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.     

In field arsenic removal from natural water by zero-valent iron assisted by solar radiation

An in situ arsenic removal method applicable to highly contaminated water is presented. The method is based in the use of steel wool, lemon juice and solar radiation. The method was evaluated using water from the Camarones River, Atacama Desert in northern Chile, in which the arsenic concentration ranges between 1000 and 1300 μg L⁻¹. Response surface method analysis was used to optimize the amount of zero-valent iron (steel wool) and the citrate concentration (lemon juice) to be used. The optimal conditions when using solar radiation to remove arsenic from natural water from the Camarones river are: 1.3 g L⁻¹ of steel wool and one drop (ca. 0.04 mL) of lemon juice. Under these conditions, removal percentages are higher than 99.5% and the final arsenic concentration is below 10 μg L⁻¹. This highly effective arsenic removal method is easy to use and inexpensive to implement.     

Effects of reduced contaminant loading on downgradient water quality in an idealized two-layer granular porous media

The following explores the issue of how reductions in contaminant loading to plumes will effect downgradient water quality. An idealized scenario of two adjacent layers of uniform geologic media, one transmissive and the other low permeability, is considered. A high concentration source, similar to a thin DNAPL pool, is introduced in the transmissive layer immediately above the low permeability layer. While the source is active, dissolved constituents are driven along the contact by advection and into the low permeability layer by transverse diffusion. Removing the source reverses the concentration gradient between the layers, driving back diffusion of contaminants from the low permeability layer. Laboratory studies involving four contaminants demonstrate that 15 to 44% of the introduced contaminant moves into the low permeability zone (along a distance of 87 cm in a sand tank) over a period of 25 days. The greatest movement of contaminants into the low permeability zone is seen with the contaminants with the greatest sorption coefficients. A unique two-dimensional analytical solution is developed for the two-layer scenario. Processes addressed include advection; transverse dispersion; adsorption and degradation in the transmissive zones; and diffusion, adsorption, and degradation in the low permeability layer. Laboratory data agree favorably with the analytical solutions. Collectively, the laboratory results and analytical solutions provide a basis for testing other modeling approaches that can be applied to more complex problems. A set of field-scale scenarios are considered using the analytical solutions. Results indicate that improvement in water quality associated with source removal diminish with distance downgradient of the source. Furthermore, contaminant degradation and contaminant adsorption in the stagnant zone are shown to be critical factors governing the timing and magnitude of downgradient improvements in water quality. For five of six scenarios considered, observed improvements in water quality 100 m downgradient of the source fall in the range of 1 to 2 orders of magnitude 15 years after complete source removal. The sixth scenario, involving a contaminant half-life of three years and no adsorption, shows greater than three order of magnitude improvements in downgradient water quality within one year of source removal.     

Hepatic monooxygenase (CYP1A and CYP3A) and UDPGT enzymatic activities as biomarkers for long-term carbofuran exposure in tench (Tinca tinca L)

The effect of a long-term exposure of tenchs to different concentrations (10 and 100 micro g/L) of the pesticide carbofuran has been evaluated. Microsomal hepatic cytochrome P450 subfamily 1A (CYP1A) and 3A (CYP3A) activities, as well as the phase II enzyme uridine diphospho-glucuronosyltransferase (UDPGT) activity were evaluated as adequate biomarkers of fish exposure to environmentally relevant concentrations of the pesticide carbofuran in freshwater ecosystems. A clear time-dependent inhibition of both CYP1A and UDPGT activities was observed in fish exposed to the highest dose of carbofuran with respect to controls, whereas in the case of CYP3A activity, values of exposed animals did not show a clear pattern of alteration during the experiment. The results of the present study demonstrated that hepatic CYP1A and UDPGT activities from tench could be considered as sensitive biomarkers for carbamate pesticides in polluted water, thus allowing future and ecologically relevant biomonitoring studies with this species.     

A photolysis coefficient for characterizing the response of aqueous constituents to photolysis

UV photolysis and UV based advanced oxidation processes (AOPs) are gaining more and more attention for drinking water treatment. Quantum yield (ø) and molar absorption coefficient (ε) are the two critical parameters measuring the effectiveness of photolysis of a compound. The product of the two was proposed as a fundamental measure of a constituent’s amenability to transformation by photolysis. It was shown that this product, named the photolysis coefficient, k _p , can be determined using standard bench tests and captures the properties that govern a constituent’s transformation when exposed to light. The development showed the photolysis coefficient to be equally useful for microbiological, inorganic and organic constituents. Values of k _p calculated by the authors based on quantum yield and molar absorption coefficient data from the literature were summarized. Photolysis coefficients among microorganisms ranged from 8500 to more than 600000 and are far higher than for inorganic and organic compounds, which varied over a range of approximately 10 to 1000 and are much less sensitive to UV photolysis than the microorganisms.     

21世纪可替代脊椎动物进行生态毒性测试的方法：过去二十年的发展和现状综述

替代脊椎动物进行化学物质和污染物危害评估的方法已成为越来越重要的需求。现在首先要考虑的是当启动一个脊椎动物生态毒性测试,必须确保不必要的脊椎动物生物的使用尽可能最小化。对于一些监管目的,脊椎动物的使用对环境风险评估(ERA)已经被禁止,而在其他情况下生物测试的数量已经大大减少了,或者测试程序严格精简了。然而,想要获得能够完全替代脊椎动物提供环境危害数据的方法仍有很长的路要走。动物替代品的发展不仅仅是基于道德的考虑,也可以降低执行脊椎动物生态毒性测试的成本以及在某些情况下能够提供更好的信息旨在改进环境风险评估。本文集中综述了在过去的几十年里生态毒性评估替代方法所发生的重大的进展。
精选自Adam Lillicrap, Scott Belanger, Natalie Burden, David Du Pasquier, Michelle R. Embry, Marlies Halder, Mark A. Lampi, Lucy Lee, Teresa Norberg-King, Barnett A. Rattner, Kristin Schirmer, Paul Thomas. Alternative approaches to vertebrate ecotoxicity tests in the 21st century: a review of developments over the last two decades and current status. Environmental Toxicology and Chemistry: Volume 35, Issue 11, pages 2637–2646, November 2016. DOI: 10.1002/etc.3603
详情请见http://onlinelibrary.wiley.com/doi/10.1002/etc.3603/full
     

Identification of a floral-derived kairomone for currant clearwing, <Emphasis Type="Italic">Synanthedon tipuliformis</Emphasis>

The currant clearwing Synanthedon tipuliformis (Clerck) (Sesiidae) is a worldwide pest of black currants, Ribes nigrum. This moth has been observed to feed on nectar of inflorescences of Canada thistles, Cirsium arvense (L.) Scop. This work was undertaken to identify floral compound(s) produced by Canada thistles inflorescences that mediate the response of the currant clearwing. Floral volatiles were collected during the day and analysed by coupled gas chromatography/electroantennographic detection (GC/EAD) and gas chromatography/mass spectrometry (GC/MS). Three compounds consistently elicited EAD response from moth antennae and were identified by GC/MS as phenylacetaldehyde, methyl salicylate and dimethyl salicylate. When the compounds were tested individually or in various combinations in field trapping experiments, a 3-component blend attracted the largest number of female and male currant clearwings. Subsequent field trapping experiments were conducted to determine the optimal attraction dose for the ternary blend using three loadings of 1, 10 and 100 mg loaded into a polyethylene sachet. The highest catches were in traps baited with the 100 mg loading. In all trials, males and mated females were caught in significant numbers, while very low numbers of virgin females were found in the traps. In recent years the efficacy of mating disruption against currant clearwing has been reported as declining. The new kairomone blend identified in this study can be used with the sex pheromone to provide an effective control option for this important pest.     

Application of Adjoint Approach to Oil Spill Problems

Adjoint method is applied to various oil spill problems. A three-dimensional model for describing the dispersion of a quasi-passive substance (a pollutant or a nutrient) and its adjoint model are considered in a limited sea region. Direct and adjoint estimates are used to get dual (equivalent) estimates of the mean concentration of the substance in important zones of the region. The role of dual estimates is illustrated with a few examples. They include such oil spill problems as the search of the most dangerous point of the oil tanker route, the oil dispersion with a climatic velocity, and the dependence of the oil concentration estimates on the oil spill rate. One more example is the application of optimal bioremediation strategy for cleaning a few zones polluted by oil. In this case, instead of oil, the model describes the dispersion of a nutrient released to marine environment. Balanced, unconditionally stable second-order finite-difference schemes based on the splitting method for the solution of the dispersion model and its adjoint are suggested. The main and adjoint difference schemes are compatible in the sense that at every fractional step of the splitting algorithm, the one-dimensional split operators of both schemes satisfy a discrete form of Lagrange identity. In the special unforced and non-dissipative case, each scheme has two conservation laws. Every split one-dimensional problem is solved by Thomas’ factorization method.