Raman lidar at 355 nm using low dead time photon counting for atmospheric aerosol measurements.

Photon counting is an effective way to enhance the dynamic range of the data acquisition system (DAQ) in Raman lidars. However, there exists a deficiency of relatively high dead times among current options, which necessitates an additional calibration procedure for the nonlinearity of the photon counting signal, thus leading to unanticipated errors. A field programmable gate array (FPGA)-based photon counting module has been proposed and implemented in a Raman lidar, offering two operational channels. Through observational experiments, it was determined that this module has an overall dead time of 1.13 ns taking advantage of the high-speed amplifier/discriminator pair and the logic design, a significant improvement compared to the 4.35 ns of a commercially used Licel transient recorder within the same counting rate range. This notably low dead time implies that its output maintains sufficient linearity even at substantially high counting rates. As a result, the need for a dead time calibration procedure prior to signal integration with the analog signal is eliminated, reducing uncertainty in the final integrated signal, and even in the retrieval result. The backscattering result of the comparison between this module and a transient recorder indicates that a more precise performance can be acquired benefiting from this hardware upgrading.

Potential of Mie-Fluorescence-Raman Lidar to Profile Chlorophyll a Concentration in Inland Waters.

Vertical distribution of phytoplankton is crucial for assessing the trophic status and primary production in inland waters. However, there is sparse information about phytoplankton vertical distribution due to the lack of sufficient measurements. Here, we report, to the best of our knowledge, the first Mie-fluorescence-Raman lidar (MFRL) measurements of continuous chlorophyll a (Chl-a) profiles as well as their parametrization in inland water. The lidar-measured Chl-a during several experiments showed good agreement with the in situ data. A case study verified that MFRL had the potential to profile the Chl-a concentration. The results revealed that the maintenance of subsurface chlorophyll maxima (SCM) was influenced by light and nutrient inputs. Furthermore, inspired by the observations from MFRL, an SCM model built upon surface Chl-a concentration and euphotic layer depth was proposed with root mean square relative difference of 16.5% compared to MFRL observations, providing the possibility to map 3D Chl-a distribution in aquatic ecosystems by integrated active-passive remote sensing technology. Profiling and modeling Chl-a concentration with MFRL are expected to be of paramount importance for monitoring inland water ecosystems and environments.

Volatile organic compounds in wintertime North China Plain: Insights from measurements of proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS).

The characteristics of wintertime volatile organic compounds (VOCs) in the North China Plain (NCP) region are complicated and remain obscure. VOC measurements were conducted by a proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS) at a rural site in the NCP from November to December 2018. Uncalibrated ions measured by PTR-ToF-MS were quantified and the overall VOC compositions were investigated by combining the measurements of PTR-ToF-MS and gas chromatography-mass spectrometer/flame ionization detector (GC-MS/FID). The measurement showed that although atmospheric VOCs concentrations are often dominated by primary emissions, the secondary formation of oxygenated VOCs (OVOCs) is non-negligible in the wintertime, i.e., OVOCs accounts for 42% ± 7% in the total VOCs (151.3 ± 75.6 ppbV). We demonstrated that PTR-MS measurements for isoprene are substantially overestimated due to the interferences of cycloalkanes. The chemical changes of organic carbon in a pollution accumulation period were investigated, which suggests an essential role of fragmentation reactions for large, chemically reduced compounds during the heavy-polluted stage in wintertime pollution. The changes of emission ratios of VOCs between winter 2011 and winter 2018 in the NCP support the positive effect of "coal to gas" strategies in curbing air pollutants. The high abundances of some key species (e.g. oxygenated aromatics) indicate the strong emissions of coal combustion in wintertime of NCP. The ratio of naphthalene to C8 aromatics was proposed as a potential indicator of the influence of coal combustion on VOCs.

Ozone pollution characteristics and sensitivity analysis using an observation-based model in Nanjing, Yangtze River Delta Region of China.

Ground-level ozone (O3) has become a critical pollutant impeding air quality improvement in Yangtze River Delta region of China. In this study, we present O3 pollution characteristics based on one-year online measurements during 2016 at an urban site in Nanjing, Jiangsu Province. Then, the sensitivity of O3 to its precursors during 2 O3 pollution episodes in August was analyzed using a box model based on observation (OBM). The relative incremental reactivity (RIR) of hydrocarbons was larger than other precursors, suggesting that hydrocarbons played the dominant role in O3 formation. The RIR values for NOX ranged from -0.41%/% to 0.19%/%. The O3 sensitivity was also analyzed based on relationship of simulated O3 production rates with reductions of VOC and NOX derived from scenario analyses. Simulation results illustrate that O3 formation was between VOCs-limited and transition regime. Xylenes and light alkenes were found to be key species in O3 formation according to RIR values, and their sources were determined using the Positive Matrix Factorization (PMF) model. Paints and solvent use was the largest contributor to xylenes (54%), while petrochemical industry was the most important source to propene (82%). Discussions on VOCs and NOX reduction schemes suggest that the 5% O3 control goal can be achieved by reducing VOCs by 20%. To obtain 10% O3 control goal, VOCs need to be reduced by 30% with VOCs/NOX larger than 3:1.

Investigation of carbonyl compound sources at a rural site in the Yangtze River Delta region of China.

Carbonyl compounds are important intermediates in atmospheric photochemistry, but their primary sources are still not understood well. In this work, carbonyls, hydrocarbons, and alkyl nitrates were continuously measured during November 2011 at a rural site in the Yangtze River Delta region of China. Mixing ratios of carbonyls and hydrocarbons showed large fluctuations during the entire measurement. The average level for total measured volatile organic compounds during the pollution episode from 25th to 27th November, 2011 was 91.6 ppb, about 7 times the value for the clean period of 7th-8th, November, 2011. To preliminarily identify toluene sources at this site, the emission ratio of toluene to benzene (T/B) during the pollution episode was determined based on photochemical ages derived from the relationship of alkyl nitrates to their parent alkanes. The calculated T/B was 5.8 ppb/ppb, significantly higher than the values of 0.2-1.7 ppb/ppb for vehicular exhaust and other combustion sources, indicating the dominant influence of industrial emissions on ambient toluene. The contributions of industrial sources to ambient carbonyls were then calculated using a multiple linear regression fit model that used toluene and alkyl nitrates as respective tracers for industrial emission and secondary production. During the pollution episode, 18.5%, 69.0%, and 52.9% of measured formaldehyde, acetaldehyde, and acetone were considered to be attributable to industrial emissions. The emission ratios relative to toluene for formaldehyde, acetaldehyde, and acetone were determined to be 0.10, 0.20 and 0.40 ppb/ppb, respectively. More research on industrial carbonyl emission characteristics is needed to understand carbonyl sources better.

Characteristics, sources of volatile organic compounds, and their contributions to secondary air pollution during different periods in Beijing, China.

Continuous measurements of volatile organic compounds (VOCs), ozone (O3), fine particulate matter (PM2.5), and related parameters were conducted between April 2020 and March 2021 in Beijing, China, to characterize potential sources of VOCs and their impacts on secondary organic aerosols (SOAs) and O3 levels. The annual average mixing ratio of VOCs was 17.4 ± 10.1 ppbv, with monthly averages ranging from 11.6 to 25.2 ppbv. According to the empirical kinetic modeling approach (EKMA), O3 formation during O3 season was "VOCs-limited", while it was in a "transition" regime during O3 pollution episodes. In the O3 season, higher ozone formation potential (OFP) of m/p-xylene, o-xylene, toluene, isopentane, and n-butane were evident during O3 pollution episodes, in line with the increasing contributions of solvent usage and coating, as well as gasoline evaporation to OFP obtained through a matrix factorization model (PMF). Aromatics contributed the most to the secondary organic aerosol formation potential (SOAFP). In the non-O3 season, the contribution of vehicle exhaust to SOAFP elevated on hazy days, thereby revealing the importance of traffic-derived VOCs for PM2.5 pollution. Our results indicate that the prior control of different VOC sources should vary by season, thereby facilitating the synergistic control of O3 and PM2.5 in Beijing.

Pollution characteristics, sources, and photochemical roles of ambient carbonyl compounds in summer of Beijing, China.

Ambient carbonyls are important precursors of radicals and ground-level ozone (O3). In this study, sources, precursors, and impacts on radicals and O3 of carbonyls were investigated based on online observations of volatile organic compounds (VOCs) at an urban site in Beijing during June 2021. Carbonyls accounted for 36% and 42% of mixing ratios and OH reactivity for total measured VOCs, respectively. Formaldehyde was the most abundant carbonyl, with the mean level of 4.13 ± 2.28 ppb. Source apportionment results based on the multi linear regression (MLR) method suggested that secondary production contributed 41%, 25%, 36%, and 30% of formaldehyde, acetaldehyde, propanal, and acetone, respectively. Key precursors of carbonyls were then identified based on the calculation of their production rates. It was found that alkenes contributed 59%-80% of aldehydes production. Impacts of carbonyls on HOx radicals (OH and HO2) and O3 production were explored using a box model based on observations (OBM). Photolysis of HONO, formaldehyde, and O3 were the dominant primary sources of HOx radicals during daytime of O3 pollution days, with average relative contributions of 52%, 28%, and 19% to the total primary production rate of HOx, respectively. Aldehydes accounted for 32% (20% from formaldehyde) of average HOx removal rates. The relative incremental reactivity (RIR) values of NOx determined by the OBM were negative, suggesting that the O3-VOCs-NOx sensitivity was in the VOCs-limited regime. Using the observed concentrations of carbonyls as constraints of OBM, the absolute values of RIR for NOx tended to increase but those for anthropogenic VOCs tended to decrease. Formaldehyde showed the largest RIR value for anthropogenic VOCs during O3 pollution days. These findings indicated the important impacts of carbonyls on O3 production and O3-VOCs-NOx sensitivity.

Roll-to-Roll Production of Electrocatalysts Achieving High-Current Alkaline Water Splitting.

Scalable production of electrocatalysts capable of performing high-current water splitting is crucial to support green energy utilization. We adopted acidic redox-assisted deposition (ARD) to realize the continuous roll-to-roll fabrication of a strongly adherent cobalt manganese oxyhydroxide (CMOH) film on Ni foam under ambient conditions in water. The as-fabricated products show uniform CMOH coverage and oxygen evolution activities with dimensions as large as 5 m length by 0.25 m width. Also, we converted CMOH into a metallic form (denoted as CM) with the preserved high adhesion to serve as a high-current hydrogen evolution electrocatalyst. Our results reveal that the insufficient adhesion of powder forms electrocatalysts (i.e., Pt and RuO2 as benchmarks), even with the binder, at high-current electrolysis (>1000 mA) can be solved using the fabricated CM||CMOH cell. With an active area of 1 cm × 1 cm assembly in anion exchange membrane (AEM) electrolyzers, we observed the remarkable record of alkaline electrolysis stably at 5000 mA. This result established a new benchmark record on the high-current water splitting research.

[Source Apportionment of Ambient Carbonyl Compounds Based on a PMF and Source Tracer Ratio Method: A Case Based on Observations in Nanjing].

Ambient carbonyl compounds play an important role in tropospheric atmospheric chemistry. Primary emissions and photochemical formation are both sources of carbonyls, and therefore it is challenging work to analyze their sources. In this study, carbonyl sources were apportioned using the source tracer ratio method (STR) and positive matrix factorization model (PMF) based on offline carbonyls observations at a site in Nanjing during March 2017. Eleven carbonyl compounds were detected, and their total concentrations were in the range of 2.57×10-9-22.83×10-9. Formaldehyde, acetaldehyde, and acetone were the main components, accounting for 36.8%, 21.6%, and 18.5% of the average concentration of eleven carbonyl compounds, respectively. The influences of tracer selection and background concentrations on the results of source apportionment using the STR method based on comparing the results of acetylene and toluene as tracers and the 5th and 10th percentages as background concentrations are presented. Five sources were resolved by PMF, including traffic emission, the petrochemical & chemical industry, paint & solvent use, secondary formation & background, and the chemical industry. Secondary formation & background sources were the largest contributors of carbonyl compounds, contributing 56.4%, 48.2%, and 58.3% to formaldehyde, acetaldehyde, and acetone, respectively. By comparing the carbonyl source apportionment results by STR and PMF, it was found that the STR depends on the selection of tracers. When the STR is applied in the areas with complex sources, it is difficult to use a tracer to indicate anthropogenic source emissions, and therefore it is not a suitable method for carbonyl source apportionment.

[Ratios of Volatile Organic Compounds in Ambient Air of Various Cities of China].

Volatile organic compounds (VOC) ratios in urban atmosphere could provide important information on VOC data quality, sources, and options for removal processes. Based on seven VOC measurement datasets, useful VOC ratios were calculated using four methods, including orthogonal distance(ODR), linear regression, geometric mean, mean, and frequency distribution. Ambient levels of m,p-xylene and o-xylene from the seven datasets showed good correlation with r ranging from 0.975 to 0.997, and their ratios (m,p-xylene/o-xylene) were close, with values of 2.78-3.05, indicating therefore that the ratio of m,p-xylene/o-xylene could be used to evaluate the quality of ambient measurement data in urban atmospheres. In addition, ratios of toluene versus benzene (T/B) and propane versus ethane (P/E) in different cities were compared, to investigate VOC sources in China. The highest T/B ratios were found in Shanghai and Guangzhou City, with values of 2.37 and 1.78, respectively, higher than the result from a tunnel study (1.52), suggesting the important influence of paint and solvent use. The T/B value for Beijing City during summer was close to that from the tunnel study, while the T/B ratios for Chengdu, Beijing during winter, and Chongqing were lower, with values ranging from 0.744 to 1.36, suggesting possible influences from biomass burning and coal combustion. The P/E value in Guangzhou was 1.27, significantly higher than the range of 0.270 to 0.645 found in other cities. The OH exposure in different cities were calculated based on o-xylene/ethylbenzene (X/E), with values ranging from 2.70×1010 to 4.45×1010 molecule·cm-3·s.

[VOCs Characteristics and Sources Apportionment in Yixing City During the G20 Summit].

A continuous measurement was conducted in Yixing city urban area from 24th August to 15th September using TH-300B continuous online GC-MS instrument during G20 summit in Hangzhou, 2016. The VOCs average mass concentrations of alkane, alkene, aromatic, acetylene, haloalkane hydrocarbons, OVOC and acetonitrile were 11.00×10-9, 1.93×10-9, 5.78×10-9, 1.23×10-9, 4.16×10-9, 10.37×10-9, 0.27×10-9, respectively. The photochemical reaction activity was calculated by using the maximum potential coefficient of Ozone Formation Potential. Alkene and aromatic hydrocarbons were the most active components of OFP. By applying the positive matrix factorization(PMF)model, five major factors were extracted to identify the sources of NMHCs in Yixing city, including industry(42.2%),vehicle exhaust(17.9%), fuel evaporation(20.8%), paint/solvent usage(7.0%)and plant(12.1%). Combined with the conditional probability function(CPF) analysis, source of anthropogenic pollution was related to the distribution of industrial enterprises in the northwest and southeast, while the plant source was related to the forest hilly region of Southwest Yixing city. The effect of air pollutant emission reduction showed that the primary emission air pollutants had declined significantly during the strict control period from 1th to 6th September in G20 summit,2016, and the industry proportion was reduced to 30.5%, whereas the plant proportion increased to 16.8%.

[Correlation Analysis Between Characteristics of VOCs and Ozone Formation Potential in Summer in Nanjing Urban District].

Volatile organic compounds (VOCs) is an important precursor of photochemical ozone pollution (O3) in the atmosphere. Their concentration variation directly affects the characteristics of the ozone pollution. The concentration, speciation of VOCs, ozone and its precursors in Nanjing were analyzed and measured using online gas detection systems in August 2013. VOCs/NOx discriminant method was used to get the sensitive control factors of ozone. The results showed that the averaged volume fraction of VOCs was 52. 05 x 10(-9), and the largest one reached 200 x 10(-9) in Nanjing urban district. The order of volume fraction of each species VOCs was alkane > oxygen-containing VOCs > alkene > aromatics. The averaged concentration of ozone was 76.5 microg x m(-1) and the exceeding concentration of hourly standard was 5.9%. The change trends of ozone precursors VOCs and NOx were basically identical and Ozone showed the obvious negative correlation during the period of high concentrations of ozone. There were some differences in the concentrations of the same VOCs in different ozone concentration periods. The ozone generation in Nanjing urban district was sensitive to VOCs, and Nanjing belonged to VOCs control area in summer.

Regional contribution to PM1 pollution during winter haze in Yangtze River Delta, China.

To quantify regional sources contributing to submicron particulate matter (PM1) pollution in haze episodes, on-line measurements combining two modeling methods, namely, positive matrix factorization (PMF) and backward Lagrangian particle dispersion modeling (LPDM), were conducted for the period of one month in urban Nanjing, a city located in the western part of Yangtze River Delta (YRD) region of China. Several multi-day haze episodes were observed in December 2013. Long-range transport of biomass burning from the southwestern YRD region largely contributed to PM1 pollution with more than 25% of total organics mass in a lasting heavy haze. The LPDM analysis indicates that regional transport is a main source contributing to secondary low-volatility production. The high-potential source regions of secondary low-volatility production are mainly located in areas to the northeast of the city. High aerosol pollution was mainly contributed by regional transport associated with northeastern air masses. Such regional transport on average accounts for 46% of total NR-PM1 with sulfate and aged low-volatility organics being the largest fractions (>65%).

Autonomous detection of pulmonary nodules on CT images with a neural network-based fuzzy system.

In this paper, a novel extension of neural network-based fuzzy model has been proposed to detect lung nodules. The proposed model can automatically identify a set of appropriate fuzzy inference rules, and refine the membership functions through the steepest gradient descent-learning algorithm. Twenty-nine clinical cases involving 583 thick section CT images were tested in this study. Receiver operating characteristic (ROC) analysis was used to evaluate the proposed autonomous pulmonary nodules detection system and yielded an area under the ROC curve of Azs=0.963. The overall detection sensitivity of the proposed method was 89.3% (with p-value less than 0.001), and the false positive was as low as 0.2 per image. This result demonstrates that the proposed neural network-based fuzzy system resolves the most suitable fuzzy rules, improves the detection rate, and reduces false positives compared to other approaches. The proposed system is fully automated with fast processing speed. The studies have shown a high potential for implementation of this system in clinical practice as a CAD tool.

[Spatial and temporal variations of ambient carbonyl compounds in Beijing and its surrounding areas].

Concentrations of 23 carbonyl compounds were measured by DNPH/HPLC method at 38 sites within Beijing and its surrounding areas on June 24, July 22, August 22, September 14 in 2010 and January 13, 2011. The average mixing ratios of total carbonyl compounds in Beijing were (16.38 +/- 6.03) x 10(-9) and (8.50 +/- 5.27) x 10(-9) in summer and winter; and the average mixing ratios in surrounding cites were (13.19 +/- 5.71) x 10(-9) and (13.05 +/- 2.44) x 10(-9) in summer and winter, respectively. The most abundant carbonyl compound was formaldehyde, followed by acetaldehyde and acetone, the sum of these 3 species accounted for 78% to 91% of the total mixing ratio of carbonyl compounds. The average mixing ratio in summer was significant higher than that in winter, and higher in morning (09:00-12:00) hours than in afternoon (13:00-16:00). The spatial distributions for carbonyl compounds showed that: in summer, high mixing ratios were typically found in city center; while in winter, a building-up trend was found from northwest to southeast, driving by the prevailing northwest wind. In summer, vehicular exhaust had important contributions to ambient carbonyls, and combined with the adverse weather conditions and the strong photochemical production, resulted in carbonyls pollutions; in winter, directly emissions were the main sources of carbonyls, such as vehicular exhaust and coal burning.