The Contribution of Groundwater Discharge to Nutrient Exports from a Coastal Catchment: Post-Flood Seepage Increases Estuarine N/P Ratios

Four months of daily nutrient and radon (a natural groundwater tracer) observations at the outlet of a heavily drained coastal wetland illustrated how episodic floods and diffuse groundwater seepage influence the biogeochemistry of a sub-tropical estuary (Richmond River, New South Wales, Australia). Our observations downstream of the Tuckean Swamp (an acid sulphate soil floodplain) covered a dry stage, a flood triggered by a 213-mm rain event and a post-flood stage when surface water chemistry was dominated by groundwater discharge. Significant correlations were found between radon and ammonium and N/P ratios and between radon and dissolved organic nitrogen (DON) during the post-flood stage. While the flood lasted for 14?% of the time of the surface water time series, it accounted for 18?% of NH₄, 32?% of NO _x , 66?% of DON, 58?% of PO₄ and 55?% of dissolved organic phosphorus (DOP) catchment exports. Over the 4-month study period, groundwater fluxes of 35.0, 3.6, 36.3, 0.5 and 0.7?mmol?m^?2?day^?1 for NH₄, NO _x , DON, PO₄ and DOP, respectively, were estimated. The groundwater contribution to the total surface water catchment exports was nearly 100?% for ammonium, and <20?% for the other nutrients. Post-flood groundwater seepage shifted the system from a DON to a dissolved inorganic N-dominated system and doubled N/P ratios in surface waters. We hypothesise that the Richmond River Estuary N/P ratios may reflect a widespread trend of tidal rivers and estuaries becoming more groundwater-dominated and phosphorus-limited as coastal wetlands are drained for agriculture, grazing and development.     

Risk-targeted seismic design maps for mainland France

In this article, the recently proposed approach known as ‘risk targeting’ for the development of national seismic design maps is investigated for mainland France. Risk targeting leads to ground-motion maps that, if used for design purposes, would lead to a uniform level of risk nationally. The Eurocode 8 design loads currently in force for France are used as the basis of this study. Because risk targeting requires various choices on, for example, the level of acceptable risk to be made a priori and these choices are not solely engineering decisions but involve input from decision makers we undertake sensitivity tests to study their influence. It is found that, in contrast to applications of this methodology for US cities, risk targeting does not lead to large modifications with respect to the national seismic hazard map nor to changes in the relative ranking of cities with respect to their design ground motions. This is because the hazard curves for French cities are almost parallel. In addition, we find that using a target annual collapse probability of about 10^?5 for seismically designed buildings and a probability of collapse when subjected to the design PGA of 10^?5 leads to reasonable results. This is again in contrast to US studies that have adopted much higher values for both these probabilities.     

Mathematical models for petroleum-forming processes: n-paraffins and isoprenoid hydrocarbons

Mathematical models have been developed which simulate both random and nonrandom thermal cracking of branched and straight-chain hydrocarbons. Application of these models to n-paraffins suggests that thermal cracking alone cannot be the dominant mechanism in formation of the n-paraffin distributions present in crude oils. Application to isoprenoid hydrocarbons indicates that nonrandom cracking could be important in producing the isoprenoid distributions found in oils.Results of the mathematical modeling show that methane formation should, as predicted from energy considerations, be kinetically disfavored. It therefore is likely that substantial quantities of methane are produced from saturated hydrocarbons only under thermal conditions more severe than those under which oil is produced.The mathematical models employed are adaptable for other geochemical applications, such as isotope fractionation.     

Effect of adsorbed metal ions on the transport of Zn- and Ni-EDTA complexes in a sand and gravel aquifer

Adsorption, complexation, and dissolution reactions strongly influenced the transport of metal ions complexed with ethylenediaminetetraacetic acid (EDTA) in a predominantly quartz-sand aquifer during two tracer tests conducted under mildly reducing conditions at pH 5.8 to 6.1. In tracer test M89, EDTA complexes of zinc (Zn) and nickel (Ni), along with excess free EDTA, were injected such that the lower portion of the tracer cloud traveled through a region with adsorbed manganese (Mn) and the upper portion of the tracer cloud traveled through a region with adsorbed Zn. In tracer test S89, Ni- and Zn-EDTA complexes, along with excess EDTA complexed with calcium (Ca), were injected into a region with adsorbed Mn. The only discernable chemical reaction between Ni-EDTA and the sediments was a small degree of reversible adsorption leading to minor retardation. In the absence of adsorbed Zn, the injected Zn was displaced from EDTA complexes by iron(III) [Fe(III)] dissolved from the sediments. Displacement of Zn by Fe(III) on EDTA became increasingly thermodynamically favorable with decreasing total EDTA concentration. The reaction was slow compared to the time-scale of transport. Free EDTA rapidly dissolved aluminum (Al) from the sediments, which was subsequently displaced slowly by Fe. In the portion of tracer cloud M89 that traveled through the region contaminated with adsorbed Zn, little displacement of Zn complexed with EDTA was observed, and Al was rapidly displaced from EDTA by Zn desorbed from the sediments, in agreement with equilibrium calculations. In tracer test S89, desorption of Mn dominated over the more thermodynamically favorable dissolution of Al oxyhydroxides. Comparison with results from M89 suggests that dissolution of Al oxyhydroxides in coatings on these sediment grains by Ca-EDTA was rate-limited whereas that by free EDTA reached equilibrium on the time-scale of transport. Rates of desorption are much faster than rates of dissolution of Fe oxyhydroxides from sediment-grain surfaces and, therefore, adsorbed metal ions can strongly influence the speciation of ligands like EDTA in soils and sediments, especially over small temporal and spatial scales.     

Oxygen isotopic compositions of IVA iron meteorites: implications for the thermal evolution derived from in situ ultraviolet laser microprobe analyses

Oxygen isotopic compositions of silicate inclusions in IVA iron meteorites have been measured with an in situ UV laser microprobe technique. The homogeneity of oxygen isotopic compositions within and among individual mineral grains has also been examined. Oxygen isotope fractionations between coexisting mineral pairs were utilized in oxygen isotope thermometry. Our measured Δ¹⁷O values, ranging from 0.97 to 1.25‰, are characteristic of a single reservoir and fully confirm the oxygen isotopic similarity between IVA irons and L/LL chondrites. Steinbach and São João Nepomuceno, containing inclusions of two silicate minerals in mutual contact, exhibit a mass-dependent fractionation of ¹⁸O/¹⁶O between tridymite and bronzite with apparent oxygen isotopic heterogeneity. The SiO₂-bearing member, Gibeon, gives homogeneous oxygen isotopic compositions without detectable fractionation of ¹⁸O/¹⁶O between tridymite and quartz. Oxygen isotope equilibrium temperatures are estimated for coexisting tridymite and bronzite in the same sample slabs or clusters in Steinbach and São João Nepomuceno. The fractionations of ¹⁸O/¹⁶O between bronzite and tridymite range from 1.6 to 2.3‰ in different sample slabs or clusters. On the basis of the closure temperature concept, cooling rates are estimated at approximately 20 to 1000°C/Myr between 800 and 1000°C, a range of temperatures not accessible to other cooling rate methods. Using the Fast Grain Boundary diffusion model, we have demonstrated that significant oxygen heterogeneity both in tridymite and bronzite is probably due to isotope exchange during cooling between minerals with various grain sizes and mineral abundances in different regions of the samples. The new estimates of cooling rate by oxygen isotope thermometry refine previous cooling curves of IVA irons and support the breakup-reassembly model for the IVA parent body.     

Diversity of recent planktonic foraminifera in the southern Indian Ocean and Late Pleistocene paleotemperatures

Planktonic foraminiferal assemblages have been examined in 25 trigger core top samples and 51 piston core top samples collected between latitudes 28° S and 55° S and longitudes 79° E and 120° E from the southern Indian Ocean during cruises of the U.S.N.S. Eltanin. Samples taken from water depths exceeding 4000 m and/or showing evidence of calcium carbonate dissolution were eliminated from further analysis. The final piston core data set consists of 34 samples; the trigger core data set containing 21 samples. A close relationship exists between changes in the planktonic foraminiferal assemblages in the surface sediments and surface water temperatures. Species diversity values were computed for each of the core top assemblages using the Shannon-Wiener Index and the Brillouin Index, each of which takes into consideration the number of species and the proportionment of individuals among the species. The Shannon and Brillouin diversity values for all samples are positively correlated (correlation coefficient (r) = +.999). Regression analysis of latitude versus Shannon diversity values in the trigger core samples clearly shows a decrease in diversity with increasing latitude (r = ?.979). Furthermore, a strong correlation (r = +.977) exists between decreasing species diversity (Shannon) and decreasing average summer-winter temperature of the overlying surface waters. A paleotemperature equation derived from the relationship of diversity in trigger core samples and surface water temperature was used to generate paleotemperature curves for five trigger cores and a 6 m piston core of Late Pleistocene age, located beneath the present position of the Subtropical Convergence. A 7–8° C temperature range is suggested between the interglacial and glacial episodes in this Late Pleistocene sequence, and probably reflects latitudinal shifts of the Subtropical Convergence and Australasian Front during the Late Pleistocene.     

Lacustrine sedimentation in a semiarid alpine setting: An example from Ladakh, northwestern Himalaya

The Lamayuru lacustrine strata in Ladakh typify many of the carbonate-rich Pleistocene alpine lakes found in the semiarid environment of the northern Himalaya. Created by a 200-m-thick landslide, the lake was in existence by at least 35,000 yr ago, and may have persisted until 500–1000 yr ago. Represented in the center by thin turbidites and laminated muds, the lacustrine sedimentation along the lake margins and low-relief deltas characteristically displays a marked contrast between (1) clastic lenses representing rapid, sporadic, matrix-poor debris flows and periglacial inputs from the alpine slopes and (2) abundant, diverse, shallow-water, biologically dominated carbonate strata, among which organism-rich, chalky beds and oncolithic and encrusted stem-rich strata predominate. Resemblances of the Lamayuru lacustrine strata and their setting to those of former lakes throughout areas north of the Greater Himalayan crest suggest that the alpine, semi-arid environment would favor diversified, spacially restricted carbonate sedimentation punctuated by occasional clastic influxes. Such a depositional regime contrasts strongly with that found immediately south of the Himalayan crest where more humid conditions promote a more continuous clastic influx into intramontane lakes.