Degradation of carbon disulphide (CS2) in soils and groundwater from a CS2-contaminated site

This study is the first investigation of biodegradation of carbon disulphide (CS₂) in soil that provides estimates of degradation rates and identifies intermediate degradation products and carbon isotope signatures of degradation. Microcosm studies were undertaken under anaerobic conditions using soil and groundwater recovered from CS₂-contaminated sites. Proposed degradation mechanisms were validated using equilibrium speciation modelling of concentrations and carbon isotope ratios. A first-order degradation rate constant of 1.25 × 10^?2 h^?1 was obtained for biological degradation with soil. Carbonyl sulphide (COS) and hydrogen sulphide (H₂S) were found to be intermediates of degradation, but did not accumulate in vials. A ¹³C/¹²C enrichment factor of ?7.5 ± 0.8 ‰ was obtained for degradation within microcosms with both soil and groundwater whereas a ¹³C/¹²C enrichment factor of ?23.0 ± 2.1 ‰ was obtained for degradation with site groundwater alone. It can be concluded that biological degradation of both CS₂-contaminated soil and groundwater is likely to occur in the field suggesting that natural attenuation may be an appropriate remedial tool at some sites. The presence of biodegradation by-products including COS and H₂S indicates that biodegradation of CS₂ is occurring and stable carbon isotopes are a promising tool to quantify CS₂ degradation.     

Functional relation of land surface albedo with climatological variables: a review on remote sensing techniques and recent research developments

Surface albedo has been documented as one of the Essential Climate Variables (ECV) of the Global Climate Observing System (GCOS) that governs the Earth's Radiation Budget. The availability of surface albedo data is necessary for a comprehensive environmental modelling study. Thus, both temporal and spatial scale issues need to be rectified. This study reports about the availability of surface albedo data through in-situ and remote sensing satellite observations. In this paper, we reviewed the existing models for surface albedo derivation and various initiatives taken by related environmental agencies in order to understand the issues of climate with respect to surface albedo. This investigation evaluated the major activities on albedo-related research specifically for the retrieval methods used to derive the albedo values. Two main existing albedo measurement methods are derived through in-situ measurement and remotely sensed observations. In-situ measurement supported with number of instruments and techniques such aspyrheliometers, pyranometers and Baseline Surface Radiation Network (BSRN) and remotely sensed observations using angularly integrated Bi-directional Reflectance Distribution Function (BRDF) by both geostationary and polar orbit satellites. The investigation results reveals that the temporal and spatial scaling is the major issues when the albedo values are needed for microclimatic study, i.e. high-resolution time-series analyses and at heterogeneity and impervious surface. Thus, an improved technique of albedo retrieval at better spatial and temporal scale is required to fulfil the need for such kind of studies. Amongst many others, there are two downscaling methods that have been identified to be used in resolving the spatial scaling biased issues: Smoothing Filter-based Intensity Modulation (SFIM) and Pixel Block Intensity Modulation (PBIM). The temporal issues can be resolved using the multiple regression techniques of land surface temperature, selected air quality parameters, aerosol and daily skylight.     

Effects of urbanization on stream hydrology and water quality: the Florida Gulf Coast

At the global scale, the population density of coastal areas is nearly three times that of inland areas, and consequently, land development represents a threat to coastal ecosystems. It is critical to understand how increasing urbanization affects coastal watersheds. To that end, the objective of this study was to examine the influence of urban development on stream water quality and hydrology in a coastal setting, a scenario that has received less attention than other physiographic regions. Stream hydrologic, physicochemical, and microbial data were collected in watersheds near Apalachicola, Florida with a range of impervious surfaces from 0 to 15%. Watersheds with greater impervious cover exhibited higher pH, specific conductance, and temperature, elevated nutrient concentrations and loads (, and total phosphorus), higher bacterial concentrations (fecal coliform and Escherichia coli), and increased maximum flow and hydrograph flashiness. Different responses to development here compared to other physiographic regions included lower total suspended solid concentrations, higher total dissolved solid concentrations, and a lack of response of base flow to increased urbanization. Additionally, Na⁺ and Cl^? concentrations were elevated to a greater extent than is often the case in non‐coastal areas. In the coming years, urban development is projected to increase substantially in coastal zones and thus there is risk of further stream degradation in coastal watersheds. Copyright © 2011 John Wiley & Sons, Ltd.     

光合作用生物膜建造的凝块:来自于辽东半岛芙蓉统长山组凝块石生物丘中的一些证据

作为一种以非纹层状组构而区别于叠层石的微生物碳酸盐岩类型,中凝块(mesoclots)是产生凝块石凝块组构关键的微结构。构成这种中凝块的离散性凝块状泥晶,似乎代表了细胞外聚合物质(EPS)复杂的钙化作用,但是,由于常常缺乏直接的微生物证据,造成其所涉及的准确成因和特殊过程还不太清楚。在辽东半岛大连金州湾和本溪田师傅剖面芙蓉统下部的长山组顶部,发育较为典型的凝块石生物丘,组成三级层序的强迫型海退体系域沉积,代表着较为壮观的沉积学现象;在这些凝块石生物丘中,毫米级别大小的暗色离散性凝块状泥晶是其最为基本的沉积组构,而且在这些凝块之中以较高密度保存的丝状蓝细菌鞘化石反映的微生物构成,意味着它们具有明显的光合作用生物膜成因。尽管穿越成岩作用过滤器去解释古代凝块石复杂的形成机理将存在着巨大的挑战,也尽管形成这些凝块石复杂的生物膜钙化作用细节需要更加深入的研究才能得到更好的了解,但是,辽东半岛芙蓉统长山组的凝块石,尤其是在凝块内较为丰富的钙化蓝细菌鞘化石所表征的直接的微生物活动证据,使其成为一个了解光合作用生物膜建造凝块的典型实例;再者,与凝块共生的三叶虫化石、底栖鲕粒和皮壳粒,以及围绕着这些多样化颗粒特别的放射纤维状方解石结壳,说明这些凝块石可能属于较厚的微生物席内多重状生物膜以及构成这些微生物席和微生物膜的细胞外聚合物质复杂的钙化作用建造物。     

寒武系张夏组鲕粒滩中微生物碳酸盐岩主导的生物丘：以河北秦皇岛驻操营剖面为例

华北地台的寒武系苗岭统,大致包括毛庄组、徐庄组、张夏组和崮山组,这些组分别组成相应的三级沉积层序,在它们的顶部集中发育着鲕粒滩相灰岩而构成强迫型海退沉积,成为时间特化的相,代表着鲕粒主导的特别的寒武纪碳酸盐岩台地类型,表现在浅海陆架中大面积分布鲕粒滩,而且在这样的鲕粒滩中生长和发育着微生物碳酸盐岩主导的生物丘;河北省秦皇岛市驻操营剖面的张夏组上部鲕粒滩相灰岩中的生物丘正是上述现象最为典型的代表。虽然类似的现象曾经被描述为"藻坪"沉积,或者笼统地归为"微生物礁",但是,河北省秦皇岛市驻操营剖面的张夏组上部鲕粒滩相灰岩中的生物丘,以下现象不但将其特征化而且代表着壮观的沉积学现象:(1)在强迫型海退体系域的下部与鲕粒滩相灰岩交互产出的主要是柱状叠层石生物丘;(2)在张夏组顶部则以集中产出的均一石和树形石生物丘为特征;(3)下部的柱状叠层石生物丘中主要包括石松藻(Lithocodium)-孢网菌(Bacinella)状组构的钙化蓝细菌;(4)在上部集中产出的均一石与树形石生物丘,则发育着丝状钙化蓝细菌、基座菌(Hedstroemia)和附枝菌(Epiphyton)之类的多样化的钙化蓝细菌。由于石松藻(Lithocodium)-孢网菌(Bacinella)状组构的钙化蓝细菌是一种灭绝了的浅海生命形式,而且是不知道分类位置归属的生命形式,尤其是石松藻(Lithocodium)状组构近年来在寒武纪微生物碳酸盐岩研究中多被解释为"硅质海绵骨针的网状物"或"非骨针角质海绵骨骼纤维",再考虑到均一石自从命名以来很少描述在古老的地层记录之中,因此,驻操营剖面张夏组上部多样化微生物碳酸盐岩所主导的生物丘,以及生物丘中特别而且多样的钙化蓝细菌化石构成,为了解蓝细菌主导的光合作用微生物席复杂的钙化作用形成微生物碳酸盐岩提供了较为典型的实例。     

1: Subduction, slab detachment and mineralization: The Neogene in the Apuseni Mountains and Carpathians

The Inner Carpathians comprise several distinct Neogene late-stage orogenic Pb–Zn–Cu–Ag–Au ore districts. The mineral deposits in these districts are closely related to volcanic and subvolcanic rocks, and represent mainly porphyry and epithermal vein deposits, which formed within short periods of time in each district. Here, we discuss possible geodynamic and structural controls that suggest why some of the Neogene volcanic districts within the Carpathians comprise abundant mineralization, while others are barren. The Neogene period has been characterized by an overall geodynamic regime of subduction, where primary roll-back of the subducted slab and secondary phenomena, like slab break-off and the development of slab windows, could have contributed to the evolution, location and type of volcanic activity. Structural features developing in the overlying lithosphere and visible in the Carpathian crust, such as transtensional wrench corridors, block rotation and relay structures due to extrusion tectonics, have probably acted in focusing hydrothermal activity. As a result of particular events in the geodynamic evolution and the development of specific structural features, mineralization formed during fluid channelling within transtensional wrench settings and during periods of extension related to block rotation.In the Slovakian ore district of the Western Carpathians, Neogene volcanism and associated mineralization were localized by sinistral, NE-trending wrench corridors, which formed part of the extruding Alcapa block. The Baia Mare ore district, in the Eastern Carpathians, reflects a transtensional wrench setting on distributed oversteps close to the termination of the Dragos Voda fault. There, mineralization was spatially controlled by the transtensional Dragos Voda master fault and associated cross-fault systems. The Golden Quadrangle Cu–Au ore district of the Southern Apuseni Mountains reflects an unusual rotated transtensional/extensional setting close to the termination of a graben system. There, fluid flow was probably localized by fault propagation at the inner tip of the graben system.The spatial and temporal evolution of the magmatism and its changing geochemical signature from (N)W to (S)E strongly suggests a link with the contemporaneous northeastward roll-back of the subducted slab and a progressive southeastward detachment during accelerating roll-back. This geodynamic evolution is further supported by the present-day overall and detailed mantle lithospheric density images, the present-day heat flow patterns, the crustal architecture and its interpreted evolution, and the spatial and temporal evolution of depocentres around the Carpathian arc. In contrast to all these features, the mineral deposits in the West Carpathians, East Carpathians and Apuseni Mountains are too synchronous with respect to their individual volcanic history and contrast too much with younger volcanics of similar style, but barren, in southeastern parts of the Carpathians to simply link them directly to the slab evolution. In all three districts, the presence of magmatic fluids released from shallow plutons and their mixing with meteoric water were critical for mineralization, requiring transtensional or extensional local regimes at the time of mineralization, possibly following initial compressional regimes.These three systems show that mineralization was probably controlled by the superposition of favourable mantle lithospheric conditions and partly independent, evolving upper crustal deformation conditions.In the 13 to 11 Ma period the dominant mineralization formed all across the Carpathians, and was superimposed on structurally favourable crustal areas with, at that time, volcanic–hydrothermal activity. The period may reflect the moment when the (upper part of the) crust failed under lithospheric extension imposed by the slab evolution. This crustal failure would have fragmented the overriding plate, possibly breaking up the thermal lid, to provoke intensive fluid flow in specific areas, and allowed subsequent accelerated tectonic development, block rotation and extrusion of a “family of sub-blocks” that are arbitrarily regarded as the Tisia–Dacia or Alcapa blocks, even though they have lost their internal entity.     

Development of modified flyash as a permeable reactive barrier medium for a former manufactured gas plant site, Northern Ireland

A sequential biological permeable reactive barrier (PRB) was determined to be the best option for remediating groundwater that has become contaminated with a wide range of organic contaminants (i.e., benzene, toluene, ethylbenzene, xylene and polyaromatic hydrocarbons), heavy metals (i.e., lead and arsenic), and cyanide at a former manufactured gas plant after 150 years of operation in Portadown, Northern Ireland. The objective of this study was to develop a modified flyash that could be used in the initial cell within a sequential biological PRB to filter complex contaminated groundwater containing ammonium. Flyash modified with lime (CaOH) and alum was subjected to a series of batch tests which investigated the modified cation exchange capacity (CEC) and rate of removal of anions and cations from the solution. These tests showed that a high flyash composition medium (80%) could remove 8.65 mol of ammonium contaminant for every kilogram of medium. The modified CEC procedure ruled out the possibility of cation exchange as the major removal mechanism. The medium could also adsorb anions as well as cations (i.e., Pb and Cr), but not with the same capacity. The initial mechanism for Pb and Cr removal is probably precipitation. This is followed by sorption, which is possibly the only mechanism for the removal of dichromate anions. Scanning electron microscopic analysis revealed very small (<1 μm) cubic highly crystalline precipitates on the flyash, although this new crystalline zeolite growth did not occur rapidly enough to enable productive zeolite formation. Surface area measurements showed that biofilm growth on the medium could be a major factor in the comparative reduction of surface area between real and synthetic contaminant groundwaters. The modified flyash was found to be a highly sorptive granular material that did not inhibit microbiological activity, however, leaching tests revealed that the medium would fail as a long-term barrier material.     

Hydrologic simulation approach for El Niño Southern Oscillation (ENSO)-affected watershed with limited raingauge stations

ABSTRACT

Since the performance of hydrological models relies on numerous factors, the selection of an appropriate modeling approach for hydrological study has always been a crucial issue. The major objective of this research is to demonstrate that data-driven models such as the Adaptive Neuro-Fuzzy Inference system (ANFIS) are more suitable in a region where spatially distributed precipitation datasets are not available. Since precipitation has a teleconnection with the El Niño Southern Oscillation (ENSO) in different parts of the world, the sea surface temperatures (SSTs) and sea level pressures (SLPs) of the equatorial Pacific can be expected to act as surrogates for the precipitation if there are insufficient raingauge stations in the watershed. Moreover, in contrast to conceptual and physically-based models, data driven models can incorporate SST and SLP in their input vectors, and hence additional forcing of SST with precipitation has been experimented with in past studies. Therefore, our second objective is to test whether the additional forcing of SST and SLP will improve the hydrologic simulation. For this, various ANFIS models for the winter season were developed considering 10 raingauge stations situated at various locations in the watershed. Rainfall from each raingauge station was considered in the ANFIS model one at a time with and without SST/SLP. The results show that the performance of the ANFIS model improved with the additional fusion of SST and SLP, especially when a raingauge station from a remote location was considered. However, this improvement was observed when the analysis was primarily focused on the winter season which is a period with a strong ENSO signal.

Editor D. Koutsoyiannis Associate editor L. See     

Tennantite-tetrahedrite series from the Madan Pb-Zn deposits,Central Rhodopes,Bulgaria

Minerals from the tennantite-tetrahedrite series (fahlores) are found as single euhedral crystals and crustiform aggregates in hydrothermal veins of the Gradishte and Petrovitsa Pb-Zn deposits of the Madan ore field, southern Bulgaria. Unusually large compositional variations and fine oscillatory crystal zoning were investigated with electron microprobe analysis. The Gradishte samples correspond dominantly to tennantite, while Petrovitsa crystals have exclusively tetrahedrite composition. Fahlore compositions at Madan correspond to zincian varieties (1.6–1.95 apfu), with low Fe-content (<0.45 apfu). Minor silver is characteristic only for the Petrovitsa samples, reaching a maximum of 0.30 apfu. The (Cu+Ag) content of the Petrovitsa tennantites and the Cu content of the Gradishte tetrahedrites systematically exceed 10 apfu resulting in compensation of the excess Cu in the structure by Fe³⁺. Textural characteristics, mineral relationships and available fluid inclusion and stable isotope data suggest that fahlores precipitated in the late stages of mineralization at Madan, at temperature interval of 300–200 °C from oxidizing fluids with mixed (magmatic-meteoric) signatures.