Precipitation regime changes in High Mountain Asia driven by cleaner air.

High Mountain Asia (HMA) has experienced a spatial imbalance in water resources in recent decades, partly because of a dipolar pattern of precipitation changes known as South Drying-North Wetting1. These changes can be influenced by both human activities and internal climate variability2,3. Although climate projections indicate a future widespread wetting trend over HMA1,4, the timing and mechanism of the transition from a dipolar to a monopolar pattern remain unknown. Here we demonstrate that the observed dipolar precipitation change in HMA during summer is primarily driven by westerly- and monsoon-associated precipitation patterns. The weakening of the Asian westerly jet, caused by the uneven emission of anthropogenic aerosols, favoured a dipolar precipitation trend from 1951 to 2020. Moreover, the phase transition of the Interdecadal Pacific Oscillation induces an out-of-phase precipitation change between the core region of the South Asian monsoon and southeastern HMA. Under medium- or high-emission scenarios, corresponding to a global warming of 0.6-1.1 °C compared with the present, the dipolar pattern is projected to shift to a monopolar wetting trend in the 2040s. This shift in precipitation patterns is mainly attributed to the intensified jet stream resulting from reduced emissions of anthropogenic aerosols. These findings underscore the importance of considering the impact of aerosol emission reduction in future social planning by policymakers.

Method development for thermal desorption-gas chromatography-tandem mass spectrometry (TD-GC-MS/MS) analysis of trace level fluorotelomer alcohols emitted from consumer products.

The scientific foundation for per- and polyfluoroalkyl substances (PFAS) measurements in water, soils, sediments, biosolids, biota, and outdoor air has rapidly expanded; however, there are limited efforts devoted to developing analytical methods to measure vapor-phase PFAS in indoor air. A gas chromatography-tandem mass spectrometry (GC-MS/MS) method coupled with thermal desorption (TD) sorbent tube analysis was developed to quantify trace levels of fluorotelomer alcohols (FTOHs) emitted from consumer products in the indoor environment. Method evaluation included determination of instrument detection limits (IDLs), quality assurance checks of target standards purchased from different vendors, sample loss during storage, and TD sorbent breakthrough with tubes coupled in-series. The IDLs for TD-GC-MS/MS analyses ranged from 0.07 - 0.09 ng/tube. No significant loss of FTOHs was observed during stability tests over 28 days with relative standard deviations (RSDs) of spiked TD tubes ranging from 3.1 - 7.7% and the RSDs of polypropylene copolymer vial storage of standard solutions ranging from 4.3 - 8.4%. TD tube breakthrough was minimal with recovered FTOHs in the second tubes <1% of the spiked concentrations in the first tubes with carrier gas volume up to 20 L. The method has been applied to determine FTOH emissions from three consumer products in micro-scale chambers. A liquid stone cleaner/sealer product contained the highest levels of 6:2, 8:2, and 10:2 FTOHs, while the mattress pad products contained lower levels of 8:2 and 10:2 FTOHs. The emission parameters, including the initial emission factors and first order decay rate constants, were obtained based on the experimental data. The developed methods are sensitive and specific for analysis of all four target FTOHs (4:2, 6:2, 8:2, 10:2 FTOHs) with chamber testing. The methods can be extended to indoor air sampling and could be applicable to ambient air sampling.

Multi-Sensor Platform for Predictive Air Quality Monitoring.

Air quality monitoring is a very important aspect of providing safe indoor conditions, and carbon dioxide (CO2) is one of the pollutants that most affects people's health. An automatic system able to accurately forecast CO2 concentration can prevent a sudden rise in CO2 levels through appropriate control of heating, ventilation and air-conditioning (HVAC) systems, avoiding energy waste and ensuring people's comfort. There are several works in the literature dedicated to air quality assessment and control of HVAC systems; the performance maximisation of such systems is typically achieved using a significant amount of data collected over a long period of time (even months) to train the algorithm. This can be costly and may not respond to a real scenario where the habits of the house occupants or the environment conditions may change over time. To address this problem, an adaptive hardware-software platform was developed, following the IoT paradigm, with a high level of accuracy in forecasting CO2 trends by analysing only a limited window of recent data. The system was tested considering a real case study in a residential room used for smart working and physical exercise; the parameters analysed were the occupants' physical activity, temperature, humidity and CO2 in the room. Three deep-learning algorithms were evaluated, and the best result was obtained with the Long Short-Term Memory network, which features a Root Mean Square Error of about 10 ppm with a training period of 10 days.

High-Precision Trace Hydrogen Sensing by Multipass Raman Scattering.

Despite its growing importance in the energy generation and storage industry, the detection of hydrogen in trace concentrations remains challenging, as established optical absorption methods are ineffective in probing homonuclear diatomics. Besides indirect detection approaches using, e.g., chemically sensitized microdevices, Raman scattering has shown promise as an alternative direct method of unambiguous hydrogen chemical fingerprinting. We investigated the suitability of feedback-assisted multipass spontaneous Raman scattering for this task and examined the precision with which hydrogen can be sensed at concentrations below 2 parts per million. A limit of detection of 60, 30, and 20 parts per billion was obtained at a pressure of 0.2 MPa in a 10-min-long, 120-min-long, and 720-min-long measurement, respectively, with the lowest concentration probed being 75 parts per billion. Various methods of signal extraction were compared, including asymmetric multi-peak fitting, which allowed the resolution of concentration steps of 50 parts per billion, determining the ambient air hydrogen concentration with an uncertainty level of 20 parts per billion.

Experimental Determination of Air/Water Partition Coefficients for 21 Per- and Polyfluoroalkyl Substances Reveals Variable Performance of Property Prediction Models.

Per- and polyfluoroalkyl substances (PFAS) are a group of chemicals of high environmental concern. However, reliable data for the air/water partition coefficients (Kaw), which are required for fate, exposure, and risk analysis, are available for only a few PFAS. In this study, Kaw values at 25 °C were determined for 21 neutral PFAS by using the hexadecane/air/water thermodynamic cycle. Hexadecane/water partition coefficients (KHxd/w) were measured with batch partition, shared-headspace, and/or modified variable phase ratio headspace methods and were divided by hexadecane/air partition coefficients (KHxd/air) to obtain Kaw values over 7 orders of magnitude (10-4.9 to 102.3). Comparison to predicted Kaw values by four models showed that the quantum chemically based COSMOtherm model stood out for accuracy with a root-mean-squared error (RMSE) of 0.42 log units, as compared to HenryWin, OPERA, and the linear solvation energy relationship with predicted descriptors (RMSE, 1.28-2.23). The results indicate the advantage of a theoretical model over empirical models for a data-poor class like PFAS and the importance of experimentally filling data gaps in the chemical domain of environmental interest. Kaw values for 222 neutral (or neutral species of) PFAS were predicted using COSMOtherm as current best estimates for practical and regulatory use.

Argon pharmacokinetics: a solubility measurement technique.

The noble gas argon has demonstrated biological activity that may prove useful as a medical intervention. Pharmacokinetics, the disposition of the drug molecule in the body through time, is fundamental necessary knowledge to drug discovery, development and even post-marketing. The fundamental measurement in pharmacokinetic studies is blood concentration of the molecule (and its metabolites) of interest. While a physiologically based model of argon pharmacokinetics has appeared in the literature, no experimental data have been published. Thus, argon pharmaceutical development requires measurement of argon solubility in blood. This paper reports on the development of a technique based on mass spectrometry for measuring argon solubility in liquids, including blood, to be further employed in pharmacokinetics testing of argon. Based on a prototype, results are reported from sensitivity experiments using ambient air, water and rabbit blood. The key takeaway is that the system was sensitive to argon during all of the testing. We believe the technique and prototype of the quadrupole mass spectrometer gas analyzer will be capable of inferring argon pharmacokinetics through the analysis of blood samples.

A supplementary assessment system of AQI-V for comprehensive management and control of air quality in chemical industrial parks.

Volatile organic compounds (VOCs) are the dominant pollutants in industrial parks. However, they are not generally considered as part of the air quality index (AQI) system, which leads to a biased assessment of pollution in industrial parks. In this study, a supplementary assessment system of AQI-V was established by analyzing VOCs characteristics with vehicle-mounted PTR-TOFMS instrument, correlation analysis and the standards analysis. Three hourly and daily scenarios were considered, and the hierarchical parameter setting was further optimized by field application. The hourly and daily assessments revealed the evaluation factors for the discriminability of different air quality levels, practiced value for regional air quality improvement, and the reservation of general dominant pollutants. Finally, the universality testing in ZPIP successfully recognized most of the peaks, with 54.76%, 38.39% and 6.85% for O3, VOCs and NO2 as the dominant pollutant, and reflected the daily ambient air quality condition, together with the dominant pollutant. The AQI-V system with VOCs sub-index is essential for air quality evaluation in industrial parks, which can further provide scientific support to control the pollution of VOCs and the secondary pollutant, therefore significantly improve the air quality in local industrial parks.

Detecting Microbiology in the Upper Atmosphere: Relative-Velocity Filtered Sampling.

The purpose of this article is to reopen from a practical perspective the question of the extent in altitude of Earth's biosphere. We make a number of different suggestions for how searches for biological material could be conducted in the mesosphere and lower thermosphere, colloquially referred to as the "ignore-osphere" because it has been generally ignored in the meteorological community compared to other regions. Relatively recent technological advances such as CubeSats in very low Earth orbit or more standard approaches such as the rocket-borne MAGIC meteoric smoke particle sampler are shown as potentially viable for sampling biological material in the ignore-osphere. The issue of contamination is discussed, and a potential solution to the problem is proposed by means of a new detector design that filters for particles based on their size and relative velocity to the detector.

Virus hunters test new surveillance tools.

Ropes, drones, insects, and dust cloths could make monitoring faster, safer, and cheaper.

Atmospheric wet deposition of mercury in urban Jinan, eastern China: Speciation, scavenging process and potential sources.

Understanding the speciation and related influence factors of Hg in wet deposition is important to predict the fate and transport of mercury in the atmosphere. In this study, event-based samples of rainwater were collected for one year in Jinan, a northern city in eastern China. The volume-weighted mean concentration of total mercury (THg) in rainwater was 34.8 ng L-1, comparable to levels in some inland cities in China and were significantly higher than those in North America, Korea and Japan. Most of the Hg in rainwater was associated with particulates, accounted for 15.2-92.9% of THg with a mean of 66.9%, which might be attributed to the scavenging effects of high particulate-bound mercury concentrations in ambient air in urban Jinan. Dissolved mercury (DHg) accounted for 33.1% of THg, in which Hg(OH)2, HgClOH, HgCl2 and Hg(NH3)22+ are the dominant species based on the chemical equilibrium modeling simulations. THg concentrations in rainwater decreased as the rainfall amount increased owing to the dilution effect and 5 mm rainfall might be a threshold for the full wash-out capability of atmospheric Hg. For a continuous rain event, the proportion of DHg in THg could increase from 7.1% to 84.8% with the rainfall processing, especially for the species of HgClOH and HgCl2 under the influence of rainwater pH. Positive matrix factorization (PMF) analysis suggested that the major sources of Hg in rainwater were combustion emissions, marine sources, industrial emissions, as well as complexation process, which contributed to 51.4%, 24.7%, 12.2%, and 11.7% of the THg, respectively. For the specific species, the main sources varied with different Hg species, in which combustion emissions contributed one third to one half of each species sum to particulate mercury (PHg), HgClOH, HgCl2, HgBrOH and HgBrCl followed by marine sources and industrial emissions. Cluster analysis of backward trajectories revealed that polluted air masses, transported from southeast Shandong, Anhui and Jiangsu Provinces, as well as Beijing-Tianjin-Hebei region, contributed to high Hg concentration in rainwater in Jinan.

Effect of crude oil exploration and exploitation activities on soil, water and air in a Nigerian community.

The continuous degradation of environmental ecosystems (land, water and soil) resulting from crude oil exploration and exploitation activities continues to gain global attention. This study investigates the effects of crude oil exploration and exploitation activities on soil, water and air in the study area. Soil samples were collected in three replicates at depths of 0-15 and 15-30 cm at sampling distances of 20, 100 and 200 m a from core oil exploitation operation area and a control point. Water samples were also taken from within the study area and analyzed using standard procedures. Major pollutants concentrations of particulate matter (PM2.5 and PM10) of the air were also measured using Air Quality Index (AQI). The results reveal that the soil, water and air parameters measured mostly at 20 m from the core oil operation area compromise the allowable standards provided for healthy living. In the same manner, some results at 100 and 200 m were slightly higher than the recommended values in some cases of heavy metals and bacteria activities in the soil. The AQI at 20 m was far above the permissible limit provided by the Environmental Protection Agency while others are gradually drawing towards the limit given for each pollutant. To safeguard the health of the residents of the host community and oil field workers, there is a need for proper and frequent environmental monitoring and assessment by authorized regulatory bodies in Nigeria. This will prevent any future exposure which may endanger the lives of the dwellers.

A High-Precision Mid-Infrared Spectrometer for Ambient HNO3 Measurements.

Precise and accurate measurements of ambient HNO3 are crucial for understanding various atmospheric processes, but its ultra-low trace amounts and the high polarity of HNO3 have strongly hindered routine, widespread, direct measurements of HNO3 and restricted field studies to mostly short-term, localized measurement campaigns. Here, we present a custom field-deployable direct absorption laser spectrometer and demonstrate its analytical capabilities for in situ atmospheric HNO3 measurements. Detailed laboratory characterizations with a particular focus on the instrument response under representative conditions for tropospheric measurements, i.e., the humidity, spectral interference, changing HNO3 amount fractions, and air-sampling-related artifacts, revealed the key aspects of our method: (i) a good linear response (R2 > 0.98) between 0 and 25 nmol·mol−1 in both dry and humid conditions with a limit of detection of 95 pmol·mol−1; (ii) a discrepancy of 20% between the spectroscopically derived amount fractions and indirect measurements using liquid trapping and ion chromatography; (iii) a systematic spectral bias due to water vapor. The spectrometer was deployed in a three-week field measurement campaign to continuously monitor the HNO3 amount fraction in ambient air. The measured values varied between 0.1 ppb and 0.8 ppb and correlated well with the daily total nitrates measured using a filter trapping method.

On-line trace monitoring of volatile halogenated compounds in air by improved thermal desorption-gas chromatography-mass spectrometry.

Volatile halogenated compounds (VHCs) are important industrial chemicals and play a crucial role in potential stratospheric ozone-depletion and global warming. Profiling of VHCs is of great significance but replete with challenges due to the species' richness and diversity. In this study, we developed a novel method employing water removal mode combined with thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) for on-line measurement of VHCs at the ultratrace level. By removing water with Nafion dryer tandem cold trap device, VHCs could achieve better separation and identification, and detection precision of VHCs lower than 10%. The proposed method exhibited limits of detection for VHCs ranging from 0.1 to 6.2 pptv. Benefiting from the improved trapping efficiency due to water removal, we successfully quantified 34 VHCs at the Shangdianzi background station and achieved a comprehensive assessment of VHCs in ambient air.

Variation of volatile organic compound levels within ambient room air and its impact upon the standardisation of breath sampling.

The interest around analysis of volatile organic compounds (VOCs) within breath has increased in the last two decades. Uncertainty remains around standardisation of sampling and whether VOCs within room air can influence breath VOC profiles. To assess the abundance of VOCs within room air in common breath sampling locations within a hospital setting and whether this influences the composition of breath. A secondary objective is to investigate diurnal variation in room air VOCs. Room air was collected using a sampling pump and thermal desorption (TD) tubes in the morning and afternoon from five locations. Breath samples were collected in the morning only. TD tubes were analysed using gas chromatography coupled with time-of-flight mass spectrometry (GC-TOF-MS). A total of 113 VOCs were identified from the collected samples. Multivariate analysis demonstrated clear separation between breath and room air. Room air composition changed throughout the day and different locations were characterized by specific VOCs, which were not influencing breath profiles. Breath did not demonstrate separation based on location, suggesting that sampling can be performed across different locations without affecting results.

Lower degree of dissociation of pyruvic acid at water surfaces than in bulk.

Understanding the acid/base behavior of environmentally relevant organic acids is of key relevance for accurate climate modelling. Here we investigate the effect of pH on the (de)protonation state of pyruvic acid at the air-water interface and in bulk by using the analytical techniques surface-specific vibrational sum frequency generation and attenuated total reflection spectroscopy. To provide a molecular interpretation of the observed behavior, simulations are carried out using a free energy perturbation approach in combination with electronic structure-based molecular dynamics. In both the experimental and theoretical results we observe that the protonated form of pyruvic acid is preferred at the air-water interface. The increased proton affinity is the result of the specific microsolvation at the interface.

Study of the Chemical Ionization of Organophosphate Esters in Air Using Selected Ion Flow Tube-Mass Spectrometry for Direct Analysis.

Organophosphate esters are an emerging environmental concern since they spread persistently across all environmental compartments (air, soil, water, etc.). Measurements of semivolatile organic compounds are important but not without challenges due to their physicochemical properties. Selected ion flow tube-mass spectrometry (SIFT-MS) can be relevant for their analysis in air because it is a direct analytical method without separation that requires little preparation and no external calibration. SIFT-MS is based on the chemical reactivity of analytes with reactant ions. For volatile and semivolatile organic compound analysis in the gas phase, knowledge of ion-molecule reactions and kinetic parameters is essential for the utilization of this technology. In the present work, we focused on organophosphate esters, semivolatile compounds that are now ubiquitous in the environment. The ion-molecule reactions of eight precursor ions that are available in SIFT-MS (H3O+, NO+, O2•+, OH-, O•-, O2•-, NO2-, and NO3-) with six organophosphate esters were investigated. The modeling of ion-molecule reaction pathways by calculations supported and complemented the experimental work. Organophosphate esters reacted with six of the eight precursor ions with characteristic reaction mechanisms, such as protonation with hydronium precursor ions and association with NO+ ions, while nucleophilic substitution occurred with OH-, O•-, and O2•-. No reaction was observed with NO2- and NO3- ions. This work shows that the direct analysis of semivolatile organic compounds is feasible using SIFT-MS with both positive and negative ionization modes.

Temporal dynamics of negative air ion concentration and its relationship with environmental factors: Results from long-term on-site monitoring.

Negative air ions (NAIs) play an important role in evaluating forest health effects and promoting human physical and mental health. In this paper, long-term on-site monitoring of NAI concentration, air temperature, and relative humidity was conducted in real time over 24 h, from July 2019 to March 2021, to explore the temporal dynamic patterns of NAIs. We found that the daily dynamics of NAI concentration showed a bimodal curve. The peak concentrations usually occurred in the early morning (5:00-7:00) and afternoon (15:00-17:00), and the lowest concentrations usually occurred at noon (11:00-13:00). At the monthly scale, NAI concentrations were relatively high in February and August and low in May and December, and at the seasonal scale, NAI concentration was significantly higher in summer than in other seasons. Autumn had the second highest NAI concentration. There was no significant difference in NAI concentration between winter and spring. A comprehensive analysis shows that the AQI was the most key factor affecting NAI concentrations compared to temperature and relative humidity, especially the two indicators of particulate matter and ozone, and that NAI concentration had a negative correlation with these indicators and was significantly higher under favorable air quality conditions than under polluted air conditions. NAI concentrations and air temperature showed marked piecewise characteristics, with NAIs increasing linearly with rising temperature only if the Ta was separated into three ranges of -5 °C-10 °C, 10 °C-30 °C, and 30 °C-40 °C. With rising relative humidity, NAI concentration increased in accordance with a quadratic function. Our research provides new insights into the NAI temporal dynamics patterns and its driving factors, and will aid in scheduling outdoor recreation and forest health activities for urban people.

Estimates of the economic damage due to the soiling of residential buildings induced by air pollution in Italy.

The soiling of the external façades of buildings caused by air pollution has economic costs that are generally not borne entirely by the polluters but by society in general. The present paper attempts to estimate the maintenance costs attributable to the soiling of the façades of residential buildings exposed to ambient air pollution in Italy. In this study, dose-response functions were used to link the environmental concentrations of pollutants to the soiling rate of the opaque and transparent surfaces of the building façades. It was assumed that the spatial distribution of façade materials follows the distribution of population. The basic assumption was that maintenance is performed when critical levels, 35% loss of reflectance for opaque surfaces and 1% haze for glass surfaces, are reached. Several important elements seem to emerge from the analysis carried out. The cost of damage to opaque surfaces due to air pollution appears to be a non-negligible fraction of the total maintenance costs of building façades incurred in Italy. Moreover, the cost of soiling damage to residential buildings from particulate matter has the potential to significantly increase total external costs due to air pollution. The costs of cleaning window panes due to air pollution also appear significant. Finally, if the levels of atmospheric pollution in the most populated areas become similar to the concentrations currently present in the most remote areas in Italy, the overall cost at national level due to the soiling of the building façades could be reduced by about 50%.

Quantitative detection of hydrogen peroxide in rain, air, exhaled breath, and biological fluids by NMR spectroscopy.

Hydrogen peroxide (H2O2) plays a key role in environmental chemistry, biology, and medicine. H2O2 concentrations typically are 6 to 10 orders of magnitude lower than that of water, making its quantitative detection challenging. We demonstrate that optimized NMR spectroscopy allows direct, interference-free, quantitative measurements of H2O2 down to submicromolar levels in a wide range of fluids, ranging from exhaled breath and air condensate to rain, blood, urine, and saliva. NMR measurements confirm the previously reported spontaneous generation of H2O2 in microdroplets that form when condensing water vapor on a hydrophobic surface, which can interfere with atmospheric H2O2 measurements. Its antimicrobial activity and strong seasonal variation speculatively could be linked to the seasonality of respiratory viral diseases.

Distinguishing Aroclor and non-Aroclor sources to Chicago Air.

Many polychlorinated biphenyl (PCB) congeners are found in both legacy Aroclor mixtures and modern materials, and both contribute to PCBs levels in ambient air. The various sources of PCBs make it difficult to quantify the relative importance of emissions from remaining legacy materials and emissions of PCBs released from production and use of modern products. To address this challenge, we utilized active and passive sampling, analytical methods optimized for PCBs, and Positive Matrix Factorization (PMF) and cos theta to examine the chemical signature of PCBs in Chicago air. Here we report our findings for over 640 samples collected over 7 years and analyzed for all 209 congeners. We conclude that Aroclor sources (1254, 1016/1242, and 1260) are consistent and dominant contributors to Chicago air. However, non-Aroclors sources accounted for 13%-16% of the total PCBs measured. Our analysis indicates non-Aroclor sources explain 99% of PCB11, 90% of PCB 68, and 58-69% of congeners with 8 to 10 chlorines in Chicago air. All of these are known to be emitted from paints or silicone polymers. Additionally, we identified over 20 congeners that have non-Aroclor contributions of more than 50% including PCB 3 (4-monochlorobiphenyl, 83% non-Aroclor) as well as 7 congeners of unknown sources: PCBs 43, 46, 55, 89, 96, 137, and 139 + 140. Non-Aroclor emission sources contribute to the entire range of congeners from mono- to deca-chlorobiphenyls. We found evidence of highly localized non-Aroclor sources including a signature similar to that of green paint. We also found source signals similar to the PCB congeners volatilizing from and absorbing to neighboring Lake Michigan. The measured profiles vary from season to season: lower chlorinated congeners dominate in winter months while higher chlorinated congeners contribute more in summer.