Hydroxyl, hydroperoxyl free radicals determination methods in atmosphere and troposphere

The hydroxyl radical (?OH) has a crucial function in the oxidation and removal of many atmospheric compounds that are harmful to health. Nevertheless, high reactivity, low atmospheric abundance, determination of hydroxyl, and hydroperoxyl radical's quantity is very difficult. In the atmosphere and troposphere, hydroperoxyl radicals (HO₂) are closely demanded in the chemical oxidation of the troposphere. But advances in technology have allowed researchers to improve the determination methods on the research of free radicals through some spectroscopic techniques. So far, several methods such as laser-induced fluorescence (LIF), high-performance liquid chromatography (HPLC), and chemical ionization mass spectroscopy have been identified and mostly used in determining the quantity of hydroxyl and hydroperoxyl radicals. In this systematic review, we have advised the use of scavenger as an advance for further researchers to circumvent some of these problems caused by free radicals. The primary goal of this review is to deepen our understanding of the functions of the most critical free radical (?OH, HO₂) and also understand the currently used methods to quantify them in the atmosphere and troposphere.     

The adsorption behavior of metals in aqueous solution by microplastics effected by UV radiation

Microplastics are considered as the carrier to heavy metals in the environment.But the sorption ability of microplastics influenced by photo-aging is remaining unclear.In the present study,the sorption of two kinds of metal ions(Cu²⁺ and Zn²⁺) in the aqueous solution by both the virgin and aged microplastics was investigated.Polyethylene terephthalate(PET) debris,one of the typical kinds of microplastics was chosen in this study.Photo-aging of microplastics in environment w...     

The onset of surface-enhanced Raman scattering for single-particle detection of submicroplastics

Microplastics represent an emerging environmental problem worldwide, raising ecological and food safety concerns. Compared to microplastics, there is growing evidence of an even higher abundance of submicro- and nanoplastics in the environment, but a reliable monitoring method for detecting these smaller-sized plastics is lacking. Herein we presented the application of surface-enhanced Raman scattering (SERS) for this purpose. Particles of polystyrene (PS; 600 nm) were used as the probe analyte. Gold nanourchins (AuNU; 50 nm), i.e. urchin-shaped nanoparticles with irregular spikes around the core, were used as the SERS-active substrate. The effectiveness of SERS on PS was evaluated at a single-particle level with different numbers of AuNU in order to determine the minimum conditions required for the onset of the SERS effect. Our findings suggest that SERS of a single particle of PS can be induced by as few as 1–5 particles of AuNU, and that the use of excitation wavelength at 785 nm is appropriate to meet the red-shifted surface plasmon resonance of AuNU upon aggregation. These specifications provide additional information for the development of SERS-based tools for detecting plastic particles < 1 µm in food and environmental samples.     

A review of the technology and applications of methods for evaluating the transport of air pollutants

A variety of methods based on air quality models, including tracer methods, the brute-force method (BFM), decoupled direct method (DDM), high-order decoupled direct method (HDDM), response surface models (RSMs) and so on forth, have been widely used to study the transport of air pollutants. These methods have good applicability for the transport of air pollutants with simple formation mechanisms. However, differences in research conclusions on secondary pollutants with obvious nonlinear characteristics have been reported. For example, the tracer method is suitable for the study of simplified scenarios, while HDDM and RSMs are more suitable for the study for nonlinear pollutants. Multiple observation techniques, including conventional air pollutant observation, lidar observation, air sounding balloons, vehicle-mounted and ship-borne technology, aerial surveys, and remote sensing observations, have been utilized to investigate air pollutant transport characteristics with time resolution as high as 1 sec. In addition, based on a multi-regional input-output model combined with emission inventories, the transfer of air pollutant emissions can be evaluated and applied to study the air pollutant transport characteristics. Observational technologies have advantages in temporal resolution and accuracy, while modeling technologies are more flexible in spatial resolution and research plan setting. In order to accurately quantify the transport characteristics of pollutants, it is necessary to develop a research method for interactive verification of observation and simulation. Quantitative evaluation of the transport of air pollutants from different angles can provide a scientific basis for regional joint prevention and control.     

High pyrolysis temperature biochar reduced the transport of petroleum degradation bacteria Corynebacterium variabile HRJ4 in porous media

Biochar has been widely applied for the remediation of petroleum-contaminated soil. However, the effect of biochar on the transport of petroleum degradation bacteria has not been studied. A typical Gram-positive petroleum degradation bacteria-Corynebacterium variabile HRJ4 was used to study the effect of different biochars on bacterial transport and retention. Results indicated that the addition of biochar in sand was effective for reducing the transport of bacteria and poplar sawdust biochar (PSBC) had a stronger hinder effect than corn straw biochar (CSBC). The hindrance was more evident with pyrolysis temperature of biochar raised from 300°C to 600°C, which was attributed to the increase of specific surface area (309 times). The hindrance effect also enhanced with higher application rate of biochar. Furthermore, the reduction of HRJ4 transport was more obvious in higher (25 mmol/L) concentration of NaCl solution owing to electrostatic attraction enhancement. The adsorption of biochar to HRJ4 was defined to contribute to the hindrance of HRJ4 transport mainly. Combining the influence of feedstocks and pyrolysis temperature on HRJ4 transport, it suggested that specific surface area had the greatest effect on HRJ4 transport, and pore-filling, electrostatic force also contributed to HRJ4 retained in quartz sand column. At last, phenol transportation experiment indicated that the restriction of biochar on HRJ4 enhanced the phenol removal rate in the column. This study provides a theoretical basis for the interaction of biochar and bacteria, which is vital for the remediation of oil-contaminated soil and groundwater in the field.     

Concentrations and distribution of novel brominated flame retardants in the atmosphere and soil of Ny-Ålesund and London Island, Svalbard, Arctic

Novel brominated flame retardants (NBFRs) were investigated in Arctic air and soil samples collected from Ny-Ålesund and London Island, Svalbard, during Chinese scientific research expeditions to the Arctic during 2014–2015. The concentrations of Σ₉NBFRs in the Arctic air and soil were 4.9–8.7 pg/m³ (average 6.8 pg/m³) and 101–201 pg/g dw (average 150 pg/g dw), respectively. The atmospheric concentration of hexabromobenzene (HBB) was significantly correlated with that of pentabromotoluene (PBT) and pentabromobenzene (PBBz), suggesting similar source and environmental fate in the Arctic air. No significant spatial difference was observed among the different sampling sites, both for air and soil samples, indicating that the effects of the scientific research stations on the occurrence of NBFRs in the Arctic were minor. The fugacities from soil to air of pentabromoethylbenzene (PBEB), 2,3-dibromopropyl 2,4,6-tribromophenyl ether (DPTE), and decabromodiphenylethane 1,2-bis (pentabromophenyl) ethane (DBDPE) were lower than the equilibrium value, indicating a nonequilibrium state of these compounds between air and soil, the dominant impact of deposition and the net transport from air to soil. The correlation analysis between the measured and predicted soil-atmosphere coefficients based on the absorption model showed that the impact of the soil organic matter on the distribution of NBFRs in the Arctic region was minor. To the best of our knowledge, this work is one of the limited reports on atmospheric NBFRs in the Arctic and the first study to investigate the occurrence and fate of NBFRs in the Arctic soil.     

Interference from HONO in the measurement of ambient air NO2 via photolytic conversion and quantification of NO

The reference method to quantify mixing ratios of the criteria air pollutant nitrogen dioxide (NO₂) is NO-O₃ chemiluminescence (CL), in which mixing ratios of nitric oxide (NO) are measured by sampling ambient air directly, and mixing ratios of NO_x (= sum of NO and NO₂) are measured by converting NO₂ to NO using, for example, heated molybdenum catalyst or, more selectively, photolytic conversion (P-CL). In this work, the nitrous acid (HONO) interference in the measurement of NO₂ by P-CL was investigated. Results with two photolytic NO₂ converters are presented. The first used radiation centered at 395 nm, a wavelength region commonly utilized in P-CL. The second used light at 415 nm, where the overlap with the HONO absorption spectrum and hence its photolysis rate are less. Mixing ratios of NO₂, NO_x and HONO entering and exiting the converters were quantified by Thermal Dissociation Cavity Ring-down Spectroscopy (TD-CRDS). Both converters exhibited high NO₂ conversion efficiency (CF_NO2; > 90%) and partial conversion of HONO. Plots of CF against flow rate were consistent with photolysis frequencies of 4.2 s^-1 and 2.9 s^-1 for NO₂ and 0.25 s^-1 and 0.10 s^?1 for HONO at 395 nm and 415 nm, respectively. CF_HONO was larger than predicted from the overlap of the emission and HONO absorption spectra. The results imply that measurements of NO₂ by P-CL marginally but systematically overestimate true NO₂ concentrations, and that this interference should be considered in environments with high HONO:NO₂ ratios such as the marine boundary layer or in biomass burning plumes.     

An intercomparison of ozone taken from the Copernicus atmosphere monitoring service and the second Modern-Era retrospective analysis for research and applications over China during 2018 and 2019

Spatiotemporal variations of ozone (O₃) taken from the Copernicus Atmosphere Monitoring Service (CAMS) and the second Modern-Era Retrospective Analysis for Research and Applications (MERRA-2) were intercompared and evaluated with ground and ozone-sonde observations over China in 2018 and 2019. Intercomparison of the surface ozone from CAMS and MERRA-2 reanalysis showed significant negative bias (CAMS minus MERRA-2, same below) at Tibetan Plateau of up to 80 µg/m³, and the average R² was about 0.6 across China. Evaluated with the ground observations from China National Environmental Monitoring Center (CNEMC), we found that CAMS and MERRA-2 reanalysis were capable of capturing the key patterns of monthly and diurnal variations of surface ozone over China except for the western region, and MERRA-2 overestimated the observations compared to CAMS. Vertically, the CAMS profiles overestimated the ozone-sonde from the World Ozone and Ultraviolet Radiation Data Center (WOUDC) above 200 hPa with the magnitude reaching up to 150 µg/m³, while little bias was found between the reanalysis and observations below 200 hPa. Intercomparison drawn from the vertical distribution between CAMS and MERRA-2 reanalysis showed that the negative bias appeared throughout the troposphere over China, while the positive bias emerged in the upper troposphere and lower stratosphere (UTLS) with high order of magnitude exceeding 100 µg/m³, indicating large uncertainties at higher altitudes. In summary, we concluded that CAMS reanalysis showed better agreement with the observations in contrast to MERRA-2, and the large discrepancy especially at higher altitudes between these two reanalysis datasets could not be ignored.     

Reactive uptake of NO2 on volcanic particles: A possible source of HONO in the atmosphere

The heterogeneous degradation of nitrogen dioxide (NO₂) on five samples of natural Icelandic volcanic particles has been investigated. Laboratory experiments were carried out under simulated atmospheric conditions using a coated wall flow tube (CWFT). The CWFT reactor was coupled to a blue light nitrogen oxides analyzer (NO_x analyzer), and a long path absorption photometer (LOPAP) to monitor in real time the concentrations of NO₂, NO and HONO, respectively. Under dark and ambient relative humidity conditions, the steady state uptake coefficients of NO₂ varied significantly between the volcanic samples probably due to differences in magma composition and morphological variation related with the density of surface OH groups. The irradiation of the surface with simulated sunlight enhanced the uptake coefficients by a factor of three indicating that photo-induced processes on the surface of the dust occur. Furthermore, the product yields of NO and HONO were determined under both dark and simulated sunlight conditions. The relative humidity was found to influence the distribution of gaseous products, promoting the formation of gaseous HONO. A detailed reaction mechanism is proposed that supports our experimental observations. Regarding the atmospheric implications, our results suggest that the NO₂ degradation on volcanic particles and the corresponding formation of HONO is expected to be significant during volcanic dust storms or after a volcanic eruption.     

The transport and retention of CQDs-doped TiO2 in packed columns and 3D printed micromodels

CQDs-doped TiO₂（C-TiO₂） has drawn increased attention in recent because of its excellent catalytic performance.Understanding the transport of C-TiO₂ in porous media is necessary for evaluating the environmental process of this new nanomaterial.Column experiments were used in this study to investigate ionic strength（IS）,dissolved organic matter（DOM）and sand grain size on the transport of C-TiO₂.The mobility of C-TiO₂ was inhibited by the incr...