require reactions between H2O2 and other reactants to yield signals and are thus likely subjective to the interferences of coexisting colored, oxidative, and reductive compounds. In order to overcome these barriers, we herein for the first time propose to analyze H2O2 by ion chromatography (IC) using an ultraviolet (UV) detector. The proposal is based on two principles: first, that H2O2 can deprotonate to hydroperoxyl ion (HO2-) when eluent pH is higher than the acid-dissociation coefficient of H2O2 (pKa = 11.6); and second, that after separation from other compounds via IC column, H2O2 can be quantified by a UV detector. Under favorable operating conditions, this method has successfully achieved acceptable recoveries (>91%) of H2O2 dosed to ultrapure and natural waters, a calibration curve with R2 > 0.99 for a wide range of H2O2 concentrations from 0.1 to 50 mg/L and a method detection limit of 0.027 mg/L. In addition, this approach was shown to be capable of distinguishing H2O2 from anions (e.g., fluoride and chloride) and organics (e.g., glycolate) and monochloramine, suggesting that it is insensitive to many neighboring compounds as long as they do not react quickly with H2O2. Hence, this study proves the combination of IC and UV detector a facile and reliable method for H2O2 measurement.

Improved analysis of dissolved organic nitrogen in water via electrodialysis pretreatment.

This study evaluated electrodialysis (ED) for direct, accurate, and precise dissolved organic nitrogen (DON) analysis in water. Unlike conventional methods that calculate DON as the difference between total dissolved nitrogen (TDN) and dissolved inorganic nitrogen (DIN), we designed a compact ED reactor as a pretreatment tool that completely separates DIN from DON in water and then measures DON by equating DON to TDN. The experiments confirmed that the ED pretreatment process can achieve 99% removal of all three major DIN species (i.e., ammonia, nitrite, and nitrate) and an average recovery rate of 88% for an array of model DON compounds of varying characteristics (e.g., urea, amino acids, tripeptide, protein, and humic substances). Variations in nitrogen removal and recovery might be explained by a combined effect of molecular weight, acid dissociation ability (pK(a)), aromaticity, and ED reactor configurations. For model solutions with DIN/DON ratios varying from 1 to 10 mg-N/mg-N, the relative standard deviations in DON concentrations were considerably lower with ED pretreatment (<10%) than without pretreatment (47%). A survey of seven field samples, including lake water, tap water, and treated wastewater, also demonstrated the benefits of using ED pretreatment as compared with a conventional DON analysis method. Overall, this study provides evidence and mechanistic insight for a new DON detection method that uses ED pretreatment. The ED unit is robust for separating DIN and DON, and thus it may facilitate more frequent detection of DON and ultimately enhances understanding of DON issues in the environmental studies.

How I- alters UV and UV/VUV processes' redox capacities: Evidences from iodine species evolution, hydrogen peroxide formation, and oxyhalides degradation?

Although UV and/or VUV tandem I- are often proposed as advanced reduction processes (ARPs) to eliminate micropollutants by generating eaq-, the fate of I- and its byproducts formation remain to be explored. Therefore, this study investigated the iodine species evolution during UV/I- and UV/VUV/I- processes under different influencing factors. Results show that UV/VUV oxidized most of I- to IO3- whereas UV only oxidized a portion of I- to intermediate reactive iodine species (RISs, including I2, HOI, and I3-); meanwhile, substantial H2O2 was generated only in UV/VUV/I- process but not in UV/I- process, proving that UV/VUV owns stronger oxidation ability than UV alone. Spiking I- into water exerted triple-sided effects by consuming •OH, generating eaq-, and shielding light, thus complicating the systems. Holistically, increasing pH or decreasing dissolved oxygen converted oxidizing environment into reducing condition and caused less RISs formation, especially for UV/VUV/I-. For oxyhalides, neither UV/I- nor UV/VUV/I- degraded ClO4-. While UV/I- cannot remove ClO3-, UV/VUV/I- reduced ClO3- to Cl-. Expectedly, both UV/I- and UV/VUV/I- reduced BrO3- to Br- more efficiently than UV and UV/VUV, confirming that I- can enhance the reduction capacities of UV/VUV and UV technologies.

Enhanced detection of monoiodoacetic acid at ng/L level by ion chromatography with novel derivatization-free pretreatment.

Concerns have recently arisen regarding the formation of carcinogenic and genotoxic iodinated haloacetic acids (HAAs), such as monoiodoacetic acid (MIAA), during the disinfection of iodine-containing water with chloramine. Existing detection methods for MIAA rely on either labor-intensive derivatization operations or expensive instruments, making analysis challenging. To bypass these issues, this study proposed a novel two-step liquid-liquid extraction strategy to enrich MIAA and then pioneered the integration of common ion chromatography (IC) with an ultraviolet detector to measure trace MIAA precisely. This novel approach achieved a remarkable 155.6-fold enrichment of MIAA and significantly reduced the need for water and chemicals, hence enhancing its efficiency and environmental friendliness. Besides, this method effectively removed coexisting anions and separated MIAA from other interferents by adjusting IC column and eluent conditions. The method detection limit of MIAA is an impressive 21.44 ng/L, and the recoveries in synthetic and real water samples ranged from 85 to 113%, with maximum deviations of 7.59%. We validated the reliability of our approach by comparing it with the USEPA 552.3 method. In conclusion, this IC-based method proves to be a robust and environment-benign solution for detecting trace MIAA in complex water components.

Insights into adsorbable organic halogen analysis: Two overlooked factors impacting water quality assessment.

Adsorbable organic halogen (AOX) represents the total amount of halogenated organics that can be adsorbed on activated carbon (AC) from samples. Measuring AOX is crucial for assessing water quality, and any erroneous estimation of AOX risks misleading decision-makers. This study demonstrated two overlooked factors that may introduce biases to AOX measurement. The first one relates to impurities in the gas transfer tubes of AOX combustion system and in the pressurized gas of AOX separation system, which resulted in significant fluctuations and high blank values (8.5-118.0 µg-Cl/L). The solutions of above issues are to warming up the combustor for several runs and replacing the pressurized air with argon gas in the separator, which could drop the blank AOX values to 9.1-10.0 µg-Cl/L. The second one involves coexisting chloride ion (Cl-) during AOX analysis, which interfered with AOX measurements (T. test, p < 0.05) even at low concentration levels (e.g., 10 mg/L Cl- in samples with 100 µg-Cl/L p-chlorophenol). Results show that AC captured 0.02-0.11 % of Cl-, resulting in 17.7-24.5 µg-Cl/L AOX responses in control samples containing 15-130 mg/L Cl- only. Furthermore, a significant mass imbalance of Cl- (3.58-8.39 %) during analysis process suggests a potential impact of residual Cl- on subsequent samples. By comparing synthetic and actual waters, samples with low dissolved organic carbon (DOC) were more susceptible to interference from Cl- on AOX measurement than those with high DOC. These findings underscore the pressing need to optimize existing AOX methods or develop alternative analytical methods to ensure accurate water quality assessment.

Towards elevated perfluorooctanoic acid (PFOA) enrichment in water: Sequential liquid-liquid extraction pretreatment for ion chromatography detection.

The widespread detection of perfluorooctanoic acid (PFOA) in the environment has raised significant concerns. The standard PFOA analytical method relies on expensive solid-phase extraction (SPE) and liquid chromatography tandem mass spectrometry (LC-MS/MS) instruments, making routine use prohibitive. We herein proposed a cost-effective yet novel enrichment method for determining PFOA at ng L-1 level. This method entailed a two-step sample preparation process: firstly, PFOA was extracted and enriched using a forward-extraction under acidic conditions, followed by a backward-extraction and enrichment step utilizing alkaline water. The enriched samples were subsequently subjected to a common ion chromatography (IC). Results reveal that maintaining a forward-extraction pH below its pKa value (2.8) is essential, as protonated PFOA proves effective in enhancing the enrichment factor (EF). The challenge lied in driving PFOA from forward-extractant to aqueous backward-extractant due to the decreased hydrophobicity of deprotonated PFOA (log Kow2 = 1.0). In addition, we found that evaporating forward-extractant with alkaline backward-extractant (containing 5% methanol) reduced potential analytical uncertainties associated with PFOA evaporation and sorption. Under optimal conditions, the method achieved a detection limit of 9.2 ng L-1 and an impressive EF value of 719. Comparison with SPE-LC-MS/MS confirmed the proposed method as a promising alternative for PFOA determination. Although initially targeted for PFOA, the novel methodology is likely applicable to preconcentration of other poly-fluoroalkyl substances.

A review of factors affecting the formation and roles of primary and secondary reactive species in UV254-based advanced treatment processes.

The presence of organic micropollutants (OMPs) in water has been threatening human health and aquatic ecosystems worldwide. Ultraviolet-based advanced treatment processes (UV-ATPs) are one of the most effective and promising technologies to transform OMPs in water; therefore, an increasing number of emerging UV-ATPs are proposed. However, appropriate selection of UV-ATPs for practical applications is challenging because each UV-ATP generates different types and concentrations of reactive species (RSs) that may not be sufficient to degrade specific types of OMPs. Furthermore, the concentrations and types of RSs are highly influenced by anions and dissolved organic matter (DOM) coexisting in real waters, making systematic understandings of their interfering mechanisms difficult. To identify and address the knowledge gaps, this review provides a comparison of the generations and variations of various types of RSs in different UV-ATPs. These analyses not only prove the importance of water matrices on formation and consumption of primary and secondary RSs under different conditions, but also highlight the non-negligible roles of optical properties and reactivities of DOM and anions. For example, different UV-ATPs may be applicable to different target OMPs under different conditions; and the concentrations and roles of secondary RSs may outperform those of primary RSs in OMP degradation for real applications. With continuous progress and outstanding achievements in the UV-ATPs, it is hoped that the findings and conclusions of this review could facilitate further research and application of UV-ATPs.

Iodine revisited: If and how inorganic iodine species can be measured reliably and what cause their conversions in water?

This study revisited a list of inorganic iodine species on their detections and conversions under different water conditions. Several surprising results were found, e.g., UV-vis spectrophotometry is the only reliable method for I3- and I2 determinations with coexisting I-/IO3-/IO4-, while alkaline eluent of IC and LC columns can convert them into I- completely; IO4- can be converted into IO3- completely in IC columns and partly in LC columns; a small portion of IO3- was reduced to I- in LC columns. To avoid errors, a method for detecting multiple coexisting iodine species is suggested as follows: firstly, detecting I3- and I2 via UV-vis spectrophotometry; then, analyzing IO4- (> 0.2 mg/L) through LC; and lastly, obtaining I- and IO3- concentrations by deducting I- and IO3- measured by IC from the signals derived from I3-/I2/IO4-. As for stability, I- or IO3- alone is stable, but mixing them up generates I2 or H2OI+ under acidic conditions. Although IO4- is stable within pH 4.0-8.0, it becomes H5IO6/H3IO62- in strongly acidic/alkaline solutions. Increasing pH accelerates the conversions of I3- and I2 into I- under basic conditions, whereas dissolved oxygen and dosage exert little effect. Additionally, spiking ICl into water produces I2 and IO3- rather than HIO.

Nitrogen origins and the role of ozonation in the formation of haloacetonitriles and halonitromethanes in chlorine water treatment.

Nitrogenous disinfection byproducts (N-DBPs) such as haloacetonitriles (HANs) and halonitromethanes (HNMs) are formed during water chlorination. Preozonation is sometimes applied to control trihalomethane (THM) formation, but this may risk promoting the formation of HNMs and HANs. The role of ozone in the formation of HANs and HNMs in natural waters remains unclear. The nitrogen sources involved in HAN and HNM formation during the chloramination of dissolved organic matter (DOM) with and without preozonation were evaluated using (15)N-labeled monochloramine. The origin of the nitrogen involved in HAN formation was found to depend on the ratio of dissolved organic carbon to nitrogen. In nitrogen-rich solutions HAN nitrogen was mainly from DOM constituents. The formation of (15)N-labeled dichloroacetontrile (DCAN) accounted for approximately 30% of the DCAN produced from all hydrophilic acidic and neutral isolates, which have low carbon to nitrogen ratios, while it reached over 50% for the hydrophobic acidic, basic, and neutral isolates with high carbon to nitrogen ratios. Unlabeled trichloronitromethane (TCNM) accounted for over 90% of the total TCNM produced from most of the isolates. The remaining less than 10% of the TCNM was probably generated through an aldehyde pathway. Preozonation reduced DCAN but enhanced the yield of TCNM. The destruction of amino acids and amine structures and subsequent formation of nitro groups by preozonation may help explain the reduced DCAN and increased TCNM formation.

Modeling volatilization and adsorption of disinfection byproducts in natural watersheds.

It is an emerging concern that a series of disinfection byproducts (DBPs) produced in wastewater effluent have adversely impacted the downstream aquatic system and drinking water resources. The occurrence, fate, and transport of DBPs on receiving waterbodies, however, are currently not well-documented. To fill the knowledge gap, this study simulated the effects of volatilization and adsorption processes on the removals of DBPs (THM, HAA, HAN, HNM, and NA) in different types of watersheds (lake, stream, river, and aquifer). The effects of a series of variables, including hydrogeological characteristics (e.g., water depth, flow rate, roughness), environmental conditions (e.g., temperature, wind velocity), and chemical properties (e.g., octanol-water partition coefficient, Henry's law constant, molecular weight, density) were evaluated and their relative importance were compared. The results indicate that volatilization mechanism was preferred in the stream-type watershed and effective in reducing THMs, but unlikely to reduce HAAs. Adsorption and removal of DBPs on settling suspended solid in surface waters appears insignificant, accounting for less than 8% of the DBP content. Adsorption of DBPs on aquifer soil does not reduce DBPs directly; nonetheless, it reduces the mobility of DBPs in the aquifer and provides a place for other mechanisms to degrade/transform DBPs. The results of this study therefore may help understand the occurrence, fate, and risk of wastewater-derived DBPs in downstream waterbodies, and trigger more laboratory tests in the future to dedicate to the mechanisms and DBPs with significant impact.