Dimethyl
sulfide (DMS) and volatile alkyl species of metaloïd (DMSe, DMTe, DMPo)
Nitrous
oxide, methane and carbon monoxyde
Biogenic
halocarbons and alkyl nitrates
Non methane hydrocarbons (NMHC)
Aerosols
:The inputs of iron from by terrestrial and extraterrestrial particles
Objective
2.1: quantification
of the flux of gases and aerosols at the ocean atmosphere interface. KEOPS will
focus on gases important in atmospheric chemistry and climate and aerosol as a
source of iron to the ocean.
General
background and interest for new carbon dioxide studies in the Southern Ocean
has been already summarised in the previous sections and is not repeated here.
Estimates of annual global DMS
emissions vary widely, but are expected to be in the range of 10
to 50 TgS yr-1 (Intergovernmental Panel on Climate Change
[IPCC], 1996). The wide range results
from uncertainties attached both to the global distribution of sea-surface DMS
concentrations and to computing DMS air-sea exchange rates. Besides reducing uncertainties on
present-day emission estimates, it is also important to investigate the climate
sensitivity of the marine DMS source. Although considerable progress has been
made in understanding the marine and atmospheric biogeochemical cycle of DMS,
the impact of global warming on marine DMS emissions remains to be established.
Bopp et al. (2002) presented a
modelled estimation of the response of DMS seawater concentrations and DMS
fluxes to climate change, following previous work on marine DMS modelling
(Aumont et al., 2002) and on the global warming impact on marine biology (Bopp
et al., 2001). At 2xCO2, the model estimates a small increase of
global DMS flux to the atmosphere (+2%) but with large spatial heterogeneity
(from 15% to +30% for the zonal mean). In the 30°S-50°S band, the model
predicts a +19% increase in the annual DMS flux (from 2.7 to 3.2 TgS yr-1).
Changes in DMS concentrations in that region result mainly from modifications
of the community structure of the ecosystem (shift from diatoms to
non-siliceous species). In situ
experiments have shown that the availability of iron and silicate in the
Southern Ocean plays an important role in controlling the structure of the
phytoplankton community (Maldonado et al. 2001) and this can modify the budget
of DMS (S. Turner pers. com.). The global 3-D ocean carbon cycle model used by
Bopp et al. (2002) did not include these nutrient limitations. Consequently,
these results strongly depend on the skill of the model to simulate marine
productivity and on the relationships used between DMS and other biological
variables. Improvements in both aspects are necessary to develop greater
confidence in such future predictions. KEOPS will allow to better quantify the
fluxes of DMS to the atmosphere and to better understand and parameterise the
production processes in the ocean (Objective 3).
In
contrast to many previous studies that have investigated the sea to air
transfer of lighter elements such as C and S, the importance of heavier
elements in these processes is less recognised. Heavier elements so-called
metalloids (Selenium (Se), Tellure (Te), Polonium(Po)) can form volatile alkyl
species with reflux to the atmosphere.
The process of alkylation can occur either directly as a consequence of
biological activity, or indirectly via abiotic reactions. The pathways leading to the volatilisation
and atmospheric transfer of selenium from oceanic environments are poorly understood.
They may however affect the global distribution of selenium and its impact on
marine and terrestrial ecosystems. Gaseous selenium compounds have been
determined in the North Atlantic ocean during a spring bloom of identified
phytoplankton species, known to be a large source of atmospheric sulfur. The
results demonstrate that significant concentrations of gaseous selenium species
occur in surface ocean waters, and their production is closely linked to the
turnover of gaseous sulfur species.
The ocean is a significant source of
the trace gases nitrous oxide (N2O), methane (CH4) and
carbon monoxide (CO), which influence the radiative and oxidative capacity of
the atmosphere. On both regional and global scales the marine source of these
climate reactive gases is related to nutrient availability and phytoplankton
production, and consequently any shift in nutrient supply, whether natural or
deliberately induced, may have profound implications for atmospheric chemistry
and climate . One such possibility is iron fertilisation of the oceans, which
may occur naturally via
climate-induced variations in supply, or by deliberate iron addition aimed at
increasing carbon sequestration (Markels and Barber , 2001). Law and Ling
(2002) reported that the decrease in radiative forcing resulting from carbon
dioxide fixation and CO2 uptake during SOIREE may be subsequently
offset by 6-12% by N2O production. It is therefore important that
the potential impact upon biogenic gas cycling and oceanic emissions is adequately
constrained (Fuhrman and Capone, 1991) for prediction of climate-induced
effects and informed consideration of any artificial fertilisation.
The KEOPS experiment represents an ideal
opportunity to examine the impact of natural fertilisation upon trace gas
cycling, offering a direct comparison between “background” conditions and the
fertilised waters in the wake of Kerguelen Island. This data will be invaluable
in assessing whether the stimulation in N2O and CO production
observed in deliberate iron fertilisations (SOIREE - Southern Ocean, Law and
Ling, 2001; SERIES - N.E. Pacific, Law, unpublished data) is also a feature of
natural fertilisation events.
The oxidising capacity of the troposphere
reflects the ability of the atmosphere to cleanse itself of man-made and
natural compounds. It is primarily determined by the concentration of hydroxyl
radicals (OH) which are formed mainly from the photodissociation of ozone by UV
radiation. The emission of trace gases containing nitrogen and halogen (Cl, Br,
I) atoms from the biosphere into the atmosphere affects the oxidising capacity,
both as a source of reactive radicals such as NO3, Cl and BrO, and
as a result of their influence on the concentration of ozone. The alkyl
nitrates are a reservoir species for NOx (=NO2 + NO).
Photolysis of NO2 is the only known way of producing ozone in the
troposphere, therefore the photochemical processes occurring in the lower
atmosphere are critically dependent on the level of nitrogen oxides. As the
alkyl nitrates are relatively long lived in the troposphere, they can act as a
source of NOx in remote environments away from continental sources
and so influence ozone concentrations on regional levels.
In general, the alkyl nitrates have
a predominantly anthropogenic source, but during the 1990s, several authors
invoked an oceanic source of the light alkyl nitrates (C1-C3)
to explain the distributions seen over remote oceanic regions (Blake,
1999). Recent studies in the Atlantic
Ocean have confirmed a seawater source of methyl and ethyl nitrate (Chuck et al
2002), and their production mechanisms are, as yet, poorly understood.
The results of our participation in EisenEx
2000, an in situ iron addition
experiment in the Southern Ocean, suggest that iron enrichment may increase
methyl nitrate concentrations and has a variable effect on the concentrations
of biogenic halocarbons (Chuck, unpublished).
Non methane hydrocarbons play a
major role in the tropospheric chemistry as precursor of tropospheric ozone and
their impact on the oxidizing capacity is relatively well known and quantified,
mainly in the polluted atmospheres and in the northern hemisphere where
anthropogenic emissions dominate .
The role of NMHC is very complex,
its influence on ozone is non linear and dependent also on the NOx
level. NMHC may act as ozone precursors or ozone consumers depending on the
considered atmosphere composition. Particularly in remote atmospheres a great
uncertainty exists regarding the amplitude of the natural sources and the
marine source. (T.J. Song, 2001). Our first estimations
(Bonsang et al. 1988), have shown the
importance of the marine source of NMHC (particularly of alkenes) which has
been estimated at roughly 35 x106 Tons of carbon/year. A recent work
by T.J. Song have shown that at levels of several hundreds pptv, this role may
be significant in the atmospheric chemistry, and the ozone or oxidants budgets.
Such atmospheric levels are compatible with the upper range of the oceanic
source. Our time series of NMHC in the southern hemisphere at Amsterdam island
are coherent with an oceanic source of the order of the upper level of the
estimations, and more generally with the relatively high mixing ratios of NMHC
observed in the southern Indian Ocean (Yokouchi et al., 1999; Saito et al, 2000).
Our recent work undertaken at
Kerguelen Island in January February
2002, confirms the existence of a significant oceanic source either on the
Kerguelen plateau or in this area of the Indian Ocean. The levels observed are
very similar to the recent results of Saito et al. (2000). In a general way it
appears clearly that subantarctic areas, particularly the southern Indian Ocean
act as a significant sources of reactive trace gases, which can not be
extrapolated to the global ocean, but should be taken into account in their geographical variability.
Recently, Johnson (2001) investigated the
iron supply and demand in the upper ocean and questioned : Is extraterrestrial
dust a significant source of bioavailable iron ? Based on input of
interplanetary dust particles in the atmosphere and on the assumption that
small particles, with a radius of the order of 1 nm, have a solubility of 100%,
Johnson estimated that bioavailable iron input in the Southern ocean from IDPs
is 0.35 106 mol Fe yr-1
this could account for 30 % of
the terrestrial input of bioavailable iron and 20 % of the iron input due to
upwelling flux in the Southern Ocean (Fung et al. 2000).
Interestingly, Johnson concludes « In
fact it is likely that we know the flux of bioavailable Fe from IDPs with
better accuracy than we know the flux of bioavailable iron from terrestrial
dust ! ». This reinforces the need for a better quantification of the
atmospheric iron deposition rate in the Southern Ocean, and for a better
knowledge of the iron dissolution processes.
Specific questions :
F What is the impact of natural iron fertilisation on the
ocean-atmosphere fluxes of biogenic gases?
F How does the magnitude and the variability of these fluxes compare in the two contrasting
environments?
F How do compare the ocean
atmosphere fluxes of biogenic gases in natural and artificial iron
fertilisation experiments?
F What is the contribution of “iron
from above” to the input of iron in surface waters of the Indian
Southern ocean?
Objective
2.2:
Quantification of the flux of carbon exported below the depth of the winter
mixed layer.
During the first iron in situ fertilisation SOIREE, the phytoplankton biomass peaked up to 3 µg l-1 11
days after the beginning of the experiment, however little export was observed. About 66 % of the photosynthetically
fixed carbon remained in the mixed layer on day 13. Lateral advection rather than grazing or export was the largest
loss term. Boyd (2002) suggests that the SOIREE bloom –which was not
significantly controled by grazing activity was not nutrient (including iron)
limited due to the exchange with surrounding HNLC waters (chemostat effect) and
hence phytoplankton remained healthy. As healthy diatoms sink relatively
slowly, loss was also slow during the SOIREE experiment. The SOIREE bloom
persisted for at least 50 days, longer than the delay observed by Buesseler et
al. (2001) (in Boyd 2002) between the development of the bloom and the
subsequent export along 170°W in the Southern Ocean. This could be due to a
physical artefact during the SOIREE experiment. The lateral loss of
phytoplankton could have prevented self-shading and phytoplankton aggregation.
The recent experiment
SOFEX (Jan.-Feb. 2002) seems to lead to the same conclusions “….it looks as if natural variability will
be as large as the iron-induced effects on particle export during this 5 week
occupation of the South patch. While the details of this story will change, we
did not witness the large-scale demise of the bloom and sinking out of carbon
taken up by phytoplankton in response to iron…” K. Buesseler in SOFeX
cruise logbook Februrary 2002.
The question of the
carbon export following iron fertilisation remained an unsolved question that
we will address during KEOPS
Related to objective 2.2, the major
specific questions to be addressed within KEOPS are
F What is the impact of the natural
iron fertilisation on the export of the biogenic material?
F What is the delay between the
development of the bloom and the export?
F How does export compare in natural and artificial iron fertilisation
experiments?
F How does the magnitude and the variability
of export fluxes compare in the two contrasting environments?
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