Search

Carcinogenic nitrosamines have been widely studied due to their risk to human health. However, the universality and evolutionary processes of their generation, particularly concerning their secondary sources, remain unclear at present. We demonstrated through laboratory flow tube experiments that corresponding nitrosamines were generated from heterogeneous reactions of nitrous acid (HONO) with five structurally diverse amines commonly found indoors, including diphenylamine (DPhA), dibenzylamine (DBzA), dioctylamine (DOtA), N -(1,3-dimethylbutyl)- N '-phenyl- p -phenylenediamine (6PPD), and N -phenyl-1-naphthylamine (PANA). The heterogeneous reaction rate constants of DBzA and DOtA with HONO (∼70 ppb) were 1.21 × 10 -3 and 2.13 × 10 -3 min -1 at 30% relative humidity (RH), resulting in a lifetime of 13.8 and 7.8 h. As compared to higher RH (∼80%), more nitrosamines were produced from the reaction of HONO with surface-sorbed DBzA, DOtA, 6PPD, and PANA at lower RH (30%), with product yields ranging from <0.1% to 0.5%. Furthermore, we observed the formation of nitroso-6PPDs and nitro-6PPDs during room air exposure of 6PPD in a genuine indoor environment, in addition to various other transformation products indicative of reactions of 6PPD with HONO, NOx, and ozone indoors. This study confirmed the universality of the heterogeneous reaction of surface-sorbed amine with HONO as a source of nitrosamines indoors.

Nitrous acid (HONO) is crucial in atmospheric chemistry as a precursor to morning peak hydroxyl radicals and significantly affects urban air quality by forming secondary pollutants, yet the mechanisms of its daytime formation is not fully understood. This study investigates the role of formic acid (HCOOH), a prevalent electron and proton donor, in the transformation of nitrogen oxides (NOx) and the formation of HONO on photoactive mineral dust. Exploiting hematite (Fe 2 O 3 ) as an environmental indicator, we demonstrate that HCOOH significantly promotes the photoreduction of NO 2 to HONO, while suppressing nitrate accumulation. This occurs through the formation of a surface ≡Fe-OOCH complex, where sunlight activates the C-H bond to generate and transfer active hydrogen, directly converting NO 2 to HONO. Additionally, HCOOH can trigger the photolysis of nitrates as predeposited on Fe 2 O 3 , further increasing HONO production. These findings show that HCOOH-mediated photochemical reactions on iron minerals may contribute to elevated atmospheric HONO levels, highlighting a crucial pathway with broad effects on atmospheric chemistry and public health.

Nitrogen fixation using low-temperature plasma, particularly in relation to plasma-treated water (PTW) and its chemical and physical properties, has received a renewed research focus. Dissolving highly concentrated nitrogen oxides (NO x = 1-3 ) generated by air discharge into water results in the formation of two aqueous oxiacids (nitrous and nitric acids; HNO y = 2,3 ) and their conjugates (nitrate and nitrite ions; NO y - ). Nonlinear formation of these species in PTW with respect to plasma conditions has been observed; however, the significance of the time-varying NO x on this nonlinearity has not yet been thoroughly investigated. Here, we demonstrate real-time observations of HNO y /NO y - as well as NO x production in a surface dielectric barrier discharge reactor containing distilled water. Synchronized two optical absorption spectroscopy systems were employed to simultaneously measure gas-phase NO x and liquid-phase HNO y /NO y - in the plasma reactor operated under different oxygen contents of 5, 20, and 50%. Our results showed that reducing the oxygen content in the reactor accelerated the chemical transition from O 3 and NO 3 to NO 1,2 , leading to a predominance of nitrite in PTW. Specifically, the NO 3 -rich period was extended with increasing O 2 content, resulting in the production of nitrate-dominant PTW at low pH levels. Our findings highlight the potential for the selective generation of HNO y /NO y - in PTW through the active and passive control of NO x in a plasma reactor. The direct, real-time observation of NO x -HNO y /NO y - conversion presented here has potential for improving the control and optimization of PTW, thereby enhancing its applicability., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The photolysis of particulate nitrate (pNO 3 - ) has been suggested to be an important source of nitrous acid (HONO) in the troposphere. However, determining the photolysis rate constant of pNO 3 - ( j pNO 3 - ) suffers from high uncertainty. Prior laboratory measurements of j pNO 3 - using aerosol filters have been complicated by the "shadow effect"─a phenomenon of light extinction within aerosol layers that potentially skews these measurements. We developed a method to correct the shadow effect on the photolysis rate constant of pNO 3 - for HONO production ( j pNO 3 -  → HONO ) using aerosol filters with identical chemical compositions but different aerosol loadings. We applied the method to quantify j pNO 3 -  → HONO over the North China Plain (NCP) during the winter haze period. After correcting for the shadow effect, the normalized average j pNO 3 -  → HONO at 5 °C increased from 5.89 × 10 -6 s -1 to 1.72 × 10 -5 s -1 . The j pNO 3 -  → HONO decreased with increasing pH and nitrate proportions in PM 2.5 and had no correlation with nitrate concentrations. A parametrization for j pNO 3 -  → HONO was developed for model simulation of HONO production in NCP and similar environments.

Gaseous nitrous acid (HONO) is identified as a critical precursor of hydroxyl radicals (OH), influencing atmospheric oxidation capacity and the formation of secondary pollutants. However, large uncertainties persist regarding its formation and elimination mechanisms, impeding accurate simulation of HONO levels using chemical models. In this study, a deep neural network (DNN) model was established based on routine air quality data (O 3 , NO 2 , CO, and PM 2.5 ) and meteorological parameters (temperature, relative humidity, solar zenith angle, and season) collected from four typical megacity clusters in China. The model exhibited robust performance on both the train sets [slope = 1.0, r 2 = 0.94, root mean squared error (RMSE) = 0.29 ppbv] and two independent test sets (slope = 1.0, r 2 = 0.79, and RMSE = 0.39 ppbv), demonstrated excellent capability in reproducing the spatiotemporal variations of HONO, and outperformed an observation-constrained box model incorporated with newly proposed HONO formation mechanisms. Nitrogen dioxide (NO 2 ) was identified as the most impactful features for HONO prediction using the SHapely Additive exPlanation (SHAP) approach, highlighting the importance of NO 2 conversion in HONO formation. The DNN model was further employed to predict the future change of HONO levels in different NO x abatement scenarios, which is expected to decrease 27-44% in summer as the result of 30-50% NO x reduction. These results suggest a dual effect brought by abatement of NO x emissions, leading to not only reduction of O 3 and nitrate precursors but also decrease in HONO levels and hence primary radical production rates ( P RO x ). In summary, this study demonstrates the feasibility of using deep learning approach to predict HONO concentrations, offering a promising supplement to traditional chemical models. Additionally, stringent NOx abatement would be beneficial for collaborative alleviation of O 3 and secondary PM2.5.

Severe ozone (O 3 ) pollution has been a major air quality issue and affects environmental sustainability in China. Conventional mitigation strategies focusing on reducing volatile organic compounds and nitrogen oxides (NO x ) remain complex and challenging. Here, through field flux measurements and laboratory simulations, we observe substantial nitrous acid (HONO) emissions ( F HONO ) enhanced by nitrogen fertilizer application at an agricultural site. The observed F HONO significantly improves model performance in predicting atmospheric HONO and leads to regional O 3 increases by 37%. We also demonstrate the significant potential of nitrification inhibitors in reducing emissions of reactive nitrogen, including HONO and NO x , by as much as 90%, as well as greenhouse gases like nitrous oxide by up to 60%. Our findings introduce a feasible concept for mitigating O 3 pollution: reducing soil HONO emissions. Hence, this study has important implications for policy decisions related to the control of O 3 pollution and climate change.

Field observations of daytime HONO source strengths have not been well explained by laboratory measurements and model predictions up until now. More efforts are urgently needed to fill the knowledge gaps concerning how environmental factors, especially relative humidity (RH), affect particulate nitrate photolysis. In this work, two critical attributes for atmospheric particles, i.e., phase state and bulk-phase acidity, both influenced by ambient RH, were focused to illuminate the key regulators for reactive nitrogen production from typical internally mixed systems, i.e., NaNO 3 and dicarboxylic acid (DCA) mixtures. The dissolution of only few oxalic acid (OA) crystals resulted in a remarkable 50-fold increase in HONO production compared to pure nitrate photolysis at 85% RH. Furthermore, the HONO production rates ( P HONO ) increased by about 1 order of magnitude as RH rose from <5% to 95%, initially exhibiting an almost linear dependence on the amount of surface absorbed water and subsequently showing a substantial increase in P HONO once nitrate deliquescence occurred at approximately 75% RH. NaNO 3 /malonic acid (MA) and NaNO 3 /succinic acid (SA) mixtures exhibited similar phase state effects on the photochemical HONO production. These results offer a new perspective on how aerosol physicochemical properties influence particulate nitrate photolysis in the atmosphere.

In the urban atmosphere, nitrogen oxide (NO x ═NO + NO 2 )-related reactions dominate the formation of nitrous acid (HONO). Here, we validated an external cycling route of HONO and NO x , i.e., formation of HONO resulting from precursors other than NO x , in the background atmosphere. A chemical budget closure experiment of HONO and NO x was conducted at a background site on the Tibetan Plateau and provided direct evidence of the external cycling. An external daytime HONO source of 100 pptv h -1 was determined. Both soil emissions and photolysis of nitrate on ambient surfaces constituted likely candidate mechanisms characterizing this external source. The external source dominated the chemical production of NO x with HONO as an intermediate tracer. The OH production was doubled as a result of the external cycling. A high HONO/NO x ratio (0.31 ± 0.06) during the daytime was deduced as a sufficient condition for the external cycling. Literature review suggested the prevalence of high HONO/NO x ratios in various background environments, e.g., polar regions, pristine mountains, and forests. Our analysis validates the prevalence of external cycling in general background atmosphere and highlights the promotional role of external cycling regarding the atmospheric oxidative capacity.

The hydroxyl radical (OH) is the dominant oxidant in the outdoor environment, controlling the lifetimes of volatile organic compounds (VOCs) and contributing to the growth of secondary organic aerosols. Despite its importance outdoors, there have been relatively few measurements of the OH radical in indoor environments. During the House Observations of Microbial and Environmental Chemistry (HOMEChem) campaign, elevated concentrations of OH were observed near a window during cooking events, in addition to elevated mixing ratios of nitrous acid (HONO), VOCs, and nitrogen oxides (NO X ). Particularly high concentrations were measured during the preparation of a traditional American Thanksgiving dinner, which required the use of a gas stove and oven almost continually for 6 h. A zero-dimensional chemical model underpredicted the measured OH concentrations even during periods when direct sunlight illuminated the area near the window, which increases the rate of OH production by photolysis of HONO. Interferences with measurements of nitrogen dioxide (NO 2 ) and ozone (O 3 ) suggest that unmeasured photolytic VOCs were emitted during cooking events. The addition of a VOC that photolyzes to produce peroxy radicals (RO 2 ), similar to pyruvic acid, into the model results in better agreement with the OH measurements. These results highlight our incomplete understanding of the nature of oxidation in indoor environments.

A selective catalytic converter has been developed to quantify nitrous acid (HONO), a photochemical precursor to NO and OH radicals that drives the formation of ozone and other pollutants in the troposphere. The converter is made from a sulfonated tetrafluoroethylene-based fluoropolymer-copolymer (Nafion) that was found to convert HONO to NO with unity yield under specific conditions. When coupled to a commercially available NO x (=NO + NO 2 ) chemiluminescence (CL) analyzer, the system measures HONO with a limit of detection as low as 64 parts-per-trillion (ppt) (1 min average) in addition to NO x . The converter is selective for HONO when tested against other common gas-phase reactive nitrogen species, although loss of O 3 on Nafion is a potential interference. The sensitivity and selectivity of this method allow for accurate measurement of atmospherically relevant concentrations of HONO. This was demonstrated by good agreement between HONO measurements made with the Nafion-CL method and those made with chemical ionization mass spectrometry in a simulation chamber and in indoor air. The observed reactivity of HONO on Nafion also has significant implications for the accuracy of CL NO x analyzers that use Nafion to remove water from sampling lines.

Nitrous acid measurements were carried out during the MEGAPOLI (Megacities: Emissions, urban, regional and Global Atmospheric POLlution and climate effects, and Integrated tools for assessment and mitigation) winter field campaign at the SIRTA observatory in Paris surroundings from the 20th of January to the 15th of February 2010. At the end of the campaign, significant snow events occurred leading to snow accumulation at the sampling site during the last days. These specific conditions gave the opportunity to examine the HONO budget with and without the presence of snow at ground. Much higher HONO sources were found for the days when the site was covered by snow. This provides evidence for the existence of a large snowpack source of HONO in mid-latitude polluted regions that needs to be investigated for a better understanding of wintertime photochemistry. [ABSTRACT FROM AUTHOR]

Quantum chemical computations and transition state theory are employed to systematically research the influence of a single molecule water on the BrO + HONO reaction. Two distinct reactions, namely BrO + trans-HONO and BrO + cis-HONO are explored for the reaction in the absence of water, which is mainly decided by the configuration of HONO. With introduction a single water molecule to the reaction, the rate coefficient of the channel starting from BrO + cis-HONO and BrO + trans-HONO are 2.43 × 10 -19 and 5.22 × 10 -22  cm 3 molecule -1 s -1 , which is larger than the reaction in the absence of water. For further comprehend the impact of water on the BrO + HONO reaction, it is necessary to compute the effective rate coefficient by taking into account the concentration of water. The water-assisted effective rate coefficients for the BrO + HONO reaction are smaller than that the reaction in the absence of water. The reaction of BrO with cis-HONO is feasible both in absence and existence of water., (Copyright © 2022 Elsevier Inc. All rights reserved.)

The still unexplained daytime HONO concentration in the Earth's atmosphere and the impact of water on the HONO chemistry have been a mystery for decades. Several pathways and many modeling methods have failed to reproduce the atmospheric measurements. We reveal in this study the first spectroscopic observation and characterization of the complex of HONO with water observed through its rotational signature. Under the experimental conditions, HONO-water is stable, particularly straightforward to form, and features intense absorption signals. This could explain both the influence of water on the HONO chemistry and the missing HONO sources, as well as the missing contribution of many other molecules of atmospheric relevance that skew the accuracy of field measurements and the full account of partitioning species in the atmosphere.

Nitrous acid (HONO) is a household pollutant exhibiting adverse health effects and a major source of indoor OH radicals under a variety of lighting conditions. The present study focuses on gas-phase HONO and condensed-phase nitrite and nitrate formation on indoor surface thin films following heterogeneous hydrolysis of NO 2 , in the presence and absence of light, and nitrate (NO 3 - ) photochemistry. These thin films are composed of common building materials including zeolite, kaolinite, painted walls, and cement. Gas-phase HONO is measured using an incoherent broadband cavity-enhanced ultraviolet absorption spectrometer (IBBCEAS), whereby condensed-phase products, adsorbed nitrite and nitrate, are quantified using ion chromatography. All of the surface materials used in this study can store nitrogen oxides as nitrate, but only thin films of zeolite and cement can act as condensed-phase nitrite reservoirs. For both the photo-enhanced heterogeneous hydrolysis of NO 2 and nitrate photochemistry, the amount of HONO produced depends on the material surface. For zeolite and cement, little HONO is produced, whereas HONO is the major product from kaolinite and painted wall surfaces. An important result of this study is that surface interactions of adsorbed nitrite are key to HONO formation, and the stronger the interaction of nitrite with the surface, the less gas-phase HONO produced.

Biocrusts covering drylands account for major fractions of terrestrial biological nitrogen fixation and release large amounts of gaseous reactive nitrogen (N r ) as nitrous acid (HONO) and nitric oxide (NO). Recent investigations suggested that aerobic and anaerobic microbial nitrogen transformations occur simultaneously upon desiccation of biocrusts, but the spatio-temporal distribution of seemingly contradictory processes remained unclear. Here, we explore small-scale gradients in chemical concentrations related to structural characteristics and organism distribution. X-ray microtomography and fluorescence microscopy revealed mixed pore size structures, where photoautotrophs and cyanobacterial polysaccharides clustered irregularly in the uppermost millimeter. Microsensor measurements showed strong gradients of pH, oxygen, and nitrite, nitrate, and ammonium ion concentrations at micrometer scales in both vertical and lateral directions. Initial oxygen saturation was mostly low (∼30%) at full water holding capacity, suggesting widely anoxic conditions, and increased rapidly upon desiccation. Nitrite concentrations (∼6 to 800 μM) and pH values (∼6.5 to 9.5) were highest around 70% WHC. During further desiccation they decreased, while emissions of HONO and NO increased, reaching maximum values around 20% WHC. Our results illustrate simultaneous, spatially separated aerobic and anaerobic nitrogen transformations, which are critical for N r emissions, but might be impacted by future global change and land management.

The nitrous acid depolymerization of chitosan enables the synthesis of singular chitosan oligosaccharides (COS) since their reducing-end unit is composed of 2,5-anhydro-d-mannofuranose (amf). In the present study, we describe a chemical method for the reducing-end conjugation of COS-amf by the commercially available dioxyamine O,O' -1,3-propanediylbishydroxylamine in high mass yields. The chemical structure of resulting dioxyamine-linked COS-amf synthesized by both oximation and reductive amination ways were fully characterized by 1 H- and 13 C-NMR spectroscopies and MALDI-TOF mass spectrometry. The coupling of chemically attractive linkers such as dioxyamines at the reducing end of COS-amf forms a relevant strategy for the development of advanced functional COS-based conjugates.

Building blocks characterization is a significant approach for understanding the molecular structure of heparin and its derivatives. Nitrous acid (HONO) depolymerization of heparin generates oligosaccharides that maintain the epimerization conformation on C5 of the uronic acids, reflecting the authentic structure of the parental chain. HONO treatment at pH 1.5 selectively cleaves the bond between N-sulfated glucosamine and hexuronic acid, resulting mainly disaccharides, as well as tetra-, tri-, and mono-saccharides. The tetrasaccharides are derived from the structure of N-acetylated domains while tri-, and mono-saccharides are derived from the reducing or the non-reducing end of the heparin chain. The resulted oligosaccharides were separated and analyzed using a UHPLC-HILIC/WAX-MS method. We succeeded in the identification of 19 tetrasaccharides, 19 trisaccharides and 4 monosaccharides species, majority of which is structurally characterized. By comparing the theoretical possibilities and actual occurrence of the well-characterized tetrasaccharides, we demonstrated that the biosynthesis of heparin is a systematic process., (Copyright © 2019. Published by Elsevier Ltd.)

Nitrogen oxyanions and oxyacids are important agents in atmospheric chemistry and medical biology. Although their chemical behavior in solution is relatively well understood, they may behave very differently at the water/air interface of atmospheric aerosols or at the membrane/water interface of cells. Here, we developed a fully classical model for molecular dynamics simulations of NO 3 - , NO 2 - , HNO 3 , and HNO 2 in the framework of the GROMOS 53A6 and 54A7 force field versions. The model successfully accounted for the poorly structured solvation shell and ion pairing tendency of NO 3 - . Accurate pure-liquid properties and hydration free energies were obtained for the oxyacids. Simulations at the water/air interface showed a local enrichment of HNO 3 and depletion of NO 3 - . The effect was discussed in light of earlier spectroscopic data and ab initio calculations, suggesting that HNO 3 behaves as a weaker acid at the surface of water. Our model will hopefully allow for efficient and accurate simulations of nitrogen oxyanions and oxyacids in solution and at microheterogeneous interface environments.

Nitrous acid was used to modify traditional de Man, Rogosa, Sharpe medium to evaluate whether the addition of sodium nitrite to MRS medium could improve the rate of growth and density of various lactic acid bacteria and nontarget species. Yogurt and Cheddar cheese were inoculated with individual bacterial species followed by the recovery and enumeration of the species using the pour plate method to compare the sensitivity between nitrous acid-modified MRS (mMRS) and traditional MRS. Lactobacillus delbrueckii ssp. bulgaricus were recovered at significantly higher counts from cheese in nitrous acid mMRS than MRS, whereas no significant difference was observed for other species and food systems. Growth curves were also generated for multiple lactic acid bacteria as well as nonstarters in both mMRS and MRS to measure the selectivity of nitrous acid mMRS. The selectivity evaluation of nitrous acid mMRS demonstrated that 5 of the tested lactic acid bacterial species (Bifidobacterium longum, Streptococcus salivarius, Lactococcus lactis, Lactobacillus acidophilus, and Lactobacillus delbrueckii ssp. bulgaricus) grew to significantly higher densities more rapidly in mMRS broth than in traditional MRS. Nontarget bacteria Enterococcus faecalis and Bacillus cereus revealed a more prolific growth rate and higher optical density readings in traditional MRS compared with mMRS. It was determined that nitrous acid mMRS is a viable alternative medium for culturing selected lactic acid bacteria, and offers an improved formulation of MRS for use in standard evaluation methods and optimization of probiotic and other dairy cultures., (The Authors. Published by FASS Inc. and Elsevier Inc. on behalf of the American Dairy Science Association®. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).)

Deacetylated hyaluronan (daHA) containing reactive free amino groups is an important intermediate for further modification. Comparing direct and indirect NMR and HPLC to characterize the degree of HA deacetylation (DD), direct NMR approach using area ratio of anomeric CH and CH-NH 2 groups was the most precise one. To describe the substitution pattern, daHA was selectively cleaved by nitrous acid generated in situ or hyaluronan lyase from Streptococcus pneumoniae. The resulting oligomers were identified by LC-ESI-MS. The experimental distribution of these oligomers was compared with theoretically expected random oligomer distribution. Independently on the starting HA molecular weight and deacetylation conditions, the experimental data differed from the random distribution model and suggested that deacetylation of certain N-acetyl-d-glucosamine had reduced the probability of deacetylation at the neighbouring disaccharide. This phenomenon was explained by conformational changes of HA caused by intra- and intermolecular interactions between positively charged amino and negatively charged carboxylic groups., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Microscale interactions in soil may give rise to highly localised conditions that disproportionally affect soil nitrogen transformations. We report mechanistic modelling of coupled biotic and abiotic processes during drying of soil surfaces and biocrusts. The model links localised microbial activity with pH variations within thin aqueous films that jointly enhance emissions of nitrous acid (HONO) and ammonia (NH 3 ) during soil drying well above what would be predicted from mean hydration conditions and bulk soil pH. We compared model predictions with case studies in which reactive nitrogen gaseous fluxes from drying biocrusts were measured. Soil and biocrust drying rates affect HONO and NH 3 emission dynamics. Additionally, we predict strong effects of atmospheric NH 3 levels on reactive nitrogen gas losses. Laboratory measurements confirm the onset of microscale pH localisation and highlight the critical role of micro-environments in the resulting biogeochemical fluxes from terrestrial ecosystems.

Nitrous acid (HONO) is an important atmospheric pollutant that can strongly absorb ultraviolet irradiation in the region of 300-400 nm, as previously reported. Since the solar irradiance that reaches the surface of the earth has wavelengths greater than 290 nm, the photodissociation of HONO is considered the major method of hydroxyl radical formation in the troposphere. Thus, the photoinduced chemical reactivity of HONO is important. The present work investigated the reaction mechanism and kinetic parameters of HONO and sulfamethazine by using a laser flash photolysis technique and liquid chromatography-mass spectrometry. The results indicated that the sulfamethazine degradation rate was influenced by the HONO concentration and the initial concentration of sulfamethazine. Hydroxyl radicals derived from the photolysis of HONO attacked the aromatic ring of sulfamethazine to form sulfamethazine-OH adducts with a second-order rate constant of (3.8 ± 0.3) × 10 9 L mol -1 s -1 . This intermediate would then react with HO· and oxygen molecules. The reaction rate constants of sulfamethazine-OH adducts with oxygen are (1.3 ± 0.1) × 10 7 L mol -1 s -1 . The generation of sulfanilic acid and pyrimidine implies that the breaking down of S-N bonds of sulfamethazine and its HO adducts probably occur at the same time.

Free nitrous acid (FNA) or freezing has been recently utilized as an efficient pretreatment method to increase short-chain fatty acids (SCFAs) yield from waste activated sludge (WAS) anaerobic fermentation (AF). But until now, the performances and mechanisms of the co-pretreatment for SCFAs production are unknown. This research aimed to investigate the AF mechanisms through studying its influence on sludge solubilization and related bioprocesses. WAS was pretreated for 48 h with FNA (1.07 mg N/L), freezing (-5 °C) and combination of FNA and freezing (0.53-2.13 mg N/L FNA at -5 °C), respectively, then conducted batch AF. Experimental results indicated that the optimal total SCFAs yield of 391.19 ± 5.54 mg COD/g VSS was achieved after 1.07 mg N/L FNA + freezing pretreatment at 9 days of AF, which was 2.2, 1.6 and 1.3-fold of the blank, freezing and FNA pretreated samples, respectively. The mechanisms analysis showed that co-pretreatment showed synergetic effects on sludge disintegration and solubilization, which could release more soluble substrates for SCFAs production. The co-pretreatment resulted in slight inhibition to hydrolysis and negligible inhibition to acidogenesis but severe inhibition to methanogenesis, maybe due to less endurance of methanogens., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The role of a single water molecule on the atmospheric reaction of HONO + ClO is systematically investigated employing quantum chemical calculation combined with harmonic transition state theory. Two reaction pathways, cis-HONO + ClO and trans-HONO + ClO, are identified for the naked reaction, which depends on the configurations of HONO. When adding a single water molecule to this reaction, the rate constants of cis-HONO + ClO and trans-HONO + ClO pathways are 7.97 × 10 -21 and 2.29 × 10 -17 cm 3 molecule -1 s -1 , respectively, larger than the corresponding naked reaction. To further understand the role of water on the HONO + ClO reaction, it is necessary to calculate the effective rate constant by considering the concentration of water. It shows that the effective rate constants of water-assisted cis-HONO + ClO pathway are much smaller than those of the naked reaction, whereas the presence of water accelerates the trans-HONO + ClO at room temperature. This study demonstrates that water has a positive role in the pathway of trans-HONO + ClO by modifying the stabilities of reactant complexes and transition states through the hydrogen bond formation, which contributes to the sink of atmospheric HONO. In addition, the kinetic branching ratio indicates that the favorable reaction is the trans-HONO + ClO instead of the cis-HONO + ClO pathway, in contrast to the naked reaction. These results reveal the importance of water in the evaluation of the fate of active species in the atmosphere. Graphical Abstract.

This study investigated the inhibitory effect of free nitrous acid (FNA) on the activity of ammonia oxidizing bacteria (AOB) and nitrite oxidizing bacteria (NOB) under anoxic conditions with different mixed liquid suspended solids (MLSS). Sequencing batch reactors were used to study the changes in the activity of AOB and NOB in nitrifying activated sludge based on four different MLSS (8398, 11254, 15998, and 19637 mg·L -1 ), after treatment, under anoxic conditions with FNA (at an initial concentration of 1.3 mg·L -1 ) for 48 h. The results showed that the pH increased by approximately 0.9, but the concentration of NO 2 - -N did not decrease significantly. With over-aeration, the concentration of NH 4 + -N gradually degraded to 0 mg·L -1 , and the removal rate of NH 4 + -N gradually increased to a maximum of 4.4-6.8 mg·(L·h) -1 which time used was shorter with the increase of the inhibition MLSS. The nitrite accumulation rate was more than 92% when the sludge concentration was 8398, 11254, 15998, and 19637 mg·L -1 and with over-aeration for 0-396 h, 0-396 h, 0-372 h, and 0-168 h, respectively. When aerated for 468 h, 468 h, 444 h, and 264 h, the NO 2 - -N concentration and NAR decreased to 0, and NO 3 - -N concentrations increased to their highest with the values of 42.6, 49.9, 42.9, and 47.9 mg·L -1 respectively.

The photochemical oxidation of di-n-butyl phthalate (DBP) by • OH radicals from nitrous acid (HONO) in atmospheric hydrometeors was explored by two techniques, steady-state irradiation, and laser flash photolysis (LFP). The effects of atmospheric liquid parameters on DBP transformation were systematically evaluated, showing that DBP does not react with HONO directly and • OH-initiated reactions are crucial steps for consumption and transformation of DBP. Two reaction channels are operative: • OH addition and hydrogen atom abstraction. The overall rate constant for the reaction of DBP with • OH is 5.7 × 10 9  M -1  s -1 , and its specific rate constant for addition is 3.7 × 10 9  M -1  s -1 determined by using laser flash photolysis technique. Comparing the individual reaction rate constant for aromatic ring addition with the total rate constant, the majority of the • OH radicals (about 65%) attack the aromatic ring. The major transformation products were identified by GC-MS, and the trends of their yields derived from both ring addition and H-abstraction with time are discussed. These results provide important insights into the photochemical transformation of DBP in atmospheric hydrometeors and contribute to atmospheric aerosol chemistry.

Low molecular weight heparins (LMWHs) are important anticoagulant drugs. Nitrous acid degradation is a major approach to produce LMWHs, such as dalteparin. Due to the foreseeable shortage of porcine intestinal mucosa heparin and other potential risks, expansion of other animal tissues for heparin preparation is necessary. Heparins from different tissues differ in structure and bioactivity potency, and these variations may be carried over to the LMWH products. Sophisticated analytical techniques have been applied to compare various versions of dalteparins produced from porcine intestinal, bovine lung and ovine intestinal heparins to elucidate the effects of different animal tissues starting materials and processing conditions on the properties of final dalteparin products. With adjusted depolymerization conditions, versions of dalteparins that qualify under the European Pharmacopeia (EP) specifications were manufactured using non-porcine heparins. Dissimilarities among the three interspecies animal tissue heparin-derived dalteparins regarding fine structures are also disclosed, and their origins are discussed., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Enzymes belonging to the aspartase/fumarase superfamily catalyze elimination of various functional groups from succinate derivatives and play an important role in primary metabolism and aromatic compound degradation. Recently, an aspartase/fumarase superfamily enzyme, CreD, was discovered in cremeomycin biosynthesis. This enzyme catalyzes the elimination of nitrous acid from nitrosuccinate synthesized from aspartate by CreE, a flavin-dependent monooxygenase. Nitrous acid generated by this pathway is an important precursor of the diazo group of cremeomycin. CreD is the first aspartase/fumarase superfamily enzyme that was reported to catalyze the elimination of nitrous acid, and therefore we aimed to analyze its reaction mechanism. The crystal structure of CreD was determined by the molecular replacement native-single anomalous diffraction method at 2.18 Å resolution. Subsequently, the CreD-fumarate complex structure was determined at 2.30 Å resolution by the soaking method. Similar to other aspartase/fumarase superfamily enzymes, the crystal structure of CreD was composed of three domains and formed a tetramer. Two molecules of fumarate were observed in one subunit of the CreD-fumarate complex. One of them was located in the active site pocket formed by three different subunits. Intriguingly, no histidine residue, which usually functions as a catalytic acid in aspartase/fumarase superfamily enzymes, was found around the fumarate molecule in the active site. Based on the mutational analysis, we propose a catalytic mechanism of CreD, in which Arg325 acts as a catalytic acid., Databases: The crystal structures of CreD and the CreD-fumarate complex were deposited to PDB under the accession numbers 5XNY and 5XNZ, respectively., Enzymes: Nitrosuccinate lyase CreD, EC4.3., (© 2018 Federation of European Biochemical Societies.)

Previous work has demonstrated that pre-treatment of waste activated sludge (WAS) with free nitrous acid (FNA i.e. HNO 2 ) enhances the biodegradability of WAS, identified by a 20-50% increase in specific methane production in biochemical methane potential (BMP) tests. This suggests that FNA pre-treatment would enhance the destruction of volatile solids (VS) in an anaerobic sludge digester, and reduce overall sludge disposal costs, provided that the dewaterability of the digested sludge is not negatively affected. This study experimentally evaluates the impact of FNA pre-treatment on the VS destruction in anaerobic sludge digestion and on the dewaterability of digested sludge, using continuously operated bench-scale anaerobic digesters. Pre-treatment of full-scale WAS for 24 h at an FNA concentration of 1.8 mg NN/L enhanced VS destruction by 17 ± 1% (from 29.2 ± 0.9% to 34.2 ± 1.1%) and increased dewaterability (centrifuge test) from 12.4 ± 0.4% to 14.1 ± 0.4%. Supporting the VS destruction data, methane production increased by 16 ± 1%. Biochemical methane potential tests indicated that the final digestate stability was also improved with a lower potential from FNA treated digestate. Further, a 2.1 ± 0.2 log improvement in pathogen reduction was also achieved. With inorganic solids representing 15-22% of the full-scale WAS used, FNA pre-treatment resulted in a 16-17% reduction in the volume of dewatered sludge for final disposal. This results in significantly reduced costs as assessed by economic analysis., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Bacillus thuringiensis Berliner (Bacillales: Bacillaceae) strain BUPM95 was known by the efficiency of its vegetative insecticidal protein (Vip3Aa16) against different Lepidoptera such as Spodoptera littoralis (Lepidoptera: Noctuidae). To overcome the problem of the low quantities of Vip3 proteins secreted by B. thuringiensis strains in the culture supernatant, classical mutagenesis of vegetative cells of BUPM95 strain was operated using nitrous acid and UV rays. The survivors were screened on the basis of their hemolytic activity and classified in three groups: unaffected, overproducing, and hypo-producing mutants. Using different mutants improved in their hemolytic activity, the supernatants showed an improved toxicity toward S. littoralis larvae (83.33-100% of mortality) compared with the wild-type supernatant (76%). After Vip3 protein quantification in the different supernatants, bioassays against S. littoralis larvae demonstrated that mutants M62, M43, and M76 were improved in the efficiency of their toxin as demonstrated by the lower values of LC50 and LC90 compared with the wild-type Vip3Aa16 protein. However, M26 and M73 mutants were improved in the toxin quantities produced in the supernatant. The improvement of the production and the efficiency of B. thuringiensis Vip3 toxins should contribute to a significant reduction of the production costs of these very interesting B. thuringineis proteins and facilitate the use of these toxins in the pest control management., (© The Author(s) 2017. Published by Oxford University Press on behalf of Entomological Society of America. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

The photochemical conversion of NO 2 to HONO on humic acids (HA) in the presence of benzophenone (BP) was investigated using a flow tube reactor coupled to a NO x analyzer at ambient pressure. BP significantly enhanced the reduction of NO 2 to HONO on HA under simulated sunlight, as shown by the increase of NO 2 uptake coefficient (γ) and HONO yield with the mass ratio of BP to HA. The γ and HONO yield on the mixtures of HA and BP obviously depended on the environmental conditions. Both γ and HONO yield increased with the increase of irradiation intensity and temperature, whereas they decreased with pH. The γ exhibited a negative dependence on the NO 2 concentration, which had slight influences on the HONO yield. There were maximum values for the γ and HONO yield at relative humidity (RH) of 22%. Finally, atmospheric implications about the photochemical reaction of NO 2 and HA in the presence of photosensitive species were discussed., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Nitrous acid (HONO) is an important precursor of OH radicals in the atmosphere. In urban areas, emissions from vehicles are the main source of air pollutants, including reactive nitrogen. Previously reported emission ratios of HONO (HONO/NO x ) from vehicles were measured in the late 1990s and need to be updated due to the significant changes in emission control technologies. We measured the emission ratio of a fleet of vehicles (38% diesel on average) from March 11 to 21, 2015, in a road tunnel in Hong Kong. The emission ratio of 1.24% (±0.35%) obtained is greater than the commonly adopted 0.8% or 0.3%. The elevated emission ratio is found to be related to the presence of vehicles equipped with diesel particle filters (DPFs). Positive correlation between HONO and black carbon (BC) shows that HONO and BC were emitted together, while the lack of correlation or even anticorrelation between HONO/NO x and BC indicates that the BC-mediated conversion of NO 2 to HONO in the dark was insignificant in the immediate vicinity of the emission sources., Implications: Vehicular emission is a key source for HONO in the urban atmosphere. However, the most commonly used emission ratio HONO/NO x in modeling studies was measured more than 15 years ago. Our tunnel study suggests that a mixed fleet nowadays has a higher emission ratio, possibly because of the diesel particle filter (DPF) retrofit program and the growing share of Euro IV or more advanced diesel vehicles. Our study also provides new insight into the role of black carbon in HONO formation from vehicles.

In this study, the stability of clusters formed by the trans- and cis-isomers of nitrous acid (HONO) with dimethylamine (DMA) and water has been characterized by density functional theory. The large red shifts of the OH-stretching transitions of both HONO isomers in the clusters indicate the formation of strong hydrogen bonds. At standard temperature and pressure, H 2 O (acceptor) binds to HONO (donor) with binding energies of -25.0 to -24.6 kJ mol -1 , less stable than those of DMA (acceptor) with HONO (donor) (-50.5 to -45.3 kJ mol -1 ). Our findings indicate that hydration enhances proton transfer from HONO to DMA, and consequently increases the interaction strength (binding energies = -67.8 to -78.6 kJ mol -1 ). The topological and generalized Kohn-Sham energy decomposition confirms strong hydrogen bond interactions. The clustering of HONO with DMA in the atmosphere is negligible as compared to the important H 2 SO 4 -DMA clusters.

Low molecular weight heparins (LMWHs) are important anticoagulant drugs that are prepared through depolymerization of unfractionated heparin. Based on the types of processing reactions and the structures of the products, LMWHs can be divided into different classifications. Enoxaparin is prepared by benzyl esterification and alkaline depolymerization, while dalteparin and nadroparin are prepared through nitrous acid depolymerization followed by borohydride reduction. Compositional analysis of their basic building blocks is an effective way to provide structural information on heparin and LMWHs. However, most current compositional analysis methods have been limited to heparin and enoxaparin. A sensitive and comprehensive approach is needed for detailed investigation of the structure of LMWHs prepared through nitrous acid depolymerization, especially their characteristic saturated non-reducing end (NRE) and 2,5-anhydro-d-mannitol reducing end (RE). A maltose modified hydrophilic interaction column offers improved separation of complicated mixtures of acidic disaccharides and oligosaccharides. A total of 36 basic building blocks were unambiguously identified by high-resolution tandem mass spectrometry (MS). Multiple reaction monitoring (MRM) MS/MS quantification was developed and validated in the analysis of dalteparin and nadroparin samples. Each group of building blocks revealed different aspects of the properties of LMWHs, such as functional motifs required for anticoagulant activity, the structure of heparin starting materials, cleavage sites in the depolymerization reaction, and undesired structural modifications resulting from side reactions., (Copyright © 2016 Elsevier B.V. All rights reserved.)

VFA production from excess sludge (ES) was greatly enhanced by a low-cost and high-efficient treatment: 0.67mg/L free nitrous acid (FNA) pretreatment combined with 0.04g/g TSS rhamnolipid (RL) addition (FNA+RL), which significantly shortened fermentation time to 3days and increased VFA production to 352.26mgCOD/g VSS (5.42 times higher than raw ES). Propionic and acetic acids were the two leading components (71.86% of the total VFA). Mechanism investigation manifested FNA+RL improved the biodegradability of ES, achieved positive synergetic effect on solubilization, hydrolysis and acidification efficiencies, and inhibited methanation. Microbial community distribution further explained the above phenomena. The bacteria related to polysaccharides/protein utilization and VFA generation, including Clostridium, Megasphaera and Proteiniborus, were mainly observed in FNA+RL, whereas gas-forming bacteria Anaerolineae and acid-consuming bacteria Proteobacteria were assuredly suppressed. Besides, Propionibacterineae associated with propionic acid generation was exclusively enriched in sole RL and FNA+RL., (Copyright © 2016. Published by Elsevier Ltd.)

The effect of free ammonia (NH 3 or FA), free nitrous acid (HNO 2 or FNA), and total alkalinity (TA) on the performance of a partial nitrification (PN) sequencing batch reactor (SBR) treating anaerobically pretreated pig slurry was studied. The SBR was operated under alternating oxic/anoxic (O/A) conditions and was fed during anoxic phases. This strategy allowed using organic matter to partially remove nitrite (NO 2 - ) and nitrate (NO 3 - ) generated during oxic phases. The desired NH 4 + to NO 2 - ratio of 1.3 g N/g N was obtained when an Ammonium Loading Rate (ALR) of 0.09 g NH 4 + -N/L·d was applied. The system was operated at a solid retention time (SRT) of 15-20 d and dissolved oxygen (DO) levels higher than 3 mg O 2 /L during the whole operational period. PN mainly occurred caused by the inhibitory effect of FNA on nitrite oxidizing bacteria (NOB). Once HNO 2 concentration was negligible, NH 4 + was fully oxidized to NO 3 - in spite of the presence of FA. The use of biomass acclimated to ammonium as inoculum avoided a possible effect of FA on NOB activity.

The photochemical reaction between biphenyl (Bp) and N(III) under irradiation at 365 nm UV light was investigated. The results showed that Bp conversion efficiency was strongly influenced by N (III) concentration, Bp initial concentration and pH. Species-specific rate constants determined by reaction of Bp with H 2 ONO + (k 1 ), HONO (k 2 ) and NO 2 - (k 3 ) were k 1  = (0.058 ± 0.005 L mol -1  s -1 ), k 2  = (0.12 ± 0.06 L mol -1  s -1 ) and k 3  = (0.0019 ± 0.0003 L mol -1  s -1 ), respectively. Laser flash photolysis studies confirmed that OH radical deriving from the photolysis of N(III) attacked aromatic ring to form Bp-OH adduct with a rate constant of 9.4 × 10 9  L mol -1  s -1 . The products analysis suggested that Bp-OH adduct could be nitrated by N (III) and NO 2 to generate nitro-compounds., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Nitrous acid (HONO) accumulates in the nocturnal boundary layer where it is an important source of daytime hydroxyl radicals. Although there is clear evidence for the involvement of heterogeneous reactions of NO2 on surfaces as a source of HONO, mechanisms remain poorly understood. We used coated-wall flow tube measurements of NO2 reactivity on environmentally relevant surfaces (Fe (hydr)oxides, clay minerals, and soil from Arizona and the Saharan Desert) and detailed mineralogical characterization of substrates to show that reduction of NO2 by Fe-bearing minerals in soil can be a more important source of HONO than the putative NO2 hydrolysis mechanism. The magnitude of NO2-to-HONO conversion depends on the amount of Fe(2+) present in substrates and soil surface acidity. Studies examining the dependence of HONO flux on substrate pH revealed that HONO is formed at soil pH < 5 from the reaction between NO2 and Fe(2+)(aq) present in thin films of water coating the surface, whereas in the range of pH 5-8 HONO stems from reaction of NO2 with structural iron or surface complexed Fe(2+) followed by protonation of nitrite via surface Fe-OH2(+) groups. Reduction of NO2 on ubiquitous Fe-bearing minerals in soil may explain HONO accumulation in the nocturnal boundary layer and the enhanced [HONO]/[NO2] ratios observed during dust storms in urban areas.

Organic aerosols provide a measure of complexity in the urban atmosphere. This is because the aerosols start as an external mixture, with many populations from varied local sources, that all interact with each other, with background aerosols, and with condensing vapors from secondary organic aerosol formation. The externally mixed particle populations start to evolve immediately after emission because the organic molecules constituting the particles also form thermodynamic mixtures - solutions - in which a large fraction of the constituents are semi-volatile. The external mixtures are thus well out of thermodynamic equilibrium, with very different activities for many constituents, and yet also have the capacity to relax toward equilibrium via gas-phase exchange of semi-volatile vapors. Here we describe experiments employing quantitative single-particle mass spectrometry designed to explore the extent to which various primary organic aerosol particle populations can interact with each other or with secondary organic aerosols representative of background aerosol populations. These methods allow us to determine when these populations will and when they will not mix with each other, and then to constrain the timescales for that mixing.

In some wastewater treatment plants (WWTPs), the ever increasing production of sludge with the expanding population overloaded the anaerobic digestion which compromises the sludge reduction efficiency. Post anaerobic digestion of anaerobically digested sludge (ADS) has been applied to enhance sludge reduction, however, to a very limited extent. This study verified the effectiveness of free nitrous acid (FNA i.e. HNO2) pre-treatment on enhancing full-scale ADS degradation in post anaerobic digestion. The ADS collected from a full-scale WWTP was subject to FNA treatment at concentrations of 0.77, 1.54, 2.31, 3.08, and 3.85 mg N/L for 24 h followed by biochemical methane potential tests. The FNA treatment at all concentrations resulted in an increase (from 1.5-3.1 % compared to the control) in sludge reduction with the highest improvement achieved at 0.77 mg HNO2-N/L. The FNA treatment at this concentration also resulted in the highest increase in methane production (40 %) compared to the control. The economic analysis indicates that FNA treatment is economically attractive for enhancing post anaerobic digestion of full-scale ADS.

Post aerobic digestion of anaerobically digested sludge (ADS) has been extensively applied to the wastewater treatment plants to enhance sludge reduction. However, the degradation of ADS in the post aerobic digester itself is still limited. In this work, an innovative free nitrous acid (HNO2 or FNA)-based pretreatment approach is proposed to improve full-scale ADS degradation in post aerobic digester. The post aerobic digestion was conducted by using an activated sludge to aerobically digest ADS for 4 days. Degradations of the FNA-treated (treated at 1.0 and 2.0 mg N/L for 24 h) and untreated ADSs were then determined and compared. The ADS was degraded by 26% and 32%, respectively, in the 4-day post aerobic digestion period while being pretreated at 1.0 and 2.0 mg HNO2-N/L. In comparison, only 20% of the untreated ADS was degraded. Economic analysis demonstrated that the implementation of FNA pretreatment can be economically favourable or not depending on the sludge transport and disposal cost., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Nitrogen oxides are essential for the formation of secondary atmospheric aerosols and of atmospheric oxidants such as ozone and the hydroxyl radical, which controls the self-cleansing capacity of the atmosphere. Nitric acid, a major oxidation product of nitrogen oxides, has traditionally been considered to be a permanent sink of nitrogen oxides. However, model studies predict higher ratios of nitric acid to nitrogen oxides in the troposphere than are observed. A 'renoxification' process that recycles nitric acid into nitrogen oxides has been proposed to reconcile observations with model studies, but the mechanisms responsible for this process remain uncertain. Here we present data from an aircraft measurement campaign over the North Atlantic Ocean and find evidence for rapid recycling of nitric acid to nitrous acid and nitrogen oxides in the clean marine boundary layer via particulate nitrate photolysis. Laboratory experiments further demonstrate the photolysis of particulate nitrate collected on filters at a rate more than two orders of magnitude greater than that of gaseous nitric acid, with nitrous acid as the main product. Box model calculations based on the Master Chemical Mechanism suggest that particulate nitrate photolysis mainly sustains the observed levels of nitrous acid and nitrogen oxides at midday under typical marine boundary layer conditions. Given that oceans account for more than 70 per cent of Earth's surface, we propose that particulate nitrate photolysis could be a substantial tropospheric nitrogen oxide source. Recycling of nitrogen oxides in remote oceanic regions with minimal direct nitrogen oxide emissions could increase the formation of tropospheric oxidants and secondary atmospheric aerosols on a global scale.

Catechins are transformed into dinitrosocatechins (diNOcats) and then oxidized to the quinones by salivary nitrite under conditions simulating the stomach. This manuscript deals with formation of stable radicals in the NO group of diNOcat during nitrite-induced oxidation of (+)-catechin and diNOcat at pH 2. We postulated two mechanisms for the stable radical formation; one is nitrous acid-induced oxidation of diNOcat in the A-ring, and the other intermolecular charge transfer from the A-ring of diNOcat and/or diNOcat quinone to the quinone moiety of the B-ring of diNOcat quinone. In addition, an unstable phenoxyl radical, which might be transformed into quinone, was also produced, accompanying the formation of the stable radical on the NO group. Taking the above results into account, we mainly focus on the adverse effects of the radicals and quinone, which may be produced from (+)-catechin in the stomach under the conditions of high salivary nitrite concentrations., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Free nitrous acid (FNA) serving as a pretreatment is an effective approach to accelerate sludge disintegration. Also, sodium dodecylbenzene sulfonate (SDBS), a type of surfactants, has been determined at significant levels in sewage sludge, which thereby affects the characteristics of sludge. Both FNA pretreatment and sludge SDBS levels can affect short-chain fatty acid (SCFA) generation from sludge anaerobic fermentation. To date, however, the combined effect of FNA pretreatment and SDBS presence on SCFA production as well as the corresponding mechanisms have never been documented. This work therefore aims to provide such support. Experimental results showed that the combination of FNA and SDBS treatment not only improved SCFA accumulation but also shortened the fermentation time. The maximal SCFA accumulation of 334.5 mg chemical oxygen demand (COD)/g volatile suspended solids (VSS) was achieved at 1.54 mg FNA/L treatment and 0.02 g/g dry sludge, which was respectively 1.79-fold and 1.41-fold of that from FNA treatment and sludge containing SDBS alone. Mechanism investigations revealed that the combined FNA pretreatment and SDBS accelerated solubilization, hydrolysis, and acidification steps but inhibited the methanogenesis. All those observations were in agreement with SCFA enhancement.

Although some diazo compounds have bioactivities of medicinal interest, little is known about diazo group formation in nature. Here we describe an unprecedented nitrous acid biosynthetic pathway responsible for the formation of a diazo group in the biosynthesis of the ortho-diazoquinone secondary metabolite cremeomycin in Streptomyces cremeus. This finding provides important insights into the biosynthetic pathways not only for diazo compounds but also for other naturally occurring compounds containing nitrogen-nitrogen bonds.

Short-chain fatty acid (SCFA) production from waste activated sludge (WAS) anaerobic fermentation is often limited by the slow hydrolysis rate and poor substrate availability, thus a long fermentation time is required. This paper reports a new pretreatment approach, i.e., using free nitrous acid (FNA) to pretreat sludge, for significantly enhanced SCFA production. Experimental results showed the highest SCFA production occurred at 1.8 mg FNA/L with time of day 6, which was 3.7-fold of the blank at fermentation time of day 12. Mechanism studies revealed that FNA pretreatment accelerated disruption of both extracellular polymeric substances and cell envelope. It was also found that FNA pretreatment benefited hydrolysis and acidification processes but inhibited the activities of methanogens, thereby promoting the yield of SCFA. In addition, the FNA pretreatment substantially stimulated the activities of key enzymes responsible for hydrolysis and acidification, which were consistent with the improvement of solubilization, hydrolysis and acidification of WAS anaerobic fermentation., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The primary S-nitrosothiol, S-nitroso-N-acetylcysteine (SNAC) is a nitric oxide donor with potential pharmaceutical applications for the oral treatment of hepatic steatosis and cirrhosis and for protection against gastric acid-peptic disorders. However, its low thermal stability precludes the preparation of stable dosage forms based on presynthesized SNAC. In this study, we describe an innovative strategy for the oral administration of SNAC based on its intratablet formation via the S-nitrosation reaction of its parent stable thiol, N-acetyl-L-cysteine by nitrous acid during the absorption of water by the tablet. The proposed strategy allows for the manufacturing of thermally stable oral dosage forms for the controlled release of SNAC in the enteric medium., (Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.)

The ceramide phosphoinositol glycan core (CPI-GC) of the lipophosphoglycan of Trichomonas vaginalis is a major virulent factor of this common genitourinary parasite. While its carbohydrate composition has been reported before, its structure has remained largely unknown. We isolated the glycan portions of CPI-GC by nitrous acid deamination and hydrofluoric acid treatment and investigated their structures by methylation analysis and 1- and 2-D NMR. We found that the α-anomer of galactose is a major constituent of CPI-GC. The β-anomer was found exclusively at the non-reducing end of CPI-GC side chains. Furthermore the data showed that the rhamnan backbone is more complex than previously thought and that the inositol residue at the reducing end is linked to a 4-linked α-glucuronic acid (GlcA) residue. This appears to be the most striking and novel feature of this GPI-anchor type molecule., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

This study presents a novel pre-treatment strategy using combined free nitrous acid (FNA i.e. HNO2) and hydrogen peroxide (H2O2) to enhance methane production from WAS, with the mechanisms investigated bio-molecularly. WAS from a full-scale plant was treated with FNA alone (1.54 mg N/L), H2O2 alone (10-80 mg/g TS), and their combinations followed by biochemical methane potential tests. Combined FNA and H2O2 pre-treatment substantially enhanced methane potential of WAS by 59-83%, compared to 13-23% and 56% with H2O2 pre-treatment alone and FNA pre-treatment alone respectively. Model-based analysis indicated the increased methane potential was mainly associated with up to 163% increase in rapidly biodegradable fraction with combined pre-treatment. The molecular weight distribution and chemical structure analyses revealed the breakdown of soluble macromolecules with the combined pre-treatment caused by the deamination and oxidation of the typical functional groups in proteins, polysaccharides and phosphodiesters. These changes likely improved the biodegradability of WAS.