Pretreatment of free nitrous acid combined with calcium hypochlorite for enhancement of hydrogen production in waste activated sludge.

A variety of variables limit the recovery of resources from anaerobic fermentation of waste activated sludge (WAS), hence pretreatment strategies are necessary to be investigated to increase its efficiency. A combination of free nitrous acid (FNA) and calcium hypochlorite [Ca(ClO)2] was employed in this investigation to significantly improve sludge fermentation performance. The yields of cumulative hydrogen for the blank and FNA treatment group were 1.09 ± 0.16 and 7.36 ± 0.21 mL/g VSS, respectively, and 6.59 ± 0.24 [0.03 g Ca(ClO)2/g TSS], 7.75 ± 0.20 (0.06), and 8.58 ± 0.22 (0.09) mL/g VSS for the Ca(ClO)2 groups. The co-treatment greatly boosted hydrogen generation, ranging from 39.97 ± 2.26 to 76.20 ± 4.78 % as compared to the solo treatment. Mechanism analysis demonstrated that the combined treatment disturbed sludge structure and cell membrane permeability even more, which released more organic substrates and enhanced biodegradability of fermentation broth. This paper describes a unique strategy to sludge pretreatment that expands the use of Ca(ClO)2 and FNA in anaerobic fermentation, with implications for sludge disposal and energy recovery.

Direct Observation of HONO Emissions from Real-World Residential Natural Gas Heating in China.

Atmospheric nitrous acid (HONO) is an important precursor of atmospheric hydroxyl radicals. Vehicle emissions and heterogeneous reactions have been identified as major sources of urban HONO. Here, we report on HONO emissions from residential natural gas (RNG) for water and space heating in urban areas based on in situ measurements. The observed HONO emission factors (EFs) of RNG heating vary between 6.03 and 608 mg·m-3 NG, which are highly dependent on the thermal load. The highest HONO EFs are observed at a high thermal load via the thermal NO homogeneous reaction. The average HONO EFs of RNG water heating in winter are 1.8 times higher than that in summer due to the increased thermal load caused by the lower inlet water temperatures in winter. The power-based HONO EFs of the traditional RNG heaters are 1085 times and 1.7 times higher than those of gasoline and diesel vehicles that meet the latest emission standards, respectively. It is estimated that the HONO emissions from RNG heaters in a typical Chinese city are gradually close to emissions from on-road vehicles when temperatures decline. These findings highlight that RNG heating is a non-negligible source of urban HONO emissions in China. With the continuous acceleration of coal-to-gas projects and the continuous tightening of NOx emission standards for vehicle exhaust, HONO emissions from RNG heaters will become more prominent in urban areas. Hence, it is urgently needed to upgrade traditional RNG heaters with efficient emission reduction technologies such as frequency-converted blowers, secondary condensers, and low-NOx combustors.

Combining high pressure homogenization with free nitrous acid pretreatment to improve anaerobic digestion of sewage sludge.

Single pretreatment of sewage sludge, either physical, chemical or biological, has its own drawbacks in term of poor sanitization, energy intensity and high operational and capital cost. To tackle these drawbacks, combined high pressure homogenization (HPH) and free nitrous acid (FNA) pretreatment for sludge solubilization and further biodegradation in anaerobic digestion was investigated. Synergistic effect of combined HPH (40 MPa) and FNA (2.49 mg/L) pretreatment (HPH-FNA) for improving anaerobic digestion was evaluated, and its effect on archaeal and bacterial community structure was analyzed. Compared with single HPH and FNA pretreatments, HPH-FNA pretreatment efficiently solubilized wasted activated sludge (WAS), subsequently improved anaerobic digestion. Cumulative biogas production from sewage sludge pretreated with HPH-FNA was 154%, 108% and 284% more than that with single pretreatment of FNA, HPH and raw sludge, respectively. In addition, volumetric biogas production of combined pretreatment system (815 ml) was more than the sum from single pretreatment (710 ml). Methane content in biogas for raw sludge, FNA, HPH and HPH-FNA pretreated sludge was 45%, 51%, 55% and 65%, respectively. Illumina MiSeq sequencing analysis revealed that HPH-FNA pretreatment promoted bacterial growth of phyla Bacteroidetes, Firmicutes and Synergistetes and archaeal genera Methanospirillum and Methanosaeta. Overall, combined HPH-FNA pretreatment of sewage sludge, prior to anaerobic digestion, is an environmentally-friendly and potentially economic technology.

Evaluation and impact factors of indoor and outdoor gas-phase nitrous acid under different environmental conditions.

As an important indoor pollutant, nitrous acid (HONO) can contribute to the concentration of indoor OH radicals by photolysis via sunlight penetrating into indoor environments, thus affecting the indoor oxidizing capability. In order to investigate the concentration of indoor HONO and its impact factors, three different indoor environments and two different locations in urban and suburban areas were selected to monitor indoor and outdoor pollutants simultaneously, including HONO, NO, NO2, nitrogen oxides (NOx), O3, and particle mass concentration. In general, the concentration of indoor HONO was higher than that outdoors. In the urban area, indoor HONO with high average concentration (7.10 ppbV) was well-correlated with the temperature. In the suburban area, the concentration of indoor HONO was only about 1-2 ppbV, and had a good correlation with indoor relative humidity. It was mainly attributed to the heterogeneous reaction of NO2 on indoor surfaces. The sunlight penetrating into indoor environments from outside had a great influence on the concentration of indoor HONO, leading to a concentration of indoor HONO close to that outdoors.

Assessing indoor gas phase oxidation capacity through real-time measurements of HONO and NOx in Guangzhou, China.

The hydroxyl radical (OH) is one of the most important oxidants controlling the oxidation capacity of the indoor atmosphere. One of the main OH sources indoors is the photolysis of nitrous acid (HONO). In this study, real-time measurements of HONO, nitrogen oxides (NOx) and ozone (O3) in an indoor environment in Guangzhou, China, were performed under two different conditions: (1) in the absence of any human activity and (2) in the presence of cooking. The maximum NOx and HONO levels drastically increased from 15 and 4 ppb in the absence of human activity to 135 and 40 ppb during the cooking event, respectively. The photon flux was determined for the sunlit room, which has a closed south-east oriented window. The photon flux was used to estimate the photolysis rate constants of NO2, J(NO2), and HONO, J(HONO), which span the range between 8 × 10-5 and 1.5 × 10-5 s-1 in the morning from 9:30 to 11:45, and 8.5 × 10-4 and 1.5 × 10-4 s-1 at noon, respectively. The OH concentrations calculated by photostationary state (PSS) approach, observed around noon, are very similar, i.e., 2.4 × 106 and 3.1 × 106 cm-3 in the absence of human activity and during cooking, respectively. These results suggest that under "high NOx" conditions (NOx higher than a few ppb) and with direct sunlight in the room, the NOx and HONO chemistry would be similar, independent of the geographic location of the indoor environment, which facilitates future modeling studies focused on indoor gas phase oxidation capacity.

Association between indoor nitrous acid, outdoor nitrogen dioxide, and asthma attacks: results of a pilot study.

The association between nitrogen dioxide (NO2) and asthma has been investigated. However, conventional NO2 assays measure nitrous acid (HONO) as NO2. In this pilot epidemiological observational study, we assessed exposure to indoor HONO and some air pollutants in pediatric asthma patients and examined possible association between exposure and asthma symptoms. Indoor HONO and nitric oxide (NO), which are primarily generated by the combustion of certain substances, were significantly associated with asthma attacks in 2010. In 2010, indoor HONO was closely correlated with indoor NO than with outdoor NO2. Conversely, in 2012, indoor HONO was closely correlated with outdoor NO2 and NO than with indoor NO2 and NO. Outdoor NO2 was significantly associated with asthma attacks in 2012. Our results highlight the need for further epidemiological studies of the association between indoor HONO and asthma symptoms using multivariate analyses to examine the role of NO2 in asthma symptoms. Abbreviations: CXCL1: the chemokine (C-X-C motif) ligand 1; EP: the entire study period; FP: the first half of study period; HONO: nitrous acid; NO: nitric oxide; NO2: nitrogen dioxide; OH radical: hydroxyl radical; SP: the second half of study period; TNF-α: tumor necrosis factor-α; US EPA: United States Environmental Protection Agency; WHO: World Health Organization.

Revisiting nitrous acid (HONO) emission from on-road vehicles: A tunnel study with a mixed fleet.

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/NOx) 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/NOx and BC indicates that the BC-mediated conversion of NO2 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/NOx 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.

Novel tracer method to measure isotopic labeled gas-phase nitrous acid (HO15NO) in biogeochemical studies.

Gaseous nitrous acid (HONO), the protonated form of nitrite, contributes up to ∼60% to the primary formation of hydroxyl radical (OH), which is a key oxidant in the degradation of most air pollutants. Field measurements and modeling studies indicate a large unknown source of HONO during daytime. Here, we developed a new tracer method based on gas-phase stripping-derivatization coupled to liquid chromatography-mass spectrometry (LC-MS) to measure the 15N relative exceedance, ψ(15N), of HONO in the gas-phase. Gaseous HONO is quantitatively collected and transferred to an azo dye, purified by solid phase extraction (SPE), and analyzed using high performance liquid chromatography coupled to mass spectrometry (HPLC-MS). In the optimal working range of ψ(15N)=0.2-0.5, the relative standard deviation of ψ(15N) is <4%. The optimum pH and solvents for extraction by SPE and potential interferences are discussed. The method was applied to measure HO15NO emissions from soil in a dynamic chamber with and without spiking 15) labeled urea. The identification of HO15NO from soil with 15N urea addition confirmed biogenic emissions of HONO from soil. The method enables a new approach of studying the formation pathways of HONO and its role for atmospheric chemistry (e.g., ozone formation) and environmental tracer studies on the formation and conversion of gaseous HONO or aqueous NO2- as part of the biogeochemical nitrogen cycle, e.g., in the investigation of fertilization effects on soil HONO emissions and microbiological conversion of NO2- in the hydrosphere.

Role of organic carbon in heterogeneous reaction of NO2 with soot.

A large uncertainty among the reported uptake coefficients of NO2 on soot highlights the importance of the composition of soot in this reaction. Soot samples with different fractions of organic carbon (OC) were prepared by combusting n-hexane under controlled conditions. The heterogeneous reaction of NO2 on soot was investigated using a flow tube reactor at ambient pressure. The soot with the highest fuel/oxygen ratio showed the largest uptake coefficient (γ(initial)) of NO2 and yield of HONO (yHONO). Compared to fresh soot samples, preheated samples exhibited a great decrease in uptake coefficient of NO2 and HONO yield due to the removal of OC from soot. Ozonized soot also showed a lower reactivity toward NO2 than fresh soot, which can be ascribed to the consumption of OC with a reduced state (OCR). A linear dependence of the NO2 uptake coefficient and yields of HONO and NO on the OCR content of the soot was established, with γ(initial)(NO2) = (1.54 ± 1.39) × 10(-6) + (1.96 ± 0.35) × 10(-7) × OCR, yHONO = (11.6 ± 16.1) + (1.3 ± 0.40) × OCR, and yNO = (13.1 ± 1.9) - (0.2 ± 0.05) × OCR, respectively.

Thirdhand smoke causes DNA damage in human cells.

Exposure to thirdhand smoke (THS) is a newly described health risk. Evidence supports its widespread presence in indoor environments. However, its genotoxic potential, a critical aspect in risk assessment, is virtually untested. An important characteristic of THS is its ability to undergo chemical transformations during aging periods, as demonstrated in a recent study showing that sorbed nicotine reacts with the indoor pollutant nitrous acid (HONO) to form tobacco-specific nitrosamines (TSNAs) such as 4-(methylnitrosamino)-4-(3-pyridyl)butanal (NNA) and 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK). The goal of this study was to assess the genotoxicity of THS in human cell lines using two in vitro assays. THS was generated in laboratory systems that simulated short (acute)- and long (chronic)-term exposures. Analysis by liquid chromatography-tandem mass spectrometry quantified TSNAs and common tobacco alkaloids in extracts of THS that had sorbed onto cellulose substrates. Exposure of human HepG2 cells to either acute or chronic THS for 24h resulted in significant increases in DNA strand breaks in the alkaline Comet assay. Cell cultures exposed to NNA alone showed significantly higher levels of DNA damage in the same assay. NNA is absent in freshly emitted secondhand smoke, but it is the main TSNA formed in THS when nicotine reacts with HONO long after smoking takes place. The long amplicon-quantitative PCR assay quantified significantly higher levels of oxidative DNA damage in hypoxanthine phosphoribosyltransferase 1 (HPRT) and polymerase ß (POLB) genes of cultured human cells exposed to chronic THS for 24h compared with untreated cells, suggesting that THS exposure is related to increased oxidative stress and could be an important contributing factor in THS-mediated toxicity. The findings of this study demonstrate for the first time that exposure to THS is genotoxic in human cell lines.

Air pollution and asthma control in the Epidemiological study on the Genetics and Environment of Asthma.

BACKGROUND: The associations between exposure to air pollution and asthma control are not well known. The objective of this study was to assess the association between long-term exposure to NO(2), O(3) and PM(10) and asthma control in the follow-up of the Epidemiological study on the Genetics and Environment of Asthma (EGEA2) (2003-2007). METHODS: Modelled outdoor NO(2), O(3) and PM(10) estimates were linked to each residential address using the 4 km grid air pollutant surface developed by the French Institute of Environment in 2004. Asthma control was assessed in 481 subjects with current asthma using a multidimensional approach following the 2006-2009 Global Initiative for Asthma guidelines. Multinomial and ordinal logistic regressions were conducted adjusted for sex, age, body mass index, education, smoking and use of inhaled corticosteroids. The association between air pollution and the three domains of asthma control (symptoms, exacerbations and lung function) was assessed. ORs are reported per IQR. RESULTS: Median concentrations (in micrograms per cubic metre) were 32 (IQR 25-38) for NO(2) (n=465), 46 (41-52) for O(3) and 21 (18-21) for PM(10) (n=481). In total, 44%, 29% and 27% had controlled, partly controlled and uncontrolled asthma, respectively. The ordinal ORs for O(3) and PM(10) with asthma control were 1.69 (95% CI 1.22 to 2.34) and 1.35 (95% CI 1.13 to 1.64), respectively. When including both pollutants in the same model, both associations persisted. Associations were not modified by sex, smoking status, use of inhaled corticosteroids, atopy, season of examination or body mass index. Both pollutants were associated with each of the three main domains of control. CONCLUSIONS: The results suggest that long-term exposure to PM(10) and O(3) is associated with uncontrolled asthma in adults, defined by symptoms, exacerbations and lung function.

Heterogeneous reaction of NO2 on diesel soot particles.

Soot particles were collected from a diesel engine using a procedure that realistically mimics exhaust gas conditions in tailpipes and during dilution at room temperature. After being sampled, the particles were exposed to NO2 concentrations and relative humidity in ranges relevant for the troposphere using 13N as tracer. Gas-phase nitrous acid(HONO) and irreversibly bound (i.e., chemisorbed) species were the main reaction products with initial yields of 80-90% and about 10%, respectively. Neither NO nor HNO3 were detectable. The HONO formation increased with increasing engine load (i.e., with a decreasing air to fuel ratio, lambda). The reaction rates of HONO and chemisorbed NO2 increased with increasing NO2 concentration and did not depend on relative humidity. At the beginning of reaction, the uptake coefficient averaged over 3 min ranged from 5 x 10(-6) to 10(-5) for NO2 concentrations between 2 and 40 ppb. The HONO formation rates decreased with time, indicating consumption of reactive surface species, while the chemisorption rates remained almost constant. The total HONO formation potential of the particles was estimated to about 1.3 x 10(17) molecules/mg of diesel soot or to about 4.7 mg/kg of diesel fuel, indicating that the reaction between NO2 and diesel soot particles does not provide a significant secondary HONO source in the atmosphere. A Langmuir-Hinshelwood type reaction mechanism was proposed that adequately describes the observed results and also allows discussing important general features of reactions on soot.

Membrane association of lipoprotein lipase and a cAMP-binding ectoprotein in rat adipocytes.

cAMP-binding ectoprotein (Gce1) and lipoprotein lipase (LPL) are anchored to plasma membranes of rat adipocytes by glycosylphosphatidylinositol (GPI) moieties as demonstrated by cleavage by bacterial phosphatidylinositol-specific phospholipase C (PI-PLC), reactivity with anti-crossreacting determinant antibodies (anti-CRD), and metabolic labeling with radiolabeled palmitic acid and myo-inositol. Quantitative release from the membrane of LPL and Gce1 requires both lipolytic removal of their GPI anchors and the presence of either 2 M NaCl or 1 mM inositol 1,2-cyclic monophosphate or inositol 1-monophosphate. PI-PLC-cleaved and released LPL or Gce1 reassociates with isolated plasma membranes of rat adipocytes and, less efficiently, with membranes of 3T3 fibroblasts. The specificity of the reassociation is demonstrated (i) by its inhibition after pretreatment of the membranes with trypsin, (ii) by its competition with inositol 1,2-cyclic monophosphate and inositol 1-monophosphate in a concentration-dependent manner, and (iii) by the limited number of binding sites. Enzymic or chemical removal as well as masking with anti-CRD antibodies of the terminal inositol (cyclic) monophosphate moiety of hydrophilic Gce1 and LPL significantly impairs the reassociation. These data suggest that in rat adipocytes GPI-proteins are not readily released from the cell surface upon lipolytic cleavage, but remain associated through a receptor which specifically recognizes the terminal inositol (cyclic) monophosphate epitope of the (G)PI-PLC-cleaved GPI moiety. This interaction may have implications for the regulated membrane release of GPI-proteins and for their possible internalization.

Changes in food proteins reacted with nitrite at gastric pH.

Casein and egg albumin were reacted with nitrite at pH 3. The reaction mixtures containing nitrite yellowed when the reaction began; after 24 hours of reaction with 7.5 X 10(-3) M nitrite, about 70% of added casein was sedimented as yellow precipitate. There was a considerable loss of lysine, arginine, tyrosine, and tryptophan residues. This was determined from the amino acid compositions of the proteins obtained by the reaction with 2.5 X 10(-2) M nitrite at pH 3 for 48 hours. An amino acid elution pattern of the treated casein showed five peaks due to new amino acids; three of these were provisionally identified to be cysteic acid, methionine sulfone, and 3-nitrotyrosine.