Atmospheric aerosols and their effect on clouds are thought to be important for anthropogenic radiative forcing of the climate, yet remain poorly understood. Globally, around half of cloud condensation nuclei originate from nucleation of atmospheric vapours. It is thought that sulfuric acid is essential to initiate most particle formation in the atmosphere, and that ions have a relatively minor role. Some laboratory studies, however, have reported organic particle formation without the intentional addition of sulfuric acid, although contamination could not be excluded. Here we present evidence for the formation of aerosol particles from highly oxidized biogenic vapours in the absence of sulfuric acid in a large chamber under atmospheric conditions. The highly oxygenated molecules (HOMs) are produced by ozonolysis of α-pinene. We find that ions from Galactic cosmic rays increase the nucleation rate by one to two orders of magnitude compared with neutral nucleation. Our experimental findings are supported by quantum chemical calculations of the cluster binding energies of representative HOMs. Ion-induced nucleation of pure organic particles constitutes a potentially widespread source of aerosol particles in terrestrial environments with low sulfuric acid pollution.

/pdf/ion-induced-nucleation-of-pure-biogenic-particles-4qmw6lrim5.pdf

Ion-induced nucleation of pure biogenic particles

SnO2 nanoparticles-reduced graphene oxide (SnO2-rGO) nanocomposites have been successfully prepared by a facile method via hydrothermal treatment of aqueous dispersion of GO in the presence of Sn salts. The combined characterizations including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) indicate the successful formation of SnO2-rGO nanocomposites. To demonstrate the product on sensing application, gas sensors are fabricated using SnO2-rGO nanocomposites as sensing materials and investigated for detection of NO2 at low operating temperature (50 °C). It is found that SnO2-rGO nanocomposites exhibit high response of 3.31 at 5 ppm NO2, which is much higher than that of rGO (1.13), and rapid response, good selectivity and reproducibility. Furthermore, the reason for enhancing sensing performance by addition of SnO2 nanoparticles has also been discussed.

SnO2 nanoparticles-reduced graphene oxide nanocomposites for NO2 sensing at low operating temperature

This study shows that residual nicotine from tobacco smoke sorbed to indoor surfaces reacts with ambient nitrous acid (HONO) to form carcinogenic tobacco-specific nitrosamines (TSNAs). Substantial levels of TSNAs were measured on surfaces inside a smoker’s vehicle. Laboratory experiments using cellulose as a model indoor material yielded a > 10-fold increase of surface-bound TSNAs when sorbed secondhand smoke was exposed to 60 ppbv HONO for 3 hours. In both cases we identified 1-(N-methyl-N-nitrosamino)-1-(3-pyridinyl)-4-butanal, a TSNA absent in freshly emitted tobacco smoke, as the major product. The potent carcinogens 4-(methylnitrosamino)-1-(3-pyridinyl)-1-butanone and N-nitroso nornicotine were also detected. Time-course measurements revealed fast TSNA formation, with up to 0.4% conversion of nicotine. Given the rapid sorption and persistence of high levels of nicotine on indoor surfaces—including clothing and human skin—this recently identified process represents an unappreciated health hazard through dermal exposure, dust inhalation, and ingestion. These findings raise concerns about exposures to the tobacco smoke residue that has been recently dubbed “thirdhand smoke.” Our work highlights the importance of reactions at indoor interfaces, particularly those involving amines and NOx/HONO cycling, with potential health impacts.

/pdf/formation-of-carcinogens-indoors-by-surface-mediated-4h0ayo6trc.pdf

Formation of carcinogens indoors by surface-mediated reactions of nicotine with nitrous acid, leading to potential thirdhand smoke hazards

https://orbit.dtu.dk/files/3249858/2007_333.pdf

Critical comparison of radiometric and mass spectrometric methods for the determination of radionuclides in environmental, biological and nuclear waste samples.

Methods for the detection and determination of nitrite and nitrate: A review.

A flow type generation system based on the reaction of sodium nitrite solution with sulfuric acid has been developed for parts per billion levels of nitrous acid. The reagent solutions are continuously pumped into a reaction vessel and drawn off to waste. A carrier gas is passed through a mixture of the reagent solutions in the vessel and continuously purges nitrous acid vapor from the mixture. Nitrous acid output of the generator is characterized by using a Na{sub 2}CO{sub 3}-impregnated filter and a chemiluminescent NO{sub x} monitor. A stable generation of nitrous acid of known concentration can readily be achieved by adjusting the concentration of sodium nitrite solution.

Continuous generation system for low-concentration gaseous nitrous acid

A continuous-flow method for measuring atmospheric HNO2 concentration in real time has been developed that uses a chemiluminescent NOx monitor. A Na2CO3 solution strips gaseous HNO2 from the atmosphere by means of pulling an air sample and the solution through a glass coil and mixing continuously with ascorbic acid solution which reduces nitrite to NO. The mixture is led into a gas-liquid separating coil consisting of microporous PTFE tubing. The NO evolved from the separating coil is swept out by a stream of clean air and detected with a chemiluminescent NOx monitor. The technique utilizes a dual flow system and dual channel NOx monitor to correct positive interferences from NO2 and peroxyacetyinitrate (PAN). The concentration of HNO2 is determined by difference between the two measurements. Sensitivity of the method is a function of the ratio of sampling flow rate to carrier gas flow rate, which permits readily a highly sensitive measurement.

Chemiluminescent method for continuous monitoring of nitrous acid in ambient air.

A flow-injection analysis method for the determination of nitrite and nitrate in natural water samples has been developed that consists of two systems based on their reduction to NO with hydrazine and/or ascorbic acid, followed by chemiluminescence detection. The procedure of sweeping the generated NO into an NOx monitor, by means of a gas-liquid separating coil consisting of microporous polytetrafluoroethylene (PTFE) tubing, offers practical advantages. The adjustment of the carrier gas-flow rates could yield the same calibration graphs for the two measurement systems, and the accumulation sweeping mode provides a higher sensitivity. Chemiluminescence detection allows a wide linear calibration range of 5 × 10-8 to 5 × 10-5 M. The detection limits for nitrate and nitrite, defined as three-times the standard deviation of measurement blanks, are 2 × 10-8 M and 1 × 10-8 M, respectively, and the average precision was 3.2% at ambient natural concentration levels. Recovery tests were between 94% and 106% for a variety of natural water samples. The method is relatively free from interferences from the substances normally found in natural water, and only ferric ion has an effect for the nitrite determination.

https://www.jstage.jst.go.jp/article/analsci/19/5/19_5_695/_pdf

Flow-injection analysis method for the determination of nitrite and nitrate in natural water samples using a chemiluminescence NOx monitor.

Carbonic anhydrases (CAs) are universal metalloenzymes that catalyze the reversible conversion of carbon dioxide (CO2) and bicarbonate (HCO3-). They are involved in various biological processes, including pH control, respiration, and photosynthesis. To date, eight evolutionarily unrelated classes of CA families (α, β, γ, δ, ζ, η, θ, and ι) have been identified. All are characterized by an active site accommodating the binding of a metal cofactor, which is assumed to play a central role in catalysis. This feature is thought to be the result of convergent evolution. Here, we report that a previously uncharacterized protein group, named “COG4337,” constitutes metal-independent CAs from the newly discovered ι-class. Genes coding for COG4337 proteins are found in various bacteria and photosynthetic eukaryotic algae. Biochemical assays demonstrated that recombinant COG4337 proteins from a cyanobacterium (Anabaena sp. PCC7120) and a chlorarachniophyte alga (Bigelowiella natans) accelerated CO2 hydration. Unexpectedly, these proteins exhibited their activity under metal-free conditions. Based on X-ray crystallography and point mutation analysis, we identified a metal-free active site within the cone-shaped α+β barrel structure. Furthermore, subcellular localization experiments revealed that COG4337 proteins are targeted into plastids and mitochondria of B. natans, implicating their involvement in CO2 metabolism in these organelles. COG4337 proteins shared a short sequence motif and overall structure with ι-class CAs, whereas they were characterized by metal independence, unlike any known CAs. Therefore, COG4337 proteins could be treated as a variant type of ι-class CAs. Our findings suggested that this novel type of ι-CAs can function even in metal-poor environments (e.g., the open ocean) without competition with other metalloproteins for trace metals. Considering the widespread prevalence of ι-CAs across microalgae, this class of CAs may play a role in the global carbon cycle.

/pdf/characterization-of-a-novel-type-of-carbonic-anhydrase-that-3v13u20sxw.pdf

Masafumi Taira

Papers

Continuous generation system for low-concentration gaseous nitrous acid

Chemiluminescent method for continuous monitoring of nitrous acid in ambient air.

Flow-injection analysis method for the determination of nitrite and nitrate in natural water samples using a chemiluminescence NOx monitor.

Characterization of a novel type of carbonic anhydrase that acts without metal cofactors

Characterization of radiolytic products from air at a high-energy electron-positron storage ring