The hydrochemistry of a semi-arid pan basin case study: Sua Pan,Makgadikgadi, Botswana

This study presents results on the fluid and salt chemistry for the Makgadikgadi, a substantial continental basin in the semi-arid Kalahari. The aims of the study are to improve understanding of the hydrology of such a system and to identify the sources of the solutes and the controls on their cycling within pans. Sampling took place against the backdrop of unusually severe flooding as well as significant anthropogenic extraction of subsurface brines. This paper examines in particular the relationship between the chemistry of soil leachates, fresh stream water, salty lake water, surface salts and subsurface brines at Sua Pan, Botswana with the aim of improving the understanding of the system’s hydrology. Occasionally during the short wet season (December–March) surface water enters the saline environment and precipitates mostly calcite and halite, as well as dolomite and traces of other salts associated with the desiccation of the lake. The hypersaline subsurface brine (up to TDS 190,000 mg/L) is homogenous with minor variations due to pumping by BotAsh mine (Botswana Ash (Pty) Ltd.), which extracts 2400 m³ of brine/h from a depth of 38 m. Notable is the decrease in TDS as the pumping rate increases which may be indicative of subsurface recharge by less saline water. Isotope chemistry for Sr (⁸⁷Sr/⁸⁶Sr average 0.722087) and S (δ³⁴S average 34.35) suggests subsurface brines have been subject to a lithological contribution of undetermined origin. Recharge of the subsurface brine from surface water including the Nata River appears to be negligible.     

Heat exchange between water and ice in the Arctic Ocean

Summary The heat balance equation for the bottom surface of floating sea ice is evaluated on the basis of observations of ice temperature, water temperature, current velocity, and ablation or accretion of ice. Assuming equality of the eddy diffusivities for momentum, heat, and salt (average 24 cm² sec^–1) it is shown that the temperature gradient in the oceanic boundary layer is extremely small (averages between 2.10^–5 and 4.10^–4°C/meter) and difficult to measure directly. It is suggested that a large part of the heat transfer from the relatively warm Atlantic water to the arctic atmosphere may occur through open leads in the ice cover.

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Zusammenfassung Die Wärmebilanzgleichung für die Unterseite von schwimmendem Meereis wird an Hand von Beobachtungen der Eistemperatur, der Wassertemperatur, der Strömungsgeschwindigkeit und der Eisdickenänderung ausgewertet. Unter der Annahme gleicher Austauschkoeffizienten für Bewegungsgröße, Wärme und Salzgehalt (im Mittel 24 cm² sec^–1) ergibt sich für die ozeanische Grenzschicht ein außerordentlich kleiner Gradient der Wassertemperatur (durchschnittlich zwischen 2.10^–5 und 4.10^–4°C/Meter), der durch direkte Beobachtungen schwer nachzuweisen ist. Es ist zu vermuten, daß ein beträchtlicher Teil der Wärmeabgabe von der relativ warmen atlantischen Wassermasse an die arktische Atmosphäre durch Öffnungen in der Meereisdecke erfolgt.

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Résumé On établit l'équation du bilan thermique valable pour la surface inférieure de la glace marine dérivante. Pour ce faire, on se sert d'observations de la température de la glace, de celle de l'eau, de la vitesse du courant et des variations de l'épaisseur de la glace. En admettant que les coefficients d'échange sont les mêmes pour la quantité de mouvement, la chaleur et le taux de salinité (en moyenne 24 cm² sec^–1), il résulte pour la couche limite un gradient extrêmement faible de la température de l'eau (situé en moyenne entre 2·10^–5 et 4·10^–4°C/m); un tel gradient est difficile à prouver au moyen d'observations directes. On peut supposer qu'une partie importante de la chaleur transmise par l'eau relativement chaude de l'Atlantique à l'atmosphère arctique passe au travers des lacunes de la couche de glace recouvrant l'océan.

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Contribution 141, Department of Atmospheric Sciences, University of Washington, Seattle. This is a thesis submitted by the author in partial fulfillment of the requirements for the degree of Master of Science.     

Solubility of hydrous ferric oxide and iron speciation in seawater

Iron solubility equilibria were investigated in seawater at 36.22‰ salinity and 25°C using several filtration and dialysis techniques. In simple filtration experiments with 0.05 μm filters and Millipore ultra-filters, ferric chlorides fluorides, sulfates, and FeOH²⁺ species were found to be insignificant relative to Fe(OH)₂⁺ at p[H⁺] = ?log [H⁺] greater than 6.0. Hydrous ferric oxide freshly precipitated from seawater yielded a solubility product of ${}^1\text{K}{}_{\mathrm{<mtext>so</mtext>}}\text{=}\text{[Fe}{}^{\mathrm{3+}}\text{][H}{}^{\mathrm{+}}\text{]}{}^{\mathrm{?3}}\text{= 4.7 · 10}{}^5$. Solubility studies based on the rates of dialysis of various seawater solutions and on the filtration of acidified seawater solutions indicated the existence of the Fe(OH)₃⁰ species. The formation constant for this species can be calculated as ${}^1\text{β}{}_3\text{=}\text{[Fe(OH)}{}_3{}^0\text{] [H}{}^{\mathrm{+}}\text{]}{}^3\text{/[Fe}{}^{\mathrm{3+}}\text{] = 2.4 · 10}{}^{\mathrm{?14}}$. The Fe(OH)₄^? species is present at concentrations which are negligible compared to Fe(OH)₂⁺ and Fe(OH)₃⁰ in the normal pH range of seawater. However, there is at least one other significant ferric complex in seawater above p[H⁺] = 8.0 (possibly with bicarbonate, carbonate, or borate ions) in addition to the Fe(OH)₂⁺ and Fe(OH)₃⁰ species.     

Metabolism of perylene by monooxygenases of the skin and liver of Ambystoma tigrinum

The prevalence of dermal neoplasia among neotenic tiger salamanders (Ambystoma tigrinum) collected from the Reese Air Force Base sewage lagoon far exceeded that among salamanders from nearby uncontaminated lagoons. Perylene was the predominant pglycyclic aromatic hydrocarbon contaminant in this lagoon. Perylene was shown to be a substrate for monooxygenases in skin and liver homogenates and formed DNA-binding metabolites. Perylene exposure appeared to augment subsequent perylene metabolism by dermal enzymes but it was not a strong inducer of hepatic monooxygenases. Aroclor 1254 induced benzo(a)pyrene and perylene metabolism by both skin and liver enzymes. However, perylene apparently was not activated by salamander enzymes, as suggested by its lack of in vitro mutagenicity and failure to induce tumors.     

Budgets of Mn,Cd and Cu in the macrotidal Gironde estuary (SW France)

The behavior and budget of Mn, Cd and Cu in the Gironde estuary were investigated through data from both the water column (WC) and sediment depth profiles. In the estuarine freshwater reaches, Mn and Cd removal from and Cu addition to the dissolved phase occurs with a magnitude equivalent to 10%, 30% and 25% of their respective annual fluvial gross dissolved input, respectively. In the saline estuary, diffusive benthic outflow is the main source of dissolved Mn (74% of the total gross dissolved input within the estuary) to the WC. In contrast, Cd (96%) and Cu (89%) are mainly released into the dissolved phase of the WC from fluvial, estuarine and dredging-related particles through complexation (Cd) and organic carbon mineralization (Cu). Anthropogenic activities (sediment dredging) induce pore water inputs, particulate sulfide oxidation and sediment resuspension, significantly contributing to the metal budget of the WC. The related amounts of metals released could be equivalent to 20–50% (Cd) and up to 70% (Cu) of their respective net dissolved addition. Mass balances suggest that a large part of the metals previously released into the dissolved phase from processes within the estuary are removed by suspended particles due to (co-)precipitation of Fe/Mn (oxy)hydroxides and scavenging on autochthonous organic matter. On an annual basis, the Gironde estuary acts as a net sink of dissolved Mn, removing 60% of the dissolved fluvial inputs, and as a net source of dissolved Cd and Cu, contributing ∼ 85% and 20–45% to the dissolved Cd and Cu fluxes to the ocean.     

Methyl halide production and loss rates in sea water from field incubation experiments

Experiments were conducted in the field to determine the non-chemical loss rate of methyl iodide in seawater and to examine production rates of methyl halides. The loss rate of added C13 labelled methyl iodide, present at concentrations similar to those found in seawater, corrected for chemical loss due to reaction with Cl⁻ varied from < 1 to 18% day^− 1, with a mean value of 7%. This rate of loss is much lower than that which was proposed by Bell et al. [Bell, N., Hsu, L., Jacob, D. J., Schultz, M. G., Blake, D. R., Butler, J. H., King, D. B., Lobert, J. M., Maier-Reimer, E., 2002. Methyl iodide: Atmospheric budget and use as a tracer of marine convection in global models, Journal of Geophysical Research-Atmospheres 107(D17), 4340-4351.] to account for the large discrepancies between observed and predicted mid-latitude concentrations of CH₃I based on their global photochemical source model. The suitability of several types of container for seawater incubations was studied and only quartz tubes appeared to be free of experimental artifact. Collapsible polyvinyl fluoride containers showed major production of methyl halides on irradiation with simulated sunlight. Polyethylene containers caused spurious production of methyl iodide at lower rates.