The dissociation constants of carbonic acid in seawater at salinities 5 to 45 and temperatures 0 to 45°C

The pK₁^* and pK₂^* for the dissociation of carbonic acid in seawater have been determined from 0 to 45°C and S = 5 to 45. The values of pK₁^* have been determined from emf measurements for the cell:

Pt](1 − X)H2 + XCO2|NaHCO3, CO2 in synthetic seawater|AgC1; Ag

where X is the mole fraction of CO₂ in the gas. The values of pK₂^* have been determined from emf measurements on the cell:

Pt, H2(g, 1 atm)|Na2CO3, NaHCO3 in synthethic seawater|AgC1; Ag

The results have been fitted to the equations:

lnK^*₁ = 2.83655 − 2307.1266/T − 1.5529413 lnT + (−0.20760841 − 4.0484/T)S^0.5 + 0.08468345S − 0.00654208S¹

InK^*₂ = −9.226508 − 3351.6106/T− 0.2005743 lnT + (−0.106901773 − 23.9722/T)S^0.5 + 0.1130822S − 0.00846934S^1.5

where T is the temperature in K, S is the salinity, and the standard deviations of the fits are σ = 0.0048 in lnK₁^* and σ = 0.0070 in lnK₂^*.Our new results are in good agreement at S = 35 (±0.002 in pK₁^*and ±0.005 in pK₂^*) from 0 to 45°C with the earlier results of Goyet and Poisson (1989). Since our measurements are more precise than the earlier measurements due to the use of the Pt, H₂|AgCl, Ag electrode system, we feel that our equations should be used to calculate the components of the carbonate system in seawater.     

Une approche innovante pour modéliser la biodégradation des composés organochlorés volatils en aquifères poreux

The goal of this study was to develop an innovative chloroethene biodegradation module based on biological, thermodynamical and mechanistic concepts. The biodegradation scheme was based on the postulate that in each part of an aquifer only one degradation mechanism is dominant: the one involving the most energetic electron acceptor. Thus, the selection of the active degradation mechanism was a function of the concentration of different electron acceptors. Modified Monod-type kinetics was used in order to take into account the possible influence of some compounds on the biodegradation of a given organic compound. The numerical model developed was applied to a simple test case, whose results are presented here. To cite this article: F. Nex et al., C. R. Geoscience 338 (2006).     

Geochemistry of silicic magmas in the Macolod Corridor, SW Luzon, Philippines: evidence of distinct, mantle-derived, crustal sources for silicic magmas

Silicic volcanic deposits (>65 wt% SiO₂), which occur as domes, lavas and pyroclastic deposits, are relatively abundant in the Macolod Corridor, SW Luzon, Philippines. At Makiling stratovolcano, silicic domes occur along the margins of the volcano and are chemically similar to the silicic lavas that comprise part of the volcano. Pyroclastic flows are associated with the Laguna de Bay Caldera and these are chemically distinct from the domes and lavas at Makiling stratovolcano. As a whole, samples from the Laguna de Bay Caldera contain lower concentrations of MgO and higher concentrations of Fe₂O_3(t) than the samples from domes and lavas. The Laguna de Bay samples are more enriched in incompatible trace elements. The silicic rocks from the domes, Makiling Volcano and Laguna de Bay Caldera all contain high alkalis and high K₂O/Na₂O ratios. Melting experiments of primitive basalts and andesites demonstrate that it is difficult to produce high K₂O/Na₂O silicic magmas by fractional crystallization or partial melting of a low K₂O/Na₂O source. However, recent melting experiments (Sisson et al., Contrib Mineral Petrol 148:635–661, 2005) demonstrate that extreme fractional crystallization or partial melting of K-rich basalts can produce these silicic magmas. Our model for the generation of the silicic magmas in the Macolod Corridor requires partial melting of mantle-derived, evolved, moderate to K-rich, crystallized calc-alkaline magmas that ponded and crystallized in the mid-crust. Major and trace element variations, along with oxygen isotopes and ages of the deposits, are consistent with this model. Electronic Supplementary Material Supplementary material is available for this article at     

A Holocene high-resolution record of aquatic productivity,seasonal anoxia and meromixis from varved sediments of Lake Łazduny,North-Eastern Poland: insight from a novel multi-proxy approach

Anthropogenic eutrophication and spreading anoxia in freshwater systems is a global concern. Little is known about anoxia in earlier historic times under weaker human impact, or under prehistoric natural conditions with different trophic, land cover and climatic regimes. We use a novel approach that combines high-resolution hyperspectral imaging with µ-XRF and HPLC-pigment data, which allows us to assess chloropigments (productivity) and bacteriopigments (anoxia) at seasonal subvarve-scale resolution. Our ~9700 cal a bp varved sediment record from NE Poland suggests that productivity increased stepwise from oligotrophic Early Holocene conditions (until ~9200 cal a bp ) to mesotrophic conditions in the Mid- and Late Holocene. Natural eutrophication was mainly a function of progressing landscape evolution with intense weathering under dense forest and warm-moist climatic conditions. Generally, anoxia increased with increasing productivity. Seasonal anoxia and some multi-decadal periods of meromixis were the common mixing patterns throughout the Holocene except for a period of persisting meromixis between ~5200 and 2000 cal a bp. Anthropogenic deforestation around 400 cal a bp resulted in substantially better lake oxygenation despite high productivity. In this small lake, aquatic productivity and lakeshore forest cover (wind shield) were more important factors controlling oxic/anoxic conditions than Holocene temperature variability.     

2D probabilistic prediction of sparsely measured earth properties constrained by geophysical imaging fully accounting for tomographic reconstruction ambiguity

Many hydrological, environmental, or engineering exploration tasks require predicting spatially continuous scenarios of sparsely measured borehole logging data. We present a methodology to probabilistically predict such scenarios constrained by ill-posed geophysical tomography. Our approach allows for transducing tomographic reconstruction ambiguity into the probabilistic prediction of spatially continuous target parameter scenarios. It is even applicable to data sets where petrophysical relations in the survey area are non-unique, i.e., different facies related petrophysical relations may be present. We employ static two-layer artificial neural networks (ANNs) for prediction and additionally evaluate, whether the training performance of the ANNs can be used to rank geophysical tomograms, which are mathematically equal reconstructions of physical parameter distributions in the ground. We illustrate our methodology using a realistic synthetic database for maximal control about the prediction performance and ranking potential of the approach. For doing so, we try to link geophysical radar and seismic tomography as input parameters to porosity of the ground as target parameter of ANN. However, the approach is flexible and can cope with any combination of geophysical tomograms and hydrologic, environmental or engineering target parameters. Ranking of equivalent geophysical tomograms based on additional borehole logging data is found to be generally possible, but risks remain that the ranking based on the ANN training performance does not fully coincide with the closeness of geophysical tomograms to ground truth. Since geophysical field data sets do usually not offer control options similar to those used in our synthetic database, we do not recommend the utilization of recurrent ANNs to learn weights for the individual geophysical tomograms used in the prediction procedure.     

Flooding a landscape: impact of Holocene transgression on coastal sedimentology and underwater archaeology in Kiladha Bay (Greece)

Franchthi Cave, bordering Kiladha Bay, in Greece, is a key archaeological site, due to its long occupation time, from?~?40,000 to?~?5000 year BP. To date, no clear evidence of Neolithic human dwellings in the cave was found, supporting the assumption that Neolithic people may have built a village where there is now Kiladha Bay. During the Neolithic period/Early Holocene, wide areas of the bay were indeed emerged above sea level. Bathymetric and seismic data identified a terrace incised by a valley in?~?1 to 2 m sediment depth. Eight sediment cores, up to 6.3-m-long, were retrieved and analysed using petrophysical, sedimentological, geochemical, and chronostratigraphic methods. The longest core extends into the exposure surface, consisting of a layer of carbonate rubble in a finer matrix, representing weathering processes. Dated organic remains place this unit at?~?8500 cal year BP. It is overlain by stiff silty mud representing an estuarine environment. This mud is capped by reduced sediments with roots marking an exposure surface. A shell-layer, dated to?~?6300 cal year BP, overlies this terrestrial sequence, reflecting the marine transgression. This layer occurs at 10.8 mbsl, 7.7 m deeper than the global sea level at that time, suggesting tectonic subsidence in the area. It is overlain by finer-grained marine carbonate-rich sediments. The top of the core shows traces of eutrophication, pebbles and marine shells, all likely a result of modern anthropogenic processes. These results are interpreted in the context of human occupation: the exposed surface contains pottery sherds, one dating to the Early to Middle Neolithic period, indicating that Neolithic people were present in this dynamic landscape interacting with a migrating coastline. Even if the artefacts are isolated, future investigations of the submerged landscape off Franchthi Cave might lead to the discovery of a Neolithic village, which eventually became buried under marine sediments.