Structural relaxation in the MnCO3–CaCO3 solid solution: a Mn K-edge EXAFS study

Mn K-edge EXAFS spectroscopy of solid-solution samples encompassing the complete MnCO₃–CaCO₃ series shows that first-shell Mn–O distances deviate little from the 2.19-Å distance observed in pure MnCO₃. Very slight lengthening is observed only in the limiting case of dilute Mn(II) calcite solid solutions, where the Mn–O distance is 2.21 Å. The observed nearly complete structural relaxation and the composition independence of the Mn–O distance are consistent with the Pauling model behavior of solid solutions, and agree with previous studies showing a high degree of relaxation around hetero-sized substituents in the calcite structure. Strain occurs through bond bending, which is facilitated by the exclusively corner-sharing topology of calcite. Observed distances from Mn to more distant neighbors show significant variation across the solid-solution series that resembles Vegard's law-type behavior but reflects averaging. The high degree of relaxation suggests modest enthalpies of mixing in the solution, consistent with calorimetric studies.     

Cu(II) adsorption at the calcite-water interface in the presence of natural organic matter: Kinetic studies and molecular-scale characterization

We have characterized the adsorption of Suwannee River humic acid (SRHA) and Cu(II) on calcite from preequilibrated solutions at pH 8.25. Sorption isotherms of SRHA on calcite follow Langmuir-type behavior at SRHA concentrations less than 15 mg C L⁻¹, whereas non-Langmuirian uptake becomes evident at concentrations greater than 15 mg C L⁻¹. The adsorption of SRHA on calcite is rapid and mostly irreversible, with corresponding changes in electrostatic properties. At pH 8.25, Cu(II) uptake by calcite in the presence of dissolved SRHA decreases with increasing dissolved SRHA concentration, suggesting that formation of Cu-SRHA aqueous complexes is the primary factor controlling Cu(II) sorption at the calcite surface under the conditions of our experiments. We also observed that surface-bound SRHA has little influence on Cu(II) uptake by calcite, suggesting that Cu(II) coordinates to calcite surface sites rather than to surface-bound SRHA.Cu K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine-structure (EXAFS) spectroscopic results show that the local coordination of Cu adsorbed at the calcite surface is very similar in the presence and absence of SRHA. Ca backscatterers at ∼3.90 Å indicate that Cu(II) forms tetragonally distorted inner-sphere adsorption complexes in both binary and ternary systems. Subtle differences in the XANES and EXAFS between binary sorption samples and ternary sorption samples, however, prevent us from ruling out the formation of ternary Cu-SRHA surface complexes. Our findings demonstrate that SRHA plays an important role in controlling the fate and transport of Cu(II) in calcite-bearing systems.     

The quaternary glacial history of the Lahul Himalaya,northern India

This paper presents the first glacial chronology for the Lahul Himalaya, Northern India. The oldest glaciation, the Chandra Glacial Stage, is represented by glacially eroded benches at altitudes greater than 4300 m above sea-level. This glaciation was probably of a broad valley type. The second glaciation, the Batal Glacial Stage, is represented by highly weathered and dissected lateral moraines, which are present along the Chandra valley and some of its tributaries. This was an extensive valley glaciation. The third major glaciation, the Kulti Glacial Stage, is represented by well-preserved moraines in the main tributary valleys of the Chandra valley. This represents a less extensive valley glaciation. Two minor glacial advances, the Sonapani I and II, are represented by small sharp-crested moraines, which are within a few hundred metres or few kilometres of the present-day glaciers. The change in style and extent of glaciation is attributed to an increase in aridity throughout the Quaternary, due either to global climatic change or uplift of the Pir Panjal mountains to the south of Lahul, which restricted the northward penetration of the south Asian summer monsoon. © 1996 John Wiley & Sons, Ltd.     

Market access,population density,and socioeconomic development explain diversity and functional group biomass of coral reef fish assemblages

There is overwhelming evidence that many local-scale human activities (e.g. fishing) have a deleterious effect on coral reef fish assemblages. Our understanding of how broad social phenomena (e.g. socioeconomic development) affect the diversity and function of coral reef fish assemblages however, is still poor. Here, we use structural equation models to reveal how human population density, socioeconomic development, and market access affect fishing pressure and coral cover to, in turn, explain the diversity and biomass of key functional groups of reef fish assemblages within Solomon Islands. Fishing pressure is predominantly driven by both market access and local population density, and has a clear negative effect on the diversity and function of coral reef fishes. The strong positive effect of market access on fishing pressure makes clear the importance of understanding social-ecological linkages in the context of increasingly connected societies. This study highlights the need to address broad social phenomena rather than focusing on proximate threats such as fishing pressure, to ensure the continued flow of coral reef goods and services in this time of rapid global social and environmental change.     

A skeletal assemblage classification system for non-tropical carbonate deposits based on New Zealand Cenozoic limestones

Cenozoic limestones in New Zealand are mainly skeletal grainstones and packstones formed under non-tropical climatic conditions in open marine shelf or ramp environments. Following petrographic analysis of the nature and abundance of the skeletal components in nearly 500 samples of these limestones, a complete linkage cluster analysis identified seven major skeletal assemblages that may be regarded as subdivisions of the single foramol skeletal association defined by Lees and Buller (1972) for temperate-region carbonate deposits. The seven assemblages are given contracted names, as follows: (a) BARNAMOL = barnacle/bivalve-dominated; (b) BIMOL = bivalve-dominated; (c) BRYOMOL = bryozoan/bivalve-dominated; (d) ECHINOFOR = echinoderm/benthic foraminiferal-dominated; (e) NANNOFOR = nannofossil/planktonic foraminiferal-dominated; (f) RHODALGAL = calcareous red algal-dominated; and (g) RHODECHFOR = calcareous red algal/echinoderm/benthic foraminiferal-dominated. A composite triangular classification diagram has been devised for naming the skeletal assemblage of an unknown sample on the basis of its three main skeletal components. The diagram successfully characterises more than 85% of the New Zealand Cenozoic limestone samples and also appears to be applicable for the skeletal assemblage designation of many overseas examples of non-tropical carbonate deposits. Limitations relate mainly to locally common skeletal types (e.g. serpulids, brachiopods) that are presently not incorporated into the New Zealand-based scheme. The general ecological preferences of the main skeletal contributors in each of the seven skeletal assemblages form a basis for relating the assemblages to broad shelf habitats. Consequently, as well as the benefits of providing a more consistent skeletal assemblage terminology for comparative studies between different workers, the scheme can assist with the paleoenvironmental interpretation of non-tropical skeletal carbonate facies.