贵州碳酸盐岩风化壳形成地球化学过程、对比及年代学研究Geochemical Processes, Comparison and Dating for the Weathering Crusts in Karst Regions of Guizhou Province

由于缺乏相应的沉积地层，贵州新生代地质、环境演化恢复一直是学术界的难点问题。夷平面研究的兴起，为陆地地壳抬升、地貌演变等反演提供了理论基础，而风化壳正是夷平面研究的重要替代对象，尤其是对各类沉积地层不发育的地区。因而，贵州高原各级台地上发育有较为广泛的红色风化壳自然地、就成了主要研究载体。然而一与其它岩类不同，碳酸盐岩风化成土作用过程研究并没有得到同等重视，其研究范围和程度均很不充分。显然，要想利用碳酸盐岩风化壳进行夷平面等地质、地貌意义研究，就必需详细了解贵州或中国南方碳酸盐岩风化成土的基本过程。也只有如此，才能明确各种对比指标的使用条件和范围，才能明确各种测年结果的具体意义，才能真正地通过贵州碳酸盐岩风化壳获取全省地质、环境演化信息。本论文通过对贵州省岩溶台地碳酸盐岩石灰土、红色风化壳剖面形成地球化学过程的剖析，开展石灰土与红色风化壳之间的关联和差异性综合对比、红色风化壳之间发育程度的比较，以及风化壳剖面尝试性的侧年等方面研究，取得了以下儿点认识：1、石灰土形成地球化学过程及对比通过矿物组成、粒度分布特征、地球化学方法判别，确定了本文所选石灰土剖面物质来源于下伏碳酸盐岩中的酸不溶物，是碳酸盐岩风化后酸不溶物原地残余堆积的结果。石灰土形成的地球化学过程都遵循碳酸盐岩风化成土之两阶段模式：母岩－酸不溶物，大量可溶性物质Ca、Mg、Mn、P、Na淋失，而Si、K·Fe、Al、Ti则相对富集。该过程的矿物组成变化表现为，伴随碳酸盐矿物（方解石、白云石等）的溶解、迁移，硅酸盐相矿物（长石、2:1型粘土矿物等）残余、累积。酸不溶物，土层或土层的演化，K、Si（长石、伊利石）不断淋失，而Al（伊利石、高岭石、三水铝石）、Fe（针铁矿、赤铁矿等）逐渐富集，体现出脱硅、富铝（铁）过程。我们强调碳酸盐岩风化成土分为两个阶段，但也认识到风化作用是综合的、复杂的：在碳酸盐矿物大量淋失过程中，同时也进行着酸不溶物的风化。石灰土分为原生和次生两种成因类型。原生石灰土的风化程度总体较低，剖面中还残留一定量的CaCO3，剖面从下到上矿物组成、地球化学各种指标具有逐渐演化的过渡特征。原生石灰上土层演化过程显示出正风化序列，从下到上风化程度逐渐增大、可溶性物质逐渐减少、稳定和相对稳定组分（Al、Fe．、REE）含量不断增大。另外，主量元素的质量迁移系数在剖面中的变化与风化程度呈明显的相关性。而次生石灰土不但具有很高的风化程度，而且剖面无过渡特征，显示可能是由遭受强烈风化作用的物质直接转变形成的。剖面中也含有一定量后期加入的碳酸盐，但与高CIA值特征不相匹配；SiO2、Al2O3、Fe2O3组分具有不同的变化特征，与）成化程度无明显关联；REE在剖面岩一上界面出现富集层。2、碳酸盐岩红色风化壳形成地球化学过程及其与石灰土的对比红色风化壳形成的地球化学过程也遵循碳酸盐岩风化成土之两阶段模式：母岩一酸不溶物，大量可溶性物质Ca、Mg、Mn、P、Na淋失，而Si、K、Fe、Al、Ti则相对富集。该过程的矿物组成变化表现为，伴随碳酸盐矿物（方解石、白云石等）的溶解、迁移，硅酸盆相矿物（长石、2:1型粘土矿物等）残余、累积。酸不济物一土层或上层的演化，K、Si（长石、伊利石）不断淋失，而Al（伊利石、高岭石、三水铝石）、Fe（针铁矿、赤铁矿等）逐渐富集，体现出脱硅、富铝（铁）过程。石灰土与红色风化壳之间既存在共性，又有一定的差异性。红色风化壳与原生石灰土一样都具有过渡特征，但后者仅在剖面下部出现一定的过渡层位；原生石灰士的城化程度远低于红色风化壳，仅与后者底部土层相当；原生石灰土不具有红色风化壳之岩-土REE（超常）富集层。总体上，原生石灰土可以作为红色风化壳的前身。次生石灰土与红色风化壳在矿物组成、风化程度等各种地球化学指标等都十分接近（略低），显示与红色风化壳之间存在某种关联：由红色风化壳物质直接转变，或由酸不溶物已强烈风化的（白云岩）岩粉、碎裂岩风化形成。3、碳酸盐岩风化成土母岩差异性碳酸盐岩风化成土存在母岩差异性，石灰土母岩差异性较为明显，而红色风化壳的母岩差异性较弱，体现出红色风化壳的均一化特征。石灰土母岩差异性体现为：母岩为灰岩的石灰土剖面主量元素含量变化特征较为一致，而白云岩则具有不同的变化；灰岩石灰土Fe3＋、Al具有不同的富集、亏损特征，且具有富集层的补偿亏损层，而白云岩石灰上两组分都呈现无补偿层位的相同富集态势；灰岩石灰土剖面出现负Eu异常和具以Gd为中心的倒“V”型MREE稀土富集特征（母岩标准化），而白云岩石灰土无明显Eu异常和具L既E或HREE稀士．富集特征；灰岩和白云岩石灰土的微量元素富集、亏损特征也有所不同，前者从上到下逐渐富集，而后者无明显变化趋势。红色风化壳形成的基本过程、主量元素地球化学行为无明显的母岩相关性，没有如石灰土剖面灰岩和白云岩之间存在的差异性，显示出红土化作用的均一化过程；微量元素中受重矿物影响的元素与母岩类型有一定的关联，但大多数元素的亏损、富集等与具体剖面的微环境关系密切。4、碳酸盐岩红色风化壳发育程度的对比及意义多利指标对比显示所选红色风化壳的风化程度有一定的强弱差别：平坝剖面＞湖潮剖面＞天龙剖面、大兴剖面＞花溪剖面、新蒲剖面，但这种差异性不足以否定各剖面隶属于贵州山盆期广泛夷平面的基本推测。各剖面之间的微弱差异是红色风化壳形成时纬度分带和垂向分带的体现。低纬度的平坝、湖潮、天龙剖面经历的风化作用强于高纬度的新蒲、大兴剖面；高海拔的新蒲剖面风化程度低于海拔低的大兴剖面。5、红色风化壳次生石英裂变径迹测年红色风化壳次生石英裂变径迹方法测年尝试，得到一定的结果和认识：晶形相对较好的石英，是次生的，与母岩中碎屑及成岩阶段没有关联；各剖面上部与中、下部次生石英的诱发裂变径迹的密度有着明显的区别，可能暗示它们的形成环境不同；名一剖面石英的形成或退火年龄分布较为分散，1.2-25.2Ma，同一剖面的石英年龄也不均一，变化较大；从下到上，年龄值呈现出逐渐减小的规律性，与风化作用的正常序列相反。如果能确切其成因，次生石英裂变径迹年代学研究将是确定风化壳形成时代及揭示主要风化作用信，却钩有利武器。

Modelling of Geochemical Processes in Mangrove Ecosystem

The mangrove ecosystem is one of the earth’s most endangered ecosystems. In this study, geochemical features of three mangrove ecosystems, Mangalavanam, Vypeen and Nettoor were compared. Water, sediment and core samples were collected from these stations for a period of one year. Nutrients, organic compounds orgnic carbon and hydrographical parameters of the samples were estimated. The present study revealed higher concentration of carbon in the surface sediments. The major temporary or ultimate sink for various pollutants in estuaries is the sedimentary reservoir, including intertidal areas. In the present study, higher values for dissolved nutrients, POC and carbohydrates were observed during low tide.

Geochemical processes and rare earth element analysis in cold-seep pore waters of Hydrate Ridge, northeast Pacific Ocean

The concentrations of rare earth elements (REEs), sulphate, hydrogen sulphide, total alkalinity, calcium, magnesium and phosphate were measured in shallow (<12 cm below seafloor) pore waters from cold-seep sediments on the northern and southern summits of Hydrate Ridge, offshore Oregon. Downward-decreasing sulphate and coevally increasing sulphide concentrations reveal sulphate reductionas dominant early diagenetic process from ~2 cm depth downwards. A strong increase of total dissolved REE concentrations is evident immediately below the sediment-water interface, which can be related to early diagenetic release of REEs into pore water resulting from the remineralization of particulate organic matter. The highest pore water REE concentrations were measured close to the sediment-water interface at ~2 cm depth. Distinct shale normalized REE patterns point to particulate organic matter and iron oxides as main REE sources in the upper ~2-cm depth interval. In general, the pore waters have shalenormalized patterns reflecting heavy REE (HREE) enrichment, which suggests preferential complexation of HREEs with carbonate ions. Below ~2 cm depth, a downward decrease in REE correlates with a decrease in pore water calcium concentrations. At this depth, the anaerobic oxidation of methane (AOM) coupled to sulphate reduction increases carbonate alkalinity through the production of bicarbonate, which results in the precipitation of carbonate minerals. It seems therefore likely that the REEs and calcium are consumed during vast AOM-induced precipitation of carbonate in shallow Hydrate Ridge sediments. The analysis of pore waters from Hydrate Ridge shed new light on early diagenetic processes at cold seeps, corroborating the great potential of REEs to identify geochemical processes and to constrain environmental conditions.

Global Rates of Free Hydrogen (H2) Production by Serpentinization and other Abiogenic Processes within Young Ocean Crust

The main conclusion of this dissertation is that global H2 production within young ocean crust (<10 Mya) is higher than currently recognized, in part because current estimates of H2 production accompanying the serpentinization of peridotite may be too low (Chapter 2) and in part because a number of abiogenic H2-producing processes have heretofore gone unquantified (Chapter 3). The importance of free H2 to a range of geochemical processes makes the quantitative understanding of H2 production advanced in this dissertation pertinent to an array of open research questions across the geosciences (e.g. the origin and evolution of life and the oxidation of the Earth’s atmosphere and oceans).

The first component of this dissertation (Chapter 2) examines H2 produced within young ocean crust [e.g. near the mid-ocean ridge (MOR)] by serpentinization. In the presence of water, olivine-rich rocks (peridotites) undergo serpentinization (hydration) at temperatures of up to ~500°C but only produce H2 at temperatures up to ~350°C. A simple analytical model is presented that mechanistically ties the process to seafloor spreading and explicitly accounts for the importance of temperature in H2 formation. The model suggests that H2 production increases with the rate of seafloor spreading and the net thickness of serpentinized peridotite (S-P) in a column of lithosphere. The model is applied globally to the MOR using conservative estimates for the net thickness of lithospheric S-P, our least certain model input. Despite the large uncertainties surrounding the amount of serpentinized peridotite within oceanic crust, conservative model parameters suggest a magnitude of H2 production (~1012 moles H2/y) that is larger than the most widely cited previous estimates (~1011 although previous estimates range from 1010-1012 moles H2/y). Certain model relationships are also consistent with what has been established through field studies, for example that the highest H2 fluxes (moles H2/km2 seafloor) are produced near slower-spreading ridges (<20 mm/y). Other modeled relationships are new and represent testable predictions. Principal among these is that about half of the H2 produced globally is produced off-axis beneath faster-spreading seafloor (>20 mm/y), a region where only one measurement of H2 has been made thus far and is ripe for future investigation.

In the second part of this dissertation (Chapter 3), I construct the first budget for free H2 in young ocean crust that quantifies and compares all currently recognized H2 sources and H2 sinks. First global estimates of budget components are proposed in instances where previous estimate(s) could not be located provided that the literature on that specific budget component was not too sparse to do so. Results suggest that the nine known H2 sources, listed in order of quantitative importance, are: Crystallization (6x1012 moles H2/y or 61% of total H2 production), serpentinization (2x1012 moles H2/y or 21%), magmatic degassing (7x1011 moles H2/y or 7%), lava-seawater interaction (5x1011 moles H2/y or 5%), low-temperature alteration of basalt (5x1011 moles H2/y or 5%), high-temperature alteration of basalt (3x1010 moles H2/y or <1%), catalysis (3x108 moles H2/y or <<1%), radiolysis (2x108 moles H2/y or <<1%), and pyrite formation (3x106 moles H2/y or <<1%). Next we consider two well-known H2 sinks, H2 lost to the ocean and H2 occluded within rock minerals, and our analysis suggests that both are of similar size (both are 6x1011 moles H2/y). Budgeting results suggest a large difference between H2 sources (total production = 1x1013 moles H2/y) and H2 sinks (total losses = 1x1011 moles H2/y). Assuming this large difference represents H2 consumed by microbes (total consumption = 9x1011 moles H2/y), we explore rates of primary production by the chemosynthetic, sub-seafloor biosphere. Although the numbers presented require further examination and future modifications, the analysis suggests that the sub-seafloor H2 budget is similar to the sub-seafloor CH4 budget in the sense that globally significant quantities of both of these reduced gases are produced beneath the seafloor but never escape the seafloor due to microbial consumption.

The third and final component of this dissertation (Chapter 4) explores the self-organization of barchan sand dune fields. In nature, barchan dunes typically exist as members of larger dune fields that display striking, enigmatic structures that cannot be readily explained by examining the dynamics at the scale of single dunes, or by appealing to patterns in external forcing. To explore the possibility that observed structures emerge spontaneously as a collective result of many dunes interacting with each other, we built a numerical model that treats barchans as discrete entities that interact with one another according to simplified rules derived from theoretical and numerical work, and from field observations: Dunes exchange sand through the fluxes that leak from the downwind side of each dune and are captured on their upstream sides; when dunes become sufficiently large, small dunes are born on their downwind sides (“calving”); and when dunes collide directly enough, they merge. Results show that these relatively simple interactions provide potential explanations for a range of field-scale phenomena including isolated patches of dunes and heterogeneous arrangements of similarly sized dunes in denser fields. The results also suggest that (1) dune field characteristics depend on the sand flux fed into the upwind boundary, although (2) moving downwind, the system approaches a common attracting state in which the memory of the upwind conditions vanishes. This work supports the hypothesis that calving exerts a first order control on field-scale phenomena; it prevents individual dunes from growing without bound, as single-dune analyses suggest, and allows the formation of roughly realistic, persistent dune field patterns.

Geochemical changes to dredged canal sediments following land spreading: a review.

This paper brings together some of the recent research on trace metals in dredged sediments, and in particular freshwater canal sediments. Following a description of the general UK background, geochemical processes that affect metal release and retention in dredged canal sediments are considered, particularly the role of redox and sulphur on metal associations, and the use of sequential extraction for the derivation of metal associations in sediments. The review outlines the importance of oxidation on metal-mobility and shows that many studies have illustrated the increase in metal-leachability from sediments during oxidation. Suggestions are given for sediment-testing requirements which should include an examination of both anoxic and oxidised sediment as well as ecotoxicology in order to account for changes to metal-speciation after disposal to land.

Mineral and geochemical characterization of a leptic aluandic soil and a thapto aluandic-ferralsol developed on trachytes in Mount Bambouto (Cameroon volcanic line)

Mineral and geochemical investigations were carried out on soil samples and fresh rock (trachytes) from two selected soil profiles (TM profile on leptic aluandic soils and TL profile on thapto aluandic-ferralsols) from Mount Bambouto to better understand geochemical processes and mineral paragenesis involved in the development of soils in this environment. In TM profile, the hydrated halloysites and goethite occur in the weathered saprolite boulders of BC horizon while dehydrated halloysite, gibbsite and goethite dominate the soils matrices of BC and A horizons. In TL profile, the dehydrated halloysites and goethite are the most abundant secondary minerals in the weathered saprolites of C and BC horizons while gibbsite, hematite and kaolinite occur in the soil matrices of BC, B and A horizons. The highest gibbsite content is in the platy nodules of B horizon. In both soil profiles, organo-metal complexes (most likely of AI and Fe) are present in the surface A horizon. Geochemically, between the fresh rock and the weathered saprolites in both soils, SiO2, K2O, CaO, Na2O and MgO contents decrease strongly while Fe2O3 and Al2O3 tend to accumulate. The molar ratio of SiO2/Al2O3 (Ki) and the sum of Ca, Mg, K and Na ions (TRB) also decreases abruptly between fresh rocks and the weathered saprolites, but increases significantly at the soil surface. The TM profile shows intense Al enrichment whereas the TL profile highlights enrichment in both AI and Fe as the weathering progresses upwards. Both soil profiles are enriched in Ni, Cu, Ba and Co and depleted in U, Th, Ta, Hf, Y, Sr, Pb, Zr and Zn relative to fresh rock. They also show a relatively low fractionation of the rare earth elements (REE: La, Nd, Sm, Eu, Tb, Yb and Lu), except for Ce which tends to be enriched in soils compared to CI chondrite. All these results give evidence of intense hydrolysis at soil deep in Mount Bambouto resulting in the formation of halloysite which progressively transforms into gibbsite and/or dehydrated halloysite. At the soil surface, the prominent pedogenetic process refers to andosolization with formation of organo-metal complexes. In TL profile, the presence of kaolinite in soil matrices BC and B horizons is consistent with ferralitization at soil deep. In conclusion, soil forming processes in Mount Bambouto are strongly influenced by local climate: (i) in the upper mountain (>2000 m), the fresh, misty and humid climate favors andosolization; whereas (ii) in the middle lands (1700-2000 m) with a relatively dry climate, both andosolization at the soil surface and ferralitization at soil deep act together. (C) 2009 Elsevier B.V. All rights reserved.

Geotechnical systems that evolve with ecological processes

Geotechnical systems, such as landfills, mine tailings storage facilities (TSFs), slopes, and levees, are required to perform safely throughout their service life, which can span from decades for levees to “in perpetuity” for TSFs. The conventional design practice by geotechnical engineers for these systems utilizes the as-built material properties to predict its performance throughout the required service life. The implicit assumption in this design methodology is that the soil properties are stable through time. This is counter to long-term field observations of these systems, particularly where ecological processes such as plant, animal, biological, and geochemical activity are present. Plant roots can densify soil and/or increase hydraulic conductivity, burrowing animals can increase seepage, biological activity can strengthen soil, geochemical processes can increase stiffness, etc. The engineering soil properties naturally change as a stable ecological system is gradually established following initial construction, and these changes alter system performance. This paper presents an integrated perspective and new approach to this issue, considering ecological, geotechnical, and mining demands and constraints. A series of data sets and case histories are utilized to examine these issues and to propose a more integrated design approach, and consideration is given to future opportunities to manage engineered landscapes as ecological systems. We conclude that soil scientists and restoration ecologists must be engaged in initial project design and geotechnical engineers must be active in long-term management during the facility’s service life. For near-surface geotechnical structures in particular, this requires an interdisciplinary perspective and the embracing of soil as a living ecological system rather than an inert construction material.

Modeling of ore-forming and geoenvironmental systems: Roles of fluid flow and chemical reaction processes

Ore-forming and geoenviromental systems commonly involve coupled fluid flowand chemical reaction processes. The advanced numerical methods and computational modeling have become indispensable tools for simulating such processes in recent years. This enables many hitherto unsolvable geoscience problems to be addressed using numerical methods and computational modeling approaches. For example, computational modeling has been successfully used to solve ore-forming and mine site contamination/remediation problems, in which fluid flow and geochemical processes play important roles in the controlling dynamic mechanisms. The main purpose of this paper is to present a generalized overview of: (1) the various classes and models associated with fluid flow/chemically reacting systems in order to highlight possible opportunities and developments for the future; (2) some more general issues that need attention in the development of computational models and codes for simulating ore-forming and geoenviromental systems; (3) the related progresses achieved on the geochemical modeling over the past 50 years or so; (4) the general methodology for modeling of oreforming and geoenvironmental systems; and (5) the future development directions associated with modeling of ore-forming and geoenviromental systems.

Physico-geochemical and mineral composition of neem tree soils and relation to organic properties

The Neem tree, the oil of which has a long history of pesticide, fertilizer and medicinal use in India, has been studied extensively for its organic compounds. Here we present a physical, mineralogical and geochemical database resulting from the analyses of two Neem soil profiles (epipedons) in India. Neem tree derivatives are used in the manufacture of a variety of products, from anti-bacterial drugs and insecticides to fertilizers and animal feeds. A preliminary geochemical and mineralogical analysis of Neem soils is made to explore the potential for chemical links between Neem tree derivatives and soils. Physical soil characteristics, including colour, texture and clay mineralogy, suggest the two pedons formed under different hydrological regimes, and hence, are products of different leaching environments, one well-drained site, the other poorly drained. Geochemically, the two Neem soils exhibit similarities, with elevated concentrations of Th and rare earth elements. These elements are of interest because of their association with phosphates, especially monazite and apatite, and the potential link to fertilizer derivatives. Higher concentrations of trace elements in the soils may be linked to nutritional derivatives and to cell growth in the Neem tree.

Controls on iron in soils and soil waters of a forested, coastal catchment in subtropical Australia

Soluble organic matter derived from exotic Pinus vegetation forms stronger complexes with iron (Fe) than the soluble organic matter derived from most native Australian species. This has lead to concern about the environmental impacts related to the establishment of extensive exotic Pinus plantations in coastal southeast Queensland, Australia. It has been suggested that the Pinus plantations may enhance the solubility of Fe in soils by increasing the amount of organically complexed Fe. While this remains inconclusive, the environmental impacts of an increased flux of dissolved, organically complexed Fe from soils to the fluvial system and then to sensitive coastal ecosystems are potentially damaging. Previous work investigated a small number of samples, was largely laboratory based and had limited application to field conditions. These assessments lacked field-based studies, including the comparison of the soil water chemistry of sites associated with Pinus vegetation and undisturbed native vegetation. In addition, the main controls on the distribution and mobilisation of Fe in soils of this subtropical coastal region have not been determined. This information is required in order to better understand the relative significance of any Pinus enhanced solubility of Fe. The main aim of this thesis is to determine the controls on Fe distribution and mobilisation in soils and soil waters of a representative coastal catchment in southeast Queensland (Poona Creek catchment, Fraser Coast) and to test the effect of Pinus vegetation on the solubility and speciation of Fe. The thesis is structured around three individual papers. The first paper identifies the main processes responsible for the distribution and mobilisation of labile Fe in the study area and takes a catchment scale approach. Physicochemical attributes of 120 soil samples distributed throughout the catchment are analysed, and a new multivariate data analysis approach (Kohonen’s self organising maps) is used to identify the conditions associated with high labile Fe. The second paper establishes whether Fe nodules play a major role as an iron source in the catchment, by determining the genetic mechanism responsible for their formation. The nodules are a major pool of Fe in much of the region and previous studies have implied that they may be involved in redox-controlled mobilisation and redistribution of Fe. This is achieved by combining a detailed study of a ferric soil profile (morphology, mineralogy and micromorphology) with the distribution of Fe nodules on a catchment scale. The third component of the thesis tests whether the concentration and speciation of Fe in soil solutions from Pinus plantations differs significantly from native vegetation soil solutions. Microlysimeters are employed to collect unaltered, in situ soil water samples. The redox speciation of Fe is determined spectrophotometrically and the interaction between Fe and dissolved organic matter (DOM) is modelled with the Stockholm Humic Model. The thesis provides a better understanding of the controls on the distribution, concentration and speciation of Fe in the soils and soil waters of southeast Queensland. Reductive dissolution is the main mechanism by which mobilisation of Fe occurs in the study area. Labile Fe concentrations are low overall, particularly in the sandy soils of the coastal plain. However, high labile Fe is common in seasonally waterlogged and clay-rich soils which are exposed to fluctuating redox conditions and in organic-rich soils adjacent to streams. Clay-rich soils are most common in the upper parts of the catchment. Fe nodules were shown to have a negligible role in the redistribution of dissolved iron in the catchment. They are formed by the erosion, colluvial transport and chemical weathering of iron-rich sandstones. The ferric horizons, in which nodules are commonly concentrated, subsequently form through differential biological mixing of the soil. Whereas dissolution/ reprecipitation of the Fe cements is an important component of nodule formation, mobilised Fe reprecipitates locally. Dissolved Fe in the soil waters is almost entirely in the ferrous form. Vegetation type does not affect the concentration and speciation of Fe in soil waters, although Pinus DOM has greater acidic functional group site densities than DOM from native vegetation. Iron concentrations are highest in the high DOM soil waters collected from sandy podosols, where they are controlled by redox potential. Iron concentrations are low in soil solutions from clay and iron oxide rich soils, in spite of similar redox potentials. This is related to stronger sorption to the reactive clay and iron oxide mineral surfaces in these soils, which reduces the amount of DOM available for microbial metabolisation and reductive dissolution of Fe. Modelling suggests that Pinus DOM can significantly increase the amount of truly dissolved ferric iron remaining in solution in oxidising conditions. Thus, inputs of ferrous iron together with Pinus DOM to surface waters may reduce precipitation of hydrous ferric oxides and increase the flux of dissolved iron out of the catchment. Such inputs are most likely from the lower catchment, where podosols planted with Pinus are most widely distributed. Significant outcomes other than the main aims were also achieved. It is shown that mobilisation of Fe in podosols can occur as dissolved Fe(II) rather than as Fe(III)-organic complexes. This has implications for the large body of work which assumes that Fe(II) plays a minor role. Also, the first paper demonstrates that a data analysis approach based on Kohonen’s self organising maps can facilitate the interpretation of complex datasets and can help identify geochemical processes operating on a catchment scale.

On-line voltammetric monitoring of dissolved Cu and Ni in the Gulf of Cadiz, south-west Spain

Geochemical processes in estuarine and coastal waters often occur on temporally and spatially small scales, resulting in variability of metal speciation and dissolved concentrations. Thus, surveys, which are aimed to improve our understanding of metal behaviour in such systems, benefit from high-resolution, interactive sampling campaigns. The present paper discusses a high-resolution approach to coastal monitoring, with the application of an automated voltammetric metal analyser for on-line measurements of dissolved trace metals in the Gulf of Cadiz, south-west Spain. This coastal sea receives metal-rich inputs from a metalliferous mining area, mainly via the Huelva estuary. On-line measurements of dissolved Cu, Zn, Ni and Co were carried out on-board ship during an eight-day sampling campaign in the study area in June 1997. A pumping system operated continuously underway and provided sampled water from a depth of ca. 4 m. Total dissolved metal concentrations measured on-line in the Gulf of Cadiz ranged between <5 nM Cu (<3 nM Ni) ca. 50 km off-shore and 60–90 nM Cu (5–13 nM Ni) in the vicinity of the Huelva estuary. The survey revealed steep gradients and strong tidal variability in the dissolved metal plume extending from the Huelva estuary into the Gulf of Cadiz. Further on-line measurements were carried out with the automatic metal monitor from the bank of the Odiel estuary over a full tidal cycle, at dissolved metal concentrations in the μM range. The application confirmed the suitability of the automated metal monitor for coastal sampling, and demonstrated its adaptability to a wide range of environmental conditions in the dynamic waters of estuaries and coastal seas. The near-real time acquisition of dissolved metal concentrations at high resolution enabled an interactive sampling campaign and therefore the close investigation of tidal variability in the development of the Huelva estuary metal plume.

Structure of glasses and melts

Wilding, M. C., Benmore, C. J. (2006). Structure and Glasses and Melts. reviews in Mineralogy and Geochemistry, 63 (1), 275-311 RAE2008

Engineering passive bioreactive barriers: risk-managing the legacy of industrial soil and groundwater pollution

Permeable reactive barriers are a technology that is one decade old, with most full-scale applications based on abiotic mechanisms. Though there is extensive literature on engineered bioreactors, natural biodegradation potential, and in situ remediation, it is only recently that engineered passive bioreactive barrier technology is being considered at the commercial scale to manage contaminated soil and groundwater risks. Recent full-scale studies are providing the scientific confidence in our understanding of coupled microbial (and genetic), hydrogeologic, and geochemical processes in this approach and have highlighted the need to further integrate engineering and science tools.