Long-term geochemical evolution of the near field repository: insights from reactive transport modelling and experimental evidences

The KBS-3 underground nuclear waste repository concept designed by the Swedish Nuclear Fuel and Waste Management Co. (SKB) includes a bentonite buffer barrier surrounding the copper canisters and the iron insert where spent nuclear fuel will be placed. Bentonite is also part of the backfill material used to seal the access and deposition tunnels of the repository. The bentonite barrier has three main safety functions: to ensure the physical stability of the canister, to retard the intrusion of groundwater to the canisters, and in case of canister failure, to retard the migration of radionuclides to the geosphere. Laboratory experiments (< 10 years long) have provided evidence of the control exerted by accessory minerals and clay surfaces on the pore water chemistry. The evolution of the pore water chemistry will be a primordial factor on the long-term stability of the bentonite barrier, which is a key issue in the safety assessments of the KBS-3 concept.In this work we aim to study the long-term geochemical evolution of bentonite and its pore water in the evolving geochemical environment due to climate change. In order to do this, reactive transport simulations are used to predict the interaction between groundwater and bentonite which is simulated following two different pathways: (1) groundwater flow through the backfill in the deposition tunnels, eventually reaching the top of the deposition hole, and (2) direct connection between groundwater and bentonite rings through fractures in the granite crosscutting the deposition hole. The influence of changes in climate has been tested using three different waters interacting with the bentonite: present-day groundwater, water derived from ice melting, and deep-seated brine. Two commercial bentonites have been considered as buffer material, MX-80 and Deponit CA-N, and one natural clay (Friedland type) for the backfill. They show differences in the composition of the exchangeable cations and in the accessory mineral content. Results from the simulations indicate that pore water chemistry is controlled by the equilibrium with the accessory minerals, especially carbonates. pH is buffered by precipitation/dissolution of calcite and dolomite, when present. The equilibrium of these minerals is deeply influenced by gypsum dissolution and cation exchange reactions in the smectite interlayer. If carbonate minerals are initially absent in bentonite, pH is then controlled by surface acidity reactions in the hydroxyl groups at the edge sites of the clay fraction, although its buffering capacity is not as strong as the equilibrium with carbonate minerals. The redox capacity of the bentonite pore water system is mainly controlled by Fe(II)-bearing minerals (pyrite and siderite). Changes in the groundwater composition lead to variations in the cation exchange occupancy, and dissolution–precipitation of carbonate minerals and gypsum. The most significant changes in the evolution of the system are predicted when ice-melting water, which is highly diluted and alkaline, enters into the system. In this case, the dissolution of carbonate minerals is enhanced, increasing pH in the bentonite pore water. Moreover, a rapid change in the population of exchange sites in the smectite is expected due to the replacement of Na for Ca.     

Phytoremediation of polyaromatic hydrocarbons, anilines and phenols

Phytoremediation technologies based on the combined action of plants and the microbial communities that they support within the rhizosphere hold promise in the remediation of land and waterways contaminated with hydrocarbons but they have not yet been adopted in large-scale remediation strategies. In this review plant and microbial degradative capacities, viewed as a continuum, have been dissected in order to identify where bottle-necks and limitations exist. Phenols, anilines and polyaromatic hydrocarbons (PAHs) were selected as the target classes of molecule for consideration, in part because of their common patterns of distribution, but also because of the urgent need to develop techniques to overcome their toxicity to human health. Depending on the chemical and physical properties of the pollutant, the emerging picture suggests that plants will draw pollutants including PAHs into the plant rhizosphere to varying extents via the transpiration stream. Mycorrhizosphere-bacteria and -fungi may play a crucial role in establishing plants in degraded ecosystems. Within the rhizosphere, microbial degradative activities prevail in order to extract energy and carbon skeletons from the pollutants for microbial cell growth. There has been little systematic analysis of the changing dynamics of pollutant degradation within the rhizosphere; however, the importance of plants in supplying oxygen and nutrients to the rhizosphere via fine roots, and of the beneficial effect of microorganisms on plant root growth is stressed. In addition to their role in supporting rhizospheric degradative activities, plants may possess a limited capacity to transport some of the more mobile pollutants into roots and shoots via fine roots. In those situations where uptake does occur (i.e. only limited microbial activity in the rhizosphere) there is good evidence that the pollutant may be metabolised. However, plant uptake is frequently associated with the inhibition of plant growth and an increasing tendency to oxidant stress. Pollutant tolerance seems to correlate with the ability to deposit large quantities of pollutant metabolites in the 'bound' residue fraction of plant cell walls compared to the vacuole. In this regard, particular attention is paid to the activities of peroxidases, laccases, cytochromes P450, glucosyltransferases and ABC transporters. However, despite the seemingly large diversity of these proteins, direct proof of their participation in the metabolism of industrial aromatic pollutants is surprisingly scarce and little is known about their control in the overall metabolic scheme. Little is known about the bioavailability of bound metabolites; however, there may be a need to prevent their movement into wildlife food chains. In this regard, the application to harvested plants of composting techniques based on the degradative capacity of white-rot fungi merits attention.     

A safety analysis of roundabouts and turbo roundabouts based on Petri nets

Objective: In this work, a roundabout and a turbo roundabout model are compared and previous modeling with continuous Petri nets and safety are analyzed through indicators of complexity. Petri nets are a graphic and mathematical representation that allow a faithful modeling of urban systems.

Method: The methodology has been designed for the transformation of a real system to small subgraphs that represent the maneuvers in roundabouts, approximated as roads and lanes of incorporation. Places within the roundabout have been located and defined as continuous places from their influence and visibility toward adjacent conditions. The transitions have been modeled by time and inhibitory arcs, which represent priorities and areas where drivers must pay attention. The created networks represent a faithful model of vehicle flow trajectories in the roundabouts.

Results: The methodology is applied to the same real road intersection. The case study is a recent transformation from roundabout to turbo roundabout. The roundabout network complexity is corroborated by a greater number of entries and exits that lead to each roundabout place (reflected in the maneuvers that can be performed) and a greater number of inhibiting arcs. In most of the turbo roundabout places, the driver’s only option is reduced to occupying next place. The possibility of choosing between several places supposes a greater trajectory intersection and an increased time for decision making. The only situation where the complexity is the same between both systems is when a vehicle accesses the inner lane of the roundabout from the left lane on a single-lane road. The main maneuvers causing accidents have been modeled and their solution in a turbo roundabout is presented.

Conclusions: The reduced complexity of the turbo roundabout is due to the strict limitations in lane changes, turning turbo roundabouts into a safer model: A lower number of possible movements that can be performed by drivers and a smaller number of trajectories with collision risk. Petri nets have proven to be perfectly applicable to the representation of traffic circular systems (such as roundabouts and turbo roundabouts) and to measure the complexity and security of the system.     

Numerical modelling of uncongested wood transport in the Rienz river

Environmental Fluid Mechanics - The Eulerian–Lagrangian model ORSA2D_WT is employed for the simulation of uncongested wood transport, with reference to a field experiment that studied the...     

Evaluation of copper-induced DNA damage in Vitis vinifera L. using Comet-FISH

The contamination of soils and water with copper (Cu) can compromise the crops production and quality. Fungicides containing Cu are widely and intensively used in viticulture contributing to environmental contamination and genotoxicity in Vitis vinifera L. Despite the difficulty in reproducing field conditions in the laboratory, hydroponic solutions enriched with Cu (1, 10, 25 and 50 μM) were used in forced V. vinifera cuttings to evaluate the DNA damage in leaves of four wine-producing varieties (‘Tinta Barroca’, ‘Tinto Cão’, ‘Malvasia Fina’ and ‘Viosinho’). Alkaline comet assay followed by fluorescence in situ hybridisation (Comet-FISH) was performed with the 45S ribosomal DNA (rDNA) and telomeric [(TTTAGGG)_n] sequences as probes. This study aimed to evaluate the tolerance of the four varieties to different concentrations of Cu and to determine which genomic regions were more prone to DNA damage. The comet assay revealed comets of categories 0 to 4 in all varieties. The DNA damage increased significantly (p < 0.001) with the Cu concentration. ‘Tinto Cão’ appeared to be the most sensitive variety because it had the highest DNA damage increase in 50 μM Cu relative to the control. Comet-FISH was only performed on slides of the control and 50 μM Cu treatments. Comets of all varieties treated with 50 μM Cu showed rDNA hybridisation on the head, ‘halo’ and tail (category III), and their frequency was significantly higher than that of control. The frequency of category III comets hybridised with the telomeric probe was only significantly different from the control in ‘Malvasia Fina’ and ‘Tinta Barroca’. Comet-FISH revealed partial damage on rDNA and telomeric DNA in response to Cu but also in control, confirming the high sensitivity of these genomic regions to DNA fragmentation.

     

莫桑比克的海洋生物学研究:过去、现在及未来

本文概述了莫桑比克包括渔业在内的海洋生物学研究的发展情况.莫桑比克的海岸线约为3000km,海洋的生物资源在莫桑比克的社会中起着重要的作用,主要是作为人们的蛋白质来源以及收入和出口创汇的来源.     

Chemical compounds of the foraging recruitment pheromone in bumblebees

When the frenzied and irregular food-recruitment dances of bumblebees were first discovered, it was thought that they might represent an evolutionary prototype to the honeybee waggle dance. It later emerged that the primary function of the bumblebee dance was the distribution of an alerting pheromone. Here, we identify the chemical compounds of the bumblebee recruitment pheromone and their behaviour effects. The presence of two monoterpenes and one sesquiterpene (eucalyptol, ocimene and farnesol) in the nest airspace and in the tergal glands increases strongly during foraging. Of these, eucalyptol has the strongest recruitment effect when a bee nest is experimentally exposed to it. Since honeybees use terpenes for marking food sources rather than recruiting foragers inside the nest, this suggests independent evolutionary roots of food recruitment in these two groups of bees.     

拉普拉塔河流域以及巴塔哥尼亚地区及相关海域水生态栖息地的改变

本文描述了南美大陆南部陆地和东南沿海地区环境特性及水生栖息地和群落的现状(GIWA巴塔哥尼亚大陆架亚区),结果来自一项GIWA项目框架任务所完成的一份全面评估,绝大部分依据的是公开发表的数据.分析主要集中在跨边界水资源目前的情况和人类活动带来的影响.内陆水体的栖息地和群落变化主要是由为发电和其他用途而建的水坝和水库引起的.从活水环境到净水环境影响了生境,造成了生物群落的改变.在拉普拉塔(La Plata)河流域,外来入侵物种使本地物种消失.过度捕捞和污染影响了生物多样性,造成了海洋栖息地质量下降.本篇文章讨论了相关的原因,讨论了布宜诺斯艾利斯省和渔业资源由两国共享的阿根廷-乌拉圭公共渔业区对沿海生态环境的政策选择.     

Uncertainty in Agricultural CH<Subscript>4</Subscript> AND N<Subscript>2</Subscript>O Emissions from Finland – Possibilities to Increase Accuracy in Emission Estimates

According to the United Nations Framework Convention on Climate Change (UNFCCC) and Kyoto Protocol under it, industrial countries have to estimate their greenhouse gas emissions annually, and assess the uncertainties in these estimates. In Finland, agricultural methane (CH₄) and nitrous oxide (N_2O) emissions represent 7% of anthropogenic greenhouse gas emissions, and globally the share is much higher. Agriculture is one of the most uncertain emission categories (representing over 20% of greenhouse gas inventory uncertainty in Finland), due to both high natural variability of the emission sources and poor knowledge of the emission-generating processes. In this paper, we present an uncertainty estimate of agricultural CH₄ and N₂O emissions from Finland in 2002. Uncertainties were estimated based on measurement data, literature and expert judgement, and total uncertainty in agriculture was calculated using Monte Carlo simulation. According to the calculations, agricultural CH₄ and N₂O emissions from Finland were 3.7 to 7.8 Tg carbon dioxide (CO₂) equivalents, 5.4 Tg being the mean value.Estimates of CH₄ emissions are more reliable than those of N₂O. N₂O from agricultural soils was the most uncertain emission category, and the uncertainty was not reduced by using available national measurement data of N₂O fluxes. Sensitivity study revealed that the uncertainty in total agricultural inventory could be 7% points lower, if more accurate emission estimation methods were used, including 1) improved data collection in area estimates of organic soils, 2) climate-specific methods for N₂O from agricultural soils as already presented in literature, and 3) more detailed CH₄ estimation methods for enteric fermentation which can be achieved by investigating national circumstances and digestible systems of animals in more detail.     

The Role of a Salt Marsh Plant on Trace Metal Bioavailability in Sediments. Estimation By Different Chemical Approaches * (7 pp)

Goal, Scope and Background The presence or absence of vegetation can condition sediment characteristics. The main aim of this work was to investigate the influence of the sea rush Juncus maritimus on metal (Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn) availability to organisms living on or in estuarine sediments, from Douro River (NW Portugal), by comparing the characteristics and chemical behaviour of rhizosediments (collected within the plant assemblage) and those of sediment (collected around the plant). In order to evaluate whether and how sediment characteristics condition the role of plants on metal availability, sandy and muddy sediments colonised by J. maritimus were studied in parallel. Methods Metal availability was estimated by enzymatic digestion with pepsin (ED), which may provide an estimate of metal availability to organisms living at estuarine sediments. Nevertheless, since no consensus exists yet on the most suitable methodologies to estimate metal bioavailability in sediments, two more conventional approaches, BCR sequential extraction (SE) and AVS/SEM model, were also used, in parallel, and the information these approaches provided was compared with that provided by ED. Total-recoverable metal contents were determined by atomic absorption spectrophotometry after sediment digestion using a high-pressure microwave system. Results and Discussion Plants could concentrate metals around its roots and rhizomes. In addition, they were capable of oxidizing (release of oxygen by the roots) the anaerobic medium surrounding their roots in muddy sediment (reducing AVS). As sulphide oxidation renders metals (Cd, Cu, Ni, Pb and Zn) into more soluble forms, according to the AVS/SEM model, metals from muddy sites would be more available in rhizosediment than in sediment. The SE approach led to a similar conclusion. Nevertheless, the results provided by ED pointed at opposite conclusion, particularly for Cd and Zn, indicating less availability at rhizosediments than in the surrounding sediment. ED results were interpreted as a consequence of an enrichment of the rhizosediment in organic ligands exuded by the roots or liberated by dead plants. The effect of complexation of metals by organic compounds, which ED could not decompose/dissolve, seemed to overcome that caused by sediment oxidation. In general, a comparison of the information about metal availability by ED, SE, AVS/SEM, showed that it did not always match and in few cases it was even contradictory. Conclusion and Outlook Therefore, a thorough evaluation of the metal availability in sediments requires a combination of different chemical approaches, so as to take into consideration differences in ways of organism exposure (interstitial water and/or ingestion of sediment particles). - * The basis of this peer-reviewed paper is a presentation at the 9th FECS Conference on 'Chemistry and Environment', 29 August to 1 September 2004, Bordeaux, France.