Dissociation constants of protonated cysteine species in seawater media

The dissociation constants (pK₁, pK₂ and pK₃) for cysteine have been measured in seawater as a function of temperature (5 to 45 °C) and salinity (S = 5 to 35). The seawater values were lower than the values in NaCl at the same ionic strength. In an attempt to understand these differences, we have made measurements of the constants in Na–Mg–Cl solutions at 25 °C. The measured values have been compared to those calculated from the Pitzer ionic interaction model. The lower values of pK₃ in the Na–Mg–Cl solutions have been attributed to the formation of Mg²⁺ complexes with Cys²⁻ anions

Mg²⁺ + Cys²⁻ = MgCys

The stability constants have been fitted to

after corrections are made for the interaction of Mg²⁺ with H⁺.The pK₁ seawater measurements indicate that H₃Cys⁺ interacts with SO₄²⁻. The Pitzer parameters β⁰(H₃CysSO₄), β¹(H₃CysSO₄) and C(H₃CysSO₄) have been determined for this interaction. The formation of CaCys as well as MgCys are needed to account for the values of pK₂ and pK₃ in seawater.The consideration of the formation of MgCys and CaCys in seawater yields model calculated values of pK₁, pK₂ and pK₃ that agree with the measured values to within the experimental error of the measurements. This study shows that it is important to consider all of the ionic interactions in natural waters when examining the dissociation of organic acids.     

海洋环境立体监测系统的设计方法

“九五”和“十五”期间,在国家海洋863计划的支持下,我国分别在上海和台湾海峡及毗邻海域建立了两个区域性海洋环境立体监测示范系统。在这两个示范系统的技术研究成果的基础上,通过分析国际海洋立体监测系统的设计模型,提出了区域性海洋环境立体监测系统的设计原则和设计方法,包括:系统结构、数据与信息服务通信网络、数据处理中心、数据流程以及系统功能等方面的设计方法。     

日本凋毛藻碳酸酐酶基因及其编码的蛋白特征

碳酸酐酶CA(EC 4.2.1.1)是含锌原子的金属蛋白酶,该酶的基本功能是催化CO₂与HCO₃-间的相互转换[1].该反应在许多生物过程中都发挥着重要的作用,例如离子交换、呼吸作用、pH稳定性、捕获CO₂和光合作用等[2~5].CA广泛分布于各种生物中,已知的CA酶根据氨基酸序列被分为-αCA,-βCA和γ-CA三种类型[5~7].这3种类型的CA酶序列间的相似性很低,被认为是由不同的途径进化而来的[7].α-型的CA酶在动物、植物、绿藻、细菌和蓝细菌中都有发现[7],在藻类中报道的α-型CA还很少.迄今为止只在衣藻中发现2种异构体,在盐藻中发现3种[8,9],在红藻中还未见报道.     

Satellite altimetry for measuring river stages in remote regions

The advent in satellite altimetry with the most accurate satellite radar altimeter since 1992 and its successive missions have enabled the routine global monitoring of water-level (or stage) for surface waters and changes in the quantities of dammed water reservoirs. However, satellite altimeter measurements typically have spatial resolution capable of observing only large water bodies, such as major lakes and rivers. This paper addresses the challenges of how to investigate water levels in medium (~?1 km in width) to small (~?100 m and narrower) rivers. Comparisons between the ENVISAT altimetry ICE-1 waveform retracking height and standard water-level measurements for multiple sections of Ohio River, Columbia River, and Red River of the North in the United States (US) reveals that the satellite altimetry measured water levels agree well with those observed at nearby US Geological Survey gaging stations over the 10-year period starting from 2002. The significant results include those obtained at Thompson, North Dakota (ND, correlation coefficient or R value of 0.76 between satellite and in situ water-level measurements) and Fargo, ND (R?=?0.74), where the stream channels of Red River are merely?~?50 m and ~?40 m wide, respectively, under normal climatic conditions. In addition, demonstrations of the approach over largely inaccessible portions of Tigris–Euphrates Rivers and Helmand River in the Middle East aided in understanding hydrology in these systems. This study demonstrates the ability of satellite radar altimetry to characterize rivers in these study regions which are much narrower than 100 m in width.     

Experimental study of quartz inclusions in garnet at pressures up to 3.0 GPa: evaluating validity of the quartz-in-garnet inclusion elastic thermobarometer

Garnet crystals with quartz inclusions were hydrothermally crystallized from oxide starting materials in piston–cylinder apparatuses at pressures from 0.5 to 3 GPa and temperatures ranging from 700 to 800 °C to study how entrapment conditions affect remnant pressures of quartz inclusions used for quartz-in-garnet (QuiG) elastic thermobarometry. Systematic changes of the 128, 206 and 464 cm^?1 Raman band frequencies of quartz were used to determine pressures of quartz inclusions in garnet using Raman spectroscopy calibrations that describe the P–T dependencies of Raman band shifts for quartz under hydrostatic pressure. Within analytical uncertainties, inclusion pressures calculated for each of the three Raman band frequencies are equivalent, which suggests that non-hydrostatic stress effects caused by elastic anisotropy in quartz are smaller than measurement errors. The experimental quartz inclusions have pressures ranging from ??0.351 to 1.247 GPa that span the range of values observed for quartz inclusions in garnets from natural rocks. Quartz inclusion pressures were used to model P–T conditions at which the inclusions could have been trapped. The accuracy of QuiG thermobarometry was evaluated by considering the differences between pressures measured during experiments and pressures calculated using published equation of state parameters for quartz and garnet. Our experimental results demonstrate that Raman measurements performed at room temperature can be used without corrections to estimate garnet crystallization pressures. Calculated entrapment pressures for quartz inclusions in garnet are less than ~?10% different from pressures measured during the experiments. Because the method is simple to apply with reasonable accuracy, we expect widespread usage of QuiG thermobarometry to estimate crystallization conditions for garnet-bearing silicic rocks.     

Opportunities provided by geographic information systems and volunteered geographic information for a timely emergency response during flood events in Cologne,Germany

The occurrence of disasters such as extreme flooding in urban environments has severe consequences, not only on the human population but also on critical infrastructures such as the road networks, which are of vital importance for everyday living and particularly for emergency response. In this article, our main goal is to present-conceptually and in praxis-a model that could be used from the emergency responders for timely and efficient emergency management and response in an urban complex environment. For the city of Cologne in Germany, we aim to indicate possible ways to decrease the emergency response time during an extreme flood scenario through the development of an accessibility indicator, which consists of different components. Therefore, we will investigate the opportunities that occur, in a flood risk scenario, from the use of geographic information in different forms such as Volunteered Geographic Information (VGI) and open-source data in an ArcGIS environment, to increase urban resilience through the decreasing emergency response time. We will focus on network analysis for the fire brigades (first acting emergency responders) during a flood scenario to calculate their emergency response ranges and emergency response routes through flooded road networks, for the assistance of the possibly affected hospitals, refugee homes and fire brigades, which can be flooded. At the end of the paper, we suggest that the vulnerable community of the refugees could be taken into consideration as a new source of VGI, as an additional component that would lead to the decrease in the emergency response time. The geo-located information that could be provided by the refugee community can be very useful in emergency situations, such as those examined in this article where timely information can be forwarded to the proper authorities for a more focused and timely emergency response, increasing the resilience of the urban population and their community.     

New results concerning the pedo- and chronostratigraphy of the loess–palaeosol sequence Attenfeld (Bavaria,Germany) derived from a multi-methodological approach

Loess–palaeosol sequences (LPS) represent important records of palaeoenvironmental dynamics throughout the Quaternary. During the Pleistocene's dry and cold phases, the Danube's riverbed was one of the major sources for loess sediments that built up LPS in southern Germany and southeastern Europe. Surprisingly, studies addressing Bavarian LPS along the Danube River often lack actuality. The Attenfeld site was one of them and is often cited as a typical LPS. Nevertheless, the site's previous interpretations are based on a few empirical data and field observations. Considering the site's closeness to the sediment's source area, the Alps, and the region's importance in Middle and Upper Palaeolithic migrational movements, those former renditions needed an evaluation. Therefore, we applied a multi-proxy approach (including analyses of grain-size distribution, element composition, and sediment colour attributes) combined with optically stimulated luminescence. Based on our findings, we conclude that the Attenfeld site's former interpretations might be too generalised. We identified units that were not mentioned by previous studies (e.g. Early Glacial dark greyish horizon). Field observations, sediment characteristics, and age estimates indicate sediment deposition of the dated units partly before MIS 4, which contrasts with previous interpretations. The results further demonstrate how sensitive LPS are to environmental settings and dynamics.     

Sedimentology of the continental end‐Permian extinction event in the Sydney Basin,eastern Australia

Upper Permian to Lower Triassic coastal plain successions of the Sydney Basin in eastern Australia have been investigated in outcrop and continuous drillcores. The purpose of the investigation is to provide an assessment of palaeoenvironmental change at high southern palaeolatitudes in a continental margin context for the late Permian (Lopingian), across the end‐Permian Extinction interval, and into the Early Triassic. These basins were affected by explosive volcanic eruptions during the late Permian and, to a much lesser extent, during the Early Triassic, allowing high‐resolution age determination on the numerous tuff horizons. Palaeobotanical and radiogenic isotope data indicate that the end‐Permian Extinction occurs at the top of the uppermost coal bed, and the Permo‐Triassic boundary either within an immediately overlying mudrock succession or within a succeeding channel sandstone body, depending on locality due to lateral variation. Late Permian depositional environments were initially (during the Wuchiapingian) shallow marine and deltaic, but coastal plain fluvial environments with extensive coal‐forming mires became progressively established during the early late Permian, reflected in numerous preserved coal seams. The fluvial style of coastal plain channel deposits varies geographically. However, apart from the loss of peat‐forming mires, no significant long‐term change in depositional style (grain size, sediment‐body architecture, or sediment dispersal direction) was noted across the end‐Permian Extinction (pinpointed by turnover of the palaeoflora). There is no evidence for immediate aridification across the boundary despite a loss of coal from these successions. Rather, the end‐Permian Extinction marks the base of a long‐term, progressive trend towards better‐drained alluvial conditions into the Early Triassic. Indeed, the floral turnover was immediately followed by a flooding event in basinal depocentres, following which fluvial systems similar to those active prior to the end‐Permian Extinction were re‐established. The age of the floral extinction is constrained to 252.54 ± 0.08 to 252.10 ± 0.06 Ma by a suite of new Chemical Abrasion Isotope Dilution Thermal Ionization Mass Spectrometry U‐Pb ages on zircon grains. Another new age indicates that the return to fluvial sedimentation similar to that before the end‐Permian Extinction occurred in the basal Triassic (prior to 251.51 ± 0.14 Ma). The character of the surface separating coal‐bearing pre‐end‐Permian Extinction from coal‐barren post‐end‐Permian Extinction strata varies across the basins. In basin‐central locations, the contact varies from disconformable, where a fluvial channel body has cut down to the level of the top coal, to conformable where the top coal is overlain by mudrocks and interbedded sandstone–siltstone facies. In basin‐marginal locations, however, the contact is a pronounced erosional disconformity with coarse‐grained alluvial facies overlying older Permian rocks. There is no evidence that the contact is everywhere a disconformity or unconformity.     

Chromium(VI) reduction by sulphur(IV) in aqueous solutions

The rates of the reduction of Cr(VI) with S(IV) were measured in deaerated NaCl solution as a function of pH, temperature and ionic strength. The rates of the reaction were found to be first order with respect to Cr(VI) and second order with respect to S(IV), in agreement with previous results obtained at concentrations two order higher than the present study. The reaction also showed a first-order dependence of the rates on the concentration of the proton and a small influence of temperature with an apparent energy of activation ΔH_app of 22.8 ± 3.4 kJ/mol. The rates were independent of ionic strength from 0.01 to 1 M. The rate of Cr(VI) reduction is described by the general expression

−d[Cr(VI)]/dt=k[Cr(VI)][S(IV)]²