MarHal
Research topics of MarHal
Our research focuses on the following topics:
- Reactive tropospheric halogen chemistry
- Marine troposphere
- Polar regions
- Salt lakes
- Free troposphere
- Volcanic plumes
- Links between halogen and mercury chemistry
- Exchange of sea salt particles and gases between the ocean and the atmosphere (DMS, organohalogens, VOC, nitrates)
- Chemistry and microphysics of sea salt aerosol
- Physical, chemical and biological processes in the ocean that lead to the release of gases from the ocean
- Chemistry - climate links in the marine troposphere such as:
- Aerosol nucleation and growth
- Chemistry induced changes of cloud microphysics
- Snow photochemistry
These research areas are motivated by an increasing number of
measurements and model studies that find reactive halogen chemistry in
the troposphere to be of potentially major importance, both in the
marine boundary layer and in the free troposphere. The main source of
halogens over the oceans is release from seasalt aerosol and organic
halides that both originate from the ocean. The international
IGAC/SOLAS task "Halogens in the Troposphere" (of which Roland von
Glasow is co-chairman) aims at elucidating halogen chemistry by
combining field, laboratory and modelling studies.
The other group of topics is within the scope of the international Surface
Ocean Lower Atmosphere Study (SOLAS)
project "To achieve quantitative understanding of the key
biogeochemical-physical interactions and feedbacks between the ocean and the
atmosphere, and how this coupled system affects and is affected by climate and
environmental change" (quote from the SOLAS science plan).
Our research topics are shown schematically in the following figure:
The main tools of this research group are numerical modelling (box,
one-dimensional, three-dimensional) and model-measurement
comparisons. Below we list some of the current/previous projects in
more detail.
Influence of halogen chemistry in the marine boundary layer
The importance of halogens for the chemistry of the stratosphere has
been proven by numerous field, laboratory and modelling studies. In
the stratosphere the most important source for halogens is
decomposition of man-made CFC. In the troposphere, however, the main
source is the emission of sea salt aerosol from the ocean surface. Sea
salt aerosol contains chloride and bromide which can get released from
the aerosol by a sequence of gas phase - aqueous phase reactions. Once
in the gas phase the halogen radicals (especially Br) have the
potential to destroy ozone and to oxidize dimethyl sulphide (DMS),
which is a main precursor for small cloud condensation nuclei in the
marine boundary layer (MBL). Another halogen source in the MBL is the
release of organic precursors that contain iodine, bromine and/or
chlorine. Photolysis rapidly releases halogen radicals.
To study these topics we use numerical models like the one-dimensional model for
the MBL MISTRA. We discussed the following
chemical effects in these publications:
- Main halogen reaction mechanism and influence on ozone (von Glasow et al., 2002a)
- Halogen chemistry in a cloudy atmosphere and oxidation of sulphur (von Glasow et al., 2002b, von Glasow and Crutzen, 2004, von Glasow, 2007)
- Bromide depletion from sea salt aerosol during INDOEX (Gabriel et al., 2002)
- Accommodation coefficient of HOBr and impact of this new measurement (Wachsmuth et al., 2002)
- Vertical profile of sea salt aerosol pH that leads to the maximum of halogen chemistry at the top of the MBL (von Glasow and Sander, 2001)
- Potential importance of BrONO2 in the release of bromine from sea salt aerosol (Sander et al., 1999)
- Assessment of the relevance of organic coatings on sea salt particles for atmospheric chemistry, esp. halogens (Smoydzin and von Glasow, 2007)
- Importance of iodine chemistry for ozone destruction in the MBL (Vogt et al., 1999, von Glasow et al., 2002a, von Glasow, 2005, Stutz et al., 2007) and new particle formation/growth (Pechtl et al., 2006)
- Quantitative understanding of particulate phase iodine chemistry (Pechtl et al., 2007)
- Long-range transport of pollution over the sea and resulting release of chlorine from sea salt (Pechtl and von Glasow, 2007, von Glasow, 2008, Lawler et al., 2009)
- The RHaMBLe campaigns aimed at elucidating the role of iodine chemistry in coastal environements (McFiggans et al., 2010) as well as in the tropical North Atlantic (Lee et al., 2010).
Chemistry in the plumes of passively degasing volcanoes
From an atmospheric point of view, the chemistry of passively degasing
erupting volcanoes, i.e. those non-explosive eruptions where the
volcanic plume remains in the troposphere, has received only little
attention until recently. The detection of the largest concentrations
of BrO found so far anywhere in the atmosphere by Bobrowski et
al. (2003) triggered many follow-up studies. We've have been involved
in comparisons of measurements in plumes with numerical model
calculations to gain a better understanding of the complex multi-phase
chemical processes occuring in volcanic plumes. The focus in these
studies is on the chemistry of halogens (Bobrowski et al., 2007) and
sulphur species (Aiuppa et al., 2007). We were able to show that a
process very similar to the polar "bromine explosion" is occuring in
volcanic plumes leading to the build-up of very large concentrations
of BrO with distance from the crater edge. The review von Glasow et al
(2009) gives an overview of the relevance of volcanic emissions on
atmospheric chemistry with a focus on the troposphere. In von Glasow
(2010) an updated version of the model used in Bobrowski et al. (2007)
is employed which I used to study more details of reactive chemistry
in volcanic plumes and the interaction of bromine and mercury
chemistry in volcanic plumes. This paper discusses teh widespread
impacts on atmospheric chemistry including strong ozone destruction in
the plume and rapid oxidation of elementary gaseous mercury. Further
studies are currently going on. We are developing an innovative
measurement platform for the in situ measurements of volcanic plumes,
a remote controlled blimp. The first test flights were successful and
we are currently finalising the payload.
Influence of halogen chemistry in the free troposphere
From the combination of ground-based, balloon-borne, and satellite
observations of BrO in the combination with a model of stratospheric
chemistry the widespread presence of BrO in the free troposphere was
postulated in the literature. We used the global 3D CTM MATCH to
investigate the influence of BrO on the oxidation power of the
atmosphere, its influence on the NOx, HOx, and
sulphur cycles and found the presence of 0.5 - 2 pmol/mol (as shown in
the observations) to be very important for chemistry of the free
troposphere (von Glasow et al., 2004).
Polar atmospheric chemistry
For more than two decades it is known that bromine is involved in the
so-called Ozone Depletion Events (ODE) during "bromine explosions" in
polar regions. Yet the details of the "birth" of ODEs are still not
fully understood (e.g., Morin et al., 2008). The international project
AICI has published a series of review papers that discuss the involved
chemistry in detail and stress the importance of snow photochemistry;
we have co-led and contributed to two of these reviews (Simpson et
al., 2007 and Grannas et al., 2007, respectively). Our work with a box
and a 1D model helped in defining time scales involved and guiding
future field and model studies (Piot and von Glasow 2008, 2010). In
collaboration with US investigators (mainly Jochen Stutz, UCLA) during
the GSHOX campaigns at Summit, Greenland we expanded our existing 1D
atmospheric model by coupling it to a 1D snow photochemistry model
(Thomas et al., 2010). We could reproduce observations of BrO and NOx
at Summit and showed quantitatively the importance of snow
photochemistry for atmospheric chemistry. This new coupled model is
currently being used in a collaboration with the British Antarctic
Survey to help analyse data from the Halley research station in
Antarctica. We are planning to develop a simplified snow
photochemistry model for inclusion into regional 3D models.
Chemistry - cloud - climate links
Dimethyl sulphide (DMS) is the main natural source of sulphur in the
marine boundary layer. It is being produced by phytoplankton in the
oceans and released to the atmosphere. Many studies in the past 20
years have been trying to elucidate links between DMS emissions, cloud
properties and climate forcing but a proof of a climate regulating
feedback as proposed by Charleson et al (1987) remains elusive. Our
work focusses on a detailed understanding of the breakdown of DMS in
the remote MBL and the role of halogens in this (von Glasow et al.,
2002b, von Glasow and Crutzen, 2004). There are still significant
uncertainties in the chemical pathways of DMS oxidation but what is
obvious is, that the assumption of fixed sulphate yields from DMS and
a related straight-forward increase of cloud droplet number and cloud
albedo is too simplistic. Our research suggests that the presence of
halogens (esp. BrO) and sea salt aerosols leads to important shifts in
DMS oxidation pathways leading to the growth of pre-existing aerosol
particles rather than nucleation of new particles. The uptake of DMS
and its oxidation products into short-lived sea salt aerosol
effectively shortcuts the marine sulphur cycle. Details can be found in
von Glasow and Crutzen (2004) and von Glasow (2007).
Effects of ship emissions on the marine boundary layer
It has been known for a long time that particle emissions of
ocean-going ships can distinctively change the albedo of marine
clouds. Only recently the importance of ship emissions for the
chemistry was realised and emission inventories became available. We
investigated the impact on the chemistry of the clean atmosphere in
another model study (von Glasow et al., 2003) and found that it is
very important to account for plume dilution. In a clean marine
environment it takes about 2 days before air in the plume is
essentially indistinguishable from unpolluted air ("chemical lifetime
of the plume"). The lifetime of nitrogen oxides - which are important
for the formation of ozone - is shorter in the ship plume,
nevertheless significant amounts of ozone are formed in the plume. We
also participated in the analysis and discussion of satellite
observations of NOx emmissions from ships in the Bay of
Bengal (Beirle et al., 2004). Satellite studies have recently found
the wide-spread presence of HCHO in ship plumes. We collaborated in
a model investigation of the most likely sources (Song et al.,
2010), showing that the oxidation of CH4 by elevated levels
of in-plume OH radicals is the most likely source for the elevated
HCHO.
Interactions between radiation fog and tall vegetation
Vegetation has a strong influence on heat and moisture fluxes to the
atmosphere. It can also impede the formation of radiation fog and lead to the
interception of cloud droplets. We investigated this using a one-dimensional
model with coupled microphysics, radiation and vegetation processes (von Glasow
and Bott,1999).