Aquatic Geochemistry最新文献

Iron(II) concentrations in fresh groundwater in Dutch aquifers range from absent up to 50?mg/l. Evaluation of extensive chemical data sets learned that the maximum logarithmic concentration of iron(II) in aquifers, between?±?6.5?<?pH?<??±?8, is a linear function of pH, governed by Siderite. It is a broad relation due to oversaturation with respect to Siderite and to variation in alkalinity. Iron(II) is continuously supplied to groundwater by reduction of hydrous ferric oxides (HFO), until becoming saturated with respect to Siderite, and from then on, HFO reduction and Siderite precipitation occur simultaneously. In Dutch aquifers, the electron supply rate (equivalent to the organic matter oxidation rate) apparently exceeds the HFO electron uptake rate (equivalent to the HFO reduction rate) and the excess supply is taken up by sulfate (equivalent to the sulfate reduction rate): HFO reduction, sulfate reduction and FeS precipitation occurring simultaneously, where the presence of Siderite prevents a dip in the iron(II) concentration. After sulfate becomes exhausted, the excess electron supply is transferred to methane production: HFO reduction and methane production occurring simultaneously. This evaluation also demonstrated that the organic matter oxidation rate and the HFO reduction rate decrease over time. The results of this study are also relevant for the behavior of As and of Co, Ni and Zn in groundwater, as HFO, Pyrite and Siderite may contain variable contents of these elements.

Fe type clay minerals, Fe–montmorillonite, are expected to form in the nuclear waste repositories over a span of few years owing to the interaction of corrosion products from overpack and/or canister with bentonite consisting of montmorillonite (Mt) as the major clay mineral. Therefore, it is important to understand the properties of altered clay minerals, Fe–Mt. In the present study, the sorption behaviour of ¹³³Ba(II), one of the high-yield fission products of uranium-based fuels and analogue of ⁹⁰Sr (t_1/2?=?28.5 y), on Fe(II)–Mt and Fe(III)–Mt has been investigated. Retention behavior of Ba(II) on Fe–Mt has been studied at varying pH (3–9), ionic strength (0.001?M–1?M) and Ba(II) concentration (10^?9–10^?3 M) by batch sorption method. The distribution coefficient (K_d) of Ba(II) on Fe–Mt was found to be nearly independent of pH while it decreased with increasing ionic strength indicating ion exchange as the dominant Ba(II) sorption mode on Fe–Mt. Adsorption isotherm of Ba(II) exhibited linearity in the entire Ba(II) concentration range. A comparison of Ba(II) sorption behavior on Fe–Mt and Na–Mt has been made. The Fe released from both Fe(III)–Mt and Fe(II)–Mt was measured in all the sorption experiments and was found to be much less in the case of Fe(III)–Mt (≤?1.7?ppm) when compared to Fe(II)–Mt (~?25?ppm). The modeling of Ba(II) sorption profiles on Fe–Mt and Na–Mt has been carried out using FITEQL 4.0.

Stream carbon fluxes are one of the major components in the global C cycle, yet the discrimination of the various sources of stream carbon remains to a large extent unclear and less is known about the biogeochemical transformations that accompany the transfer of C from soils to streams. Here, we used patterns in stream water and groundwater δ¹³C values in a small forested tropical headwater catchment to investigate the source and contribution from the soil carbon pools to stream organic and inorganic carbon behavior over seasonal scales. Stream organic carbon (DOC and POC) comes mainly from the upper rich soil organic carbon horizons and derived from total organic carbon (TOC) of biogenic source. The isotopic compositions δ¹³C_TOC, δ¹³C_DOC and δ¹³C_POC of these carbon species were very close (??30‰ to ??26‰) and typical of the forested C3 vegetation. The relationship observed between DOC and log pCO₂ and δ¹³C_DIC indicated that besides the considerable CO₂ evasion that occurs as DIC is transported from soils to streams, there were also other processes affecting the stream DIC pool. In-stream mineralization of DOC and mixing of atmospheric carbon had a significant influence on the δ¹³C_DIC values. These processes which varied seasonally with hydrological changes represent the main control on DOC and DIC cycling in the wet tropical milieu. The rapid turnover of carbon on hillside soils, the transformation of TOC to DOC in wetland soils and further mineralization of stream DOC to DIC favor the evasion of C, making the zone a source of carbon to the atmosphere.

In aquatic systems a reaction between tetrathionate and cyanide results in the formation of thiocyanate. We have studied kinetics of the reactions of tetrathionate with free cyanide and two cyanide complexes, hexacyanoferrate(II) and hexacyanoferrate(III), at the environmentally relevant conditions. For the reaction between tetrathionate and free cyanide, the rate constant and the activation energy, but not the reaction order, strongly depend on pH. Our observations allow to propose the following pathways of thiocyanate formation by the reactions of free cyanide with tetrathionate: (1) tetrathionate reacts relatively slow with hydrogen cyanide at acidic and neutral conditions; and (2) tetrathionate reacts relatively fast with cyanide anion under highly alkaline conditions. Depending on environmental conditions, the half-lives of the reaction between free cyanide and tetrathionate will be in the ranges of hours to several years. Reactions of tetrathionate with hexacyanoferrate(II) and hexacyanoferrate(III) have no environmental significance as they are slower than the decomposition of tetrathionate. Strategy for improvement of analytical protocols for analysis of tetrathionate and cyanide is proposed based on the detected kinetics parameters.