A rapid, partial leach and organic separation for the sensitive determination of Ag, Bi, Cd, Cu, Mo, Pb, Sb, and Zn in surface geologic materials by flame atomic absorption

A solution of dilute hydrochloric acid, ascorbic acid, and potassium iodide has been found to dissolve weakly bound metals in soils, stream sediments, and oxidized rocks. Silver, Bi, Cd, Cu, Mo, Pb, Sb, and Zn are selectively extracted from this solution by a mixture of Aliquat 336 (tricaprylyl methyl ammonium chloride) and MIBK (methyl isobutyl ketone). Because potentially interfering major and minor elements do not extract, the organic separation allows interference-free determinations of Ag and Cd to the 0.05 ppm level, Mo, Cu, and Zn to 0.5 ppm, and Bi, Pb, and Sb to 1 ppm in the sample using flame atomic absorption spectroscopy. The analytical absorbance values of the organic solution used in the proposed method are generally enhanced more than threefold as compared to aqueous solutions, due to more efficient atomization and burning characteristics. The leaching and extraction procedures are extremely rapid; as many as 100 samples may be analyzed per day, yielding 800 determinations, and the technique is adaptable to field use.The proposed method was compared to total digestion methods for geochemical reference samples as well as soils and stream sediments from mineralized and unmineralized areas. The partial leach showed better anomaly contrasts than did total digestions. Because the proposed method is very rapid and is sensitive to pathfinder elements for several types of ore deposits, it should be useful for reconnaissance surveys for concealed deposits.     

The effect of early diagenesis on the Fe isotope compositions of porewaters and authigenic minerals in continental margin sediments

Iron isotope compositions in marine pore fluids and sedimentary solid phases were measured at two sites along the California continental margin, where isotope compositions range from δ⁵⁶Fe = −3.0‰ to +0.4‰. At one site near Monterey Canyon off central California, organic matter oxidation likely proceeds through a number of diagenetic pathways that include significant dissimilatory iron reduction (DIR) and bacterial sulfate reduction, whereas at our other site in the Santa Barbara basin DIR appears to be comparatively small, and production of sulfides (FeS and pyrite) was extensive. The largest range in Fe isotope compositions is observed for Fe(II)_aq in porewaters, which generally have the lowest δ⁵⁶Fe values (minimum: −3.0‰) near the sediment surface, and increase with burial depth. δ⁵⁶Fe values for FeS inferred from HCl extractions vary between ∼−0.4‰ and +0.4‰, but pyrite is similar at both stations, where an average δ⁵⁶Fe value of −0.8 ± 0.2‰ was measured. We interpret variations in dissolved Fe isotope compositions to be best explained by open-system behavior that involves extensive recycling of Feflux. This study is the first to examine Fe isotope variations in modern marine sediments, and the results show that Fe isotopes in the various reactive Fe pools undergo isotopic fractionation during early diagenesis. Importantly, processes dominated by sulfide formation produce high-δ⁵⁶Fe values for porewaters, whereas the opposite occurs when Fe(III)-oxides are present and DIR is a major pathway of organic carbon respiration. Because shelf pore fluids may carry a negative δ⁵⁶Fe signature it is possible that the Fe isotope composition of ocean water reflects a significant contribution of shelf-derived iron to the open ocean. Such a signature would be an important means for tracing iron sources to the ocean and water mass circulation.     

Holocene landscape evolution and the development of models for human interaction with the environment: An example from the mississippi headwaters region

Integration of a record of Holocene landscape evolution with the cultural record from a multicomponent archaeological site in northern Minnesota has fostered the development of a regional model of human interaction with the changing physical environment. Excavation of 21-CA-169 near Nushka Lake revealed two components, an aceramic Archaic zone where processing of large mammals was the major activity and an upper zone with artifacts suggestive of wild rice processing. Seasonal occupation of the lower zone occurred during a period of falling regional lake levels resulting from natural stream network evolution. The upper zone represents human occupation in a physical and biological setting that was quite different than during earlier occupation. Integration of the geomorphic history of the region along with an interpretation of the types of cultural activities occurring on the changing landscape have provided a model to understand land use and to predict the location of other sites. © 1993 John Wiley & Sons, Inc.     

Cave bears and paleolithic artifacts in Yarimburgaz Cave,Turkey: Dissecting a palimpsest

This article addresses the taphonomic issues surrounding artifact-bear associations in Yarimburgaz Cave, northwestern Turkey. Our purpose is to evaluate the circumstances of bone assemblage formation in the Middle Pleistocene deposits of the cave, identifying the agencies responsible for the accumulations and the causes of bone damage before and following deposition. Pleistocene species representation, bone damage, body part representation, and mortality data indicate that cave bear remains in Yarimburgaz are unrelated to hominid use of the same site. None of the observations on the cave bear remains contradicts the expectations developed from modern wildlife accounts of modern bear behavior; these accumulations resulted from mortality normally associated with hibernation over many generations of den use. Nonursid carnivores also played roles in bone collection and/or modification. We conclude that at least three distinct biological processes contributed to the formation of the Middle Pleistocene faunas: hibernating bears, bone-collecting carnivores such as wolves, and hominids in descending order of importance. The Yarimburgaz faunas represent palimpsests or overlays of many short-term depositional events, the close spatial associations of which are explained by slow or uneven sedimentation rates inside the cave. Although occupations by hominids appear to have been ephemeral in nature, hominids ultimately discarded nearly 1700 stone artifacts in Yarimburgaz Cave. The hominids did not discard many ungulate bones in the same circumstances. These observations suggest that hominid foraging efforts focused on resources other than large game while at the cave. © 1996 John Wiley & Sons, Inc.