Solubility and near-equilibrium dissolution rates of quartz in dilute NaCl solutions at 398-473 K under alkaline conditions

The dissolution-precipitation of quartz controls porosity and permeability in many lithologies and may be the best studied mineral-water reaction. However, the rate of quartz-water reaction is relatively well characterized far from equilibrium but relatively unexplored near equilibrium. We present kinetic data for quartz as equilibrium is approached from undersaturation and more limited data on the approach from supersaturated conditions in 0.1 molal NaCl + NaOH + NaSiO(OH)₃ solutions with pH 8.2-9.7 at 398, 423, 448, and 473 K. We employed a potentiometric technique that allows precise determination of solution speciation within 2 kJ mol⁻¹ of equilibrium without the need for to perturb the system through physical sampling and chemical analysis. Slightly higher equilibrium solubilities between 423 and 473 K were found than reported in recent compilations. Apparent activation energies of 29 and 37 kJ mol⁻¹ are inferred for rates of dissolution at two surface sites with different values of connectedness: dissolution at Q¹ or Q² silicon sites, respectively. The dissolution mechanism varies with ΔG such that reactions at both sites control dissolution up until a critical free energy value above which only reactions at Q¹ sites are important. When our near-equilibrium dissolution rates are extrapolated far from equilibrium, they agree within propagated uncertainty at 398 K with a recently published model by Bickmore et al. (2008). However, our extrapolated rates become progressively slower than model predictions with increasing temperature. Furthermore, we see no dependence of the postulated Q¹ reaction rate on pH, and a poorly-constrained pH dependence of the postulated Q² rate. Our slow extrapolated rates are presumably related to the increasing contribution of dissolution at Q³ sites far from equilibrium. The use of the potentiometric technique for rate measurement will yield both rate data and insights into the mechanisms of dissolution over a range of chemical affinity. Such measurements are needed to model the evolution of many natural systems quantitatively.     

Simulating flow in karst aquifers at laboratory and sub-regional scales using MODFLOW-CFP

Groundwater flow in a well-developed karst aquifer dominantly occurs through bedding planes, fractures, conduits, and caves created by and/or enlarged by dissolution. Conventional groundwater modeling methods assume that groundwater flow is described by Darcian principles where primary porosity (i.e. matrix porosity) and laminar flow are dominant. However, in well-developed karst aquifers, the assumption of Darcian flow can be questionable. While Darcian flow generally occurs in the matrix portion of the karst aquifer, flow through conduits can be non-laminar where the relation between specific discharge and hydraulic gradient is non-linear. MODFLOW-CFP is a relatively new modeling program that accounts for non-laminar and laminar flow in pipes, like karst caves, within an aquifer. In this study, results from MODFLOW-CFP are compared to those from MODFLOW-2000/2005, a numerical code based on Darcy’s law, to evaluate the accuracy that CFP can achieve when modeling flows in karst aquifers at laboratory and sub-regional (Woodville Karst Plain, Florida, USA) scales. In comparison with laboratory experiments, simulation results by MODFLOW-CFP are more accurate than MODFLOW 2005. At the sub-regional scale, MODFLOW-CFP was more accurate than MODFLOW-2000 for simulating field measurements of peak flow at one spring and total discharges at two springs for an observed storm event.     

Volcanic tsunamis and prehistoric cultural transitions in Cook Inlet,Alaska

The 1883 eruption of Augustine Volcano produced a tsunami when a debris avalanche traveled into the waters of Cook Inlet. Older debris avalanches and coeval paleotsunami deposits from sites around Cook Inlet record several older volcanic tsunamis. A debris avalanche into the sea on the west side of Augustine Island ca. 450 years ago produced a wave that affected areas 17 m above high tide on Augustine Island. A large volcanic tsunami was generated by a debris avalanche on the east side of Augustine Island ca. 1600 yr BP, and affected areas more than 7 m above high tide at distances of 80 km from the volcano on the Kenai Peninsula. A tsunami deposit dated to ca. 3600 yr BP is tentatively correlated with a southward directed collapse of the summit of Redoubt Volcano, although little is known about the magnitude of the tsunami. The 1600 yr BP tsunami from Augustine Volcano occurred about the same time as the collapse of the well-developed Kachemak culture in the southern Cook Inlet area, suggesting a link between volcanic tsunamis and prehistoric cultural changes in this region of Alaska.     

华北燕山带东部三叠纪和侏罗纪大地构造演化：来自备受争议的邓杖子组及相邻地层的线索

位于辽西凌源市南部的牛营子-邓杖子地区侏罗系地质问题多年来困扰着地质学家。争论最多的构造形迹是一套平面上呈狭长矩形,以断层为界的近直立中元古界常州沟组石英岩,及局部长城系顶部地层。这套地层绵延35 km,呈北北东展布。其西界为近直立的大齐子断层（新命名断层）和大部分向东倒转的陡倾下侏罗统邓杖子组;东界为近直立的朱杖子断层（新命名断层）和西倾的中侏罗统郭家店组。前人的构造解释倾向于大齐子断层为邓杖子组一侧下降的陡倾正断层,朱杖子断层为郭家店组一侧下降的陡倾逆断层。文中不同意这样的解释,并发现有证据表明上述两个断层都形成于之前尚未识别出的侏罗纪构造事件时期。将大齐子断层解释为早侏罗世晚期-中侏罗世早期形成的一条向西逆冲的断层,沿着它使长城系推覆于邓杖子组之上,然后,该逆冲断层上、下盘地层共同卷入后期褶皱变形当中。朱杖子断层原本为正断层,形成于原来未识别出的中侏罗世伸展变形阶段,并构成了郭家店半地堑边界断层。朱杖子断层沿着向东倾斜的常州沟组石英岩与串岭沟组页岩的界面发育。随着断层的发育,位于常州沟组石英岩之上的串岭沟组及长城系上部地层发生拆离沉降并被埋藏在半地堑之下。随后,发生在中侏罗世晚期或晚侏罗世早期收缩构造变形,改造了邓杖子-常州沟-郭家店组构造组合的几何形态。本期改造导致以下结果：（1）朱杖子正断层发生反转成为逆断层;（2）蓟县系沿着杨杖子-瓦房店逆冲断层向东掩覆于断层围限的长城系地层及相邻侏罗系之上。同时,邓杖子组倾角加大并向东倒转。研究表明,辽西地区的侏罗纪构造演化过程远比原先所认为的要复杂。     

Rio Tinto estuary (Spain): 5000 years of pollution

 Mining of massive sulfide deposits in southwestern Spain extending back to the Copper and Bronze Ages has resulted in the pollution of the Rio Tinto fluvial-estuarine complex, the site of Columbus' departure for the New World in 1492. Additional sources of potential pollution include the large industrial complex at Huelva near the lower portion of the estuary. Extensive analysis of surface sediment samples and cores has established that there are no geographic trends in the distribution of the pollutants, which include Cu, Fe, Pb, Zn, Ti, Ba, Cr, V and Co. These data have, however, demonstrated that tidal flux within the estuary carries phosphorus and perhaps other elements from the industrial complex at Huelva to the tidal limit of the system, several kilometers upstream from the discharge site. Radiometric analysis of short cores shows that sedimentation rates over at least the past couple of centuries have been about 0.3 cm/year. These data and that from a single deep core demonstrate that the estuary was polluted from mining activity long before the large-scale operations began in the late nineteenth century. Received: 3 May 1999 · Accepted: 18 October 1999     

Post-Miocene stratigraphy and depositional environments of valley-fill sequences at the mouth of Tampa Bay, Florida

Post-Miocene sea-level low stands allowed rivers and karst processes to incise the exposed carbonate platform along the Gulf Coast of Florida. Few Miocene to mid-Pleistocene deposits survived erosion along the present coast except within incised valleys. Since their formation, these valleys have been filled and incised multiple times in response to sea-level changes. The thick sedimentary sequences underlying the mouth of Tampa Bay have been recorded as a range of depositional environments and multiple sea-level incursions and excursions during pre-Holocene time and subsequent to the accumulation of the Miocene carbonate sequences. Sediment analysis of cores collected from a north–south transect across the mouth of Tampa Bay has enabled the identification of lithofacies, ranging from well-sorted, quartz sand to dense, fossiliferous, phosphatic grainstone. These facies were deposited in freshwater, estuarine, and shallow, open marine environments. As a result of channel development and migration within the paleovalley, and cut-and-fill associated with individual transgressions and regressions, correlation of the lithofacies does not extend across the entire transect. Fining-upward sequences truncated by tidal ravinement surfaces that extend throughout the paleovalley can, however, be identified. Age determinations based on 14-C analysis, amino-acid racemization, and strontium isotope analysis dating of numerous samples yield ages of Miocene, Pliocene, early Pleistocene, and late Pleistocene, as well as Holocene for sequences that accumulated and were preserved in this valley-fill complex. Numerous inconsistencies in the stratigraphic organization of the age determinations indicate that there are bad dates, considerable reworking of shells that were dated, or both. For this reason as well as the lack of detailed correlation among the three relatively complete cores, it is not possible to place these strata in a sequence stratigraphic framework.     

Neodymium isotopic evidence for the tectonic assembly of Late Archean crust in the Slave Province,northwest Canada

The ca. 2.7–2.5 Ga Slave Province is a granitegreenstone terrane comprising deformed sedimentary and subordinate volcanic belts extensively intruded by granitoid rocks. The Nd isotopic data are reported for 58 samples of supracrustal and granitoid rocks exposed along a 400 km, east-west, transect at 65°N across the structural grain of the province. Initial _Nd values reveal distinctly different crustal sources in the eastern compared to the western parts of the province, as expected from tectonic assembly of the province through accretion of juvenile crust to older continental crust. Supracrustal sequences (ca. 2.71–2.65 Ga) from the central and eastern parts of the province have positive _Nd(1) values (+0.3 to +3.6), consistent with juvenile sources and formation remote from significantly older crust. Syn to late-deformation (ca. 2.63–2.60 Ga), mantle-derived diorites and related tonalites (type I) from the central and eastern parts of the province have similar initial _Nd values (-0.1 to +2.7). In contrast, samples from the westernmost plutons, which intrude exposed pre-3.1 Ga crust, have much lower _Nd(1) values (-1.0 to4.6) suggesting contamination of these magmas by older crust. The _Nd(1) values of post-deformation granites (s.s.) (type II) also vary systematically across the province: values for granites west of longitude 110°30W range from-0.2 to -5.3; those to the east range from +0.6 to +3.7. These data suggest mixed crustal sources dominated by Mid to Early Archean material ( _Nd-2.6 to- 17 at 2.6 Ga) for the western granitoid rocks and juvenile sources for the eastern granites. The Nd isotopic data are consistent with the geology of the province in that exposures of Mid to Early Archean crustal rocks, predating the principal 2.7–2.5 Ga orogenic event are restricted to the western part of the province. The asymmetric pattern defined by the Nd isotopic data indicates the presence of distinct crustal rocks beneath the Slave Province. Similar isotopic variations observed across Phanerozoic collisional orogens have been interpreted to reflect tectonic assembly of crust by accretion of juvenile crustal terranes to an older continental margin. This process may also have been an important mechanism in the cratonization of the Slave Province.