Molecular formulae of marine and terrigenous dissolved organic matter detected by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

The chemical structure of refractory marine dissolved organic matter (DOM) is still largely unknown. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS) was used to resolve the complex mixtures of DOM and provide valuable information on elemental compositions on a molecular scale. We characterized and compared DOM from two sharply contrasting aquatic environments, algal-derived DOM from the Weddell Sea (Antarctica) and terrigenous DOM from pore water of a tropical mangrove area in northern Brazil. Several thousand molecular formulas in the mass range of 300-600 Da were identified and reproduced in element ratio plots. On the basis of molecular elemental composition and double-bond equivalents (DBE) we calculated an average composition for marine DOM. O/C ratios in the marine samples were lower (0.36 ± 0.01) than in the mangrove pore-water sample (0.42). A small proportion of chemical formulas with higher molecular mass in the marine samples were characterized by very low O/C and H/C ratios probably reflecting amphiphilic properties. The average number of unsaturations in the marine samples was surprisingly high (DBE = 9.9; mangrove pore water: DBE = 9.4) most likely due to a significant contribution of carbonyl carbon. There was no significant difference in elemental composition between surface and deep-water DOM in the Weddell Sea. Although there were some molecules with unique marine elemental composition, there was a conspicuous degree of similarity between the terrigenous and algal-derived end members. Approximately one third of the molecular formulas were present in all marine as well as in the mangrove samples. We infer that different forms of microbial degradation ultimately lead to similar structural features that are intrinsically refractory, independent of the source of the organic matter and the environmental conditions where degradation took place.     

Response of precipitation over Greenland and the adjacent ocean to North Pacific warm spells during Dansgaard–Oeschger stadials

ABSTRACT Palaeoceanographic reconstructions from the North Atlantic indicate massive ice breakouts from East Greenland near the onset of cold Dansgaard–Oeschger (D–O) stadials. In contrast to these coolings in the North Atlantic area, a new sea-surface temperature record reveals concomitant warm spells in the northern North Pacific. A sensitivity experiment with an atmospheric general circulation model is used to test the potential impact of sea-surface warmings by 3.5 °C in the North Pacific, on top of otherwise cold stadial climate conditions, on the precipitation regime over the Northern Hemisphere ice sheets. The model predicts a maximum response over East Greenland and the Greenland Sea, where a 40% increase in net annual snow accumulation occurs. This remote effect of North Pacific warm spells on the East Greenland snow-accumulation rate may play an important role in generating D–O cycles by rebuilding the ice lost during ice breakouts. In addition, the increased precipitation over the Greenland Sea may help to sustain the D–O stadial climate state.     

The respective roles of surface temperature driven feedbacks and tropospheric adjustment to CO2 in CMIP5 transient climate simulations

An overview of radiative climate feedbacks and ocean heat uptake efficiency diagnosed from idealized transient climate change experiments of 14 CMIP5 models is presented. Feedbacks explain about two times more variance in transient climate response across the models than ocean heat uptake efficiency. Cloud feedbacks can clearly be identified as the main source of inter-model spread. Models with strong longwave feedbacks in the tropics feature substantial increases in cloud ice around the tropopause suggestive of changes in cloud-top heights. The lifting of the tropical tropopause goes together with a general weakening of the tropical circulation. Distinctive inter-model differences in cloud shortwave feedbacks occur in the subtropics including the equatorward flanks of the storm-tracks. Related cloud fraction changes are not confined to low clouds but comprise middle level clouds as well. A reduction in relative humidity through the lower and mid troposphere can be identified as being the main associated large-scale feature. Experiments with prescribed sea surface temperatures are analyzed in order to investigate whether the diagnosed feedbacks from the transient climate simulations contain a tropospheric adjustment component that is not conveyed through the surface temperature response. The strengths of the climate feedbacks computed from atmosphere-only experiments with prescribed increases in sea surface temperatures, but fixed CO₂ concentrations, are close to the ones derived from the transient experiment. Only the cloud shortwave feedback exhibits discernible differences which, however, can not unequivocally be attributed to tropospheric adjustment to CO₂. Although for some models a tropospheric adjustment component is present in the global mean shortwave cloud feedback, an analysis of spatial patterns does not lend support to the view that cloud feedbacks are dominated by their tropospheric adjustment part. Nevertheless, there is positive correlation between the strength of tropospheric adjustment processes and cloud feedbacks across different climate models.     

Catchment precipitation processes in the San Francisco valley in southern Ecuador: combined approach using high-resolution radar images and in situ observations

The precise estimation of precipitation quantities in tropical mountain regions is in great demand by ecological and hydrological studies, due to the heterogeneity of the rainfall distribution and the lack of meteorological station data. This study uses radar images and ground station data to provide the required high-resolution precipitation maps. Also wind data are taken into account, due to its influence on the precipitation formation and to demonstrate the relation between synoptic wind, topography and the precipitation distribution inside small mountain valleys. The study analyses the rainfall distribution and amounts of 4 days inside the San Francisco Valley, a small catchment in the tropical Andes of southern Ecuador, representing different seasons and the typical atmospheric flows, which are correlated to the annual precipitation map. The results show that the rainfall distribution and amounts are generally defined by the wind direction and velocity, besides the topographic location in relation to the main barriers and pathways. The dominant wind direction causes a division of the catchment in a wetter eastern and a dryer western part. Moreover, the annual seasons are reversed; the main rainy season for the eastern part occurs between June and August, while the western part reaches the precipitation maximum between January and March. This may have influence on the species composition at the different slopes and the annual hydrological cycle inside the catchment.     

Wave Flow Simulations Over Arctic Leads

We investigate the flow over Arctic leads using a mesoscale numerical model, typical of both summer and winter, under idealised conditions. We find that Arctic leads may be the source of standing atmospheric internal gravity waves during both seasons. The summertime wave may be compared with the wave generated by a small ridge, though with the phase reversed. The mechanism for exciting the wave is found to be the internal boundary layer developing due to horizontal variations in surface temperature and roughness length. During the more exploratory wintertime simulations, with substantial temperature difference between the lead and the ice surface, we find that secondary circulations and intermittent wave-breaking may occur. The effects of the lead appear far downstream.     

iVINE – Ionization in the parallel tree/sph code VINE: first results on the observed age-spread around O-stars

We present a three-dimensional, fully parallelized, efficient implementation of ionizing ultraviolet (UV) radiation for smoothed particle hydrodynamics ( sph ) including self-gravity. Our method is based on the sph / tree code vine . We therefore call it iVINE (for Ionization + VINE). This approach allows detailed high-resolution studies of the effects of ionizing radiation from, for example, young massive stars on their turbulent parental molecular clouds. In this paper, we describe the concept and the numerical implementation of the radiative transfer for a plane-parallel geometry and we discuss several test cases demonstrating the efficiency and accuracy of the new method. As a first application, we study the radiatively driven implosion of marginally stable molecular clouds at various distances of a strong UV source and show that they are driven into gravitational collapse. The resulting cores are very compact and dense exactly as it is observed in clustered environments. Our simulations indicate that the time of triggered collapse depends on the distance of the core from the UV source. Clouds closer to the source collapse several 10⁵ yr earlier than more distant clouds. This effect can explain the observed age spread in OB associations where stars closer to the source are found to be younger. We discuss possible uncertainties in the observational derivation of shock front velocities due to early stripping of protostellar envelopes by ionizing radiation.     

Interaction of bentonite colloids with Cs, Eu, Th and U in presence of humic acid: A flow field-flow fractionation study

The interaction of Cs(I), Eu(III), Th(IV) and U(VI) with montmorillonite colloids was investigated in natural Grimsel Test Site groundwater over a 3 years period. The asymmetric flow field-flow fractionation combined with various detectors was applied to study size variations of colloids and to monitor colloid association of trace metals. The colloids suspended directly in the low ionic strength (I), slightly alkaline granitic groundwater (I = 10⁻³ mol/L, pH 9.6) showed a gradual agglomeration with a size distribution shift from initially 10-200 nm to 50-400 nm within over 3 years. The Ca²⁺ concentration of 2.1 × 10⁻⁴ mol/L in the ground water is believed to be responsible for the slow agglomeration due to Ca²⁺ ion exchange against Li⁺ and Na⁺ at the permanently charged basal clay planes. Furthermore, the Ca²⁺ concentration lies close to the critical coagulation concentration (CCC) of 10⁻³ mol L⁻¹ for clay colloids. Slow destabilization may delimit clay colloid migration in this specific groundwater over long time scales. Eu(III) and Th(IV) are found predominantly bound to clay colloids, while U(VI) prevails as the UO₂(OH)₃⁻ complex and Cs(I) remains mainly as aquo ion under our experimental conditions. Speciation calculations qualitatively represent the experimental data. A focus was set on the reversibility of metal ion-colloid binding. Addition of humic acid as a competing ligand induces rapid metal ion dissociation from clay colloids in the case of Eu(III) even after previous aging for about 3 years. Interestingly only partial dissociation occurs in the case of Th(IV). Experiments and calculations prove that the humate complexes dominate the speciation of all metal ions under given conditions. The partial irreversibility of clay bound Th(IV) is presently not understood but might play an important role for the colloid-mediated transport of polyvalent actinides over wide distances in natural groundwater.