Does iodine gas released from seaweed contribute to dietary iodine intake?

Thyroid hormone levels sufficient for brain development and normal metabolism require a minimal supply of iodine, mainly dietary. Living near the sea may confer advantages for iodine intake. Iodine (I(2)) gas released from seaweeds may, through respiration, supply a significant fraction of daily iodine requirements. Gaseous iodine released over seaweed beds was measured by a new gas chromatography-mass spectrometry (GC-MS)-based method and iodine intake assessed by measuring urinary iodine (UI) excretion. Urine samples were obtained from female schoolchildren living in coastal seaweed rich and low seaweed abundance and inland areas of Ireland. Median I(2) ranged 154-905 pg/L (daytime downwind), with higher values (~1,287 pg/L) on still nights, 1,145-3,132 pg/L (over seaweed). A rough estimate of daily gaseous iodine intake in coastal areas, based upon an arbitrary respiration of 10,000L, ranged from 1 to 20 µg/day. Despite this relatively low potential I(2) intake, UI in populations living near a seaweed hotspot were much higher than in lower abundance seaweed coastal or inland areas (158, 71 and 58 µg/L, respectively). Higher values >150 µg/L were observed in 45.6% of (seaweed rich), 3.6% (lower seaweed), 2.3% (inland)) supporting the hypothesis that iodine intake in coastal regions may be dependent on seaweed abundance rather than proximity to the sea. The findings do not exclude the possibility of a significant role for iodine inhalation in influencing iodine status. Despite lacking iodized salt, coastal communities in seaweed-rich areas can maintain an adequate iodine supply. This observation brings new meaning to the expression "Sea air is good for you!"

Multi axis differential optical absorption spectroscopy (MAX-DOAS) of gas and aerosol distributions.

We present and demonstrate a relatively simple algorithm, which converts a set of slant column density measurements of oxygen dimers (O4) and NO2 at several different elevation angles to determine the atmospheric aerosol extinction and the absolute concentration and mixing ratio of NO2 within the atmospheric boundary layer. In addition the height of the atmospheric boundary layer can usually be derived, also the technique can be readily extended to determine the concentration of several other trace gases including SO2, CH2O, or glyoxal. The algorithm is based on precise radiation transport modelling determination, taking into account the actual aerosol scenario as determined from the O4 measurements. The required hardware is simple encompassing essentially a miniature spectrometer, a small telescope, a pointing mechanism, and a Personal Computer (PC). Effectively the technique combines the simplicity of a passive MAX-DOAS observation with the capability of a much more complex active DOAS instrument to determine path-averaged, absolutely calibrated mixing ratios of atmospheric trace gases at relatively high accuracy.

Assessing methane emissions from global space-borne observations.

In the past two centuries, atmospheric methane has more than doubled and now constitutes 20% of the anthropogenic climate forcing by greenhouse gases. Yet its sources are not well quantified, introducing uncertainties in its global budget. We retrieved the global methane distribution by using spaceborne near-infrared absorption spectroscopy. In addition to the expected latitudinal gradient, we detected large-scale patterns of anthropogenic and natural methane emissions. Furthermore, we observed unexpectedly high methane concentrations over tropical rainforests, revealing that emission inventories considerably underestimated methane sources in these regions during the time period of investigation (August through November 2003).

The role of halogen species in the troposphere.

While the role of reactive halogen species (e.g. Cl, Br) in the destruction of the stratospheric ozone layer is well known, their role in the troposphere was investigated only since their destructive effect on boundary layer ozone after polar sunrise became obvious. During these 'Polar Tropospheric Ozone Hole' events O(3) is completely destroyed in the lowest approximately 1000 m of the atmosphere on areas of several million square kilometres. Up to now it was assumed that these events were confined to the polar regions during springtime. However, during the last few years significant amounts of BrO and Cl-atoms were also found outside the Arctic and Antarctic boundary layer. Recently even higher BrO mixing ratios (up to 176 ppt) were detected by optical absorption spectroscopy (DOAS) in the Dead Sea basin during summer. In addition, evidence is accumulating that BrO (at levels around 1-2 ppt) is also occurring in the free troposphere at all latitudes. In contrast to the stratosphere, where halogens are released from species, which are very long lived in the troposphere, likely sources of boundary layer Br and Cl are autocatalytic oxidation of sea salt halides (the 'Bromine Explosion'), while precursors of free tropospheric BrO and coastal IO probably are short-lived organo-halogen species. At the levels suggested by the available measurements reactive halogen species have a profound effect on tropospheric chemistry: In the polar boundary layer during 'halogen events' ozone is usually completely lost within hours or days. In the free troposphere the effective O(3)-losses due to halogens could be comparable to the known photochemical O(3) destruction. Further interesting consequences include the increase of OH levels and (at low NO(X)) the decrease of the HO(2)/OH ratio in the free troposphere.

Detection of bromine monoxide in a volcanic plume.

The emission of volcanic gases usually precedes eruptive activity, providing both a warning signal and an indication of the nature of the lava soon to be erupted. Additionally, volcanic emissions are a significant source of gases and particles to the atmosphere, influencing tropospheric and stratospheric trace-gas budgets. Despite some halogen species having been measured in volcanic plumes (mainly HCl and HF), little is known about bromine compounds and, in particular, gas-phase reactive bromine species. Such species are especially important in the stratosphere, as reactive bromine-despite being two orders of magnitude less abundant than chlorine-accounts for about one-third of halogen-catalysed ozone depletion. In the troposphere, bromine-catalysed complete ozone destruction has been observed to occur regularly during spring in the polar boundary layers as well as in the troposphere above the Dead Sea basin. Here we report observations of BrO and SO2 abundances in the plume of the Soufrière Hills volcano (Montserrat) in May 2002 by ground-based multi-axis differential optical absorption spectroscopy. Our estimate of BrO emission leads us to conclude that local ozone depletion and small ozone 'holes' may occur in the vicinity of active volcanoes, and that the amount of bromine emitted from volcanoes might be sufficiently large to play a role not only in the stratosphere, but also in tropospheric chemistry.

Differential optical absorption spectroscopy instrument for stratospheric balloonborne trace-gas studies.

A newly developed UV-visible instrument for differential optical absorption spectroscopic measurements of atmospheric trace gases from balloon platforms is described. Direct solar light at daytime in the near-ultraviolet (320.6-422.6-nm) and the visible (417.6-670.7-nm) spectral ranges can be simultaneously analyzed for the atmospheric column abundances or profiles of O(3), NO(2), NO(3), BrO, OClO, O(4), H(2)O, and possibly other species (HNO(2), IO, CH(2)O). Compared with previously used balloonborne UV-visible spectrometers, the instrument has the superior properties of low mass (42 kg), low power consumption (30 W), decreased spectral drift that is caused by temperature and pressure changes, low detector dark current, and low spectrometer stray light. The three last-named characteristics are achieved by enclosure of the entire spectrometer in a pressurized and thermostated container and by inclusion of separately thermostated photodiode array detectors. The optical setup is simplified to reduce its weight. The spectral stray light is reduced by suppression of the higher-order and zero-order grating reflections by use of light traps and in the UV by addition of a dispersive prism preanalyzer. The major instrumental design characteristics and the instrumental performance as tested in the laboratory and during several stratospheric balloon flights are reported.

DOAS measurements of tropospheric bromine oxide in mid-latitudes

Episodes of elevated bromine oxide (BrO) concentration are known to occur at high latitudes in the Arctic boundary layer and to lead to catalytic destruction of ozone at those latitudes; these events have not been observed at lower latitudes. With the use of differential optical absorption spectroscopy (DOAS), locally high BrO concentrations were observed at mid-latitudes at the Dead Sea, Israel, during spring 1997. Mixing ratios peaked daily at around 80 parts per trillion around noon and were correlated with low boundary-layer ozone mixing ratios.

Improving long-path differential optical absorption spectroscopy with a quartz-fiber mode mixer.

Long-path differential optical absorption spectroscopy (DOAS) has become an increasingly important method for determination of the concentration of tropospheric trace gases (e.g., O(3), NO(2), BrO, ClO). The use of photodiode array (PDA) detectors enhances long-path DOAS systems considerably owing to PDA's higher sensitivity resulting from the multiplex advantage. The detection limits of these systems are expected to be 1 order of magnitude lower than systems of similar optical setup with scanning detectors. When the scanning detector is simply replaced by a PDA, unwanted spectral structures of as much as 8 x 10(-3) appear. The size of these randomly changing structures exceeds the photon noise level by 2-3 orders of magnitude thus severely limiting the sensitivity. We show that an angular dependence of the response of the PDA causes this structure in combination with unavoidable changes in the illumination. A quartz-fiber mode mixer, which makes the illumination of the spectrograph-detector system nearly independent of the angular intensity distribution of the measured light, was developed and tested. This new device reduces the unwanted structures in laboratory and field experiments by a factor of 10. The detection limits of long-path DOAS instruments with PDA detectors are improved by the same amount and are thus lower than those of currently used systems with scanning detectors. At the same time a much shorter measurement time (by ~1 order of magnitude) becomes possible.

Numerical analysis and estimation of the statistical error of differential optical absorption spectroscopy measurements with least-squares methods.

Differential optical absorption spectroscopy (DOAS) has become a widely used method to measure trace gases in the atmosphere. Their concentration is retrieved by a numerical analysis of the atmospheric absorption spectra, which often are a combination of overlapping absorption structures of several trace gases. A new analysis procedure was developed, modeling atmospheric spectra with the absorption structures of the individual trace gases, to determine their concentrations. The procedure also corrects differences in the wavelength-pixel mapping of these spectra. A new method to estimate the error of the concentrations considers the uncertainty of this correction and the influence of random residual structures in the absorption spectra.

Detection of atmospheric OH radicals.

The detection of atmospheric OH radicals by laser long path absorption spectroscopy is described. This technique is specific to OH and easily calibrated. In various field measurements from below the detection limit (5*10(5)/cm3) up to 8.7*10(6) OH radicals/cm3 have been observed. Measurements of meteorologic parameters and mixing ratios of other trace gases simultaneously with OH allow comparison of observed OH levels with reaction kinetic model calculations.