Dissolution kinetics of calcite at 50-70 °C: An atomic force microscopic study under near-equilibrium conditions

Direct measurements of calcite faces were performed using in situ atomic force microscopy (AFM) to reveal the dissolution processes as a function of solution saturation state and temperature. Time-sequential AFM images demonstrated that step velocities at constant temperature increased with increasing undersaturation. The anisotropy of obtuse and acute step velocities appeared to become more significant as solutions approached equilibrium and temperature increased. At saturation state Ω > 0.02, a curvilinear boundary was formed at the intersection of two acute steps and the initially rhombohedral etch pit exhibited a nearly triangular shape. This suggests that the and steps may not belong to the calcite-aqueous solution equilibrium system. Further increase in the saturation state (Ω ? 0.3) led to a lack of etch pit formation and dissolution primarily occurred at existing steps, in accordance with Teng (2004). Analysis of step kinetics at different temperatures yielded activation energies of 25 ± 6 kJ/mol and 14 ± 13 kJ/mol for obtuse and acute steps, respectively. The inconsistencies in etch pit morphology, step anisotropy, and step activation energies from the present study with those of studies far-from-equilibrium can be explained by increased influence of the backward reaction, or growth, near-equilibrium. We propose that the backward reaction occurs preferentially at the acute-acute kink sites. The kinetics and effective activation energies of near-equilibrium calcite dissolution presented in this work provide accurate experimental data under likely CO₂ sequestration conditions, and thus are crucial to the development of robust geochemical models that predict the long-term performance of mineral-trapped CO₂.     

L'archivage des activités humaines par les neiges et glaces polaires : le cas du plomb

The investigation of the occurrence of lead in dated snow and ice from Greenland and Antarctica has played a major role in our understanding of the history of the pollution of the atmosphere of our planet by this metal. Such studies have however proved to be very demanding, mainly because of the extreme purity of polar snow and ice. Reliable measurements can be obtained only if ultra-clean and highly sensitive procedures are used, as pioneered by Clair Patterson. The Greenland data show evidence of large-scale pollution of the atmosphere of the Northern Hemisphere for lead as early as two millennia ago during Greco–Roman times, especially because of mining and smelting activities in southern Spain. It peaked at the end of the 1960s, with lead concentrations in snow about 200 times higher than natural values, before declining during recent times because of the fall in the use of leaded gasoline. Lead pollution in Antarctica was already significant at the end of the 19th century as a consequence of whaling activities, the traffic of coal-powered ships crossing the Cape Horn, and mining activities in South America, South Africa and Australia. After declining because of the opening of the Panama Canal, the great economic depression and World War II, it reached a maximum during the 1980s, with lead concentrations 20 times higher than natural values. Other studies focus on past natural variations of lead in ancient ice dated from the last climatic cycles. To cite this article: C. Boutron et al., C. R. Geoscience 336 (2004).     

A field evaluation of enhanced reductive dechlorination of chlorinated solvents in groundwater,New York Metropolitan Area

An initial assessment of an old manufacturing site with groundwater impacted by trichloroethene (TCE) contamination in the metropolitan New York area showed that the TCE was being removed naturally by reductive dechlorination. However, complete dechlorination was not expected at the site because the process was progressing too slowly under transitional to aerobic conditions at a degradation constant of –0.0013 and a TCE half life of 533 days. A pilot test was conducted at the site in which a carbohydrate substrate (molasses) was injected into the groundwater to create an In-Situ Reactive Zone (IRZ). Post-pilot test groundwater sampling and analysis indicated that an IRZ was created successfully as the total organic carbon (TOC) content and conductivity increased significantly while oxidation-reduction (REDOX) potential and dissolved oxygen (DO) decreased. The created IRZ caused enhanced reductive dechlorination of TCE at the site, found to proceed with a degradation constant of –0.0158 and a TCE half life of 44 days.     

A cross-ecosystem comparison of spatial and temporal patterns of covariation in the recruitment of functionally analogous fish stocks

Temporal and spatial patterns of recruitment (R) and spawning stock biomass (S) variability were compared among functionally analogous species and similar feeding guilds from six marine ecosystems. Data were aggregated into four regions including the Gulf of Maine/Georges Bank, the Norwegian/Barents Seas, the eastern Bering Sea, and the Gulf of Alaska. Variability was characterized by calculating coefficients of variation and anomalies for three response variables: ln(R), ln(R/S), and stock–recruit model residuals. Patterns of synchrony and asynchrony in the response variables were examined among and between ecosystems, between- and within-ocean basins and among functionally analogous species groups using pair-wise correlation analysis corrected for within-time series autocorrelation, multivariate cross-correlation analyses and regime shift detectors. Time series trends in response variables showed consistent within basin similarities and consistent and coherent differences between the Atlantic and Pacific basin ecosystems. Regime shift detection algorithms identified two broad-scale regime shift time periods for the pelagic feeding guild (1972–1976 and 1999–2002) and possibly one for the benthic feeding guild (1999–2002). No spatial patterns in response variable coefficients of variation were observed. Results from multivariate cross-correlation analysis showed similar trends. The data suggest common external factors act in synchrony on stocks within ocean basins but temporal stock patterns, often of the same species or functional group, between basins change in opposition to each other. Basin-scale results (similar within but different between) suggest that the two geographically broad areas are connected by unknown mechanisms that, depending on the year, may influence the two basins in opposite ways. This work demonstrates that commonalities and synchronies in recruitment fluctuations can be found across geographically distant ecosystems but biophysical causes of the fluctuations remain difficult to identify.     

Reproductive Cycle of the Caribbean Feather Star Nemaster rubiginosa (Echinodermata: Crinoidea)

Abstract. The reproductive cycle of the comatulid crinoid Nemaster rubiginosa from Discovery Bay, Jamaica is described histologically. The cycle is annual and may be divided into (1) a "resting" phase (summer) in which most adults possess immature, unsexable gonads, (2) a recovery phase (early fall) marked by the re-initiation of gametogenesis and rapid gonadal growth, (3) a breeding phase (late fall and winter) during which the gonads are mature and repeated spawning likely takes place, and (4) a post-spawning phase (spring) during which relict gametes are removed from the shrinking gonads. Although unsexable individuals predominate during the "resting" phase, a small proportion of the adult population is unsexable at all times of the year. The reproductive condition of animals in the same month in two successive years was very similar, suggesting that the timing of reproduction is quite predictable from year to year. The re-initiation of gametogenesis in the early fall is correlated with both rising sea temperature and shortening daylength, and the October to March breeding season corresponds to the period of short daylengths at the study site. The well-defined and synchronized annual reproductive cycle of Nemaster rubiginosa contrasts with the more prolonged and variable reproductive cycles reported for other tropical crinoids and points to a diversity of breeding patterns among tropical crinoids.     

Erosion rates and mechanisms of knickzone retreat inferred from 10Be measured across strong climate gradients on the northern and central Andes Western Escarpment

A steep escarpment edge, deep gorges and distinct knickzones in river profiles characterize the landscape on the Western Escarpment of the Andes between ~5°S and ~18°S (northern Peru to northern Chile). Strong north–south and east–west precipitation gradients are exploited in order to determine how climate affects denudation rates in three river basins spanning an otherwise relatively uniform geologic and geomorphologic setting. Late Miocene tectonics uplifted the Meseta/Altiplano plateau (~3000 m a.s.l.), which is underlain by a series of Tertiary volcanic‐volcanoclastic rocks. Streams on this plateau remain graded to the Late Miocene base level. Below the rim of the Meseta, streams have responded to this ramp uplift by incising deeply into fractured Mesozoic rocks via a series of steep, headward retreating knickzones that grade to the present‐day base level defined by the Pacific Ocean. It is found that the Tertiary units on the plateau function as cap‐rocks, which aid in the parallel retreat of the sharp escarpment edge and upper knickzone tips. ¹⁰Be‐derived catchment denudation rates of the Rio Piura (5°S), Rio Pisco (13°S) and Rio Lluta (18°S) average ~10 mm ky^?1 on the Meseta/Altiplano, irrespective of precipitation rates; whereas, downstream of the escarpment edge, denudation rates range from 10 mm ky^?1 to 250 mm ky^?1 and correlate positively with precipitation rates, but show no strong correlation with hillslope angles or channel steepness. These relationships are explained by the presence of a cap‐rock and climate‐driven fluvial incision that steepens hillslopes to near‐threshold conditions. Since escarpment retreat and the precipitation pattern were established at least in the Miocene, it is speculated that the present‐day distribution of morphology and denudation rates has probably remained largely unchanged during the past several millions of years as the knickzones have propagated headward into the plateau. Copyright © 2011 John Wiley & Sons, Ltd.     

Reconstruction of MODIS total suspended matter time series maps by DINEOF and validation with autonomous platform data

In situ measurements of total suspended matter (TSM) over the period 2003–2006, collected with two autonomous platforms from the Centre for Environment, Fisheries and Aquatic Sciences (Cefas) measuring the optical backscatter (OBS) in the southern North Sea, are used to assess the accuracy of TSM time series extracted from satellite data. Since there are gaps in the remote sensing (RS) data, due mainly to cloud cover, the Data Interpolating Empirical Orthogonal Functions (DINEOF) is used to fill in the TSM time series and build a continuous daily “recoloured” dataset. The RS datasets consist of TSM maps derived from MODIS imagery using the bio-optical model of Nechad et al. (Rem Sens Environ 114: 854–866, 2010). In this study, the DINEOF time series are compared to the in situ OBS measured in moderately to very turbid waters respectively in West Gabbard and Warp Anchorage, in the southern North Sea. The discrepancies between instantaneous RS, DINEOF-filled RS data and Cefas data are analysed in terms of TSM algorithm uncertainties, space–time variability and DINEOF reconstruction uncertainty.     

Cloning of a chub metallothionein cDNA and development of competitive RT-PCR of chub metallothionein mRNA as a potential biomarker of heavy metal exposure

Metallothionein has been assayed in a range of aquatic animal tissues as an indicator of metal exposure. We sequenced chub (Leuciscus cephalus) metallothionein cDNA which showed over 90% homology to common carp, goldfish and stone loach and 77% homology to rainbow trout sequences for metallothionein. We then used the extended primer method to develop an accurate quantitative competitive RT-PCR assay for metallothionein mRNA. RT-PCR was used to measure metallothionein mRNA in feral chub from a range of field sites, with different levels of heavy metal pollution, in the West Midlands, UK. Measurements were complemented by analysis of liver and gill metallothionein protein by capillary electrophoresis. There was no significant difference in the metallothionein protein levels between fish of different rivers and there was no evidence of elevation of mRNA at the sites of highest metal exposure. The level of metal exposure (e.g. zinc, nickel and cadmium each ranging between 15 and 28 microg/l ) at the pH (7.5-8.5) of these rivers appears insufficient to elevate hepatic or gill metallothionein in chub. A lack of elevation of hepatic metallothionein mRNA in chub exposed to zinc, copper and manganese for 24 h and 10 days in the laboratory also suggests a non-responsiveness of this species.     

利用基于环境因子的动态产量模型评估西南大西洋阿根廷滑柔鱼

西南大西洋阿根廷滑柔鱼,Illex argentinus,巴塔哥尼亚南部群体是重要的经济种类。海洋环境因子在柔鱼资源分布中起着重要的作用。本研究利用基于环境因子的动态产量模型评估2000-2010年的滑柔鱼的资源量。假设海洋环境因子（滑柔鱼产卵场最适宜海表温度占比）影响动态产量模型的参数K,DIC值表明在正态分布和均匀分布下均是基于环境因子的评估模型优于基本的动态产量模型。阿根廷滑柔鱼的最大可持续产量（MSY）在351600吨到685 100吨之间,资源生物量在1322400吨到1 803 000吨之间,其捕捞死亡系数均小于F_0.1和F_MSY,资源处在良好状态,没有遭受过度捕捞。本研究为应用环境因子在柔鱼类的资源评估与管理提中供了科学的参考方法。     

Factors influencing biodeposit production by the New Zealand freshwater mussel Echyridella menziesii

Laboratory experiments on the New Zealand freshwater mussel Echyridella menziesii were used to investigate the short-term effects (7–8 days) of food type on rates of biodeposition and benthic substrate respiration. Post-feeding biodeposition rates ranged from 0.34 to 1.52?mg?g^?1?h^?1 (mean?=?0.50?mg g^?1?h^?1) and were unaffected by the addition of toxin-producing Microcystis. Addition of suspended sediment (30?mg?L^?1) visibly altered substrate composition, and increased total and inorganic biodeposit production rates by 24–33% compared to mussels fed commercial phytoplankton stock. Biodeposition rates of mussels in lake bed substrates were 38% higher than those in silica sand for identical feeding regimes, suggesting that a significant proportion of material produced in this experiment could have been derived from feeding on organic matter in the lake bed sediments. Respiration rates were higher in treatments with Microcystis but were unaffected by the presence of mussels. This laboratory study suggests that biodeposition by E. menziesii is resilient to short-term exposure to Microcystis, and highlights the ability of mussels to alter benthic substrate composition by incorporating suspended sediment into substrates.