A photoelectric detector for the measurement of photolysis frequencies of ozone and other atmospheric molecules

Photoelectric detectors for the measurement of photolysis frequencies of different trace gases in the atmosphere are described. They exhibit uniform response characteristics over one hemisphere (2 sr) and wavelength characteristics closely matched to those of the photolysis frequencies J _O1D, J _NO2, and J _NO3, respectively. Absolute calibration of the J _O1D detector was performed by chemical actinometry with an accuracy of ±16 percent. Simultaneous measurements of J _NO2 and J _O1D are presented.     

Stabilization of extracellular polymeric substances (Bacillus subtilis) by adsorption to and coprecipitation with Al forms

Extracellular polymeric substances (EPS) are continuously produced by bacteria during their growth and metabolism. In soils, EPS are bound to cell surfaces, associated with biofilms, or released into solution where they can react with other solutes and soil particle surfaces. If such reaction results in a decrease in EPS bioaccessibility, it may contribute to stabilization of microbial-derived organic carbon (OC) in soil. Here we examined: (i) the chemical fractionation of EPS produced by a common Gram positive soil bacterial strain (Bacillus subtilis) during reaction with dissolved and colloidal Al species and (ii) the resulting stabilization against desorption and microbial decay by the respective coprecipitation (with dissolved Al) and adsorption (with Al(OH)_3(am)) processes. Coprecipitates and adsorption complexes obtained following EPS-Al reaction as a function of pH and ionic strength were characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The stability of adsorbed and coprecipitated EPS against biodegradation was assessed by mineralization experiments for 1100 h. Up to 60% of the initial 100 mg/L EPS-C was adsorbed at the highest initial molar Al:C ratio (1.86), but this still resulted only in a moderate OC mass fraction in the solid phase (17 mg/g Al(OH)_3(am)). In contrast, while coprecipitation by Al was less efficient in removing EPS from solution (maximum values of 33% at molar Al:C ratios of 0.1-0.2), the OC mass fraction in the solid product was substantially larger than that in adsorption complexes. Organic P compounds were preferentially bound during both adsorption and coprecipitation. Data are consistent with strong ligand exchange of EPS phosphoryl groups during adsorption to Al(OH)_3(am), whereas for coprecipitation weaker sorption mechanisms are also involved. X-ray photoelectron analyses indicate an intimate mixing of EPS with Al in the coprecipitates, which is not observed in the case of EPS adsorption complexes. The incubation experiments showed that both processes result in overall stabilization of EPS against microbial decay. Stabilization of adsorbed or coprecipitated EPS increased with increasing molar Al:C ratio and biodegradation was correlated with EPS desorption, implying that detachment of EPS from surface sites is a prerequisite for microbial utilization. Results indicate that the mechanisms transferring EPS into Al-organic associations may significantly affect the composition and stability of biomolecular C, N and P in soils. The observed efficient stabilization of EPS might explain the strong microbial character of organic matter in subsoils.     

The significance of isotope specific diffusion coefficients for reaction-transport models of sulfate reduction in marine sediments

Modeling isotopic signatures in systems affected by diffusion, advection, and a reaction which modifies the isotopic abundance of a given species, is a discipline in its infancy. Traditionally, much emphasis has been placed on kinetic isotope effects during biochemical reactions, while isotope effects caused by isotope specific diffusion coefficients have been neglected. A recent study by Donahue et al. (2008) suggested that transport related isotope effects may be of similar magnitude as microbially mediated isotope effects. Although it was later shown that the assumed differences in the isotope specific diffusion coefficients were probably overstated by one or two orders of magnitude (Bourg, 2008), this study raises several important issues: (1) Is it possible to directly calculate isotopic enrichment factors from measured concentration data without modeling the respective system? (2) Do changes in porosity and advection velocity modulate the influence of isotope specific diffusion coefficients on the fractionation factor α? (3) If one has no a priori knowledge whether diffusion coefficients are isotope specific or not, what is the nature and magnitude of the error introduced by either assumption? Here we argue (A) That the direct substitution of measured data into a differential equation is problematic and cannot be used as a replacement for a reaction-transport model; (B) That the transport related fractionation scales linearly with the difference between the respective diffusion coefficients of a given isotope system, but depends in a complex non-linear way on the interplay between advection velocity, and downcore changes of temperature and porosity. Last but not least, we argue that the influence of isotope specific diffusion coefficients on microbially mediated sulfate reduction in typical marine sediments is considerably smaller than the error associated with the determination of the fractionation factor.     

Uranium speciation and stability after reductive immobilization in aquifer sediments

It has generally been assumed that the bioreduction of hexavalent uranium in groundwater systems will result in the precipitation of immobile uraninite (UO₂). In order to explore the form and stability of uranium immobilized under these conditions, we introduced lactate (15 mM for 3 months) into flow-through columns containing sediments derived from a former uranium-processing site at Old Rifle, CO. This resulted in metal-reducing conditions as evidenced by concurrent uranium uptake and iron release. Despite initial augmentation with Shewanella oneidensis, bacteria belonging to the phylum Firmicutes dominated the biostimulated columns. The immobilization of uranium (∼1 mmol U per kg sediment) enabled analysis by X-ray absorption spectroscopy (XAS). Tetravalent uranium associated with these sediments did not have spectroscopic signatures representative of U-U shells or crystalline UO₂. Analysis by microfocused XAS revealed concentrated micrometer regions of solid U(IV) that had spectroscopic signatures consistent with bulk analyses and a poor proximal correlation (μm scale resolution) between U and Fe. A plausible explanation, supported by biogeochemical conditions and spectral interpretations, is uranium association with phosphoryl moieties found in biomass; hence implicating direct enzymatic uranium reduction. After the immobilization phase, two months of in situ exposure to oxic influent did not result in substantial uranium remobilization. Ex situ flow-through experiments demonstrated more rapid uranium mobilization than observed in column oxidation studies and indicated that sediment-associated U(IV) is more mobile than biogenic UO₂. This work suggests that in situ uranium bioimmobilization studies and subsurface modeling parameters should be expanded to account for non-uraninite U(IV) species associated with biomass.     

Fragility curves for masonry structures submitted to permanent ground displacements and earthquakes

Usually, the vulnerability of structures is treated considering only one single hazard, for example either seismic hazard or ground instability. However, historical monuments, cultural heritage structures or old masonry structures can be affected, over the past centuries of existence, by a succession of different hazards. The objective of this paper was to quantify the changes in the seismic vulnerability of a given structure previously damaged by quasi-static differential settlements. In view of this, a soil-structure model of the masonry building is constructed using TREMURI software by putting springs at the base of the building to account for the soil behaviour. Classical empirical relationships are used for setting the mechanical properties of these foundation springs. The chosen equations are valid for both static and dynamic situations. The soil-structure model is first submitted to differential settlements with maximum magnitudes ranging from 5 to 25 cm. Then, the damaged structures are submitted to a set of time-histories. Fragility curves taking into consideration permanent differential settlements are finally obtained, using a modified regression technique accounting for the presence of residual drift due to the prior static loading.     

Satellite estimates and subpixel variability of rainfall in a semi-arid grassland

卫星估雨精度的不确定性受到当地降雨类型和像元内降雨非均匀性影响,而结合这两个关键因素开展半干旱草原卫星估雨的研究有限.2009年夏,我们在中国锡林郭勒半干旱草原用多部微雨雷达和雨量计构建了9 km卫星像元降雨观测网,观测了像元内降雨非均匀性(空间变异系数CV),并评估了卫星估雨精度.结果表明:(1)CV值受像元内平均降雨量,降雨类型,降雨云面积及移向等影响,如高Cv值的降雨过程大多为平均降雨量小,对流性降雨过程,降雨云边缘像元CV值较高;(2)TRMM 3B42V7卫星估雨产品适用性较好,CMORPH和PERSIANN次之,但TRMM 3B42V7易在半干旱草原湖泊处高估降雨.     

Subgrid-Scale Dynamics of Water Vapour, Heat, and Momentum over a Lake

We examine the dynamics of turbulence subgrid (or sub-filter) scales over a lake surface and the implications for large-eddy simulations (LES) of the atmospheric boundary layer. The analysis is based on measurements obtained during the Lake-Atmosphere Turbulent EXchange (LATEX) field campaign (August–October, 2006) over Lake Geneva, Switzerland. Wind velocity, temperature and humidity profiles were measured at 20 Hz using a vertical array of four sonic anemometers and open-path gas analyzers. The results indicate that the observed subgrid-scale statistics are very similar to those observed over land surfaces, suggesting that the effect of the lake waves on surface-layer turbulence during LATEX is small. The measurements allowed, for the first time, the study of subgrid-scale turbulent transport of water vapour, which is found to be well correlated with the transport of heat, suggesting that the subgrid-scale modelling of the two scalars may be coupled to save computational resources during LES.     

A New Tethered Balloon-Borne Payload for Fine-Scale Observations in the Cloudy Boundary Layer

A new scientific payload is introduced for fine-scale measurements of meteorological (wind vector, static air temperature, humidity, and air pressure) and microphysical (aerosol particles and cloud droplets) properties, suspended below a tethered balloon. The high resolution sensors and the tethered balloon are described. Measurements in a lifted fog layer from a first field campaign are presented.The detailed investigation of the fog/haze and the temperature inversion layer demonstrates the damping influence of the fog on temperature fluctuations, while thewind fluctuations are significantly decreased by theevolving temperature inversion, whichwas about 30 m above the fog layer.From spectral analysis the noise floors of the high-resolution sensors are determined to10^-6 kg m^-3 for the LWC (liquid water content) and 4 mK for the fast temperature sensor (UFT-B). The correlation betweentemperature and LWC structures in shallow haze layers is investigated. The release of latent heat and the corresponding warming in the haze of about 0.1 K could be quantified.     

A novel ozone sensor for direct eddy flux measurements

A small, lightweight (1.5 kg) and fast-response ozone sensor for direct eddy flux measurements has been built. The basis for detection is the chemiluminescence of an organic dye adsorbed on dry silica gel in the reaction with ozone. The chemiluminescence is monitored with a cheap and small blue-sensitive photomultiplier. At a flow rate of 100 l min^-1 the ozone sensor has a 90% response time of significantly better than 0.1 s with a detection limit lower than 50 ppt at S/N=3. There are no interferences from other atmospheric trace gases like NO_x, H₂O₂ and PAN. Water vapour and SO₂ enhance the chemiluminescence efficiency of the ozone sensor. Since their response times are 22 seconds and 30 minutes, respectively, no correlation between rapid ozone fluctuations and those of these two trace gases is noticed by the ozone sensor when operating at a frequency of 10 Hz.The ozone sensor was tested for several weeks in continuous measurements of ozone fluxes and deposition velocities over different croplands using the eddy correlation technique. Good agreement was found between ozone dry deposition velocities derived from profile measurements and by eddy correlation.