Abstract. Severe winter haze accompanied by high concentrations of fine particulate matter (PM2.5) occurs frequently in the North China Plain and threatens public health. Organic matter (OM) and sulfate are recognized as major components of PM2.5, while atmospheric models often fail to predict their high concentrations during severe winter haze due to incomplete understanding of secondary aerosol formation mechanisms. By using a novel combination of single-particle mass spectrometry and an optimized ion chromatography method, here we show that hydroxymethanesulfonate (HMS), formed by the reaction between formaldehyde (HCHO) and dissolved SO2 in aerosol water, is ubiquitous in Beijing during winter. The HMS concentration and the molar ratio of HMS to sulfate increased with the deterioration of winter haze. High concentrations of precursors (SO2 and HCHO) coupled with low oxidant levels, low temperature, high relative humidity, and moderately acidic pH facilitate the heterogeneous formation of HMS, which could account for up to 15 % of OM in winter haze and lead to up to 36 % overestimates of sulfate when using traditional ion chromatography. Despite the clean air actions having substantially reduced SO2 emissions, the HMS concentration and molar ratio of HMS to sulfate during severe winter haze increased from 2015 to 2016 with the growth in HCHO concentration. Our findings illustrate the significant contribution of heterogeneous HMS chemistry to severe winter haze in Beijing, which helps to improve the prediction of OM and sulfate and suggests that the reduction in HCHO can help to mitigate haze pollution.

The mass resolution of a time-of-flight (TOF) mass spectrometer is directly proportional to its total flight pathlength. Multi-turn or multi-passage ion optical geometries are necessary to obtain fight distances of sufficient length within reasonable size limitations. We have investigated ion optics for a multi-turn TOF mass spectrometer with electrostatic sectors. The concept of 'perfect' focusing conditions is introduced. Furthermore, a new type of multi-turn TOF mass spectrometer, the MULTUM Linear plus, was developed. It consists of four cylindrical electric sectors and 28 electric quadrupole lenses. It has a vacuum chamber 60 × 70 × 20 cm in size. Mass resolution is demonstrated to increase according to the number of ion cycles. A mass resolution of 350 000 (m/z = 28, FWHM) was achieved after 501.5 cycles. The MULTUM Linear plus analyzer is not simple, however; 28 electric quadrupole lenses are used. In order to reduce the number of ion optical parts, an improved multi-turn TOF mass spectrometer, the MULTUM II, consisting of only four toroidal electric sectors, was also developed. The possibility of tandem mass spectrometric applications using multi-turn TOF mass spectrometers is also discussed.

A new miniature multiturn time-of-flight (TOF) analyzer "MULTUM-S II" has been designed and constructed. This instrument consists of an electron ionization source, the multiturn TOF ion optics, a detector, vacuum system, and electronic circuits. The multiturn TOF analyzer consists of four electrostatic toroidal sectors and two additional electric toroidal sectors for the purpose of ion injection/ejection. The size and weight of the system is less than 50 cm × 57 cm × 30 cm and 35 kg (including vacuum pumps and electronic circuits). The multiturn TOF analyzer is capable of high mass resolution because of its infinite flight path utilizing perfect space and time focused closed flight orbit. To evaluate the resolution in MULTUM-S II, separation of pyridine (¹²C₅H₅N) and the isotopic component of benzene (¹³C¹²C₅H₆) was performed at a mass resolution of about 20,000. Another performance characteristic of the MULTUM-S II was demonstrated by the separation of the greenhouse gas doublet CO₂ and N₂O (Δm = 0.0113 Da). While the mass difference is a mere 0.01 Da, the instrument could easily separate the two peaks at a calculated mass resolution of 31,600. The MULTUM-S II offers high mass resolution mass spectrometry in a miniaturized/portable enclosure.

Doubly charged tungsten hexacarbonyl W(CO)(6) (2+) ions were made to collide with Ar and K targets to give singly and doubly charged positive ions by collision-induced dissociation (CID). The resulting ions were analyzed and detected by using a spherical electrostatic analyzer. Whereas the doubly charged fragment ions resulting from collisional activation (CA) were dominant with the Ar target, singly charged fragment ions resulting from electron transfer were dominant with the K target. The internal energy deposition in collisionally activated dissociation (CAD) evaluated with the Ar target was broad and decreased with increasing internal energy. The predominant peaks observed with the K target were associated with singly charged W(CO)(2) (+) and W(CO)(3) (+) ions: these ions were not the result of CA, but arose from dissociation induced by electron transfer (DIET). The internal energy deposition resulting from the electron transfer was very narrow and centered at a particular energy, 7.8 eV below the energy level of the W(CO)(6) (2+) ion. This narrow internal energy distribution was explained in terms of electron transfer by Landau-Zener potential crossing at a separation of 5.9 x 10(-8) cm between a W(CO)(6) (2+) ion and a K atom, and the coulombic repulsion between singly charged ions in the exit channel. A large cross section of 1.1 x 10(-14) cm(2) was estimated for electron capture of the doubly charged W(CO)(6) (2+) ion from the alkali metal target, whose ionization energy is very low. The term "collision-induced dissociation," taken literally, includes all dissociation processes induced by collision, and therefore encompasses both CAD and DIET processes in the present work. Although the terms CID and CAD have been defined similarly, we would like to propose that they should not be used interchangeably, on the basis that there are differences in the observed ions and in their intensities with Ar and K targets.

A new type of multi‐turn time‐of‐flight mass spectrometer was constructed, consisting of four cylindrical electric sectors and 28 electric quadrupole lenses, the size of the vacuum chamber being 60×70×20 cm. It was demonstrated that the mass resolution can be increased according to the number of cycles of the ions through the ion optical system. Copyright © 2000 John Wiley & Sons, Ltd.