Hyalotekite, (Ba,Pb,K)(4)(Ca,Y)(2)Si-8(B,Be)(2)(Si,B)(2)O28F, a Tectosilicate Related to Scapolite: New Structure Refinement, Phase Transitions and a Short-Range Ordered 3B Superstructure

Hyalotekite, a framework silicate of composition (Ba,Pb,K)(4)(Ca,Y)(2)Si-8(B,Be)(2) (Si,B)(2)O28F, is found in relatively high-temperature(greater than or equal to 500 degrees C) Mn skarns at Langban, Sweden, and peralkaline pegmatites at Dara-i-Pioz, Tajikistan. A new paragenesis at Dara-i-Pioz is pegmatite consisting of the Ba borosilicates leucosphenite and tienshanite, as well as caesium kupletskite, aegirine, pyrochlore, microcline and quartz. Hyalotekite has been partially replaced by barylite and danburite. This hyalotekite contains 1.29-1.78 wt.% Y2O3, equivalent to 0.172-0.238 Y pfu or 8-11% Y on the Ca site; its Pb/(Pb+Ba) ratio ranges 0.36-0.44. Electron microprobe F contents of Langban and Dara-i-Pioz hyalotekite range 1.04-1.45 wt.%, consistent with full occupancy of the F site. A new refinement of the structure factor data used in the original structural determination of a Langban hyalotekite resulted in a structural formula, (Pb1.96Ba1.86K0.18)Ca-2(B1.76Be0.24)(Si1.56B0.44)Si8O28F, consistent with chemical data and all cations with positive-definite thermal parameters, although with a slight excess of positive charge (+57.14 as opposed to the ideal +57.00). An unusual feature of the hyalotekite framework is that 4 of 28 oxygens are non-bridging; by merging these 4 oxygens into two, the framework topology of scapolite is obtained. The triclinic symmetry of hyalotekite observed at room temperature is obtained from a hypothetical tetragonal parent structure via a sequence of displacive phase transitions. Some of these transitions are associated with cation ordering, either Pb-Ba ordering in the large cation sites, or B-Be and Si-B ordering on tetrahedral sites. Others are largely displacive but affect the coordination of the large cations (Pb, Ba, K, Ca). High-resolution electron microscopy suggests that the undulatory extinction characteristic of hyalotekite is due to a fine mosaic microstructure. This suggests that at least one of these transitions occurs in nature during cooling, and that it is first order with a large volume change. A diffuse superstructure observed by electron diffraction implies the existence of a further stage of short-range cation ordering which probably involves both (Pb,K)-Ba and (BeSi,BB)-BSi.

Response of a First-Order Stream in Maine to Short-Term In-Stream Acidification

An experimental short-term acidification with HCl at a first-order stream in central Maine, USA was used to study processes controlling the changes in stream chemistry and to assess the ability of stream substrate to buffer pH. The streambed exerted a strong buffering capacity against pH change by ion exchange during the 6-hour acidification. Streambed substrates had substantial cation and anion exchange capacity in the pH range of 4.1 to 6.5. The ion exchange for cations and SO42- were rapid and reversible. The speed of release of cations from stream substrates was Na1+ > Ca2+ > Mg2+ > Aln+ > Be2+, perhaps relating to charge density of these cations. Ca2+ desorption dominated neutralisation of excess H+ for the first 2 hr. As the reservoir of exchangeable Ca diminished, desorption land possibly dissolution) of Al3+ became the dominant neutralising mechanism. The exchangeable land possibly soluble) reservoir of Al was not depleted during the 6-hour acidification. Sulphate adsorption during the acidification reduced the concentration of SO42- in stream water by as much as 20 mu eq L-1 (from 70 mu eq L-1). Desorption of SO42- and adsorption of base cat ions after the artificial acidification resulted in a prolongation of the pH depression. The streambed had the capacity to buffer stream water chemistry significantly during an acidifying event affecting the entire upstream catchment.