Impact of nitrogenous fertilizers on carbonate dissolution in small agricultural catchments: Implications for weathering CO2 uptake at regional and global scales

The goal of this study was to highlight the occurrence of an additional proton-promoted weathering pathway of carbonate rocks in agricultural areas where N-fertilizers are extensively spread, and to estimate its consequences on riverine alkalinity and uptake of CO₂ by weathering. We surveyed 25 small streams in the calcareous molassic Gascogne area located in the Garonne river basin (south-western France) that drain cultivated or forested catchments for their major element compositions during different hydrologic periods. Among these catchments, the Hay and the Montoussé, two experimental catchments, were monitored on a weekly basis. Studies in the literature from other small carbonate catchments in Europe were dissected in the same way. In areas of intensive agriculture, the molar ratio (Ca + Mg)/HCO₃ in surface waters is significantly higher (0.7 on average) than in areas of low anthropogenic pressure (0.5). This corresponds to a decrease in riverine alkalinity, which can reach 80% during storm events. This relative loss of alkalinity correlates well with the content in surface waters. In cultivated areas, the contribution of atmospheric/soil CO₂ to the total riverine alkalinity (CO_{2 ATM-SOIL}/HCO₃) is less than 50% (expected value for carbonate basins), and it decreases when the nitrate concentration increases. This loss of alkalinity can be attributed to the substitution of carbonic acid (natural weathering pathway) by protons produced by nitrification of N-fertilizers (anthropogenic weathering pathway) occurring in soils during carbonate dissolution. As a consequence of these processes, the alkalinity over the last 30 years shows a decreasing trend in the Save river (one of the main Garonne river tributaries, draining an agricultural catchment), while the nitrate and calcium plus magnesium contents are increasing.We estimated that the contribution of atmospheric/soil CO₂ to riverine alkalinity decreased by about 7-17% on average for all the studied catchments. Using these values, the deficit of CO₂ uptake can be estimated as up to 0.22-0.53 and 12-29 Tg¹ yr⁻¹ CO₂ on a country scale (France) and a global scale, respectively. These losses represent up to 5.7-13.4% and only 1.6-3.8% of the total CO₂ flux naturally consumed by carbonate dissolution, for France and on a global scale, respectively. Nevertheless, this loss of alkalinity relative to the Ca + Mg content relates to carbonate weathering by protons from N-fertilizers nitrification, which is a net source of CO₂ for the atmosphere. This anthropogenic CO₂ source is not negligible since it could reach 6-15% of CO₂ uptake by natural silicate weathering and could consequently partly counterbalance this natural CO₂ sink.     

Fast kimberlite ascent rates estimated from hydrogen diffusion profiles in xenolithic mantle olivines from southern Africa

Fourier transform infrared spectrometry (FTIR) analyses of olivines from peridotite xenoliths found in southern African kimberlites indicate 0 to 80 ppm H₂O concentrations. OH absorbance profiles across olivine grains show homogeneous H contents from core to edge for most samples. In one sample the olivines are H-free, while another has olivines characterized by lower H contents at the grain edges compared to the cores, indicating H loss during transport of the xenolith to the surface. Flat or near-flat H profiles place severe constraints on the duration of H loss from olivine grains, with implications for kimberlite magma ascent rates. Diffusion equations were used to estimate times of H loss of about 4 h for the sample with heterogeneous olivine H contents. Resulting kimberlite ascent rates are calculated to be 5-37 m s⁻¹ minimum, although these estimates are highly dependent on volatile contents and degassing behavior of the host kimberlite magma. Xenolithic olivines from alkali basalts generally have lower H contents and more pronounced H diffusion profiles than do those from kimberlites. This difference is likely caused by higher magma temperatures and lower ascent rates of alkali basalts compared to kimberlites.     

Thermal evolution and physics of melt extraction on the ureilite parent body

We develop a physical model of the thermal history of the ureilite parent body (UPB) that numerically tracks the history of its heating, hydration, dehydration, partial melting and smelting as a function of its formation time and the initial values of its composition, formation temperature and water ice content. Petrologic and chemical data from the main group (non-polymict) ureilite meteorites, which sample the interior of the UPB between depths corresponding to pressures in the range 3-10 MPa, are used to constrain the model. We find that to achieve the ∼30% melting inferred for ureilites from all sampled depths, the UPB must have had a radius between ∼80 and ∼130 km and must have accreted about 0.55 Ma after CAI formation. Melting began in the body at ∼1 Ma after CAI, and the time at which 30% melting was reached varied with depth in the asteroid but was always between ∼4.5 and ∼5.8 Ma after CAI. The total rate at which melt was produced in the UPB varied from more than 100 m³ s⁻¹ in the very early stages of melting at ∼1 Ma after CAI to ∼5 m³ s⁻¹ between 2 and 3 Ma after CAI, decreasing to extremely small values as the end of melting was approached beyond ∼5 Ma. Although the initial period of high melt production occupied only a short time around 1 Ma after CAI, it corresponded to ∼half (16%) of total silicate melting, and all strictly basaltic (i.e. plagioclase-saturated) melts must have been produced during this period.A very efficient melt transport network, consisting of a hierarchy of veins and larger pathways (dikes), developed quickly at the start of melting, ensuring rapid (timescales of months) transport of any single parcel of melt to shallow levels, thus ensuring that chemical interaction between melts and the rocks through which they subsequently passed was negligible. Volatile (mainly carbon monoxide) production due to smelting began at the start of silicate melting in the shallowest parts of the UPB and at later times at greater depths. Except at the very start and very end of melting, the volatile content of the melts produced was always high - generally between 15 and 35 mass % - and most of the melt produced was erupted at the surface of the UPB with speeds well in excess of the escape velocity and was lost into space. However, we show that 30% melting at the 3 MPa pressure level was only possible if ∼15% of the total melt produced in the asteroid was retained as a small number (∼5) of very extensive, sill-like intrusions centered at a depth of ∼7 km below the surface, near the base of the ∼8 km thick outer crust of the asteroid that was maintained at temperatures below the basalt solidus by conductive heat loss to the surface. The horizontal extents of these sills occupied about 75% of the surface area of the UPB, and the sills acted as buffers between the steady supply of melt from depth and the intermittent explosive eruption of the melt into space. We infer that samples from these intrusions are preserved as the rare feldspathic (loosely basaltic) clasts in polymict ureilites, and show that the cooling histories of the sills are consistent with these clasts reaching isotopic closure at ∼5 Ma after CAI, as given by ²⁶Al-²⁶Mg, ⁵³Mn-⁵³Cr and Pb-Pb age dates.     

The Dynamics of Covering Behaviour in Dominant Echinoid Populations from American and European West Coasts

Abstract.  The so-called 'covering behaviour' of echinoids is known to vary with habitat according to the types of covering items available, but the full extent of the role played by habitat characteristics in this behaviour is not known. Moreover, whether or not different species inhabiting similar environmental conditions and habitats also show similar patterns of this particular behaviour has yet to be investigated. In this study, two prominent west coast echinoid species, Paracentrotus lividus and Strongylocentrotus purpuratus , were examined with respect to covering behaviour and spatial organisation. Populations of both species are found in exposed intertidal zones, occupying boreholes within tidepools. Important similarities were found in the spatial organisation of both species' populations, with lowest densities in upper shore pools. However, the size distributions of the two populations differed significantly; P. lividus within upper shore pools were significantly larger than those in mid or lower shore pools, whereas S. purpuratus on the lower shore were significantly larger than those at other shore heights. We found significant between-species variability in covering item use, although the number of covering items available at both sites was not significantly different. For example, greater densities of covering items were used by P. lividus than by S. purpuratus . We also found that the percent of echinoid surface area covered varied significantly in space for both species. These data emphasise the complex and multifaceted nature of covering behaviour, but most importantly, they also strongly suggest that habitat characteristics can only partly explain the extent of this behavioural variability amongst echinoid species.     

The expression of CYP1A,vitellogenin and zona radiata proteins in Atlantic salmon (Salmo salar) after oral dosing with two commercial PBDE flame retardant mixtures: absence of short-term responses

The short-term effects of the commercial PBDE flame retardant mixtures Penta-BDE and cta-BDE on the expression of cytochrome P450 1A (CYP1A), vitellogenin (Vtg) and zona radiata proteins (Zrp) were investigated in juvenile salmon (Salmo salar). For this purpose, groups of fish were dosed twice (oral intake at days I and 4) with 10 and 50 mg/kg body weight of both commercial mixtures. The fishes were sacrificed at day 7 (n = 5 for each group) and 14 (n = 6 for each group), and blood, liver, fillet, and brain were collected. Blanks and positive controls were also part of the experiment. The expressions of Vtg, Zrp, and CYPIA were measured with several techniques (EROD, ELISA, Western, Northern and Slot Blot). The values in the groups of fish treated with Penta-BDE or Octa-BDE did not significantly differ from the reference group for any of the parameters tested. In contrast, the positive control groups treated with estradiol-17beta for Vtg and Zrp expression, and beta-naphthoflavone for CYP1A expression did show a significant response, indicating the potential sensitivity of the fishes for the parameters measured. Since the results of the chemical analyses showed concentrations of a number of PBDE congeners in liver, fillet, and brain that were about three orders of magnitude above those of fish from the North Sea, it is concluded that the short-term toxicity of both commercial PBDE mixtures for these endpoints was low.     

Development of two novel CYP-antibodies and their use in a PCB exposure experiment with Mytilus edulis

In an attempt to learn more about the cytochrome P450 (CYP) system of mussels, we used protein databases and alignment software to extract highly conserved CYP sequences. From these alignments synthetic peptides were produced and used for rabbit immunisation, which yielded polyclonal antibodies against the CYP families 2 and 4. The antibodies were evaluated with Western Blot and ELISA assays, using digestive gland microsomal samples from the mussel Mytilus edulis. Western Blots revealed immunoreactions for both antibodies. The anti-CYP2 sequence rendered one major immunopositive protein of approximately 49 kDa size, and weak signals for proteins of approximately 41 and 56 kDa size. The anti-CYP4 sequence rendered two major bands of approximately 56 and 59 kDa size, and also a weak immunoreaction with a protein of approximately 43 kDa size. ELISA rendered only weak signals even with a 1:50 dilution of IgG-purified serum. A 10-day exposure to Aroclor 1254 did not appear to affect any of the immunopositive proteins, while total PCBs in soft bodies increased from 14-40 ng/g DW in controls to 373-638 ng/g DW in exposed mussels.     

Vertical habitat partitioning by large calanoid copepods in the oceanic subarctic Pacific during Spring

The copepods Neocalanus plumchrus, N. flemingeri, N. cristatus, and Eucalanus bungii dominate the net zooplankton throughout the subarctic Pacific Ocean. All four species have an extensive seasonal ontogenetic vertical migration, completing most or all of their feeding and somatic growth in spring and early summer. We used stratified tows with MOCNESS and BIONESS instrumented net systems to resolve their upper ocean vertical distributions in May and June of 1984, 1987 and 1988. In each year the feeding copepodite stages of all four species were concentrated above the permanent halocline (roughly from 0 to 150m). However, the four species showed strong vertical species zonation and segregation within this layer. We consistently found a near-surface pair (N. plumchrus and N. flemingeri) and a subsurface pair (N. cristatus and E. bungii). The boundary between these groups shifts vertically, but was sharply defined and was very often coincident with a weak and transient thermocline marking the base of the layer actively mixed by surface wind and wave energy. Diel vertical migration was very limited during our sampling periods.The data suggest that the vertical distribution patterns of the copepods could be set by responses to the local intensity of turbulent mixing in the watercolumn. N. plumchrus and N. flemingeri occupied a stratum characterized by strong turbulence. N. cristatus and E. bungii occupied a stratum that was a local minimum in turbulence profiles. The depth of the boundary between the species pairs was deeper when winds and surface energy inputs were strong. The vertical partition pattern may also be determined by a difference in feeding strategy between the species pairs. N. plumchrus and N. flemingeri may feed on the enhanced protozoan population of the mixed layer, while N. cristatus and E. bungii feed on particle aggregates settling from above.