Metal binding to dissolved organic matter and adsorption to ferrihydrite in shallow peat groundwaters: Application to diamond exploration in the James Bay Lowlands,Canada

The speciation and solubility of kimberlite pathfinder metals (Ni, Nd, Ba and K) in shallow peat groundwaters is investigated over the Yankee, Zulu and Golf kimberlites in the Attawapiskat region, James Bay Lowlands, Canada. The purpose of this study is to examine the relationship between dissolved organic matter (DOM) complexation with kimberlite pathfinder metals and determine the spatial distribution of those metals in shallow peat groundwaters along sampling transects over subcropping kimberlites. Nickel, Nd, Ba and K complexation with DOM and the adsorption of these metals onto ferrihydrite were calculated using Visual MINTEQ 3.0 and the NICA-Donnan database. Calculations predict almost 100% of soluble Nd, Ni and Ba form complexes with DOM at sampling sites with little to no contribution from upwelling groundwater (i.e., dissolved organic C (DOC) concentrations = 40–132 mg/L, pH = 3.9–5.5, and log ionic strength ??3). In only the most ombrotrophic peat groundwater conditions does a majority fraction of K bind to DOM. By contrast, under conditions with large contributions from upwelling groundwaters (i.e., DOC concentrations ?40 mg/L, pH = 5.5–6.5, and log ionic strength = ?3 to ?2), as little as 10% of Nd and Ni, and 0% K and Ba are predicted to complex with DOM. The modeling calculations suggest the dominant control on metal–DOM complexation, particularly with respect to Ni and Nd, is competitive effects for DOM binding sites due to elevated ionic strength where there is evidence of strong groundwater upwelling. Visual MINTEQ modeling of metal adsorption on ferrihydrite surfaces predicts that under strong upwelling conditions, Ni and Nd are scavenged from solution due to increased ferrihydrite precipitation and decreased fractions of metals complexed with DOM. Analytical geochemical data are consistent with model predictions of metal adsorption on ferrihydrite. Total dissolved Ni and Nd concentrations at sites of strong upwelling are up to five times lower than waters with little to no upwelling and log ferrihydrite saturation indices (logSI_ferr) indicate precipitation (values up to 5) at sites of strong groundwater upwelling. Where the majority of Ni and Nd complex with DOM and ferrihydrite is highly under saturated (logSI_ferr = ?18 to ?5), the concentrations of total Ni and Nd are elevated compared to other sites along sampling transects. Metal complexation with DOM effectively inhibits metal scavenging from solution via adsorption and/or from forming secondary mineral precipitates. Also, because alkaline earth metals do not compete strongly with Ni and Nd for adsorption sites on ferrihydrite surfaces, but do compete strongly for insoluble organic sites, Ni and Nd are more likely to adsorb onto ferrihydrite.     

Aspects of wave behaviour in the mid‐ and upper troposphere of the southern Hemisphere

Abstract

The zonal wavenumber spectra of the geopotential heights of the 300‐ and 500‐mb surfaces in the Southern Hemisphere were determined for each month between May 1972 and November 1979 using daily operational analyses produced by the Australian Bureau of Meteorology. During over one‐quarter of the “summer” months (November through March) there are very prominent peaks at zonal wavenumber five in the region of the mid‐latitude jet (～35–60°S). Frequently wavenumber five totally dominates the eddy fields in individual daily maps so that height contours in mid‐latitudes take on virtually pentagonal shapes. During periods when wavenumber 5 is prominent, it is observed to propagate eastward in a very regular manner with a period of about eleven days. All these findings are consistent with Salby's (1982) earlier results concerning the Southern Hemisphere height fields during the first few months of the FGGE experiment.

There is little evidence for a similar phenomenon in the winter circulation of the Southern Hemisphere.     

Modelling and mass balance assessments of nutrient retention in a seasonally-flowing estuary (Swan River Estuary,Western Australia)

An integrated mass balance and modelling approach for analysis of estuarine nutrient fluxes is demonstrated in the Swan River Estuary, a microtidal system with strong hydrological dependence on seasonal river inflows. Mass balance components included estimation of gauged and ungauged inputs to the estuary and losses to the ocean (outflow and tidal exchange). Modelling components included estimation of atmospheric (N fixation, denitrification) and sediment–water column nutrient exchanges. Gross and net denitrification derived using two independent methods were significantly correlated (r² = 0.49, p < 0.01) with net rates averaging 40% of gross. Annual nitrogen (N) and phosphorus (P) loads from major tributaries were linearly correlated with annual freshwater discharge and were 3-fold higher in wet years than in dry years. Urban drains and groundwater contributed, on average, 26% of N inputs and 19% of P inputs, with higher relative contributions in years of low river discharge. Overall, ungauged inputs accounted for almost 35% of total nitrogen loads. For N, elevated loading in wet years was accompanied by large increases in outflow (7x) and tidal flushing (2x) losses and resulted in overall lower retention efficiency (31%) relative to dry years (70%). For P, tidal flushing losses were similar in wet and dry years, while outflow losses (4-fold higher) were comparable in magnitude to increases in loading. As a result, P retention within the estuary was not substantially affected by inter-annual variation in water and P loading (ca. 50% in all years). Sediment nutrient stores increased in most years (remineralisation efficiency ca. 50%), but sediment nutrient releases were significant and in some circumstances were a net source of nutrients to the water column.     

Dynamics of the Tropical Middle Atmosphere: A Tutorial Review*

Abstract

The general circulation of the tropical stratosphere, mesosphere and lowermost thermosphere is discussed at a tutorial level. Observations of the quasi‐biennial and semiannual oscillations by both in situ and satellite techniques are first reviewed. The basic dynamics controlling the zonal‐mean component of the circulation are then discussed. The role of radiative diabatic cooling in constraining the zonal‐mean circulation in the middle atmosphere is emphasized. It is shown that the effectiveness of this radiative constraint is reduced at low latitudes, allowing for the sustained mean flow accelerations over long periods of time characteristic of the quasi‐biennial and semiannual oscillations in the tropics.

The current view is that the dominant driving for the equatorial mean flow accelerations seen in the middle atmosphere derives from vertically‐propagating waves. This process is illustrated here in its simplest context, i.e. the Plumb (1977) model of the interaction of monochromatic internal gravity waves with the mean flow (based on earlier work of Lindzen and Holton, 1968; Holton and Lindzen, 1972). It is shown that the dynamics illustrated by this simple model can serve as the basis for an explanation of the quasi‐biennial oscillation.

The paper then describes some of recent developments in the theory of the quasi‐biennial and semiannual oscillations, including aspects related to the interaction between tropics and midlatitudes in the middle atmosphere. The paper concludes with a discussion of the effects of the long period dynamical variations in the tropical circulation on the chemical composition of the stratosphere.     

Biomarker characterisation and hydrous pyrolysis of bitumens from Tertiary volcanics, queen Charlotte islands, British Columbia, Canada

A number of bitumen samples have been recovered from vugs and fractures in outcropping Tertiary basalts of the Queen Charlotte Islands off the west coast of British Columbia, Canada. n-Alkanes and acyclic isoprenoids are not present and the polycyclic biomarker distribution of the four samples analyzed by GC and GC-MS has been altered. One sample contains no remaining recognizable biomarkers. Two bitumens were also obtained from Lower Jurassic potential source rocks, including one from the Sandilands Formation, which was considered previously to be the most likely source of the Tertiary bitumens. Although these two bitumens were also taken from outcrops, they are considerably less biodegraded. The Sandilands Formation bitumen contains 28, 30-bisnorhopanes and since these compounds were not detected in the Tertiary bitumens, there is no evidence from the initial results for a Sandilands Formation contribution to the hydrocarbons in the Tertiary basalts. The presence of 18α(H)-oleanane in the saturate fraction of two of the Tertiary bitumens from widely separated locations indicates that they are at least partially sourced from Tertiary organic matter.Because the distribution of biomarkers in some samples has been severely affected by biodegradation, the asphaltenes of the bitumens were hydrously-pyrolysed and the saturate fractions of the resulting pyrolysates analysed for possible additional information on the origin of the bitumens. The pyrolysates from the more degraded samples contain compounds not detected in the saturate fractions of the original bitumen and show some of the expected characteristics of the original non-degraded bitumen. However, the compounds most useful for correlation are not present in the pyrolysates apparently due to their non-incorporation into the kerogen macromolecule. Our results suggest that hydrous-pyrolysis of asphaltenes is of limited use in the correlation of biodegraded samples and in determining their origins.     

Late Pleistocene Vertebrates and Other Fossils from Epiguruk, Northwestern Alaska

Sediments exposed at Epiguruk, a large cutbank on the Kobuk River about 170 km inland from Kotzebue Sound, record multiple episodes of glacial-age alluviation followed by interstadial downcutting and formation of paleosols. Vertebrate remains from Epiguruk include mammoth, bison, caribou, an equid, a canid, arctic ground squirrel, lemmings, and voles. Radiocarbon ages of bone validated by concordant ages of peat and wood span the interval between about 37,000 and 14,000 yr B.P. The late Pleistocene pollen record is dominated by Cyperaceae, with Artemisia, Salix, Betula, and Gramineae also generally abundant. The fossil record from Epiguruk indicates that the Kobuk River valley supported tundra vegetation with abundant riparian willows during middle and late Wisconsin time. Large herbivores were present during the height of late Wisconsin glaciation as well as during its waning stage and the preceding interstadial interval. The Kobuk River valley would have been a favorable refugium for plants, animals, and possibly humans throughout the last glaciation.     

A Sm-Nd isotopic study of atmospheric dusts and particulates from major river systems

¹⁴³Nd/¹⁴⁴Nd ratios, and Sm and Nd abundances, are reported for particulates from major and minor rivers of the Earth, continental sediments, and aeolian dusts collected over the Atlantic, Pacific, and Indian Oceans. Overall, Sm/Nd ratios and Nd isotopic compositions in contemporary continental erosion products vary within the small ranges of ¹⁴⁷Sm/¹⁴⁴Nd= 0.115 ± 0.01 and¹⁴³Nd/¹⁴⁴Nd= 0.51204 ± 0.0002 (ε_Nd = −11.4 ± 4). The average period of residence in the continental crust is estimated to be1.70 ± 0.35Ga.

These results combined with data from the literature have implications for the age, history, and composition of the sedimentary mass and the continental crust: (1) The average “crustal residence age” of the whole sedimentary mass is about 1.9 Ga. (2) The range of Nd isotope compositions in the continent derived particulate input to the oceans is the same as Atlantic sediments and seawater, but lower than those of the Pacific, demonstrating the importance of Pacific volcanism to Pacific Nd chemistry. (3) The average ratio of Sm/Nd is about 0.19 in the upper continental crust, and has remained so since the early Archean. This precludes the likelihood of major mafic to felsic or felsic to mafic trends in the overall composition of the upper continental crust through Earth history. (4) Sediments appear to be formed primarily by erosion of continental crust having similar Sm/Nd ratios, rather than by mixing of mafic and felsic compositions. (5) The average ratio of ¹⁴³Nd/¹⁴⁴Nd≈ 0.5117 (ε_Nd ≈ −17) in the upper continental crust, assuming its mean age is about 2 Ga. (6) The uniformity of the SmNd isotopic systematics in river and aeolian particulates primarily reflects efficient recycling of old sediment by sedimentary processes on a short time scale compared to the amount of time the material has resided in the crust.