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.     

The ClBrI composition of 3.23 Ga modified seawater: implications for the geological evolution of ocean halide chemistry

Fluid inclusion leachates obtained from vug and vein quartz samples from an Archean (3.23 Ga) Fe-oxide hydrothermal deposit in the west-central part of the Barberton greenstone belt, South Africa, were analyzed by ion chromatography for chloride, bromide, and iodide. The deposit, known as the ironstone pods, formed by seafloor hydrothermal activity and fluid discharge. Quartz is dominated by type I liquid-vapor, aqueous inclusions with a bimodal salinity distribution (0–0.25 M_Cl⁻ and 0.9–1.8 M_Cl⁻). Bulk analytical salinities range from 0.45 to 0.99 M_Cl⁻ represent averages of type I inclusions. Bulk fluid inclusion bromide and iodide concentrations are 1.44–3.32 mM and 0.01–0.12 mM, respectively. For comparison, modern seawater has halogen contents of 590 mM chloride, 0.9 mM bromide, and 0.5 μM total iodine. In the fluids from the ironstone pods, bromide and iodide are enriched relative to chloride, when compared with modern seawater.Approximate Br⁻Cl⁻ and I⁻Cl⁻ ratios of 3.2 Ga Barberton seawater are 2.5 × 10⁻³ and 40 × 10⁻⁶, respectively. Dispersion to higher values was caused principally by reaction with organic sediments whose trends are similar to those seen for modern vent fluids at unsedimented and sedimented ridges, relative to modern seawater. These halide ratios are greater than those of modern seawater, suggesting a change in the halide ratios of seawater over geological time. The analytical data are consistent with a model in which marine organic sedimentation has fractionated bromine and iodine out of seawater relative to chloride, thereby causing the halide ratios of seawater to decrease from high early and mid-Archean values towards their present day values.     

Simultaneous analyses and applications of multiple fluorobenzoate and halide tracers in hydrologic studies

An analytical method that employs ion chromatography has been developed to exploit the use of fluorobenzoic acids (FBAs) and halides more fully as hydrologic tracers. In a single run, this reliable, sensitive, and robust method can simultaneously separate and quantify halides (fluoride, chloride, bromide, and iodide) and up to seven FBAs from other common groundwater constituents (e.g. nitrate and sulphate). The usefulness of this analytical method is demonstrated in both field and laboratory tracer experiments. The field study examines the hydrologic response of fractures and the matrix to different flow rates and the contribution of matrix diffusion in chemical transport. Laboratory tracer experiments with eight geologic media from across the USA—mostly from Department of Energy facilities where groundwater contamination is prevalent and where subsurface characterization employing tracers has been ongoing or is in need—reveal several insights about tracer transport behaviour: (1) bromide and FBAs are not always transported conservatively; (2) the delayed transport of these anionic tracers is likely related to geologic media characteristics, such as organic matter, pH, iron oxide content, and clay mineralogy; (3) use of iodine as a hydrologic tracer should take into account the different sorption behaviours of iodide and iodate and the possible conversion of iodine's initial chemical form; (4) the transport behaviour of potential FBA and halide tracers under relevant geochemical conditions should be evaluated before beginning ambitious, large‐scale field tracer experiments. Copyright © 2005 John Wiley & Sons, Ltd.     

Laboratory Determination of the Carbon Kinetic Isotope Effects (KIEs) for Reactions of Methyl Halides with Various Nucleophiles in Solution

Large carbon kinetic isotope effects (KIEs) were measured for reactions of methyl bromide (MeBr), methyl chloride (MeCl), and methyl iodide (MeI) with various nucleophiles at 287 and 306 K in aqueous solutions. Rates of reaction of MeBr and MeI with H₂O (neutral hydrolysis) or Cl⁻ (halide substitution) were consistent with previous measurements. Hydrolysis rates increased with increasing temperature or pH (base hydrolysis). KIEs for hydrolysis were 51 ± 6%₀ for MeBr and 38 ± 8%₀ for MeI. Rates of halide substitution increased with increasing temperature and greater reactivity of the attacking nucleophile, with the fastest reaction being that of MeI with Br⁻. KIEs for halide substitution were independent of temperature but varied with the reactant methyl halide and the attacking nucleophile. KIEs were similar for MeBr substitution with Cl⁻ and MeCl substitution with Br⁻ (57 ± 5 and 60 ± 9%₀, respectively). The KIE for halide exchange of MeI was lower overall (33 ± 8%₀) and was greater for substitution with Br⁻ (46 ± 6%₀) than with Cl⁻ (29 ± 6%₀).