The passivation of calcite by acid mine water. Column experiments with ferric sulfate and ferric chloride solutions at pH 2

Column experiments, simulating the behavior of passive treatment systems for acid mine drainage, have been performed. Acid solutions (HCl or H₂SO₄, pH 2), with initial concentrations of Fe(III) ranging from 250 to 1500 mg L⁻¹, were injected into column reactors packed with calcite grains at a constant flow rate. The composition of the solutions was monitored during the experiments. At the end of the experiments (passivation of the columns), the composition and structure of the solids were measured. The dissolution of calcite in the columns caused an increase in pH and the release of Ca into the solution, leading to the precipitation of gypsum and Fe–oxyhydroxysulfates (Fe(III)–SO₄–H⁺ solutions) or Fe–oxyhydroxychlorides (Fe(III)–Cl–H⁺ solutions). The columns worked as an efficient barrier for some time, increasing the pH of the circulating solutions from 2 to 6–7 and removing its metal content. However, after some time (several weeks, depending on the conditions), the columns became chemically inert. The results showed that passivation time increased with decreasing anion and metal content of the solutions. Gypsum was the phase responsible for the passivation of calcite in the experiments with Fe(III)–SO₄–H⁺ solutions. Schwertmannite and goethite appeared as the Fe(III) secondary phases in those experiments. Akaganeite was the phase responsible for the passivation of the system in the experiments with Fe(III)–Cl–H⁺ solutions.     

Controls of δS and δO in dissolved sulphate: Learning from a detailed survey in the Llobregat River (Spain)

The S and O isotopic composition of dissolved SO₄, used as a tracer for SO₄ sources, was applied to the water of the Llobregat River system (NE Spain). The survey was carried out at 30 sites where surface water was sampled on a monthly basis over a period of 2a. The concentration of dissolved SO₄ varied from 20 to 1575 mg L⁻¹. Sulphur isotopic compositions clustered in two populations: one – 93% of the samples – had positive values with a mode of +9‰; the other had negative values and a mode of −5‰. Data for δ¹⁸O_SO4 showed a mean value of +11‰, with no bi-modal distribution, though lower values of δ¹⁸O corresponded to samples with negative δ³⁴S. These values can not be explained solely by the contribution of bedrock SO₄ sources: that is, sulphide oxidation and the weathering of outcrops of sulphates, though numerous chemical sediments exist in the basin. Even in a river with a high concentration of natural sources of dissolved SO₄, such as the Llobregat River, the δ³⁴S values suggest that dissolved SO₄ is controlled by a complex mix of both natural and anthropogenic sources. The main anthropogenic sources in this basin are fertilizers, sewage, potash mine effluent and power plant emissions. Detailed river water sampling, together with the chemical and isotopic characterisation of the main anthropogenic inputs, allowed determination of the influence of redox processes, as well as identification of the contribution of natural and anthropogenic SO₄ sources and detection of spatial variations and seasonal changes among these sources. For instance, in the Llobregat River the input of fertilisers is well marked seasonally. Minimum values of δ³⁴S are reported during fertilization periods – from January to March – indicating a higher contribution of this source. The dual isotope approach, δ³⁴S and δ¹⁸O, is useful to better constrain the sources of SO₄. Moreover, in small-scale studies, where the inputs are well known and limited, the mixing models can be enhanced and the contribution of the different sources can be quantified to some extent.     

Observations Of Nocturnal Drainage Flow In A Shallow Gully

The formation of cold air drainage flows in a shallow gully is studied during CASES-99 (Cooperative Atmosphere-Surface Exchange Study). Fast and slow response wind and temperature measurements were obtained on an instrumented 10-m tower located in the gully and from a network of thermistors and two-dimensional sonic anemometers, situated across the gully. Gully flow formed on clear nights even with significant synoptic flow. Large variations in surface temperature developed within an hour after sunset and in situ cooling was the dominant factor in wind sheltered locations. The depth of the drainage flow and the height of the down-gully wind speed maximum were found to be largest when the external wind speed above the gully flow is less than 2 m s^-1. The shallow drainage current is restricted to a depth of a few metres, and is deepest when the stratification is stronger and the external flow is weaker. During the night the drainage flow breaks down, sometimes on several occasions, due to intermittent turbulence and downward fluxes of heat and momentum. The near surface temperature may increase by 6 ° C in less than 30 min due to the vertical convergence of downward heat flux. The mixing events are related to acceleration of the flow above the gully flow and decreased Richardson number. These warming events also lead to warming of the near surface soil and reduction of the upward soil heat flux. To examine the relative importance of different physical mechanisms that could contribute to the rapid warming, and to characterize the turbulence generated during the intermittent turbulent periods, the sensible heat budget is analyzed and the behaviour of different turbulent parameters is discussed.     

A profile of General Carlos Ibáñez e Ibáñez de Ibero: first president of the International Geodetic Association

 The exploits of the multifaceted scientist (engineer-geodesist-metrologist) General Carlos Ibá?ez e Ibá?ez de Ibero (1825–1891), Marqués de Mulhacén, are recounted. A bibliography of his relevant work is included. Received 27 September 1996; Accepted 2 October 1996     

A mass transfer model of bauxite formation

The formation of bauxite due to weathering of a granitic protolith has been simulated by means of a one-dimensional flow and reaction model based on the mass transfer principle. The model couples mineral dissolution and precipitation reactions, speciation in solution, and advective solute transport in a porous medium. A very important aspect of the modeling study is the use of mineral reaction rates determined experimentally in the laboratory. The important effects of solution saturation state and pH have been incorporated into the kinetic rate laws governing the heterogeneous reactions. The values of these parameters have been obtained from the scientific literature to guarantee that realistic reaction rates are used in the simulations. Albite and quartz are the minerals that make up the parent rock in the model. Gibbsite, kaolinite, and a Na-mica (as a surrogate for smectite) are the secondary minerals that have been taken into account. Long-term simulations (>1 Ma) have been run, and the formation of a bauxitic profile, with an upper gibbsite-rich and a lower kaolinite-rich zone, is predicted. In early stages of the process (up to a few hundreds of thousands of years), both gibbsite and kaolinite precipitate directly from solution as a consequence of albite dissolution. In later stages, the bulk of gibbsite precipitation derives from the incongruent dissolution of kaolinite, while kaolinite precipitation is still caused by the dissolution of albite. This is also reflected by the formation of two reaction fronts in the profile. These results are compared with weathering sequences from the Los Pijiguaos bauxite deposit, Venezuela. The overlap between the gibbsite and kaolinite zones and the replacement of kaolinite by gibbsite are consistent with model calculations. Mechanical denudation has to be called upon to explain the limited thicknesses of the weathering profiles in the field. The role of mechanical erosion is supported by the presence of microsedimentary structures in the bauxite and the balance between dissolved and suspended loads in the streams draining the area.     

The palaeoenvironmental and palaeohydrological evolution of Padul Peat Bog (Granada, Spain) over one million years, from elemental, isotopic and molecular organic geochemical proxies

The elemental (concentration of organic carbon, atomic H/C and C/N ratios), isotopic (δ¹³C values of organic matter) and molecular (predominant n-alkane chain length and carbon preference index (CPI)) organic components were measured for 600 samples taken from a 107-m long core from the Padul Basin (Andalusia, Spain). The record runs from the Lower Pleistocene (ca. 1 Ma B.P.) to the mid-Holocene (ca. 4.5 ka B.P.) with, in general, little diagenesis (removal of components). Two markedly different hydrogeological scenarios were interpreted: (1) From ca. 1 Ma to ca. 400 ka B.P. run-off recharge was significant and water depths were greater (lacustrine scenario). From ca. 400 to 4.5 ka B.P., the Padul Basin became a peat bog s.s. with the major water input coming from groundwater inflow. From ca. 400 to ca. 180 ka B.P. alternating episodes with either predominant grasses, trees or aquatic macrophytes which were linked to wet/dry phases, took place. An important deglaciation episode has been interpreted to occur between ca. 180 and 170 ka B.P. The global climatic changes occurring from ca. 170 to 25 ka B.P. were not recorded in the proxies, though they do show important variations linked to the Last Glacial Maximum and the beginning of the Holocene (ca. 25–10 ka B.P.): (2) Cold phases coexisting with dry periods produced the recession of forests and the development of grasses. After these periods, as both temperature and precipitation increased, forests expanded and the water level, linked to thaw, rose, especially at ca. 20 ka B.P. Few changes occurred during the Holocene, although there were short alternations between wet and dry episodes. Overall, the techniques applied proved to be excellent palaeoenvironmental proxies for studying the basin’s palaeoclimatological and palaeohydrological evolution.     

近20年渤海叶绿素a浓度时空变化

浮游植物作为食物链的基础,对海洋生态系统具有重要作用。渤海作为我国最大的内海和重要渔业生物的产卵场、育幼场和索饵场,该区浮游植物研究具有重要意义。叶绿素a浓度是反映浮游植物生物量的重要指标。利用Google Earth Engine平台,对1997–2010年的宽视场海洋观测传感器(SeaWiFS)叶绿素a浓度数据和2002–2018年的水色卫星中分辨率成像光谱仪传感器(MODIS Aqua)叶绿素a浓度数据进行合并,并研究其时空变化特征。研究表明,近20年来,渤海全年叶绿素a浓度增加了14.1%,且增加显著。叶绿素a浓度在所有季节都呈现增加趋势;除11月外,其他各月都呈现稳定或增加趋势。从滦河入河口沿岸至渤海海峡的渤海中部,叶绿素a浓度增加较明显。同时也分析了海洋表面温度、风速和降水量数据。夏季渤海周边区域降水量和风速增加以及秋季海表温度的降低都有助于同季叶绿素a浓度的升高。渤海浮游植物可能受陆源营养物质输入影响较大。     

基于2002-2018年MODIS数据的黄海叶绿素a时空变化研究

浮游植物作为食物链的基础,对海洋生态系统具有重要影响。黄海作为我国重要的渔场,渔业资源面临枯竭的危险,因此对该区浮游植物进行研究具有重要意义。叶绿素a浓度是反映浮游植物生物量的重要指标。利用谷歌地球引擎平台对2002-2018年的MODIS Aqua叶绿素a浓度数据进行处理,并研究其时空分布与变化特征,然后结合区域气候、水文与地理特征以及海洋表面温度、风速、盐度、光合有效辐射和混合层厚度数据分析了其分布与变化的原因。研究发现:受陆源营养物质输入、近岸上升流以及黄海中央冷水团影响,叶绿素a浓度分布呈现由近岸向黄海中部递减特征;在季风、气候、水文的控制下,受风速、海洋表面温度、光合有效辐射、中央冷水团的影响,叶绿素a浓度的最大值出现在4月份,而最小值出现在6、7月份;受苏北沿岸海域海水污染和水体富营养化影响,沿岸海域盐度明显增加,海州湾叶绿素a浓度增速较大;影响黄海叶绿素a浓度变化的环境因子较复杂,除了部分月份存在显著的相关影响因子外,在全年和各季中不存在主导影响因子。