6
I. K. Larin
in range from 0,1 to 1, measured in conditions of a flow with use ionizing mass
spectrometry. This conclusion has been used for an estimation of the sink of OH
on carbonaceous aerosols in conditions of the top troposphere. Calculations of
authors have shown, that loss of OH on this channel in the top troposphere can
be rather considerable, that can be explained both low diffusion restrictions, and
weak temperature dependence of the effect.
Besides laboratory measurements quantum‑chemical calculations of rate con‑
stants of atmospheric chemical reactions were studied also. So, in [8] quan‑
tum‑chemical research of a primary stage of joining
of ozone to double bond of
ethylene, and in [9] — to acetylene has been made. In [10] influence of defor‑
mation of double bond in chlorine ethylene on the
rate and the mechanism of
reaction with ozone, and in [11] — a competition of the co-ordinated and not
co-ordinated joining of ozone to double bond has been considered. In [12] reac‑
tion of ozone with butene has been studied by methods of quantum chemistry. It
has been similarly studied adsorption of ammonia by water clusters [13]. At last,
note a work on water clusters, captured molecules of methane [14] that is direct‑
ly connected with a formation of clathrates of methane huge stocks which are in
zones of the permafrost menacing by strengthening the global warming at its
thawing.
The important data on the chemical processes
proceeding in polluted city
air, can be received from data about a chemical composition and acidity of city
precipitations. Such data are reported in works of researchers of the Meteoro‑
logical observatory of Geographical faculty of the Moscow State University
[15]–[25]. It is shown, in particular, that in 2005–2013 acidity of precipitations
in Moscow has raised in comparison with long-term observations. It is shown
also, that last years there is prevalence of chloride-ions over sulphates that can
be explained by growing use of containing chlorides anti-icing reagents. Like
it in [26] results of long-term investigations (1999–2010) of the ionic and ele‑
ment composition of atmospheric precipitations at stations of monitoring in the
Baikal region (Irkutsk, Lisnvjanka, Mondy) are presented. Annual flux of stud‑
ied components on underlaing surface are calculated. The various factors in‑
fluencing interannual and intraannual dynamics of a chemical composition of
precipitations are considered. It is shown, that in Irkutsk and Lisnvjanka the
total content of the basic ions and water-soluble elements in precipitations has
increased.
In conclusion of this part we will refer to the works of the general character
connected with chemistry of the troposphere. So, in [27] the mechanism of trop‑
ospheric oxidation of methane, in [28], [29] the tropospheric chemical processes
occuring at night are considered, and in [30] the question of day and night life‑
times of small atmospheric components in troposphere is analyzed.
7
Atmospheric
Chemistry
2. Heterophase processes
The significant amount of works in 2011–2014 has been devoted to studying
of heterophase reactions and processes with participation of aerosol particles. We
remind, that these processes have played a key role in depletion of the ozone
layer in the end of 20
th
century and in formation of the Antarctic
and Arctic ozone
holes. As an example we refer to work [31] in which long-term changes of the
basic characteristics of spring Antarctic ozone anomaly are considered. It is
shown, that since the end of 1980
th
change of the basic
characteristics of ozone
anomaly for the first 10 years in appreciable degree have been connected with
changes in temperature in the low stratosphere, and the next 10 years of changes
in temperature and ozone were not observed. In [32] occurrence of polar strato‑
spheric clouds over Tomsk on January, 10th, 2010 which could be formed over
the Scandinavian mountains and over mountain ridges of Polar Urals Mountains
and New Land is described. Besides high-altitude processes, aerosol particles
make considerable impact on composition of small atmospheric components,
including ozone. In this connection we refer to the work [33] in which ozone
depletion on a surface of white sand was studied. In the work the parametres
characterising initial activity of sand and rate of its deactivation under the influ‑
ence of 145 ppb of ozone have been defined. In [34] on the basis of the estab‑
lished empirical dependence between a change of concentration of ozone and
aerosol at the ground level in Tomsk and a course of solar activity in 21
st
–3
rd
eleven-year cycles on literary data about the forecast of solar activity for 24
th
eleven-year cycle, the forecast of change of mid-annual concentration of ozone
and aerosol till 2021 is given. In connection with observable anomalies of con‑
centration of ozone in coastal sea zones in [35] a formation of chemically active
haloids in the low troposphere in heterogeneous reactions of NO
3
and ClONO
2
with sea aerosol was studied and the algorithm of extrapolation of laboratory data
to real tropospheric conditions for the purpose of including the given class of
elementary reactions in modern models to forecast long‑term composition of the
troposphere over the coastal industrially developed regions has been received.
Additional data on this question are reported in [36]. In [37] hydration of nega‑
tive ions of trichloroacetic acid (ТCA) in water solutions was studied. By means
of a mass spectrographic method of electrodispersion of
solutions of electrolits
(EDSE) the mass spectrum of negative ions of water solution ТCA has been
studied. In work [38] features of an annual course of concentration of aerosol in
the surface air of Moscow suburbs were considered. On materials of daily meas‑
urements of characteristics of atmospheric aerosol in Golgoprudny (20 km from
the centre of Moscow), executed within 2006–2009, seasonal variations of con‑
centration of particles of the different sizes in the
surface layer of atmosphere
have been studied. It is established, that steady changes of monthly average