海洋钙离子非保守行为及海洋钙问题

钙离子是海洋11种常量离子之一,与钠、钾等离子的保守性不同,钙离子在海洋中的分布表现出微小但系统的变化。钙离子的变化往往与海洋碳酸钙的形成和溶解过程有关,所以,钙离子可直接指示海洋碳酸钙通量（深层海洋碳通量的主要组成部分）。同时,碳酸钙沉淀或溶解又会改变总碱度和溶解无机碳,通过钙离子变化也能间接探讨海洋碳酸盐系统和海洋吸收CO2的能力。介绍了以碳酸钙溶解形成超额钙为主的海洋钙离子多种非保守行为及其控制过程,讨论这些过程对海水组成和海洋碳酸盐系统的影响,探讨未来海洋酸化条件下钙离子可能的变化及其潜在的效应,最后展望在南海开展钙离子精细行为的研究意义。      

The history and impact of air pollution at Čertovo Lake,southwestern Czech Republic

This multi-disciplinary investigation documents the longterm effects of atmospheric pollution of metals and acids on a geologically sensitive catchment in the umava Mountains, southwestern Czech Republic, a region with a long history of human disturbance. A 30 cm long sediment core (I) from ertovo Lake was analyzed for natural and artifical radionuclides, metals, diatoms, chrysophytes, and pollen in sediments accumulated during the last 200 years. A second core (II), extending to 95 cm, included sediment judged to be free of atmospheric deposition of pollutants associated with the Industrial Revolution. Chronostratigraphic markers include several changes in the pollen assemblages corresponding to well-documented changes in land-use, and distinct distributions of ¹³⁷Cs, ¹³⁴Cs and ²⁴¹Am from weapons testing and the 1986 nuclear accident at Chernobyl, Russia. These markers corroborate the ²¹⁰Pb dating and, together, produce a reliable chronology extending back nearly to 1800 A.D.Stratigraphic profiles of Cu, Pb, and Zn in Core I are unlike any previously reported in the literature. Concentrations of Cu, Pb, and Zn remain generally above 100, 400, and 200 g g^-1, respectively, for the 200 years represented by Core I. These values are unusually high for sediments from a watershed with no known heavy-metal ore bodies. Accumulation rates for Cu, Pb, and Zn, which include both atmospheric and watershed contributions, are also high (ca 1, > 1 and > 1 g cm^-2 yr^-1, respectively) for the same period, although the anthropogenic contribution of Zn rose from nearly zero at 1800 A.D. The Cu and Pb accumulation rates rose dramatically about 1640 A.D.Accumulation rates of anthropogenically-derived Be, a relatively abundant element in the soft coals of the region, are also elevated by about 0.01 g cm^-2 yr^-1 in sediments of this period. Vanadium accumulation rates increased only since 1980 A.D., presumably along with increased consumption of oil.Diatom assemblages illustrate that the lake was acidic (pH between 4.5 and 5) through at least the past 200 years. The pH declined significantly (from ca 5 to 4) between 1960 and 1985 with a slight increase to 4.5 in the last few years. Recent diatom and chrysophyte assemblages suggest high trace metal concentrations, consistent with the present lake-water chemistry.     

Streams in the Harz National Parks (Germany) — a hydrochemical and hydrobiological evaluation

Between 1995 and 2001, 16 measuring points at small and medium sized brooks in the Harz National Parks were sampled. The samples have been evaluated by means of hydrochemistry and macroinvertebrate biology. Although nearly all streams are largely uncontaminated by oxygen-consuming substances, they are settled only by a small number of macroinvertebrate species. There is a clear correlation between this number and pH. The reduction in species number with decrease of pH is mainly caused by the absence of most Ephemeroptera, some Coleoptera and Trichoptera. Comparing biological evaluation of acidity with physico-chemical measurements, a unacceptable underestimation was found. The reason could be that different sensitivities to acidification between regional populations seem to exist.

Despite of the low species number, there is a very specific macroinvertebrate fauna that emphasizes the conservation value of the Harz National Parks.     

Lithium and lithium isotope profiles through the upper oceanic crust: a study of seawater-basalt exchange at ODP Sites 504B and 896A

Ocean Drilling Program (ODP) Hole 504B near the Costa Rica Rift is the deepest hole drilled in the ocean crust, penetrating a volcanic section, a transition zone and a sheeted dike complex. The distribution of Li and its isotopes through this 1.8-km section of oceanic crust reflects the varying conditions of seawater alteration with depth. The upper volcanic rocks, altered at low temperatures, are enriched in Li (5.6-27.3 ppm) and have heavier isotopic compositions (δ⁷Li=6.6-20.8‰) relative to fresh mid-ocean ridge basalt (MORB) due to uptake of seawater Li into alteration clays. The Li content and isotopic compositions of the deeper volcanic rocks are similar to MORB, reflecting restricted seawater circulation in this section. The transition zone is a region of mixing of seawater with upwelling hydrothermal fluids and sulfide mineralization. Li enrichment in this zone is accompanied by relatively light isotopic compositions (−0.8-2.1‰) which signify influence of basalt-derived Li during mineralization and alteration. Li decreases with depth to 0.6 ppm in the sheeted dike complex as a result of increasing hydrothermal extraction in the high-temperature reaction zone. Rocks in the dike complex have variable isotopic values that range from −1.7 to 7.9‰, depending on the extent of hydrothermal recrystallization and off-axis low-temperature alteration. Hydrothermally altered rocks are isotopically light because ⁶Li is preferentially retained in greenschist and amphibolite facies minerals. The δ⁷Li values of the highly altered rocks of the dike complex are complementary to those of high-temperature mid-ocean ridge vent fluids and compatible to equilibrium control by the alteration mineral assemblage. The inventory of Li in basement rocks permits a reevaluation of the role of oceanic crust in the budget of Li in the ocean. On balance, the upper 1.8 km of oceanic crusts remains a sink for oceanic Li. The observations at 504B and an estimated flux from the underlying 0.5 km of gabbro suggest that the global hydrothermal flux is at most 8×10⁹ mol/yr, compatible with geophysical thermal models. This work defines the distribution of Li and its isotopes in the upper ocean crust and provides a basis to interpret the contribution of subducted lithosphere to arc magmas and cycling of crustal material in the deep mantle.     

Groundwater acidification in Triassic sandstones: prediction with MAGIC modelling

 Acidification of groundwater lags behind acid deposition due to the relatively long water residence time in conjunction with various buffering processes in the soil zone and deeper aquifer (chemical weathering, cation exchange, sulfate sorption, and N uptake by the biomass). Extensive field data from eight forested catchments in the Bunter Sandstone of the Black Forest, including results from water budget studies and hydrochemical analysis of stream and spring waters, were used to simulate the future evolution of ground-water acidification with the MAGIC model. The present acid deposition exceeds the “critical load” (here meaning buffering due to chemical weathering and protonation of organic acids) in six of eight catchments. Two catchments are well buffered because they contain carbonate-bearing layers in the Upper Bunter sandstone. Transient buffering (i.e., cation exchange, N uptake, the sulfate sorption) thus far prevents worse acidification, but this effect will decline in the future. For one of the poorly buffered catchments (Seebach), a two-layer simulation was carried out, based on extensive data from 10 years of measurements. Validation of the long-term simulations by hydrochemical and soil data was hampered by strong annual variations but generally supported by paleolimnological studies. In the future, reductions in the S deposition by 20% and the N deposition by 10% up to the year 2030 are assumed as the most probable scenario. N uptake through soil and vegetation will come to an end as suggested by decreasing C/N ratios of the organic matter. This process is arbitrarily included in the simulations. In the periglacial soil layer, acidification will decrease until the year 2030 and then approach a steady-state condition. In the fractured aquifer, acidification will also proceed at a decreasing rate; however, sulfate desorption up to the year 2130, the end of simulated period, will prevent earlier remediation. Despite a significant reduction in S deposition since the mid-1980s, further efforts are necessary to reduce the emission of acidifying substances. Liming in the recharge area is partially effective to ameliorate “shallow” groundwater but largely fails to ameliorate “deeper” groundwater in the sandstone aquifer. Received: 30 July 1996/Accepted: 23 January 1997     

Removal of Cu(Ⅱ) from Wastewater Using Acidified Sewage Sludge Ash

Sewage sludge ash (SSA), the waste generated in sewage sludge incineration, was obtained from Wuhan Sewage Treatment Plant and used as a low-cost sorbent for removing Cu(Ⅱ) from wastewaters. The sorbent was first modified with 5 % sulfuric acid to increase its sorption capacity. The specific surface area, porosity, cation-exchange capacity (CEC) and pHZPC of the sorbent were measured. Batch experiments were made to study the effect of contact time, solution pH value and temperature on sorption. Both Langmuir and Freundlich models well described the Cu(Ⅱ) sorption process, with correlation coefficient (R2) values of 0.993 4 and 0.989 9 respectively. And the sorption process follows the Lagergren first order kinetic model. The equilibrium sorption capacity of acidified SSA to Cu(Ⅱ) is estimated to be 7.78 mg/g under optimal conditions.     

Precise/ Small Sample Size Determinations of Lithium Isotopic Compositions of Geological Reference Materials and Modern Seawater by MC-ICP-MS

The Li isotope ratios of four international rock reference materials, USGS BHVO-2, GSJ JB-2, JG-2, JA-1 and modern seawater (Mediterranean, Pacific and North Atlantic) were determined using multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). These reference materials of natural samples were chosen to span a considerable range in Li isotope ratios and cover several different matrices in order to provide a useful benchmark for future studies. Our new analytical technique achieves significantly higher precision and reproducibility (< ± O.3%o 2s) than previous methods, with the additional advantage of requiring very low sample masses of ca . 2 ng of Li.     

The influence of particle composition on thorium scavenging in the NE Atlantic ocean (POMME experiment)

²³⁰Th, ²³²Th and ²³⁴Th were analyzed in sinking particles collected by moored and drifting sediment traps in the NE Atlantic Ocean (POMME experiment) in order to constrain the phase(s) carrying Th isotopes in the water column. It reveals a contrasted behaviour between ²³⁴Th and ²³⁰Th. ²³⁴Th is correlated to the particulate organic carbon suggesting that it is primarily scavenged by organic compounds in the surface waters. ²³⁰Th_xs is correlated with Mn, Ba and the lithogenic fraction that are enriched in small suspended particles and incorporated in the sinking particulate flux throughout the water column. The lack of correlation between ²³⁰Th_xs and CaCO₃ or biogenic silica (bSi) indicates that CaCO₃ and bSi are not responsible for ²³⁰Th scavenging in the deep waters of this oceanic region. ²³⁰Th is generally correlated with the lithogenic content of the trapped material but this correlation disappears in winter during strong atmospheric dust inputs suggesting that lithogenic matter is not directly responsible for ²³⁰Th scavenging in the deep waters or that sufficient time is required to achieve particle–solution equilibration. MnO₂ could be the prevalent ²³⁰Th_xs-bearing phase. The narrow range of K_{d_MnO2}^Th obtained for very contrasted oceanic environments supports a global control of ²³⁰Th_xs scavenging by MnO₂ and raises the possibility that the ²³⁰Th–²³¹Pa fractionation is controlled by the amount of colloidal MnO₂ in seawater.     

Elastic lateral dynamic impedance functions for a rigid cylindrical shell type foundation

Elastic lateral dynamic impedance functions are defined as the ratio of the lateral dynamic force/moment to the corresponding lateral displacement/rotation at the top ending of a foundation at very small strains. Elastic lateral dynamic impedance functions have a defining influence on the natural frequencies of offshore wind turbines supported on cylindrical shell type foundations, such as suction caissons, bucket foundations, and monopiles. This paper considers the coupled horizontal and rocking vibration of a cylindrical shell type foundation embedded in a fully saturated poroelastic seabed in contact with a seawater half‐space. The formulation of the coupled seawater–shell–seabed vibration problem is simplified by treating the shell as a rigid one. The rigid shell vibration problem is approached by the integral equation method using ring‐load Green's functions for a layered seawater‐seabed half‐space. By considering the boundary conditions at the shell–soil interface, the shell vibration problem is reduced to Fredholm integral equations. Through an analysis of the corresponding Cauchy singular equations, the intrinsic singular characteristics of the problem are rendered explicit. With the singularities incorporated into the solution representation, an effective numerical method involving Gauss–Chebyshev method is developed for the governing Fredholm equations. Selected numerical results for the dynamic contact load distributions, displacements of the shell, and lateral dynamic impedance functions are examined for different shell length–radius ratio, poroelastic materials, and frequencies of excitation. Copyright © 2016 John Wiley & Sons, Ltd.     

Investigation of the elevation of saltwater wedge due to subsurface dams

Subsurface dams are rather effective and used for the prevention of saltwater intrusion in coastal regions around the world. We carried out the laboratory experiments to investigate the elevation of saltwater wedge after the construction of subsurface dams. The elevation of saltwater wedge refers to the upward movement of the downstream saltwater wedge because the subsurface dams obstruct the regional groundwater flow and reduce the freshwater discharge. Consequently, the saltwater wedge cannot further extend in the longitudinal direction but rises in the vertical profile resulting in significant downstream aquifer salinization. In order to quantitatively address this issue, field-scale numerical simulations were conducted to explore the influence of various dam heights, distances, and hydraulic gradients on the elevation of saltwater wedge. Our investigation shows that the upward movement of the saltwater wedge and its areal extension in the vertical domain of the downstream aquifer become more severe with a higher dam and performed a great dependence on the freshwater discharge. Furthermore, the increase of the hydraulic gradient and the dam distance from the sea boundary leads to a more pronounced wedge elevation. This phenomenon comes from the variation of the freshwater discharge due to the modification of dam height, location, and hydraulic gradient. Large freshwater discharge can generate greater repulsive force to restrain the elevation of saltwater wedge. These conclusions provide theoretical references for the behaviour of the freshwater–seawater interface after the construction of subsurface dams and help optimize the design strategy to better utilize the coastal groundwater resources.