Sedimen-water nutrient fluxes: Preliminary results of in situ measurements in Alfaques Bay, Ebro River Delta.

Sediment-water exchanges of oxygen, ammonium, nitrate, total dissolved nitrogen, phosphate and total dissolved phosphorus were measured by means of an in situ incubator of 7 1 volume and 700 cm2 base area. The incubations lasted for three hours and were done over a whole season on different kinds of sediments in Alfaques Bay. We present some preliminary results on: i) methodological aspects, ii) spatial and temporal variability of fluxes, and iii) estimates of contribution of benthic nutrient regeneration relative to total nutrient loading of the Bay. Oxygen uptake averaged 1700 mmo1 m-2 h-1 (range 200-3500); no differences were found between sandy and muddy sediments. The release of ammonia from the sediment averaged 70 mmo1 m-2 h-1 and was higher in muddy sediments than in sandy ones. Very low to null nitrate and nitrite fluxes and only small fluxes of organic nitrogen were detected. We conclude that ammonium release from sediment is the major path of nitrogen regeneration. Some sediments removed dissolved reactive phosphorus (DRP) from the water and released dissolved organic phosphorus (DOP). Additional manipulative experiments revealed DRP release under particular conditions (turbulence, anoxia). From these data, we estimate that at least 50% of the nitrogen requirements of phytoplankton in the area may be supplied by benthic remineralization.

Improved understanding of drought controls on seasonal variation in Mediterranean forest canopy CO2 and water fluxes through combined in situ measurements and ecosystem modelling

Water stress is a defining characteristic of Mediterranean ecosystems, and is likely to become more severe in the coming decades. Simulation models are key tools for making predictions, but our current understanding of how soil moisture controls ecosystem functioning is not sufficient to adequately constrain parameterisations. Canopy-scale flux data from four forest ecosystems with Mediterranean-type climates were used in order to analyse the physiological controls on carbon and water flues through the year. Significant non-stomatal limitations on photosynthesis were detected, along with lesser changes in the conductance-assimilation relationship. New model parameterisations were derived and implemented in two contrasting modelling approaches. The effectiveness of two models, one a dynamic global vegetation model ('ORCHIDEE'), and the other a forest growth model particularly developed for Mediterranean simulations ('GOTILWA+'), was assessed and modelled canopy responses to seasonal changes in soil moisture were analysed in comparison with in situ flux measurements. In contrast to commonly held assumptions, we find that changing the ratio of conductance to assimilation under natural, seasonally-developing, soil moisture stress is not sufficient to reproduce forest canopy CO2 and water fluxes. However, accurate predictions of both CO2 and water fluxes under all soil moisture levels encountered in the field are obtained if photosynthetic capacity is assumed to vary with soil moisture. This new parameterisation has important consequences for simulated responses of carbon and water fluxes to seasonal soil moisture stress, and should greatly improve our ability to anticipate future impacts of climate changes on the functioning of ecosystems in Mediterranean-type climates.

A method for estimating the turbulent kinetic energy dissipation rate from a vertically pointing Doppler lidar, and independent evaluation from balloon-borne in situ measurements

A method of estimating dissipation rates from a vertically pointing Doppler lidar with high temporal and spatial resolution has been evaluated by comparison with independent measurements derived from a balloon-borne sonic anemometer. This method utilizes the variance of the mean Doppler velocity from a number of sequential samples and requires an estimate of the horizontal wind speed. The noise contribution to the variance can be estimated from the observed signal-to-noise ratio and removed where appropriate. The relative size of the noise variance to the observed variance provides a measure of the confidence in the retrieval. Comparison with in situ dissipation rates derived from the balloon-borne sonic anemometer reveal that this particular Doppler lidar is capable of retrieving dissipation rates over a range of at least three orders of magnitude. This method is most suitable for retrieval of dissipation rates within the convective well-mixed boundary layer where the scales of motion that the Doppler lidar probes remain well within the inertial subrange. Caution must be applied when estimating dissipation rates in more quiescent conditions. For the particular Doppler lidar described here, the selection of suitably short integration times will permit this method to be applicable in such situations but at the expense of accuracy in the Doppler velocity estimates. The two case studies presented here suggest that, with profiles every 4 s, reliable estimates of ϵ can be derived to within at least an order of magnitude throughout almost all of the lowest 2 km and, in the convective boundary layer, to within 50%. Increasing the integration time for individual profiles to 30 s can improve the accuracy substantially but potentially confines retrievals to within the convective boundary layer. Therefore, optimization of certain instrument parameters may be required for specific implementations.

Assessing the diurnal evolution of surface radiation balance over the western region of Tropical Atlantic Ocean using in situ measurements carried out during the FluTuA balance Project

In this work, the diurnal evolution of the radiation balance components over the tropical Atlantic Ocean is described and analysed. The analysis is based on measurements carried Out on board a Brazilian Navy ship during the observational campaign of the FluTuA Project (`Fluxos Turbulentos sobre o Atlantico`), from 15 to 23 May 2002. The observations indicated that the albedo responds its expected to atmospheric attenuation effects with a diurnal evolution similar to the Fresnel albedo. In general, the observed longwave radiation values agreed better with the estimated values obtained without longwave reflection. In agreement with the literature, the average surface emissivity was around 0.97. The net radiation, estimated from published equations for albedo, atmospheric transmissivity and surface emissivity, agreed with the observations, indicating that these parameters are representative of the radiometric properties of the air-sea interface in the region between Natal (6 degrees S, 35.2 degrees W) and the Sao Pedro and Sao Paulo Archipelago (1 degrees N, 29.3 degrees W). Copyright (C) 2008 Royal Meteorological Society

The role of hydration on the mechanism of allosteric regulation: In situ measurements of the oxygen-linked kinetics of water binding to hemoglobin

We report here the first direct measurements of changes in protein hydration triggered by a functional binding. This task is achieved by weighing hemoglobin (Hb) and myoglobin films exposed to an atmosphere of 98%, relative humidity during oxygenation. The binding of the first oxygen molecules to Hb tetramer triggers a change in protein conformation, which increases binding affinity to the remaining empty sites giving rise to the appearance of cooperative phenomena. Although crystallographic data have evidenced that this structural change increases the protein water-accessible surface area, isobaric osmotic stress experiments in aqueous cosolutions have shown that water binding is linked to Hb oxygenation. Now we show that the differential hydration between fully oxygenated and fully deoxygenated states of these proteins, determined by weighing protein films with a quartz crystal microbalance, agree with the ones determined by osmotic stress in aqueous cosolutions, from the linkage between protein oxygen affinity and water activity. The agreements prove that the changes in water activity brought about by adding osmolytes to the buffer solution shift biochemical equilibrium in proportion to the number of water molecules associated with the reaction. The concomitant kinetics of oxygen and of water binding to Hb have been also determined. The data show that the binding of water molecules to the extra protein surface exposed on the transition from the low-affinity T to the high-affinity R conformations of hemoglobin is the rate-limiting step of Hb cooperative reaction. This evidences that water binding is a crucial step on the allosteric mechanism regulating cooperative interactions, and suggests the possibility that environmental water activity might be engaged in the kinetic control of some important reactions in vivo.

Chlorophyll a spatial inference using artificial neural network from multispectral images and in situ measurements

Considering the importance of monitoring the water quality parameters, remote sensing is a practicable alternative to limnological variables detection, which interacts with electromagnetic radiation, called optically active components (OAC). Among these, the phytoplankton pigment chlorophyll a is the most representative pigment of photosynthetic activity in all classes of algae. In this sense, this work aims to develop a method of spatial inference of chlorophyll a concentration using Artificial Neural Networks (ANN). To achieve this purpose, a multispectral image and fluorometric measurements were used as input data. The multispectral image was processed and the net training and validation dataset were carefully chosen. From this, the neural net architecture and its parameters were defined to model the variable of interest. In the end of training phase, the trained network was applied to the image and a qualitative analysis was done. Thus, it was noticed that the integration of fluorometric and multispectral data provided good results in the chlorophyll a inference, when combined in a structure of artificial neural networks.

Airborne in situ measurements of ice particles in the tropical tropopause layer

Ice clouds have a strong effect on the Earth-atmosphere radiative energy balance, on the distribution of condensable gases in the atmosphere, as well as on the chemical composition of the air. The ice particles in these clouds can take on a variety of shapes which makes the description of the cloud microphysical properties more difficult. In the tropical upper troposphere/lower stratosphere (UTLS), a region where ice cloud abundance is relatively high, different types of ice clouds can be observed. However, in situ measurements are rare due to the high altitude of these clouds and the few available research aircraft, only three worldwide, that can fly at such altitudes.rnThis work focuses on in situ measurements of the tropical UTLS clouds performedrnwith a Cloud Imaging Probe (CIP) and a Forward Scattering Spectrometer Probern(FSSP-100), whereof the CIP is the key instrument of this thesis. The CIP is anrnairborne in situ instrument that obtains two-dimensional shadow images of cloud particles. Several cloud microphysical parameters can be derived from these measurements, e.g. number concentrations and size distributions. In order to obtain a high quality data set, a careful image analysis and several corrections need to be applied to the CIP observations. These methods are described in detail.rnMeasurements within the tropical UTLS have been performed during two campaigns:rnSCOUT-O3, 2005 in Northern Australia and SCOUT-AMMA, 2006 inWest Africa. Thernobtained data set includes first observations of subvisible cirrus clouds over a continental area and observations of the anvils of deep convective clouds. The latter can be further divided into clouds in mesoscale convective system outflows of different ages and clouds in overshooting cloud turrets that even penetrated the stratosphere. The microphysical properties of these three cloud types are discussed in detail. Furthermore, the vertical structure of the ice clouds in the UTLS is investigated. The values of the microphysical parameters were found to decrease with increasing altitude in the upper troposphere. Particle numbers and maximum sizes were also decreasing with increasing age of the outflow clouds. Further differences between the deep convective clouds and subvisible cirrus were found in the particle morphology as well as in the ratio of the observed aerosol particles to cloud particles which indicates that the different freezing processes (deposition, contact, immersion freezing) play different roles in the formation of the respective clouds. For the achievementrnof a better microphysical characterisation and description numerical fits have been adjusted onto the cloud particle size distributions of the subvisible cirrus as well as on the size distributions of the clouds at different altitudes in the UTLS.

Stationary in-situ measurements of aerosols, gaseous pollutants and meteorology : chemical and physical characterization of natural and anthropogenic sources

Natural and anthropogenic emissions of gaseous and particulate matter affect the chemical composition of the atmosphere, impact visibility, air quality, clouds and climate. Concerning climate, a comprehensive characterization of the emergence, composition and transformation of aerosol particles is relevant as their influence on the radiation budget is still rarely understood. Regarding air quality and therefore human health, the formation of atmospheric aerosol particles is of particular importance as freshly formed, small particles penetrate into the human alveolar region and can deposit. Additionally, due to the long residence times of aerosol particles in the atmosphere it is crucial to examine their chemical and physical characteristics.This cumulative dissertation deals with stationary measurements of particles, trace gases and meteorological parameters during the DOMINO (Diel Oxidant Mechanism In relation to Nitrogen Oxide) campaign at the southwest coast of Spain in November/December 2008 and the ship emission campaign on the banks of the Elbe in Freiburg/Elbe in April 2011. Measurements were performed using the Mobile research Laboratory “MoLa” which is equipped with state-of-the-art aerosol particle and trace gas instruments as well as a meteorological station.

Ground-based and airborne in-situ measurements of the Eyjafjallajökull volcanic aerosol plume in Switzerland in spring 2010

The volcanic aerosol plume resulting from the Eyjafjallajökull eruption in Iceland in April and May 2010 was detected in clear layers above Switzerland during two periods (17–19 April 2010 and 16–19 May 2010). In-situ measurements of the airborne volcanic plume were performed both within ground-based monitoring networks and with a research aircraft up to an altitude of 6000 m a.s.l. The wide range of aerosol and gas phase parameters studied at the high altitude research station Jungfraujoch (3580 m a.s.l.) allowed for an in-depth characterization of the detected volcanic aerosol. Both the data from the Jungfraujoch and the aircraft vertical profiles showed a consistent volcanic ash mode in the aerosol volume size distribution with a mean optical diameter around 3 ± 0.3 μm. These particles were found to have an average chemical composition very similar to the trachyandesite-like composition of rock samples collected near the volcano. Furthermore, chemical processing of volcanic sulfur dioxide into sulfate clearly contributed to the accumulation mode of the aerosol at the Jungfraujoch. The combination of these in-situ data and plume dispersion modeling results showed that a significant portion of the first volcanic aerosol plume reaching Switzerland on 17 April 2010 did not reach the Jungfraujoch directly, but was first dispersed and diluted in the planetary boundary layer. The maximum PM10 mass concentrations at the Jungfraujoch reached 30 μgm−3 and 70 μgm−3 (for 10-min mean values) duri ng the April and May episode, respectively. Even low-altitude monitoring stations registered up to 45 μgm−3 of volcanic ash related PM10 (Basel, Northwestern Switzerland, 18/19 April 2010). The flights with the research aircraft on 17 April 2010 showed one order of magnitude higher number concentrations over the northern Swiss plateau compared to the Jungfraujoch, and a mass concentration of 320 (200–520) μgm−3 on 18 May 2010 over the northwestern Swiss plateau. The presented data significantly contributed to the time-critical assessment of the local ash layer properties during the initial eruption phase. Furthermore, dispersion models benefited from the detailed information on the volcanic aerosol size distribution and its chemical composition.

Surface in situ measurements of atmospheric CO, CH4, and CO2 combined with selected meteorological measurements at the University of Wollongong, Australia

Wollongong, Australia is an urban site at the intersection of anthropogenic, biomass burning, biogenic and marine sources of atmospheric trace gases. The location offers a valuable opportunity to study drivers of atmospheric composition in the Southern Hemisphere. Here, a record of surface carbon monoxide (CO), methane (CH4) and carbon dioxide (CO2) was measured with an in situ Fourier transform infrared trace gas analyser between April 2011 and August 2014. Clean air was found to arrive at Wollongong in approximately 10% of air masses. Biomass burning influence was evident in the average annual cycle of clean air CO during austral spring. A significant negative short-term trend was found in clean air CO (-1.5 nmol/mol/a), driven by a reduction in northern Australian biomass burning. Significant short-term positive trends in clean air CH4 (5.4 nmol/mol/a) and CO2 (1.9 ?mol/mol/a) were consistent with the long-term global average trends. Polluted Wollongong air was investigated using wind-direction/wind-speed clustering, which revealed major influence from local urban and industrial sources from the south. High values of CH4, with anthropogenic DCH4/DCO2 enhancement ratio signatures, originated from the northwest, in the direction of local coal mining. A pollution climatology was developed for the region using back trajectory analysis and DO3/DCO enhancement ratios. Ozone production environments in austral spring and summer were associated with anticyclonic meteorology on the east coast of Australia, while ozone depletion environments in autumn and winter were associated with continental transport, or fast moving trajectories from southern latitudes. This implies the need to consider meteorological conditions when developing policies for controlling air quality.