Process Optimization of Electrochemical Treatment of COD and Total Nitrogen Containing Wastewater

In this work, an electrochemical method for chemical oxygen demand (COD) and total nitrogen (TN, including ammonia, nitrate, and nitrite) removal from wastewater using a divided electrolysis cell was developed, and its process optimization was investigated. This process could effectively relieve the common issue of NO3−/NO2− over-reduction or NH4+ over-oxidation by combining cathodic NO3−/NO2− reduction with anodic COD/NH4+ oxidation. The activity and selectivity performances toward pollutant removal of the electrode materials were investigated by electrochemical measurements and constant potential electrolysis, suggesting that Ti electrode exhibited the best NO3−/NO2− reduction and N2 production efficiencies. In-situ Fourier transform infrared spectroscopy was used to study the in-situ electrochemical information of pollutants conversion on electrode surfaces and propose their reaction pathways. The effects of main operating parameters (i.e., initial pH value, Cl− concentration, and current density) on the removal efficiencies of COD and TN were studied. Under optimal conditions, COD and TN removal efficiencies from simulated wastewater reached 92.7% and 82.0%, respectively. Additionally, reaction kinetics were investigated to describe the COD and TN removal. Results indicated that COD removal followed pseudo-first-order model; meanwhile, TN removal followed zero-order kinetics with a presence of NH4+ and then followed pseudo-first-order kinetics when NH4+ was completely removed. For actual pharmaceutical wastewater treatment, 79.1% COD and 87.0% TN were removed after 120 min electrolysis; and no NH4+ or NO2− was detected.

Assessment of the Performance of TROPOMI NO2 and SO2 Data Products in the North China Plain: Comparison, Correction and Application

The TROPOspheric Monitoring Instrument (TROPOMI) aboard the Sentinel-5 Precursor satellite has been used to detect the atmospheric environment since 2017, and it is of great significance to investigate the accuracy of its products. In this work, we present comparisons between TROPOMI tropospheric NO2 and total SO2 products against ground-based MAX-DOAS at a single site (Xianghe) and OMI products over a seriously polluted region (North China Plain, NCP) in China. The results show that both NO2 and SO2 data from three datasets exhibit a similar tendency and seasonality. In addition, TROPOMI tropospheric NO2 columns are generally underestimated compared with collocated MAX-DOAS and OMI data by about 30–60%. In contrast to NO2, the monthly average SO2 retrieved from TROPOMI is larger than MAX-DOAS and OMI, with a mean bias of 2.41 (153.8%) and 2.17 × 1016 molec cm−2 (120.7%), respectively. All the results demonstrated that the TROPOMI NO2 as well as the SO2 algorithms need to be further improved. Thus, to ensure reliable analysis in NCP area, a correction method has been proposed and applied to TROPOMI Level 3 data. The revised datasets agree reasonably well with OMI observations (R > 0.95 for NO2, and R > 0.85 for SO2) over the NCP region and have smaller mean biases with MAX-DOAS. In the application during COVID-19 pandemic, it showed that the NO2 column in January-April 2020 decreased by almost 25–45% compared to the same period in 2019 due to the lockdown for COVID-19, and there was an apparent rebound of nearly 15–50% during 2021. In contrast, a marginal change of the corresponding SO2 is revealed in the NCP region. It signifies that short-term control measures are expected to have more effects on NO2 reduction than SO2; conversely, we need to recognize that although the COVID-19 lockdown measures improved air quality in the short term, the pollution status will rebound to its previous level once industrial and human activities return to normal.

Biomass Juncus derived carbon decorated with cobalt nanoparticles for high-efficiency ammonia electrosynthesis by nitrite reduction

Electrochemical nitrite (NO2–) reduction reaction (NO2RR) is not only a promising strategy to degrade harmful NO2– contaminant in the environment but an attractive alternative to the Haber-Bosch process for sustainable...

Numerical analysis of NOX formation in CO2 diluted biogas premixed combustion

A further investigation of premixed biogas combustion towards the NOx formation is presented in this study. The purpose of the simulation is to determine the addition of CO2 in biogas fuel to the combustion behavior of premixed biogas on NOx formation, and to determine the occurrence of NOx in the pre-mixed biogas combustion. In this study, the Counterflow Premixed Flame class is used where this class is based on the One Dim class which is the basis for simulations with a 1-dimensional domain. The Counterflow Premixed Flame class uses an axisymmetric stagnation flow domain which has been written based on the equations. Cantera uses Newton's method to solve them. Completion is carried out in two stages. The first stage is to solve the solution using the equilibrium at each z coordinate point that has been determined. Many estimation starting points are determined from the start of the program. The second stage is the recalculation process at each point and then subdivided to get a smoother solution. The premixed excess CO2 biogas fuel and air combustion analyzed using a 1-dimensional numerical study. The diluted CO2 mass fraction ranged between 0–40 %. The CH4/CO2/air volume flow rate was maintained in ±L/min. The analysis implements the 1-D Counter Flow approach. Two counterflow nozzles were 20mm in diameter and the flame stagnation point at 10 mm. The results show that NOx mass fraction formed only on a fuel-lean mixture of CH4/CO2/air and its values decreased along with CO2 added. The addition of CO2 could reduce the NO species mass fraction down to 18 %, and NO2 reduction down to 7 %. This is mainly caused by a decreasing heat release rate of NO+N↔N2+O, N+O2↔NO+O, N+OH↔NO+H, and N+CO2↔NO+CO reactions. The N+CO2↔NO+CO reaction increased as CO2 was added but its values were not as much as the decline of three other reactions

COVID-19 lockdowns highlight a risk of increasing ozone pollution in European urban areas

In March 2020, non-pharmaceutical intervention measures in the form of lockdowns were applied across Europe to urgently reduce the transmission of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), the virus which causes the COVID-19 disease. The aggressive curtailing of the European economy had widespread impacts on the atmospheric composition, particularly for nitrogen dioxide (NO2) and ozone (O3). To investigate these changes, we analyse data from 246 ambient air pollution monitoring sites in 102 urban areas and 34 countries in Europe between February and July 2020. Counterfactual, business-as-usual air quality time series are created using machine-learning models to account for natural weather variability. Across Europe, we estimate that NO2 concentrations were 34 % and 32 % lower than expected for respective traffic and urban background locations, whereas O3 was 30 % and 21 % higher (in the same respective environments) at the point of maximum restriction on mobility. To put the 2020 changes into context, average NO2 trends since 2010 were calculated, and the changes experienced across European urban areas in 2020 was equivalent to 7.6 years of average NO2 reduction (or concentrations which might be anticipated in 2028). Despite NO2 concentrations decreasing by approximately a third, total oxidant (Ox) changed little, suggesting that the reductions in NO2 were substituted by increases in O3. The lockdown period demonstrated that the expected future reductions in NO2 in European urban areas are likely to lead to widespread increases in urban O3 pollution unless additional mitigation measures are introduced.

The physiological potential of anammox bacteria as revealed by their core genome structure

We present here the second complete genome of anaerobic ammonium oxidation (anammox) bacterium, Candidatus (Ca.) Brocadia pituitae, along with those of a nitrite oxidizer and two incomplete denitrifiers from the anammox bacterial community (ABC) metagenome. Although NO2- reduction to NO is considered to be the first step in anammox, Ca. B. pituitae lacks nitrite reductase genes (nirK and nirS) responsible for this reaction. Comparative genomics of Ca. B. pituitae with Ca. K. stuttgartiensis and six other anammox bacteria with nearly complete genomes revealed that their core genome structure contains 1,152 syntenic orthologs. But nitrite reductase genes were absent from the core, whereas two other Brocadia species possess nirK and these genes were horizontally acquired from multiple lineages. In contrast, at least 5 paralogous hydroxylamine oxidoreductase genes containing candidate ones (hao2 and hao3) encoding another nitrite reductase were observed in the core. Indeed, these two genes were also significantly expressed in Ca. B. pituitae as in other anammox bacteria. Because many nirS and nirK genes have been detected in the ABC metagenome, Ca. B. pituitae presumably utilises not only NO supplied by the ABC members but also NO and/or NH2OH by self-production for anammox metabolism.

Rapid Ammonia Carriers for SCR Systems Using MOFs [M2(adc)2(dabco)] (M = Co, Ni, Cu, Zn)

Ammonia is one of the most common reductants for the automotive selective catalytic reduction (SCR) system owing to its high NO2 reduction (deNOx) efficiency. However, ammonia carriers for the SCR system have sluggishly evolved to achieve rapid ammonia dosing. In this study, the MOFs [M2(adc)2(dabco)] (M = Co, Ni, Cu, Zn) were synthesized and characterized as ammonia carriers. Among the four obtained MOFs, Ni2(adc)2(dabco) possessed the highest surface area, 772 m2/g, highest ammonia uptake capacity, 12.1 mmol/g, and stable cyclic adsorption-desorption performance. All the obtained MOFs demonstrated physisorption of ammonia and rapid kinetics of ammonia adsorption and desorption. Compared with halide ammonia carrier MgCl2, the obtained MOFs showed four times faster adsorption kinetics to reach 90% of the ammonia uptake capacity. For the ammonia desorption, the Ni2(adc)2(dabco) provided 6 mmol/g ammonia dosing when temperature reached 125 °C in the first 10 min, which was six times of the ammonia dosing from Mg(NH3)6Cl2. The results offer a solution to shorten the buffering time for ammonia dosing in the SCR system.

Impact of reactive surfaces on the abiotic reaction between nitrite and ferrous iron and associated nitrogen and oxygen isotope dynamics

Anaerobic nitrate-dependent Fe(II) oxidation (NDFeO) is widespread in various aquatic environments and plays a major role in iron and nitrogen redox dynamics. However, evidence for truly enzymatic, autotrophic NDFeO remains limited, with alternative explanations involving the coupling of heterotrophic denitrification with the abiotic oxidation of structurally bound or aqueous Fe(II) by reactive intermediate nitrogen (N) species (chemodenitrification). The extent to which chemodenitrification is caused (or enhanced) by ex vivo surface catalytic effects has not been directly tested to date. To determine whether the presence of either an Fe(II)-bearing mineral or dead biomass (DB) catalyses chemodenitrification, two different sets of anoxic batch experiments were conducted: 2 mM Fe(II) was added to a low-phosphate medium, resulting in the precipitation of vivianite (Fe3(PO4)2), to which 2 mM nitrite (NO2-) was later added, with or without an autoclaved cell suspension (∼1.96×108 cells mL−1) of Shewanella oneidensis MR-1. Concentrations of nitrite (NO2-), nitrous oxide (N2O), and iron (Fe2+, Fetot) were monitored over time in both set-ups to assess the impact of Fe(II) minerals and/or DB as catalysts of chemodenitrification. In addition, the natural-abundance isotope ratios of NO2- and N2O (δ15N and δ18O) were analysed to constrain the associated isotope effects. Up to 90 % of the Fe(II) was oxidized in the presence of DB, whereas only ∼65 % of the Fe(II) was oxidized under mineral-only conditions, suggesting an overall lower reactivity of the mineral-only set-up. Similarly, the average NO2- reduction rate in the mineral-only experiments (0.004±0.003 mmol L−1 d−1) was much lower than in the experiments with both mineral and DB (0.053±0.013 mmol L−1 d−1), as was N2O production (204.02±60.29 nmol L−1 d−1). The N2O yield per mole NO2- reduced was higher in the mineral-only set-ups (4 %) than in the experiments with DB (1 %), suggesting the catalysis-dependent differential formation of NO. N-NO2- isotope ratio measurements indicated a clear difference between both experimental conditions: in contrast to the marked 15N isotope enrichment during active NO2- reduction (15εNO2=+10.3 ‰) observed in the presence of DB, NO2- loss in the mineral-only experiments exhibited only a small N isotope effect (<+1 ‰). The NO2--O isotope effect was very low in both set-ups (18εNO2 <1 ‰), which was most likely due to substantial O isotope exchange with ambient water. Moreover, under low-turnover conditions (i.e. in the mineral-only experiments as well as initially in experiments with DB), the observed NO2- isotope systematics suggest, transiently, a small inverse isotope effect (i.e. decreasing NO2- δ15N and δ18O with decreasing concentrations), which was possibly related to transitory surface complexation mechanisms. Site preference (SP) of the 15N isotopes in the linear N2O molecule for both set-ups ranged between 0 ‰ and 14 ‰, which was notably lower than the values previously reported for chemodenitrification. Our results imply that chemodenitrification is dependent on the available reactive surfaces and that the NO2- (rather than the N2O) isotope signatures may be useful for distinguishing between chemodenitrification catalysed by minerals, chemodenitrification catalysed by dead microbial biomass, and possibly true enzymatic NDFeO.

Impact of reactive surfaces on the abiotic reaction between nitrite and ferrous iron and associated nitrogen and oxygen isotope dynamics

Anaerobic nitrate-dependent Fe(II) oxidation (NDFeO) is widespread in various aquatic environments, and plays a major role in iron and nitrogen redox dynamics. However, evidence for truly enzymatic, autotrophic NDFeO remains limited, with alternative explanations involving coupling of heterotrophic denitrification with abiotic oxidation of structurally-bound or aqueous Fe(II) by reactive intermediate N species (chemodenitrification). The extent to which chemodenitrification is caused, or enhanced, by ex vivo surface catalytic effects has, so far, not been directly quantified. To determine whether the presence of either a Fe(II)-bearing mineral or dead biomass (DB) catalyses chemodenitrification, two different sets of anoxic batch experiment were conducted: 2 mM Fe(II) was added to a low-phosphate medium, resulting in the precipitation of vivianite (Fe3(PO4)2), to which later 2 mM nitrite (NO2−) were added, with or without an autoclaved cell suspension (~ 1.96 × 108 cells ml−1) of Shewanella oneidensis MR-1. Concentrations of nitrite, nitrous oxide (N2O) and iron (Fe2+, Fetot) were monitored over time to assess the impact of Fe(II) minerals and/or DB as catalysts of chemodenitrification in the two setups. In addition, the natural-abundance isotope ratios of NO2− and N2O (𝛿15N and 𝛿18O) were analysed to constrain associated isotope effects. Up to 90 % of the Fe(II) was oxidized in the presence of DB, while only ~ 65 % were oxidized under mineral-only conditions, suggesting an overall lower reactivity of the mineral-only setup. Similarly, the average NO2− reduction rate (0.004 ± 0.003 mmol L−1 day−1) in the mineral-only experiments was much lower compared to experiments with mineral plus dead biomass (0.053 ± 0.013 mmol L−1 day−1), as was N2O production (204.02 ± 60.29 nmol/L*day). The N2O yield per mole NO2− reduced was higher in the mineral-only setups (4 %) compared to the experiments with dead biomass (1 %), suggesting the catalysis-dependent differential formation of NO. N-NO2− isotope ratio measurements indicated a clear difference between both experimental conditions: in contrast to the marked 15N isotope enrichment during active NO2− reduction (−15εNO2 = +10.3 ‰) observed in the presence of DB, NO2− loss in the mineral-only experiments exhibited only a small N isotope effect (