Differential Absorption Spectroscopy Research Articles

Measurement report: Combined use of MAX-DOAS and AERONET ground-based measurements in Montevideo, Uruguay, for the detection of distant biomass burning

Abstract. Biomass burning releases large amounts of aerosols and chemical species into the atmosphere, representing a major source of air pollutants. Emissions and by-products can be transported over long distances, presenting challenges in quantification. This is mainly done using satellites, which offer global coverage and data acquisition for places that are difficult to access. In this study, ground-based observations are used to assess the abundance of trace gases and aerosols. On 24 November 2020, a significant increase in formaldehyde was observed with a Multi-AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) instrument located in Montevideo (Uruguay), and its vertical column densities reached values of 2.4×1016 molec. cm−2, more than twice the values observed during the previous days. This was accompanied by an increase in the aerosol levels measured by an AErosol RObotic NETwork (AERONET) photometer located at the same site. The aerosol optical depth (AOD) at 440 nm reached values close to 1, an order of magnitude larger than typical values in Montevideo. Our findings indicate that the increase was associated with the passage of a plume originating from distant biomass burning. This conclusion is supported by TROPOspheric Monitoring Instrument (TROPOMI) satellite observations as well as HYbrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) simulations. The profiles of the gases and aerosols retrieved from the MAX-DOAS observations are consistent with the HYSPLIT analysis, showing the passage of a plume over Montevideo on 24 November located at a height of ∼ 1.5 km. This corroborates the finding that biomass burning events occurring about 800 km north of Montevideo can affect the local atmosphere through long-distance emissions transport. This study underscores the potential of ground-based atmospheric monitoring as a tool for detection of such events. Furthermore, it demonstrates greater sensitivity compared to satellite when it comes to detection of relatively small amounts of carbonyls like glyoxal and formaldehyde.

Sensitive Detection of OCS Using Thermal Conversion Combined with Spectral Reconstruction Filtering Differential Optical Absorption Spectroscopy.

Carbonyl sulfide (OCS) is a toxic gas produced during industrial processes that poses risks to both human health and industrial equipment. Therefore, detecting OCS concentrations plays a crucial role in early hazard warning. This paper presents an online system for detecting OCS at the ppb level using thermal conversion and spectral reconstruction filtering differential optical absorption spectroscopy (SRF-DOAS). First, OCS, which is not suitable for DOAS due to its weak absorption characteristics, is completely transformed into SO2 with strong absorption characteristics under high-temperature conditions. Then, the spectral reconstruction filtering method (SRF) is proposed to eliminate the noise and interference. The core idea of the method is to arrange the spectrum according to the spectral intensity from small to large rather than wavelength, reconstructing the spectrum into a new spectrum with linear characteristics. The reconstructed spectrum can remove noise and interference by linear fitting and retain the characteristic of SO2 oscillation absorption. Next, we demonstrate the ability of the reconstructed spectral method to remove noise and interference by comparing the spectra of the inverse-reconstructed gas mixture and SO2. The relative deviation of 0.88% at 100 ppb and detection limit of 7.26 ppb*m for OCS were obtained using the SRF-DOAS method. Finally, the reliability of the system was confirmed by measurements of OCS concentrations in mixture gas of OCS and air, as well as in human exhaled breath.

An ultra-sensitive optical H2S sensor based on thermal conversion combined with UV-DOAS: Dynamic detection from ppm to ppb level

Hydrogen sulfide (H2S) as a common gas plays an important role in both industrial production and clinical pathology. Therefore, the realization of dynamic detection of trace H2S gas is of great significance. In this paper, an ultra-sensitive optical H2S sensor based on thermal conversion and ultraviolet differential optical absorption spectroscopy (UV-DOAS) is developed for dynamic measurement of H2S concentration. The H2S concentration can be derived from the measurement of the change in sulfur dioxide (SO2) concentration before and after conversion. First, the evaluation method of SO2 concentration based on UV-DOAS is presented, and the performance indicators of SO2 concentration measurement are given. Second, the conversion characteristics of H2S under different temperatures and flow rates are investigated, and H2S can be efficiently converted to SO2 in the flowing gas state by controlling the conversion conditions. Finally, the performance indicators of H2S sensor are evaluated. The sensor realizes H2S measurements with a detection limit of 14 ppb * m, while its sensitivity and reliability of measuring H2S concentration increase tenfold, making it suitable for dynamic measurements of trace H2S. In addition, the feasibility of the sensor for applications in atmospheric monitoring and human exhaled breath detection is demonstrated by practical tests.

Estimating emission flux of H2S from fumarolic fields using vertical sensor array system

The emission flux of volatiles from each fumarolic field in volcanic and geothermal areas can be used to evaluate the current state of magmatic activity and predict its future trends. The emission flux of SO2 has been quantified in many fumarolic fields using remote sensing techniques, such as differential optical absorption spectroscopy (DOAS). However, most of these remote sensing techniques are inapplicable to fumarolic fields emitting volatiles depleted in SO2 to which most of the geothermal fields are classified. In this study, we developed a vertical sensor array system to quantify the emission flux of H2S from each fumarolic field by integrating the cross-sectional distributions of H2S concentrations in the volcanic plume using the vertical sensor array system. In Iwo-yama of the Kirishima volcanic complex, the cross-sectional distribution of H2S concentrations was determined using the walking traverse method by moving the vertical sensor array system in the plume perpendicular to the direction of plume transport. The emission flux of SO2 (2.2 ± 0.4 ton SO2/day) was estimated from that of H2S using the walking traverse method (2.6 ± 0.5 ton H2S/day) and the molar ratio of the plume (SO2/H2S=0.45) corresponds well with that estimated optically by JMA. We concluded that the emission flux quantified using the vertical sensor array system was reliable. In the Oyunuma pond in the Kuttara volcano, the emission flux of H2S was quantified as 2.0 ton H2S/day through the fixed point method, wherein the vertical sensor array system was fixed in one point, whereas the cross sectional distribution of H2S in the plume was estimated using the natural variation in wind direction. The topography is often irregular and wind direction is variable in most fumarolic fields; thus, in general, the fixed point method should be more suitable to determine the emission flux of H2S from fumarolic fields, wherein H2S occupies a major portion of the total sulfur emission.

The investigation of retrieval method for aerosol and water vapor profiles based on MAX-DOAS technology

Simultaneously obtaining the vertical distribution and profile of aerosol and water vapor is crucial for in-depth understanding of the Earth's radiation balance, regional water cycle, and the causes of frequent haze weather in China. This study developed a system and inversion method based on multi-axis differential optical absorption spectroscopy (MAX-DOAS) to simultaneously retrieve tropospheric aerosol and water vapor profiles. The absorption of dioxy (O4) was obtained by multi-elevation measurement using the developed ground-based MAX-DOAS system. By minimizing a cost function combining an atmospheric radiative transfer model, aerosol extinction profiles were first inverted, followed by water vapor profiles. Optimized parameter selection in the look-up table method reduced reliance on prior profile information, enhancing pollutant distribution retrieval accuracy. In the monitoring period in Huaibei region, aerosols were mainly below 1.5 km, while water vapor concentrations decreased with altitude. Comparisons of water vapor vertical column densities (VCDs) retrieved through the look-up table method with the European Centre for Medium-Range Weather Forecasts(ECMWF) ERA5 model and geometric approximation showed good agreement, with correlation coefficients of 0.93 and 0.98, respectively. To comprehend water vapor sources at various vertical layers, a 24-h backward trajectory clustering analysis was conducted using the HYSPLIT model based on observed wind fields. Findings revealed that at 500 m altitude, water vapor primarily emanated from the southeast, whereas at 1 km and 2 km altitudes, it predominantly originated from the southwest. The study advances simultaneous tropospheric aerosol and water vapor profile retrieval, providing reliable technical support for the investigation of regional pollution.

MAX-DOAS observations of pollutant distribution and transboundary transport in typical regions of China

Studying the spatiotemporal distribution and transboundary transport of aerosols, NO2, SO2, and HCHO in typical regions is crucial for understanding regional pollution causes. In a 2-year study using multi-axis differential optical absorption spectroscopy in Qingdao, Shanghai, Xi'an, and Kunming, we investigated pollutant distribution and transport across Eastern China-Ocean, Tibetan Plateau-Central and Eastern China, and China-Southeast Asia interfaces. First, pollutant distribution was analyzed. Kunming, frequently clouded and misty, exhibited consistently high aerosol optical depth throughout the year. In Qingdao and Shanghai, NO2 and SO2, as well as SO2 in Xi'an, increased in winter. Elevated HCHO in summer in Shanghai and Xi'an, especially Xi'an, suggests potential ozone pollution issues. Subsequently, pollutant transportation across interfaces was studied. At the Eastern China-Ocean interface, the gas transport flux was the largest among other interfaces, with the outflux exceeding the influx, especially in winter and spring. The input of pollutants from the Tibetan Plateau to central-eastern China was larger than the output in winter and spring, with SO2 having the highest transport flux in winter. The pollution input from Southeast Asia to China significantly exceeded the output, with spring and winter inputs being 3.22 and 3.03 times the output, respectively. Lastly, the transportation characteristics of a pollution event at Kunming were studied. During this period, pollutants were transported from west to east, with the maximum SO2 transport flux at an altitude of 2.87 km equaling 27.74 µg/(m2·s). It is speculated that this pollution was caused by the transport from Southeast Asian countries to Kunming.

Research on Automatic Wavelength Calibration of Passive DOAS Observations Based on Sequence Matching Method

Passive differential optical absorption spectroscopy (DOAS) is widely used to monitor the three-dimensional distribution of atmospheric pollutants. However, the observational and retrieval accuracy of this technique is significantly influenced by the precise wavelength calibration of solar spectra. Current calibration methods face challenges in automation when dealing with complex remote-sensing conditions. We introduce a novel automatic wavelength calibration algorithm for passive DOAS based on sequence-matching technology to estimate the spectral parameters of the spectrometer channels, integrating advanced processing measures such as feature structure enhancement and sub-pixel interpolation. These measures significantly reduce the dependency on reference spectrum resolution and accurately correct even minor spectral shifts. We perform sensitivity experiments using synthetic spectra to determine optimal retrieval configurations, followed by field tests at four cities on the Yangtze River Delta, China, to calibrate and compare passive DOAS instruments of various resolutions. Comparative verification in these field studies demonstrated that our algorithm was suitable for rapid spectral calibration within a wider resolution range of 0.03 nm to 0.1 nm with a wavelength inversion error < 0.01 nm. This highlights the applicability and calibration precision of our algorithm.

Effect of TX-100 on solubilizing power of CTAB and CPC for H Acid: An experimental and computational analysis

The present research work investigates the solubility of an anionic dye 8-amino-1-naphthol-3,6-disulfonic acid (H Acid) within the micellar mediaof two cationic surfactants cetylpyridinium chloride (CPC) and cetyltrimethylammonium bromide (CTAB) as well as in the mixed micellar mediaof each cationic surfactant with Triton X-100 (TX-100). The data from differential absorption spectroscopy across a concentration range spanning from pre-micellar to post-micellar regions was used to determine the degree of solubilization by calculating the partition coefficient (Kx), binding constant (Kb) and Gibbs free energy associated with the relevant processes. Electrical conductivity of each cationic surfactant in the presence of H Acid was recorded in aqueous media and used to determine the CMC and subsequent thermodynamic parameters including entropy (ΔSm), enthalpy (ΔHm) and Gibbs free energy change (ΔGm) associated with the process of micellization. The computational analysis was carried out with GAUSSIAN 09 using a 6-311G + basis set with a DFT/ B3LYP hybrid approach and each set of energy minimization was executed to perform frequency calculations for Frontier molecular orbital analysis and to evaluate absorption spectra. Moreover, the molecular electrostatic potential surfaces (MESP) were also computed to find their suitable hydrophobic and hydrophilic interactions.

Application of bi-directional long short-term memory in separating NO and SO2 ultraviolet differential absorption spectrum signals

To safeguard the environment, it is crucial to monitor the emissions of nitrogen oxide (NO) and sulfur dioxide (SO2), harmful pollutants generated during fossil fuel combustion in industries. However, accurately measuring ultra-low concentrations of SO2 and NO remains a challenge. In this study, we developed an optical measurement system based on ultraviolet differential optical absorption spectroscopy (UV-DOAS) to address this issue. The 200–230 nm cross-sensitivity band was chosen for SO2 and NO. Experimental data with a mixed gas concentration range of 1–25 ppm for SO2 and NO was utilized. We proposed a fast algorithm based on Bi-directional Long Short-Term Memory (Bi-LSTM) to extract the differential optical density, overcoming the mutual interference between SO2 and NO. A nonlinear calibration model was employed to invert the separated differential absorption spectra and determine the gas concentrations. The results demonstrated a detection limit (DL) of 0.27 ppm and a full-scale error of 3.15 % for SO2, while for NO, the DL was 0.32 ppm and the full-scale error was 2.81 %. The uncertainties in SO2 and NO detection were calculated as 1.73 % and 1.96 %, respectively.

Vertical distribution characteristics and potential sources of atmospheric pollutants in the North China Plain basing on the MAX-DOAS measurement

The mechanism for the generation of atmospheric pollution sources can be further investigated through the examination of atmospheric evolution and diffusion characteristics. The authors of this study conducted a 3-month MAX-DOAS (multi-axis differential optical absorption spectroscopy) vertical observation in Shijiazhuang City, North China Plain, in the summer of 2020 in response to the long-standing air pollution issues in the region. The vertical distribution profiles of aerosol, NO2, HCHO, and CHOCHO were generated, and the inversion findings showed good agreement with the TROPOMI (tropospheric monitoring instrument) satellite remote sensing validation, demonstrating the validity and accuracy of the observations. The near-surface boundary layer is home to the majority of the NO2, HCHO, and CHOCHO species. The species’ daytime evolution trends varied, with the highest NO2 peaks occurring in the morning and evening commute, the highest HCHO peaks occurring in the morning at 10:00 a.m., and CHOCHO's concentration during the day declined. Two minor aerosol pollution processes took place in Shijiazhuang City during the summer observation period. The elevated concentrations of NO2, CO, and the PM2.5/PM10 ratio during the pollution processes suggest that anthropogenic emissions, particularly biomass burning, were responsible for the large number of fine particles generated during the pollution events. Based on the examination of pollutant concentration profiles and meteorological data, it was determined that local emissions and north wind transport were the primary causes of Shijiazhuang's high NO2 values. Meanwhile, the southern region of Shijiazhuang was primarily responsible for the majority of the potential sources of atmospheric HCHO, and local emissions were also a major factor affecting the high CHOCHO values. Shijiazhuang's local near-surface volatile organic compounds (VOCs) are mostly caused by human emissions, although biomass burning and its regional transportation have a greater influence on the middle and upper boundary layers. This study systematically sorted the evolution characteristics and potential sources of pollutants in Shijiazhuang City during the summer based on the joint observations of various pollutants, including NO2, HCHO, and CHOCHO. These results can be used to support the development of appropriate policies for the prevention and control of pollutants in the Shijiazhuang local area of the North China Plain.

Structure-property inquiry of UV-emitting Gd3+-activated phosphate glasses

Phosphate glasses containing Gd3+ ions as ultraviolet (UV) type B light emitters are of interest for applications in phototherapy lamps for treating skin diseases. The composition-structure-property relation in this type of glass systems is thus of interest from fundamental and applied perspectives. In this work, Gd3+-containing glasses were prepared by melting with 50P2O5-(50 – x)BaO-xGd2O3 (x = 0, 1, 2, 3, 4, 5 mol %) nominal compositions, and studied comprehensively by X-ray diffraction (XRD), densitometry, Raman spectroscopy, differential scanning calorimetry (DSC), dilatometry, optical absorption, and photoluminescence (PL) spectroscopy with emission dynamics appraisal. XRD supported the amorphous nature of the glasses, whereas the densities of the Gd3+-containing glasses were found to increase with Gd2O3 content. The Raman spectra evolution was indicative of glass depolymerization being induced by Gd3+ ions. DSC results showed that the glass transition temperatures increased with Gd3+ concentration while the glasses exhibited decreased susceptibility for crystallization. Dilatometry ultimately revealed a steady decrease in the coefficient of thermal expansion for the Gd3+-containing glasses indicating tighter networks were realized. The PL evaluation showed that the UVB emission intensity at 312 nm increased linearly with Gd3+ concentration, even though the 6P7/2 state lifetime reached a maximum for 2 mol % Gd2O3. The PL intensities finally showed strong linear correlations with the thermal parameters linked to the structural evolution thus supporting the interconnection between the properties.

Ground-based MAX-DOAS observations of formaldehyde and glyoxal in Xishuangbanna, China

Multi-axial differential optical absorption spectroscopy (MAX-DOAS) measurements were conducted in Xishuangbanna, Yunnan, China, between November 1, 2021 and June 30, 2022 to obtain vertical distributions of formaldehyde (HCHO) and glyoxal (CHOCHO). The observations show an increase in vertical column densities (VCDs) and volume mixing ratios (VMRs) for both HCHO and CHOCHO concentrations during periods of biomass combustion. The VCDs of HCHO and CHOCHO from TROPOMI are in good agreement with the MAX-DOAS observations. (R2HCHO = 0.71; R2CHOCHO = 0.70). Regarding seasonal variations, HCHO predominantly occupies the upper layer (400-800 m) during the biomass burning, possibly attributed to the formation of secondary HCHO as the plume ascends during combustion. CHOCHO is primarily found in the lower layer (0-200 m), suggesting a longer lifespan for HCHO compared to CHOCHO, preventing the latter from diffusing to higher altitudes. Concerning the daily variation patterns, both HCHO and CHOCHO VMRs exhibited peaks at 9:00 and 13:00, which were attributed to the nighttime accumulation and midday oxidation. Furthermore, we also investigated the sources of volatile organic compounds (VOCs) using the CHOCHO to HCHO ratio (RGF). During the period of biomass burning, there are minimal differences in the daily RGF across layers, indicating that biomass burning is the predominant source. During the non-biomass burning period, the daily RGF shows significant differences among layers, indicating that emissions from biological and anthropogenic sources primarily contribute during the period.

O3 sensitivity and vertical distribution of summertime HCHO, NO2, and SO2 in Shihezi, China

Shihezi City has experienced severe ozone pollution. The vertical observation of ozone precursors (NO2 and HCHO) and SO2 in this area was conducted by multi-axis differential optical absorption spectroscopy in summer, 2023. During this experiment, ozone was measured at an average concentration of 94.89 ± 37.46 μg/m3, and it mainly increased when the northerly wind dominated, accompanied by the increasing of its precursors. In addition, SO2 had a relatively high concentration and elevated with the rising ozone concentration, remarkably different from other cities in China. The average vertical distribution of HCHO in the ozone pollution period was a Gaussian type, with the peak value at about 0.2 km. In contrast, the vertical distribution of NO2 and SO2 decreased exponentially with the rise of vertical height, and their concentrations dropped rapidly within 0–1 km. The RFN range of the transitional regime in Shihezi City was [1.26, 2.80]. Given that ozone pollution mostly occurred when RFN was 1–2, the chemical production of near-surface ozone in Shihezi City was controlled by a transition regime. The RFN vertical pattern was Gaussian type and reached a maximal value at 400–600 m. RFN increased at the middle altitude (0.4–1.2 km), and the ozone formation was controlled by the transitional regime. RFN decreased above 1.2 km, and the photochemical ozone formation was mainly controlled by a VOCs-limited regime. This study provides an improved understanding of O3 precursors vertical distribution and O3 formation sensitivity in Shihezi City.

A universal model to predict yields of THMs and HAAs based on UV–Visible absorption spectra

Differential absorption spectroscopy (DAS) quantifies changes in the UV–Visible absorbance of dissolved organic matter (DOM) caused by reactions of its chromophores. As a result of its precision and sensitvity, DAS serves as a powerful tool for characterizing the formation of disinfection by-products (DBPs) in generated in DOM chlorination reactions. However, the nonlinear relationship between the intensity of DAS and DBP concentrations as well as the need to develop site-specific fitting parameters limit its practical applications. This study investigated the physico-chemical nature of DAS of chlorinated DOM through experimental measurements and theoretical calculations. Results of this study provide molecular-level evidence that electrophilic substitution reactions involving DOM reactive sites result in the emergence of DAS feaures ascribed to the "fast" chromophores. The ring opening in the cyclic enones-like structures which can be present either in the original DOM or are generated as intermediates in its chlorination, leads to the emergence of DAS features associated with the "slow" chromophores and high yields of DBPs. The kinetic study of chlorination of real waters reveals a strong linear relationship (R2 > 0.91) between ln([DBP]) and the long-wavelength (λ > 325 nm) parameter of the DAS, notably (ln(-DA350)). This relationship varies among different water sources due to the differences in the heterogeneity of Band A3 whose maximum is near 350 nm. Band A3 is one of the Gaussian bands that comprise the overall UV–Visible spectrum of DOM. A new function (f(−DA350)) is proposed in this study to quantify DBP formation. This function, which is determined by the Band A3's area, allows establishing a universal linear relationship between f(−DA350) and ln([THMs]), as well as f(−DA350) and ln([HAAs]), across various water sources. The findings of this study will stimulate further development of spectroscopy-based DBP monitoring technology for monitoring and optimization of water disinfection processes.

Vertical Characteristics of HCHO and NO2 in Suburban Shanghai: Understanding of Ozone formation sensitivity via Secondary HCHO

Abstract Since ozone (O3) pollution in China is on the rise, vertical distribution of nitrogen dioxide (NO2) and formaldehyde (HCHO) and their role towards O3 formation are critical towards designing O3 control strategies. Seasonal characteristics of aerosols, HCHO and NO2 were investigated over suburban Shanghai using Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) from June 2020 to May 2021. For HCHO, the highest average vertical mixing ratios (VMRs) were observed for summer (0.775 ppb), followed by autumn (0.719 ppb), spring (0.718 ppb) and winter (0.672 ppb) at ground level. Seasonal trends in NO2 VMRs were observed to be opposite to that of HCHO with peak values occurring during winter (2.212 ppb) at the ground level followed by autumn (1.881 ppb), spring (1.415 ppb) and summer (1.124 ppb). In vertical, aerosols depicted a Gaussian shape with a higher values between 0.2 - 0.5 km. An exponential decay in NO2 VMRs is observed from 0.0 km to 3.0 km while the integral component of HCHO was found to be concentrated up to 2.0 km particularly during summer months. The vertical distribution of NO2 in different seasons mainly appeared below 0.5 km, while that of HCHO appeared within the range of 0.2-1.0 km. Both aerosols and NO2 tend to be higher during haze days compared to non-haze days while HCHO was found to be higher during clear days owing to high photochemical activity on a clear day. Based on the ratio of HCHO to NO2 (RFN), this study attempted to quantify the vertical characteristics of O3 sensitivity for different seasons. The results indicated that the O3 sensitivity was VOC-limited both at lower (generally, 0.0 - 0.6 km) and higher heights (1.8 - 3.0 km) while some transition limited scenarios were found at middle height (0.7 – 1.7 km) particularly during daytime. The results depicted that secondary HCHO is a crucial factor controlling on O3 sensitivity over Shanghai where enhanced ratio of VOC limited regime was observed with secondary HCHO for all the seasons.

Vertical Evolution of Ozone Formation Sensitivity Based on Synchronous Vertical Observations of Ozone and Proxies for Its Precursors: Implications for Ozone Pollution Prevention Strategies.

Photochemical ozone (O3) formation in the atmospheric boundary layer occurs at both the surface and elevated altitudes. Therefore, the O3 formation sensitivity is needed to be evaluated at different altitudes before formulating an effective O3 pollution prevention and control strategy. Herein, we explore the vertical evolution of O3 formation sensitivity via synchronous observations of the vertical profiles of O3 and proxies for its precursors, formaldehyde (HCHO) and nitrogen dioxide (NO2), using multi-axis differential optical absorption spectroscopy (MAX-DOAS) in urban areas of the Beijing-Tianjin-Hebei (BTH), Yangtze River Delta (YRD), and Pearl River Delta (PRD) regions in China. The sensitivity thresholds indicated by the HCHO/NO2 ratio (FNR) varied with altitude. The VOC-limited regime dominated at the ground level, whereas the contribution of the NOx-limited regime increased with altitude, particularly on heavily polluted days. The NOx-limited and transition regimes played more important roles throughout the entire boundary layer than at the surface. The feasibility of extreme NOx reduction to mitigate the extent of the O3 pollution was evaluated using the FNR-O3 curve. Based on the surface sensitivity, the critical NOx reduction percentage for the transition from a VOC-limited to a NOx-limited regime is 45-72%, which will decrease to 27-61% when vertical evolution is considered. With the combined effects of clean air action and carbon neutrality, O3 pollution in the YRD and PRD regions will transition to the NOx-limited regime before 2030 and be mitigated with further NOx reduction.

Ultrasensitive Online NO Sensor Based on a Distributed Parallel Self-Regulating Neural Network and Ultraviolet Differential Optical Absorption Spectroscopy for Exhaled Breath Diagnosis.

The concentration of fractional exhaled nitric oxide (FeNO) is closely related to human respiratory inflammation, and the detection of its concentration plays a key role in aiding diagnosing inflammatory airway diseases. In this paper, we report a gas sensor system based on a distributed parallel self-regulating neural network (DPSRNN) model combined with ultraviolet differential optical absorption spectroscopy for detecting ppb-level FeNO concentrations. The noise signals in the spectrum are eliminated by discrete wavelet transform. The DPSRNN model is then built based on the separated multipeak characteristic absorption structure of the UV absorption spectrum of NO. Furthermore, a distributed parallel network structure is built based on each absorption feature region, which is given self-regulating weights and finally trained by a unified model structure. The final self-regulating weights obtained by the model indicate that each absorption feature region contributes a different weight to the concentration prediction. Compared with the regular convolutional neural network model structure, the proposed model has better performance by considering the effect of separated characteristic absorptions in the spectrum on the concentration and breaking the habit of bringing the spectrum as a whole into the model training in previous related studies. Lab-based results show that the sensor system can stably achieve high-precision detection of NO (2.59-750.66 ppb) with a mean absolute error of 0.17 ppb and a measurement accuracy of 0.84%, which is the best result to date. More interestingly, the proposed sensor system is capable of achieving high-precision online detection of FeNO, as confirmed by the exhaled breath analysis.

Exploring Urban XCO2 Patterns Using PRISMA Satellite: A Case Study in Shanghai

As global warming intensifies, monitoring carbon dioxide (CO2) has increasingly become a focal point of research. Investigating urban XCO2 emission systems holds paramount importance, given the pivotal role of cities as major contributors to carbon emissions. Consequently, this study centers on urban locales, employing Shanghai as a case study for a comprehensive evaluation of regional XCO2 levels. We utilized high spatial resolution imagery from the PRecursore IperSpettrale della Missione Applicativa (PRISMA) satellite to conduct an XCO2 assessment over the Baoshan District with a 30 m spatial resolution from April 2021 to October 2022. Our XCO2 analysis was conducted in two steps. Firstly, we conducted a sensitivity analysis on key parameters in the inversion process, where cloud cover severely interfered with inversion accuracy. Therefore, we developed the Fmask 4.0 cloud removal and iterative maximum a posteriori differential optical absorption spectroscopy (FIMAP-DOAS) algorithm. This novel integration eliminated cloud interference during the inversion process, achieving high-precision CO2 detection in the region. Secondly, we compared the XCO2 of the region with Level-2 data from carbon monitoring satellites such as OCO-2. The comparison results showed a strong consistency, with a root mean squared error (RMSE) of 0.75 ppm for Shanghai XCO2 data obtained from the PRISMA satellite compared to OCO-2 Level-2 data and an RMSE of 1.49 ppm compared to OCO-3. This study successfully established a high-accuracy and high-spatial-resolution XCO2 satellite monitoring system for the Shanghai area. The efficacy of the FIMAP-DOAS algorithm has been demonstrated in CO2 monitoring and inversion within urban environments, with potential applicability to other cities.

Identification of O3 Sensitivity to Secondary HCHO and NO2 Measured by MAX-DOAS in Four Cities in China

This study analyzed the differences in ozone (O3) sensitivity in four different urban areas in China from February 2019 to January 2020 based on data on various near-surface pollutants from passive multi-axis differential optical absorption spectroscopy (MAX-DOAS) sites and nearby China National Environmental Monitoring Center (CNEMC) sites. Across the four cities, the nitrogen dioxide (NO2) and formaldehyde (HCHO) concentrations varied seasonally. Xianghe consistently displayed the lowest NO2 levels, suggesting reduced emissions compared to other cities. Guangzhou, a city with a robust economy and a high level of vehicle ownership, exhibited higher concentrations in spring. Summer brought elevated HCHO levels in Guangzhou, Xianghe, and Shenyang due to intensified photochemical processes. Autumn and winter showed higher HCHO concentrations in Guangzhou and Xianghe compared to Lanzhou and Shenyang. Overall, Guangzhou recorded the highest annual averages, due to its developed economy, while Xianghe’s lower NO2 levels were offset by the elevated HCHO due to higher O3 values. The analysis delved into primary and secondary HCHO sources across seasons and used carbon monoxide (CO) and O3 data. Xianghe showcased the dominance of secondary sources in summer and autumn, while Lanzhou was characterized by primary dominance throughout the year. Shenyang mirrored Xianghe’s evolution due to industrial emissions. In Guangzhou, due to the high levels of vehicular traffic and sunlight conditions, secondary sources predominantly influenced HCHO concentrations. These findings highlight the interplay between primary and secondary emissions in diverse urban settings. This study explored O3 sensitivity variations across seasons. Xianghe exhibited a balanced distribution among volatile organic compound (VOC)-limited conditions, nitrogen oxide (NOx)-limited conditions, and transitional influences. Lanzhou was mainly affected by VOC-limited conditions in winter and NOx-limited conditions in other seasons. Shenyang’s sensitivity varied with the seasons and was primarily influenced by transitions between VOCs and NOx in autumn and NOx-limited conditions otherwise. Guangzhou experienced varied influences. During periods of high O3 pollution, all regions were affected by NOx-limited conditions, indicating the necessity of NOx monitoring in these areas, especially during summer in all regions and during autumn in Xianghe and Guangzhou.

Development of broadband ultraviolet pulsed laser using Ce:LiCAF crystal to determine SO\(_2\) gas concentration by differential absorption spectroscopy

Earth’s atmosphere is a mixture of many gases which include pollutants such as SO2, NO2, NO, and O3 that have absorption in the ultraviolet (UV) wavelength region. Therefore, the development of broadband UV laser sources that are useful in a differential absorption spectroscopy (DOAS) system for environmental research is necessary. In this research, we present the DOAS system using the Ce:LiCAF laser for determining SO2 gas concentration in the atmosphere. The Ce:LiCAF laser has a full width at half maximum of 2 nm with a wavelength range from 286 to 291 nm and a peak wavelength of 288.5 nm. The results show that the DOAS system accurately determines the gas concentration with a measurement error of 6 %. This result can serve as the basis for developing practical DOAS systems with the ability to monitor a wide range of gasses and survey many other types of pollutants.