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Aquatic Geochemistry (v.12, #2)
Diurnal Variations of Hydrochemistry in a Travertine-depositing Stream at Baishuitai, Yunnan, SW China by Zaihua Liu; Qiang Li; Hailong Sun; Changjun Liao; Huaju Li; Jinliang Wang; Kongyun Wu (pp. 103-121).
Diurnal variations of hydrochemistry were monitored at a spring and two pools in a travertine-depositing stream at Baishuitai, Yunnan, SW China. Water temperature, pH and specific conductivity were measured in intervals of 5 and 30 min for periods of 1 to 2 days. From these data the concentrations of Ca2+, HCO3−, calcite saturation index, and CO2 partial pressure were derived. The measurements in the spring of the stream did not show any diurnal variations in the chemical composition of the water. Diurnal variations, however, were observed in the water of the two travertine pools downstream. In one of them, a rise in temperature (thus more CO2 degassing) during day time and consumption of CO2 due to photosynthesis of submerged aquatic plants accelerated deposition of calcite, whereas in the other pool, where aquatic plants flourished and grew out of the water (so photosynthesis was taking place in the atmosphere), the authors suggest that temperature-dependent root respiration underwater took place, which dominated until noon. Consequently, due to the release of CO2 by the root respiration into water, which dominated CO2 production by degassing induced by temperature increase, the increased dissolution of calcite was observed. This is the first time anywhere at least in China that the effect of root respiration on diurnal hydrochemical variations has been observed. The finding has implications for sampling strategy within travertine-depositing streams and other similar environments with stagnant water bodies such as estuaries, lakes, reservoirs, pools and wetlands, where aquatic plants may flourish and grow out of water.
Keywords: root respiration; photosynthesis; aquatic plants; calcite precipitation/dissolution; CO2 degassing; hydrochemistry; diurnal variations; travertine; China
Experimental Study of Dissolution Rates of Fluorite in HCl–H2O Solutions by Ronghua Zhang; Shumin Hu; Xuetong Zhang (pp. 123-159).
The experiments of the dissolution kinetics of fluorite were performed in aqueous HCl solutions over the temperature range of 25–100 °C using a flow-through experimental apparatus. With a constant input of aqueous HCl solution through the reactor, output concentrations of the dissolved species Ca, F, Cl vary with flow rate, as well as with the surface compositions. Measured output concentrations of dissolved species and the pH can be used to determine a rate law for fluorite dissolution. Fluorite dissolution rates are found to be pH dependent. Usually, dissolution rates of fluorite decreases with increasing dissolved Ca in the output solution at 25 and 100 °C. Dissolution rate can be expressed as 1a $$-r=k((a_{
m H}^{+})^{2}/(a_{
m Ca}^{2+}))^{alpha} $$ where k is the rate constant and α is the order with respect to the hydrogen ion activity vs. the activity of dissolved Ca. The α was obtained from kinetic experiments. For the fluorite sample passed through 18–35 mesh, α =1.198 at 100 °C and k = 10−0.983, while fluorite dissolved in HCl–H2O solution at pH 2.57 of input solution. Adsorption of a proton and Cl−1onto the fluorite surface, surface cation exchange and the formation of the surface complex Ca(F, Cl)2 and/or (H2x, Ca1−x)(F, Cl)2 control dissolution rates. Investigation of the fluorite surface before and after dissolution by using X-ray photoelectron spectroscopy (XPS) indicate that surface modifications affect reaction rates.
Keywords: dissolution rates; kinetics; proton adsorption; surface modifications
Concentration, Molecular Weight Distribution and Neutral Sugar Composition of DOC in Maritime Antarctic Lakes of Differing Trophic Status by Wendy C. Quayle; Peter Convey (pp. 161-178).
The molecular weight distributions and hydrolysable neutral sugar composition of dissolved organic carbon (DOC) was investigated in four maritime Antarctic lakes on Signy Island of different trophic status; Heywood Lake (eutrophic), Light Lake (oligo-mesotrophic), Sombre Lake and Moss Lake (both oligotrophic). Tangential flow ultra-filtration (TFU) was used to separate DOC into high molecular weight (HMW; >1000 Da) and low molecular weight (LMW; < 1000 Da) size fractions. Pulsed amperometric detection-high performance liquid chromatography (PAD-HPLC) was used to determine the hydrolysable neutral sugar molecular composition of each size fraction. Total DOC concentrations defined the trophic trend in the four lakes and ranged from 8 to 303 μM. The <1000 Da fraction of all the lakes dominated the DOC distribution, comprising 76% in Light Lake which also had the highest chl-a concentrations. Heywood Lake was relatively enriched in >1000 Da total organic carbon and had extremely high concentrations of total hydrolysable neutral sugars (11 μM) corresponding to 43% of total DOC. However, no clear pattern was apparent with regard to lake trophic status and potential sources of DOC, and the measured variations in individual aldose concentration, composition and their various molecular weight fractions.
Keywords: dissolved neutral sugar; carbohydrates; dissolved organic carbon; Signy Island; eutrophic; mesotrophic; oligotrophic; lakes
Dissolved Fe2+ and ∑H2S Behavior in Sediments Seasonally Overlain by Hypoxic-to-anoxic Waters as Determined by CSV Microelectrodes by Karen S. Sell; John W. Morse (pp. 179-198).
Variability of dissolved Fe2+ and ∑H2S concentrations in porewaters were studied, using cathodic stripping voltammetry (CSV) microelectrodes, in sediments overlain by hypoxic waters in the summer from the southeastern region of Corpus Christi Bay, Texas (CCB) and the Mississippi River Bight (MRB), Louisiana. These measurements were complimented by sediment microcosm studies where oxygen concentrations in the overlying water were manipulated. Sulfate reduction rates, benthic oxygen demand, total reduced sulfide, porewater sulfate, and total organic carbon were also determined. Fe2+ and ∑H2S were the major dissolved redox-reactive dissolved species in these sediments. During hypoxic conditions, an upward migration of porewater Fe2+ and ∑H2S occurred, with Fe2+ reaching much higher maximum concentrations than ∑H2S. Statistically significant (p < 0.05) differences in both Fe2+ and ∑H2S occurred between sediments at the CCB and MRB study sites. Although both sites were Fe-dominated, reactive and dissolved iron were higher while ∑H2S was lower at the MRB site. However, there were no statistically significant (p > 0.05) difference in regard to ∑H2S between microcosm and field monitoring studies. Results indicated that, for Fe2+ and ∑H2S, relatively large and rapid changes occurred in both the concentrations and distributions of these important porewater constituents in response to relatively short-term changes in overlying water oxygen content. Model calculations indicated that conditions in the sediments can be responsible for the induction of hypoxic conditions in the formation of hypoxic overlying waters in <6 days at CCB and ~20 days at MRB.
Keywords: benthic oxygen demand; hypoxia; microelectrodes; porewater iron and sulfide; sedimentary biogeochemistry