Electron paramagnetic resonance spectroscopy: A suggested approach to trace metal analysis in marine environments

Electron paramagnetic resonance (EPR) spectroscopy analysis of marine samples from different environments appears to differentiate between adsorbed and structural Mn (II) and Fe (III) sites in the sediment. This suggests that EPR may provide a means of distinguishing different environmental influences on sediment. Acid extract solutions from sediment samples exhibit clearly defined EPR spectra due to Mn(II), Ti(III), Fe(III), and VO(IV), which are amenable to qualitative and quantitative analysis at concentrations below one part per million. Spectra of several shellfish vary considerably, both between species, and within a species, depending on sampling localities. Resonances from Mn(II), Mo(V), and Fe(III) can be obtained. Mn(II) is substituted for Ca(II) in the calcite structure of some shells. The low detection limits, small sample size, required and identification of oxidation states by EPR complement other analytical techniques and may prove useful in marine systems.     

Chemical studies of copper-organic complexes isolated from estuarine waters using C18 reverse-phase liquid chromatography

Dissolved organic matter (DOM) and dissolved copper-organic complexes were isolated from the estuarine waters of Narragansett Bay, RI, using reverse-phase liquid chromatography employing C₁₈ Sep-Pak cartridges (Waters Associates). The cartridges were found to have a constant retention efficiency for processing ? 1-l volumes of seawater. Fractionation of the isolated material, by sequential elution of the Sep-Pak with water: methanol mixtures of increasing organic solvent concentration, yielded a fraction of the organic matter with a specific copper activity six times greater than the overall activity for the isolated DOM. Analysis of this fraction by high performance liquid chromatography suggested that the organic components are of intermediate polarity and have appreciable aromatic character.An investigation of the protonation characteristics of the isolated complexes indicated that most of the copper is associated with a broad range of acidic sites on the DOM. Analysis by electron paramagnetic resonance spectroscopy confirmed the organic association of the isolated copper and also suggested the presence of several types of binding sites which probably involve oxygen donor ligands.Studies of the exchange of ⁶⁴Cu with these binding sites on the isolated DOM indicated that 70% of the sites undergo rapid exchange with copper in seawater while 20% of these sites did not exchange in a 24-h time period.     

Evaluation of extraction schemes for organic matter in anoxic estuarine sediments

A persistent criticism of studies of organic matter in sediments and soils has been that the extracted products used in these investigations may not resemble the original material, particularly if harsh extractants such as NaOH, Na₄P₂O₇ or HCl are employed. To minimize chemical changes, a mild separation procedure has been developed for obtaining soluble organic matter from anoxic estuarine sediments. The resulting complex mixture of organic compounds can be analyzed by reversed-phase liquid and size-exclusion chromatographic methods, which monitor the relative molecular polarity and size, respectively. The effects of the strong reagents NaOH, Na₄P₂O₇ and HCl, as well as exposure to the atmosphere and bacterial activity on this anoxic sedimentary extract has been investigated. In each instance, significant degradation of anoxic organic matter occurs, producing molecules of increased polarity and reduced molecular weight. These data indicate that extreme care is necessary to avoid artifacts in preparation and handling of samples.     

Molybdenum in pore waters of anoxic marine sediments by electron paramagnetic resonance spectroscopy

Pore water samples of anoxic sediments from Great Bay, N.H. and Jeffrey's Basin, New England continental shelf, have been analyzed for dissolved molybdenum by the electron paramagnetic resonance (EPR) spectroscopy technique of Hanson et al. (1977). The method has been modified so that only 0.50 ml of pore water sample is utilized for the analysis. The concentrations of Mo in the Jeffrey's Basin pore fluids are as much as an order of magnitude higher than that of the overlying water, while the estuarine water concentrations are only twice that of the overlying water.The Mo in the pore water is negatively correlated to dissolved Fe²⁺ and positively correlated to the precent of organic carbon in the sediments. This suggests that Mo is remobilized by the anaerobic degradation of sedimentary organic matter and is not directly incorporated into iron pyrite during early diagenesis.     

Vanadium-fulvic acid chemistry: conformational and binding studies by electron spin probe techniques

Two fractions of soil fulvic acid (FA) were separated by gel filtration chromatography. An observed increase in volume of the heavier fraction (FA I) with increasing pH was attributed to aggregation, intramolecular negative charge repulsions and the rupture of hydrogen bonds, which control molecular conformation. Optical absorption properties and elemental analyses of both fractions were determined. The stability constants and stoichiometries of FA complexes with vanadyl, VO²⁺, at pH 5.0 and ionic strength of 0.04 M were measured by electron paramagnetic resonance (EPR) spectroscopy. EPR spectra of model VO²⁺ complexes with phthalic and salicylic acids, which are the probable functional groups present in FA, are identical to those of the VO²⁺-FA complexes. Aggregation of FA I occurs in the presence of VO²⁺ to form a complex that can be approximated as ‘(VO)₂(FA I)₆’. The average site distance between vanadyl ions in this complex is shown to be greater than 1.2 nm. EPR parameters for FA I suggest binding by carboxylate groups. These parameters are compared with those of other vanadyl complexes with fulvic and humic acids reported by others. Reduction of VO₃^? to VO²⁺ by these materials is discussed.