Additional HONO and OH Generation from Photoexcited Phenyl Organic Nitrates in the Photoreaction of Aromatics and NOx.

HONO acts as a major OH source, playing a vital role in secondary pollutant formation to deteriorate regional air quality. Strong unknown sources of daytime HONO have been widely reported, which significantly limit our understanding of radical cycling and atmospheric oxidation capacity. Here, we identify a potential daytime HONO and OH source originating from photoexcited phenyl organic nitrates formed during the photoreaction of aromatics and NOx. Significant HONO (1.56-4.52 ppb) and OH production is observed during the photoreaction of different kinds of aromatics with NOx (18.1-242.3 ppb). We propose an additional mechanism involving photoexcited phenyl organic nitrates (RONO2) reacting with water vapor to account for the higher levels of measured HONO and OH than the model prediction. The proposed HONO formation mechanism was evidenced directly by photolysis experiments using typical RONO2 under UV irradiation conditions, during which HONO formation was enhanced by relative humidity. The 0-D box model incorporated in this mechanism accurately reproduced the evolution of HONO and aromatic. The proposed mechanism contributes 5.9-36.6% of HONO formation as the NOx concentration increased in the photoreaction of aromatics and NOx. Our study implies that photoexcited phenyl organic nitrates are an important source of atmospheric HONO and OH that contributes significantly to atmospheric oxidation capacity.

Favipiravir biotransformation by a side-stream partial nitritation sludge: Transformation mechanisms, pathways and toxicity evaluation.

Information on biotransformation of antivirals in the side-stream partial nitritation (PN) process was limited. In this study, a side-stream PN sludge was adopted to investigate favipiravir biotransformation under controlled ammonium and pH levels. Results showed that free nitrous acid (FNA) was an important factor that inhibited ammonia oxidation and the cometabolic biodegradation of favipiravir induced by ammonia oxidizing bacteria (AOB). The removal efficiency of favipiravir reached 12.6% and 35.0% within 6 days at the average FNA concentrations of 0.07 and 0.02 mg-N L-1, respectively. AOB-induced cometabolism was the sole contributing mechanism to favipiravir removal, excluding AOB-induced metabolism and heterotrophic bacteria-induced biodegradation. The growth of Escherichia coli was inhibited by favipiravir, while the AOB-induced cometabolism facilitated the alleviation of the antimicrobial activities with the formed transformation products. The biotransformation pathways were proposed based on the roughly identified structures of transformation products, which mainly involved hydroxylation, nitration, dehydrogenation and covalent bond breaking under enzymatic conditions. The findings would provide insights on enriching AOB abundance and enhancing AOB-induced cometabolism under FNA stress when targeting higher removal of antivirals during the side-stream wastewater treatment processes.

Modeling Free Nitrous Acid Inhibition on the Removal of Nitrogen and Atenolol during Sidestream Partial Nitritation Processes.

Sidestream serves as an important reservoir collecting pharmaceuticals from sludge. However, the knowledge on sidestream pharmaceutical removal is still insufficient. In this work, atenolol biodegradation during sidestream partial nitritation (PN) processes characterized by high free nitrous acid (FNA) accumulation was modeled. To describe the FNA inhibition on ammonia oxidation and atenolol removal, Vadivelu-type and Hellinga-type inhibition kinetics were introduced into the model framework. Four inhibitory parameters along with four biodegradation kinetic parameters were calibrated and validated separately with eight sets of batch experimental data and 60 days' PN reactor operational data. The developed model could accurately reproduce the dynamics of nitrogen and atenolol. The model prediction further revealed that atenolol biodegradation efficiencies by ammonia-oxidizing bacteria (AOB)-induced cometabolism, AOB-induced metabolism, and heterotrophic bacteria-induced biodegradation were 0, ∼ 60, and ∼35% in the absence of ammonium and FNA; ∼ 14, ∼ 29, and ∼28% at 0.03 mg-N L-1 FNA; and 7, 15, and 5% at 0.19 mg-N L-1 FNA. Model simulation showed that the nitritation efficiency of ∼99% and atenolol removal efficiency of 57.5% in the PN process could be achieved simultaneously by controlling pH at 8.5, while 89.2% total nitrogen and 57.1% atenolol were removed to the maximum at pH of 7.0 in PN coupling with the anammox process. The pH-based operational strategy to regulate FNA levels was mathematically demonstrated to be effective for achieving the simultaneous removal of nitrogen and atenolol in PN-based sidestream processes.

Revisiting the Ultraviolet Absorption Cross Section of Gaseous Nitrous Acid (HONO): New Insights for Atmospheric HONO Budget.

Nitrous acid (HONO) is an important source of hydroxyl radicals (OH) in the atmosphere. Precise determination of the absolute ultraviolet (UV) absorption cross section of gaseous HONO lays the basis for the accurate measurement of its concentration by optical methods and the estimation of HONO loss rate through photolysis. In this study, we performed a series of laboratory and field intercomparison experiments for HONO measurement between striping coil-liquid waveguide capillary cell (SC-LWCC) photometry and incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS). Specified HONO concentrations prepared by an ultrapure standard HONO source were utilized for laboratory intercomparisons. Results show a consistent ∼22% negative bias in measurements of the IBBCEAS compared with a SC-LWCC photometer. It is confirmed that the discrepancies occurring between these techniques are associated with the overestimation of the absolute UV absorption cross sections through careful analysis of possible uncertainties. We quantified the absorption cross section of gaseous HONO (360-390 nm) utilizing a custom-built IBBCEAS instrument, and the results were found to be 22-34% lower than the previously published absorption cross sections widely used in HONO concentration retrieval and atmospheric chemical transport models (CTMs). This suggests that the HONO concentrations retrieved by optical methods based on absolute absorption cross sections may have been underestimated by over 20%. Plus, the daytime loss rate and unidentified sources of HONO may also have evidently been overestimated in pre-existing studies. In summary, our findings underscore the significance of revisiting the absolute absorption cross section of HONO and the re-evaluation of the previously reported HONO budgets.

Low alkalinity, free ammonia, and free nitrous acid cooperatively stabilize partial nitrification under excessive aeration condition.

In this study, a lab-scale sequencing batch reactor (SBR) was established to assess the feasibility of maintaining partial nitrification in treating high-ammonium wastewater under the condition of excessive aeration (1 L/min, 1289 min). Results showed that the average ammonia (NH4+-N) removal efficiency (ARE) was 93.4 ± 2.7% and the average nitrite accumulation ratio (NAR) was 90.7 ± 2.8% during 15-50 d. In a typical cycle, free ammonia (FA) and free nitrous acid (FNA) alternately inhibited the activity of nitrite oxidizing bacteria (NOB), while low alkalinity limited further nitrification at even excessive aeration. Metagenomic analysis revealed that the relative abundance of Nitrosomonas, as the ammonia oxidizing bacteria (AOB), was up to 1.61%, while NOB were not detected. Taken together, this study indicated partial nitrification was almost not affected by excessive aeration, demonstrating its robustness depending on the cooperative strategy of the low alkalinity limitation and the inhibition of FA and FNA.

Limitations of a biokinetic model to predict the seasonal variations of nitrous oxide emissions from a full-scale wastewater treatment plant.

A biokinetic model based on BioWin's Activated Sludge Digestion Model (ASDM) coupled with a nitrous oxide (N2O) model was setup and calibrated for a full-scale wastewater treatment plant (WWTP) Amsterdam West, in the Netherlands. The model was calibrated using one year of continuous data to predict the seasonal variations of N2O emissions in the gaseous phase. This, according to our best knowledge, is the most complete full-scale data set used to date for this purpose. The results obtained suggest that the currently available biokinetic model predicted the winter, summer, and autumn N2O emissions well but failed to satisfactorily simulate the spring peak. During the calibration process, it was found that the nitrifier denitrification pathway could explain the observed emissions during all seasons while a combination of the nitrifier denitrification and incomplete heterotrophic denitrification pathways seemed to be dominant during the emissions peak observed during the spring season. Specifically, kinetic parameters related to free nitrous acid (FNA) displayed significant sensitivity leading to increased N2O production. The obtained values of two kinetic parameters, i.e., the FNA half-saturation during ammonia oxidising bacteria (AOB) denitrification and the FNA inhibition concentration related to heterotrophic denitrification, suggested a strong influence of the FNA bulk concentration on the N2O emissions and the observed seasonal variations. Based on the suboptimal performance and limitations of the biokinetic model, further research is needed to better understand the biochemical processes behind the seasonal peak and the influence of FNA.

Atmospheric HONO emissions in China: Unraveling the spatiotemporal patterns and their key influencing factors.

Nitrous acid (HONO) can be photolyzed to produce hydroxyl radicals (OH) in the atmosphere. OH plays a critical role in the formation of secondary pollutants like ozone (O3) and secondary organic aerosols (SOA) via various oxidation reactions. Despite the abundance of recent HONO studies, research on national HONO emissions in China remains relatively limited. Therefore, this study employed a "wetting-drying" model and bottom-up approach to develop a high-resolution gridded inventory of HONO emissions for mainland China using multiple data. We used the Monte Carlo method to estimate the uncertainty in HONO emissions. In addition, the primary sources of HONO emissions were identified and their spatiotemporal distribution and main influencing factors were studied. The results indicated that the total HONO emissions in mainland China in 2016 were 0.77 Tg N (R50: 0.28-1.42 Tg N), with soil (0.42 Tg N) and fertilization (0.26 Tg N) as the primary sources, jointly contributing to over 87% of the total. Notably, the North China Plain (NCP) had the highest HONO emission density (3.51 kg N/ha/yr). Seasonal HONO emissions followed the order: summer (0.38 kg N/ha) > spring (0.19 kg N/ha) > autumn (0.17 kg N/ha) > winter (0.06 kg N/ha). Moreover, HONO emissions were strongly correlated with fertilization, cropland, temperature, and precipitation. This study provides vital scientific groundwork for the atmospheric nitrogen cycle and the formation of secondary pollutants.

Unveiling the effect of O2 on the photochemical reaction of NO2 with polycyclic aromatic hydrocarbons.

The photochemical reaction of NO2 with organics may be a source of atmospheric HONO during the daytime. Here, the conversion of NO2 to HONO on polycyclic aromatic hydrocarbons (PAHs) under solar irradiation under aerobic and anaerobic conditions was investigated using a flow tube reactor coupled to a NOx analyzer. O2 played an inhibition role in NO2 uptake and HONO formation on PAHs, as shown by 7%-45% and 15%-52% decrease in NO2 uptake coefficient (γ) and HONO yield (YHONO), respectively. The negative effect of O2 on the reaction between NO2 and PAHs should be attributed to three reasons. First, O2 could compete with NO2 for the available sites on PAHs. Second, the quenching of the triple excited state of PAHs (3PAHs*) by O2 inhibited the NO2 uptake. Third, NO3- formed under aerobic conditions reduced the conversion efficiency of NO2 to HONO. The environmental implications suggested that the NO2 uptake on PAHs could contribute to a HONO source strength of 10-120 ppt h-1 in the atmosphere.

Quantifying the Nitrogen Sources and Secondary Formation of Ambient HONO with a Stable Isotopic Method.

Nitrous acid (HONO) is a reactive gas that plays an important role in atmospheric chemistry. However, accurately quantifying its direct emissions and secondary formation in the atmosphere as well as attributing it to specific nitrogen sources remains a significant challenge. In this study, we developed a novel method using stable nitrogen and oxygen isotopes (δ15N; δ18O) for apportioning ambient HONO in an urban area in North China. The results show that secondary formation was the dominant HONO formation processes during both day and night, with the NO2 heterogeneous reaction contributing 59.0 ± 14.6% in daytime and 64.4 ± 10.8% at nighttime. A Bayesian simulation demonstrated that the average contributions of coal combustion, biomass burning, vehicle exhaust, and soil emissions to HONO were 22.2 ± 13.1, 26.0 ± 5.7, 28.6 ± 6.7, and 23.2 ± 8.1%, respectively. We propose that the isotopic method presents a promising approach for identifying nitrogen sources and the secondary formation of HONO, which could contribute to mitigating HONO and its adverse effects on air quality.

Effect of free nitrous acid on extracellular polymeric substances production and membrane fouling in a nitritation membrane bioreactor.

The membrane bioreactor (MBR) with nitritation based nitrogen removal processes has attracted growing interest in recent years, although membrane fouling in the nitritation MBR is a challenging issue. In this study, the inhibitory effect of free nitrous acid (FNA) on microbial extracellular polymeric substances (EPS) production and membrane fouling in a nitritation MBR was investigated. Results showed that EPS played a critical role in the biofouling process, and EPS production was affected by FNA concentration. As FNA concentration increased from 5.10 × 10-3 mg N/L to 1.34 × 10-2 mg N/L, protein (PN) and polysaccharide (PS) contents increased from 8.20 to 60.28 mg/g VSS and 4.74-30.46 mg/g VSS, respectively. However, when FNA concentration was 1.48 × 10-2 mg N/L, PN and PS reduced by 20.0% and 10.9%, respectively, indicating that the higher FNA concentration could reduce EPS production. The EPS reduction could be attributed to reduction in the loosely bound (LB) and tightly bound (TB) EPS but not the soluble microbial products (SMP). It was further revealed that higher FNA concentrations up to 1.48 × 10-2 mg N/L consequently mitigate trans-membrane pressure (TMP) rate in terms of dTMP/dt by 25.5% in the nitritation MBR. High throughput sequencing analysis revealed that the increase in FNA led to enrichment of Nitrosomonas but reduction in heterotrophic bacteria. This study showed that the appropriate FNA concentration affected EPS production and hence membrane fouling, leading to the possibility of membrane fouling mitigation by in-situ generated FNA in the nitritation MBR.

A novel free nitrous acid (FNA)-generation pathway via ferric salts hydrolysis to mitigate sulfide and methane production in sewer: Insights into the performance and microbial mechanisms.

Ferric chloride (FeCl3) served as a solid acid has attracted attention recently. However, the feasibility of FeCl3 combined with nitrite for free nitrous acid (FNA) generation in controlling sulfide and methane as well as the triggering mechanisms in the complex syntrophic consortium (i.e., sewer biofilm) remain largely unknown. This work disclosed FeCl3 as an alternative acid source could obtain comparable sulfide and methane mitigations at a low FNA dose (i.e., 0.26 mg N/L), compared to that of HCl acid source. Whereas, a faster recovery rate of sulfide production was observed using FeCl3 under a higher FNA dose (i.e., 0.81 mg N/L) despite the methane control still being comparable. The toxicological mechanisms revealed FNA reacted with proteins amide Ⅰ in extracellular polymeric substances and destroyed protein hydrogen bond. Enzymatic and genic analysis unveiled the overall suppression of hydrolysis, acidogenesis, acetogenesis, sulfidogenesis and methanogenesis steps due to the inactivation of viable cells by reactive nitrogen species. Economic and environmental assessments demonstrated that the ferric-based FNA strategy reduced chemical costs and N2O emission (ca. 26.5% decrease) compared to the traditional HCl-based FNA method. This work broadens the application of iron salt-based technology in urban water system, together with understanding the biological mechanisms of FNA-based technology.

Comparison of typical nitrite oxidizing bacteria suppression strategies and the effect on nitrous oxide emissions in a biofilm reactor.

In mainstream partial nitritation/anammox (PN/A), suppression of nitrite oxidizing bacteria (NOB) and mitigation of N2O emissions are two essential operational goals. The N2O emissions linked to three typical NOB suppression strategies were tested in a covered rotating biological contactor (RBC) biofilm system at 21 °C: (i) low dissolved oxygen (DO) concentrations, and treatments with (ii) free ammonia (FA), and (iii) free nitrous acids (FNA). Low emerged DO levels effectively minimized NOB activity and decreased N2O emissions, but NOB adaptation appeared after 200 days of operation. Further NOB suppression was successfully achieved by periodic (3 h per week) treatments with FA (29.3 ± 2.6 mg NH3-N L-1) or FNA (3.1 ± 0.3 mg HNO2-N L-1). FA treatment, however, promoted N2O emissions, while FNA did not affect these. Hence, biofilm PN/A should be operated at relatively low DO levels with periodic FNA treatment to maximize nitrogen removal efficiency while avoiding high greenhouse gas emissions.

Enhanced methane yield in anaerobic digestion of waste activated sludge by combined pretreatment with fungal mash and free nitrous acid.

This study explores a novel approach for enhancing anaerobic digestion of waste activated sludge (WAS) through the combined pretreatment of fungal mash and free nitrous acid (FNA). Aspergillus PAD-2, a fungal strain with superior hydrolase secretion, was isolated from WAS and cultivated in-situ on food waste to produce fungal mash. The solubilization of WAS by fungal mash achieved a high soluble chemical oxygen demand release rate of 548 mg L-1 h-1 within first 3 h. The combined pretreatment of fungal mash and FNA further improved the sludge solubilization by 2-fold and resulted in a doubled methane production rate of 416±11 mL CH4 g-1 volatile solids. The Gompertz model analysis revealed a higher maximum specific methane production rate and shortened lag time by the combined pretreatment. These results demonstrate that the combined fungal mash and FNA pretreatment offers a promising alternative for fast anaerobic digestion of WAS.

Free nitrous acid prediction in ANAMMOX process using hybrid deep neural network model.

Free nitrous acid (FNA) is a critical metric for stabilization of ANAMMOX but can not be directly and immediately measured by sensors or chemical measurement method, which hinders the effective management and operation for ANAMMOX. This study focuses on FNA prediction using hybrid model based on temporal convolutional network (TCN) combined with attention mechanism (AM) optimized by multiobjective tree-structured parzen estimator (MOTPE), called MOTPE-TCNA. A case study in an ANAMMOX reactor is carried out. Results show that nitrogen removal rate (NRR) is highly correlated with FNA concentration, indicating that it can forecast the operational status by predicting FNA. Then, MOTPE successfully optimizes the hyperparameters of TCN, helping TCN achieve a high prediction accuracy, and AM furtherly improves model accuracy. MOTPE-TCNA obtains the highest prediction accuracy, whose R2 value gets 0.992, increasing 1.71-11.80% compared to other models. As a deep neural network model, MOTPE-TCNA has more advantages than traditional machine learning methods in FNA prediction, which is beneficial to maintain the stable operation and easy control for ANAMMOX process.

Direct Formation of Electronic Excited NO2 Contributes to the High Yield of HONO during Photosensitized Renoxification.

Photosensitized renoxification of HNO3 is found to produce HONO in an unexpectedly high yield, which has been considered an important source for atmospheric HONO. Conventionally, the production of HONO is ascribed to the secondary photolysis of the primarily formed NO2. In this study, by using humic acid (HA) as a model environmental photosensitizer, we provide evidence of the direct formation of NO2 in its electronic excited state (NO2*) as a key intermediate during the photosensitizing renoxification of HNO3. Moreover, the high HONO yield originates from the heterogeneous reaction of the primarily formed NO2* with the co-adsorbed water molecules on HA. Such a mechanism is supported by the increase of the product selectivity of HONO with relative humidity. Further luminescence measurements demonstrate clearly the occurrence of an electronic excited state (NO2*) from photolysis of adsorbed HNO3 on HA. This work deepens our understanding of the formation of atmospheric HONO and gives insight into the transformation of RNS.

Identification and Analysis of the Biosynthetic Gene Cluster for the Hydrazide-Containing Aryl Polyene Spinamycin.

Natural products containing nitrogen-nitrogen (N-N) bonds have attracted much attention because of their bioactivities and chemical features. Several recent studies have revealed the nitrous acid-dependent N-N bond-forming machinery. However, the catalytic mechanisms of hydrazide synthesis using nitrous acid remain unknown. Herein, we focused on spinamycin, a hydrazide-containing aryl polyene produced by Streptomyces albospinus JCM3399. In the S. albospinus genome, we discovered a putative spinamycin biosynthetic gene (spi) cluster containing genes that encode a type II polyketide synthase and genes for the secondary metabolism-specific nitrous acid biosynthesis pathway. A gene inactivation experiment showed that this cluster was responsible for spinamycin biosynthesis. A feeding experiment using stable isotope-labeled sodium nitrite and analysis of nitrous acid-synthesizing enzymes in vitro strongly indicated that one of the nitrogen atoms of the hydrazide group was derived from nitrous acid. In vitro substrate specificity analysis of SpiA3, which is responsible for loading a starter substrate onto polyketide synthase, indicated that N-N bond formation occurs after starter substrate loading. In vitro analysis showed that the AMP-dependent ligase SpiA7 catalyzes the diazotization of an amino group on a benzene ring without a hydroxy group, resulting in a highly reactive diazo intermediate, which may be the key step in hydrazide group formation. Therefore, we propose the overall biosynthetic pathway of spinamycin. This study expands our knowledge of N-N bond formation in microbial secondary metabolism.

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.

Free ammonia-free nitrous acid based partial nitrification in sequencing batch membrane aerated biofilm reactor.

Membrane aerated biofilm reactor (MABR) has attracted a lot of attention as an energy-efficient integrated nitrogen removing technology in recent years. However, it is lacking of understanding to realize stable partial nitrification in MABR because of its unique oxygen transfer mode and biofilm structure. In this study, free ammonia (FA) and free nitrous acid (FNA) based control strategies for partial nitrification with low NH4+-N concentration were proposed in a MABR of sequencing batch mode. The MABR was operated for over 500 days under different influent NH4+-N concentrations. With the influent NH4+-N of around 200 mg-N/L, partial nitrification could be established with relatively low concentration of FA (0.4-2.2 mg-N/L) which suppressed nitrite oxidizing bacteria (NOB) on the biofilm. With lower influent NH4+-N concentration of around 100 mg-N/L, the FA concentration was lower and strengthened suppression strategies based on FNA were needed. With the final pH of operating cycles below 5.0, the FNA produced in the sequencing batch MABR could stabilize partial nitrification by eliminating NOB on the biofilm. Since the activity of ammonia oxidizing bacteria (AOB) was lower without the blow-off of dissolved carbon dioxide in the bubbleless MABR, longer hydraulic retention time was required to reach a low pH for high concentration of FNA to suppress NOB. After exposures to FNA, the relative abundance of Nitrospira was decreased by 94.6%, while the abundance of Nitrosospira increased greatly which became another dominant AOB genus in addition to Nitrosomonas.

Free nitrous acid-assisted asymmetrical alternating current electrochemistry (FNA-AACE) for multi-heavy metals decontamination in waste activated sludge.

Heavy metal contamination of waste activated sludge (WAS) is a key factor limiting the land application of sludge for nutrients recovery. This study proposes a novel free nitrous acid (FNA)-assisted asymmetrical alternating current electrochemistry (FNA-AACE) process to achieve high-efficiency decontamination of multi-heavy metals (Cd, Pb, and Fe) in WAS. The optimal operating conditions, the heavy metal removal performance of FNA-AACE, and the related mechanisms for maintaining the high performance were systematically investigated. During the FNA-AACE process, FNA treatment was optimal with an exposure time of 13 h at a pH of 2.9 and an FNA concentration of 0.6 mg/g TSS. Then the sludge was washed with EDTA in a recirculating leaching system under asymmetrical alternating current electrochemistry (AACE). The 6-h working and the following electrode cleaning were defined as a working circle of AACE. After three cycles of working-cleaning periods in AACE treatment, the cumulative removal efficiency of the toxic metals Cd and Pb reached over 97% and 93%, respectively, whilst that of Fe was greater than 65%. This surpasses most previously reported efficiencies and possesses a shorter treatment duration and sustainable EDTA circulation. The mechanism analysis suggested that FNA pretreatment provoked the migration of heavy metals for leaching enhancement, as well as reduced the demand for EDTA eluent concentration and increased conductivity, which can improve the AACE efficiency. Meanwhile, the AACE process absorbed the anionic chelates of heavy metals and reduced them to zero-valent particles on the electrode, regenerating the EDTA eluent and maintaining its high extraction efficiency for heavy metals. In addition, FNA-AACE could provide different electric field operation modes, allowing it to have flexibility for the real application processes. This proposed process is expected to be coupled with anaerobic digestion in wastewater treatment plants (WWTPs) for high efficiency of heavy metal decontamination, sludge reduction, and resource/energy recovery.

Exploring HONO formation and its role in driving secondary pollutants formation during winter in the North China Plain.

Daytime HONO photolysis is an important source of atmospheric hydroxyl radicals (OH). Knowledge of HONO formation chemistry under typical haze conditions, however, is still limited. In the Multiphase chemistry experiment in Fogs and Aerosols in the North China Plain in 2018, we investigated the wintertime HONO formation and its atmospheric implications at a rural site Gucheng. Three different episodes based on atmospheric aerosol loading levels were classified: clean periods (CPs), moderately polluted periods (MPPs) and severely polluted periods (SPPs). Correlation analysis revealed that HONO formation via heterogeneous conversion of NO2 was more efficient on aerosol surfaces than on ground, highlighting the important role of aerosols in promoting HONO formation. Daytime HONO budget analysis indicated a large missing source (with an average production rate of 0.66 ± 0.26, 0.97 ± 0.47 and 1.45 ± 0.55 ppbV/hr for CPs, MPPs and SPPs, respectively), which strongly correlated with photo-enhanced reactions (NO2 heterogeneous reaction and particulate nitrate photolysis). Average OH formation derived from HONO photolysis reached up to (0.92 ± 0.71), (1.75 ± 1.26) and (1.82 ± 1.47) ppbV/hr in CPs, MPPs and SPPs respectively, much higher than that from O3 photolysis (i.e., (0.004 ± 0.004), (0.006 ± 0.007) and (0.0035 ± 0.0034) ppbV/hr). Such high OH production rates could markedly regulate the atmospheric oxidation capacity and hence promote the formation of secondary aerosols and pollutants.