The influence of pH on the kinetics, reversibility and mechanisms of Pb(II) sorption at the calcite-water interface

Pb(II) sorption experiments with calcite powders were conducted in suspensions equilibrated at atmospheric PCO_2(g) and ambient temperature at pH 7.3, 8.2 and 9.4. Pb fractional sorption was low at pH 7.3 and 9.4 relative to pH 8.2, and correlated well with PbCO₃⁰_(aq) speciation. Desorption experiments conducted for initial sorption times ranging from 0.5 h to 12 d reveal an almost completely reversible process at pH 8.2, attributed to the dominance of an adsorption mechanism, with slight and pronounced irreversibility at pH 7.3 and 9.4 respectively. Similarities in X-ray absorption near edge spectra (XANES) for 24 h and 12 d pH 7.3 and 9.4 sorption samples indicate no effect of initial sorption time. Results from linear combination (LC) fits of XANES spectra for samples sorbed at pH 9.4 confirm ∼75% adsorbed and ∼25% coprecipitated components. The coprecipitated fraction was attributed to the non-exchangeable metal observed in desorption experiments. At pH 7.3, ∼95% adsorbed and ∼5% coprecipitated components were obtained. A comparison of results from desorption experiments and LC-XANES alludes to an irreversibly bound adsorbed component for the pH 9.4 12 d sorption sample. Extended X-ray absorption fine structure spectroscopy (EXAFS) analysis of pH 7.3 and 9.4 12 d sorption samples confirms the presence of both adsorbed and coprecipitated metal. At pH 7.3 a first-shell Pb-O bond length of 2.38 Å is intermediate between that of adsorbed (2.34 Å) and coprecipitated (2.51 Å) Pb. At pH 9.4, two first-shell Pb-O distances at 2.35 Å and 2.51 Å were obtained, indicative of the occurrence of both adsorption and coprecipitation and a larger coprecipitated fraction relative to that at pH 7.3, consistent with LC-XANES results. We propose that the disparity in the fraction of coprecipitated metal with pH may be linked to the ability of sorbed Pb to inhibit near-surface dynamic exchange of Ca and CO₃ species, which dictates step advance and retreat. Less effective inhibition of step motion at pH 9.4, due to lower fractional sorption, combined with highest rates of dynamic exchange results in a significant fraction of coprecipitated Pb at this pH. At low pH, though fractional sorption is also low, lower rates of exchange prohibit significant coprecipitation. At pH 8.2, effective inhibition of surface processes due to higher fractional sorption and lower rates of exchange compared to pH 7.3 and 9.4 preclude detectable coprecipitation. Other factors such as changes in surface speciation and solubility of the Pb-Ca solid solution with pH may also come into play. Overall, this study presents evidence for the influence of pH on Pb sorption mechanisms, and addresses the efficiency of Pb immobilization in calcitic systems.     

The Potential for Rural Heritage Tourism in the Clarence Valley of Northern New South Wales

In the past, heritage tourism has been associated with urban sites but there is now an acceptance of the application of this concept to rural areas. In the Clarence Valley in northern New South Wales there is potential for an extension of agritourism associated with working dairy farms to include safari tours to clusters of dairy heritage sites which are scattered throughout the area. Remnants of the old dairy industry, which began in the Clarence River Valley of New South Wales in the late nineteenth century, are scattered throughout the landscape. Over 300 dairy milking bails remain—ghosts of the former thriving industry when over 2000 dairy farms were operating. Concrete foundations of some creameries built in the 1890s can still be found, and three factory buildings still stand. These relics are disappearing quite rapidly and if the importance of the industry is to be recognised by future generations then it seems that some heritage conservation is overdue. At the same time, in order to survive in a post-deregulated economic environment, the remaining 10 dairy farmers in the Clarence Valley are diversifying their activities, with one form of pluriactivity being agritourism. Currently few of these farmers have entered this field but most of them see its potential to broaden their income base. Associated with agritourism at the farm level, the local government authorities see heritage tourism as a way of increasing employment in the region.     

A surge of Skobreen, Svalbard

Surging glaciers are common in Svalbard yet relatively few glaciers have been observed during a surge. This paper presents observations of the currently surging glacier Skobreen, in southern Spitsbergen. The study is based on examinations of new and archival photographs and maps. Skobreen, an 18 km² valley glacier terminating into the lower part of the glacier Paulabreen, has not been registered previously as a surging glacier. Skobreen experienced a build-up in its upper part, while there has been a lowering of the surface in the terminal region. Photographs from 1990 show incipient crevassing in the upper part. Photographs from 2003 show a slight advance of the terminus and marginal crevassing, indicating an initiation period of about 15 years for a surge of this glacier. In June 2005 transverse crevassing appeared in the upper part of the glacier, while the middle section moved as a block with strong shear margins and a pronounced drawdown of the ice surface. No traces of a surge front could be seen in the crevasse pattern. However, the crevasse pattern indicates an initiation area in the transition zone between the transverse crevassing in the upper part and the block of ice in the middle region.     

Local thickening of the Cascadia forearc crust and the origin of seismic reflectors in the uppermost mantle

Seismic reflection profiles from three different surveys of the Cascadia forearc are interpreted using P wave velocities and relocated hypocentres, which were both derived from the first arrival travel time inversion of wide-angle seismic data and local earthquakes. The subduction decollement, which is characterized beneath the continental shelf by a reflection of 0.5 s duration, can be traced landward into a large duplex structure in the lower forearc crust near southern Vancouver Island. Beneath Vancouver Island, the roof thrust of the duplex is revealed by a 5–12 km thick zone, identified previously as the E reflectors, and the floor thrust is defined by a short duration reflection from a < 2-km-thick interface at the top of the subducting plate. We show that another zone of reflectors exists east of Vancouver Island that is approximately 8 km thick, and identified as the D reflectors. These overlie the E reflectors; together the two zones define the landward part of the duplex. The combined zones reach depths as great as 50 km. The duplex structure extends for more than 120 km perpendicular to the margin, has an along-strike extent of 80 km, and at depths between 30 km and 50 km the duplex structure correlates with a region of anomalously deep seismicity, where velocities are less than 7000 m s^− 1. We suggest that these relatively low velocities indicate the presence of either crustal rocks from the oceanic plate that have been underplated to the continent or crustal rocks from the forearc that have been transported downward by subduction erosion. The absence of seismicity from within the E reflectors implies that they are significantly weaker than the overlying crust, and the reflectors may be a zone of active ductile shear. In contrast, seismicity in parts of the D reflectors can be interpreted to mean that ductile shearing no longer occurs in the landward part of the duplex. Merging of the D and E reflectors at 42–46 km depth creates reflectivity in the uppermost mantle with a vertical thickness of at least 15 km. We suggest that pervasive reflectivity in the upper mantle elsewhere beneath Puget Sound and the Strait of Georgia arises from similar shear zones.     

1997年9月26日意大利中部Umbria-marche地震前的水文地质变化

分析了1997年9月26日意大利中部Umbria与marche交界地区的Umbria-marche地震序列引起的水文体系的变化。为了量化水文体系的变化,从地方当局和矿泉水公司收集了地下水位、泉水的流量以及河水流速等的资料,这些资料可以确定异常的影响面积,并且可以通过与从震前几年资料估算出的年平均体系的对比来量化异常的变化,试图对异常进行判定。分析结果表明,两个含水单元,即Umbria-marche山峰和Val-nerina单元,具有紧密的联系,它们都由于水文系统的改变而受到影响。地震前几个月两条河流测量站记录到了异常变化,认为是地震前兆异常。     

Rare gas abundances in MORB

Data are presented for He, Ar and Xe in a number of MORB glasses and crystalline rocks. The rare gases in the latter group are characterized by atmospheric Ar and Xe, coupled with loss of trapped mantle He, Ar and Xe. The glass data also show clear signs of an atmospheric-like component for Ar and Xe. A reasonably constant world-wide average trapped mantle gas value of ⁴⁰Ar/³⁶Ar ˜15000 ±3000 is suggested. Anomalies are seen in the ¹²⁹Xe/¹³²Xe ratio, but at least part of this might be due to mass fractionation rather than to ¹²⁹I decay. Correlating the data with those from oceanic island basalts in Ar-Xe space indicates that the latter samples are probably also greatly influenced by an atmospheric component rather than (or in addition to) trapping gases from an undepleted mantle source.     

Mineralogic variability of the uppermost mantle along mid-ocean ridges

Modal analyses of 273 different peridotites representing 43 dredge stations in the Atlantic, Caribbean, and Indian Oceans define three separate melting trends. Peridotites dredged in the vicinity of “mantle plumes” or hot spots have the most depleted compositions in terms of basaltic components, while peridotites dredged at locations removed from such regions are systematically less depleted. The modal data correlate well with mineral compositions, with the peridotites most depleted in pyroxene also having the most refractory mineral compositions. This demonstrates that they are the probable residues of variable degrees of mantle melting. Further, there is a good correlation between the modal compositions of the peridotites and the major element composition of spatially associated dredged basalts. This demonstrates for the first time that the two must be directly related, as is frequently postulated. The high degree of depletion of the peridotites in basaltic major element components in the vicinity of some documented mantle plumes provides direct evidence for a thermal anomaly in such regions—justifying their frequent designation as “hot spots”. The high incompatible element concentrations in these “plume” basalts, however, are contrary to what is expected for such high degrees of melting, and thus require either selective contributions from locally more abundant enriched veins and/or contamination by a volatile-rich metasomatic front from depth.