Microextraction techniques coupled to liquid chromatography with mass spectrometry for the determination of organic micropollutants in environmental water samples

[EN]Until recently, sample preparation was carried out using traditional techniques, such as liquid–liquid extraction (LLE), that use large volumes of organic solvents. Solid-phase extraction (SPE) uses much less solvent than LLE, although the volume can still be significant. These preparation methods are expensive, time-consuming and environmentally unfriendly. Recently, a great effort has been made to develop new analytical methodologies able to perform direct analyses using miniaturised equipment, thereby achieving high enrichment factors, minimising solvent consumption and reducing waste. These microextraction techniques improve the performance during sample preparation, particularly in complex water environmental samples, such as wastewaters, surface and ground waters, tap waters, sea and river waters. Liquid chromatography coupled to tandem mass spectrometry (LC/MS/MS) and time-of-flight mass spectrometric (TOF/MS) techniques can be used when analysing a broad range of organic micropollutants. Before separating and detecting these compounds in environmental samples, the target analytes must be extracted and pre-concentrated to make them detectable. In this work, we review the most recent applications of microextraction preparation techniques in different water environmental matrices to determine organic micropollutants: solid-phase microextraction SPME, in-tube solid-phase microextraction (IT-SPME), stir bar sorptive extraction (SBSE) and liquid-phase microextraction (LPME). Several groups of compounds are considered organic micropollutants because these are being released continuously into the environment. Many of these compounds are considered emerging contaminants. These analytes are generally compounds that are not covered by the existing regulations and are now detected more frequently in different environmental compartments. Pharmaceuticals, surfactants, personal care products and other chemicals are considered micropollutants. These compounds must be monitored because, although they are detected in low concentrations, they might be harmful toward ecosystems.

Laboratory study of grouted macadams impregnated with mine waste geopolymeric binder

A new type of pavement has been gaining popularity over the last few years in Europe. It comprises a surface course with a semi-flexible material that provides significant advantages in comparison to both concrete and conventional asphalt, having both rut resistance and a degree of flexibility. It also provides good protection against the ingress of water to the foundation, since it has an impermeable surface. The semi-flexible material, generally known as grouted macadam, comprises an open-graded asphalt skeleton with 25% to 35% voids into which a cementitious slurry is grouted. This hybrid mixture provides good rut resistance and a surface highly resistant to fuel and oil spillage. Such properties allow it to be used in industrial areas, airports and harbours, where those situations are frequently associated with heavy and slow traffic. Grouted Macadams constitute a poorly understood branch of pavement technology and have generally been relegated to a role in certain specialist pavements whose performance is predicted on purely empirical evidence. Therefore, the main objectives of this project were related to better understanding the properties of this type of material, in order to predict its performance more realistically and to design pavements incorporating grouted macadam more accurately. Based on a standard mix design, several variables were studied during this project in order to characterise the behaviour of Grouted Macadams in general, and the influence of those variables on the fundamental properties of the final mixture. In this research project, one approach was used to the design of pavements incorporating Grouted Macadams: a traditional design method, based on laboratory determined of the stiffness modulus and the compressive strength.

Valorisation of organic waste: new developments from proton nuclear magnetic resonance characterization

The last half-century has seen a continuing population and consumption growth, increasing the competition for land, water and energy. The solution can be found in the new sustainability theories, such as the industrial symbiosis and the zero waste objective. Reducing, reusing and recycling are challenges that the whole world have to consider. This is especially important for organic waste, whose reusing gives interesting results in terms of energy release. Before reusing, organic waste needs a deeper characterization. The non-destructive and non-invasive features of both Nuclear Magnetic Resonance (NMR) relaxometry and imaging (MRI) make them optimal candidates to reach such characterization. In this research, NMR techniques demonstrated to be innovative technologies, but an important work on the hardware and software of the NMR LAGIRN laboratory was initially done, creating new experimental procedures to analyse organic waste samples. The first results came from soil-organic matter interactions. Remediated soils properties were described in function of the organic carbon content, proving the importance of limiting the addition of further organic matter to not inhibit soil processes as nutrients transport. Moreover NMR relaxation times and the signal amplitude of a compost sample, over time, showed that the organic matter degradation of compost is a complex process that involves a number of degradation kinetics, as a function of the mix of waste. Local degradation processes were studied with enhanced quantitative relaxation technique that combines NMR and MRI. The development of this research has finally led to the study of waste before it becomes waste. Since a lot of food is lost when it is still edible, new NMR experiments studied the efficiency of conservation and valorisation processes: apple dehydration, meat preservation and bio-oils production. All these results proved the readiness of NMR for quality controls on a huge kind of organic residues and waste.

Hydrologic and Water Quality Assessment of Miller Run: A Study of Bucknell University’s Impact

Human development causes degradation of stream ecosystems due to impacts on channel morphology, hydrology, and water quality. Urbanization, the second leading cause of stream impairment, increases the amount of impervious surface cover, thus reducing infiltration and increasing surface runoff of precipitation, which ultimately affects stream hydrologic process and aquatic biodiversity. The main objective of this study was to assess the overall health of Miller Run, a small tributary of the Bull Run and Susquehanna River watersheds, through an integrative hydrologic and water quality approach in order to determine the degree of Bucknell University’s impact on the stream. Hydrologic conditions, including stage and discharge, and water quality conditions, including total suspended solids, ion, nutrient, and dissolved metal concentrations, specific conductivity, pH, and temperature, were measured and evaluated at two sampling sites (upstream and downstream of Bucknell’s main campus) during various rain events from September 2007 to March 2008. The primary focus of the stream analysis was based on one main rain event on 26 February 2008. The results provided evidence that Miller Run is impacted by Bucknell’s campus. From a hydrologic perspective, the stream’s hydrograph showed the exact opposite pattern of what would be expected from a ‘normal’ stream. Miller run had a flashier downstream hydrograph and a broader upstream hydrograph, which was more than likely due to the increased amount of impervious surface cover throughout the downstream half of the watershed. From a water quality perspective, sediment loads increased at a faster rate and were significantly higher downstream compared to upstream. These elevated sediment concentrations were probably the combined result of sediment runoff from upstream and downstream construction sites that were being developed over the course of the study. Sodium, chloride, and potassium concentrations, in addition to specific conductivity, also significantly increased downstream of Bucknell’s campus due to the runoff of road salts. Calcium and magnesium concentrations did not appear to be impacted by urbanization, although they did demonstrate a significant dilution effect downstream. The downstream site was not directly affected by elevated nitrate concentrations; however, soluble reactive phosphorus concentrations tended to increase downstream and ammonium concentrations significantly peaked partway through the rain event downstream. These patterns suggest that Miller Run may be impacted by nutrient runoff from the golf course, athletic fields, and/or fertilizers applications on the main campus. Dissolved manganese and iron concentrations also appeared to slightly increase downstream, demonstrating the affect of urban runoff from roads and parking lots. pH and temperature both decreased farther downstream, but neither showed a significant impact of urbanization. More studies are necessary to determine how Miller Run responds to changes in season, climate, precipitation intensity, and land-use. This study represents the base-line analysis of Miller Run’s current hydrologic and water quality conditions; based on these initial findings, Bucknell should strongly consider modifications to improve storm water management practices and to reduce the campus’s overall impact on the stream in order to enhance and preserve the integrity of its natural water resources.

Transport of Hydraulic Fracturing Water and Wastes in the Susquehanna River Basin, Pennsylvania

The development of the Marcellus Shale gas play in Pennsylvania and the northeastern United States has resulted in significant amounts of water and wastes transported by truck over roadways. This study used geographic information systems (GIS) to quantify truck travel distances via both the preferred routes (minimum distance while also favoring higher-order roads) as well as, where available, the likely actual distances for freshwater and waste transport between pertinent locations (e. g., gas wells, treatment facilities, freshwater sources). Results show that truck travel distances in the Susquehanna River Basin are greater than those used in prior life-cycle assessments of tight shale gas. When compared to likely actual transport distances, if policies were instituted to constrain truck travel to the closest destination and higher-order roads, transport mileage reductions of 40-80% could be realized. Using reasonable assumptions of current practices, greenhouse gas (GHG) emissions associated with water and waste hauling were calculated to be 70-157 MT CO2 eq per gas well. Furthermore, empty so-called backhaul trips, such as to freshwater withdrawal sites or returning from deep well injection sites, were found to increase emissions by an additional 30%, underscoring the importance of including return trips in the analysis. The results should inform future life-cycle assessments of tight shale gases in managed watersheds and help local and regional governments plan for impacts of transportation on local infrastructure. (C) 2013 American Society of Civil Engineers.

Study of water use and supply in the district of Independencia, Peru

Peru is a developing country with abundant fresh water resources, yet the lack of infrastructure leaves much of the population without access to safe water for domestic uses. The author of this report was a Peace Corps Volunteer in the sector of water & sanitation in the district of Independencia, Ica, Peru. Independencia is located in the arid coastal region of the country, receiving on average 15 mm of rain annually. The water source for this district comes from the Pisco River, originating in the Andean highlands and outflowing into the Pacific Ocean near the town of Pisco, Peru. The objectives of this report are to assess the water supply and sanitation practices, model the existing water distribution system, and make recommendations for future expansion of the distribution system in the district of Independencia, Peru. The assessment of water supply will be based on the results from community surveys done in the district of Independencia, water quality testing done by a detachment of the U.S. Navy, as well as on the results of a hydraulic model built in EPANET 2.0 to represent the distribution system. Sanitation practice assessments will be based on the surveys as well as observations from the author while living in Peru. Recommendations for system expansions will be made based on results from the EPANET model and the municipality’s technical report for the existing distribution system. Household water use and sanitation surveys were conducted with 84 families in the district revealing that upwards of 85% store their domestic water in regularly washed containers with lids. Over 80% of those surveyed are drinking water that is treated, mostly boiled. Of those surveyed, over 95% reported washing their hands and over 60% mentioned at least one critical time for hand washing when asked for specific instances. From the surveys, it was also discovered that over 80% of houses are properly disposing of excrement, in either latrines or septic tanks. There were 43 families interviewed with children five years of age or under, and just over 18% reported the child had a case of diarrhea within the last month at the time of the interview. Finally, from the surveys it was calculated that the average water use per person per day is about 22 liters. Water quality testing carried out by a detachment of the U.S. Navy revealed that the water intended for consumption in the houses surveyed was not suitable for consumption, with a median E. coli most probable number of 47/100 ml for the 61 houses sampled. The median total coliforms was 3,000 colony forming units per 100 ml. EPANET was used to simulate the water delivery system and evaluate its performance. EPANET is designed for continuous water delivery systems, assuming all pipes are always flowing full. To account for the intermittent nature of the system, multiple EPANET network models were created to simulate how water is routed to the different parts of the system throughout the day. The models were created from interviews with the water technicians and a map of the system created using handheld GPS units. The purpose is to analyze the performance of the water system that services approximately 13,276 people in the district of Independencia, Peru, as well as provide recommendations for future growth and improvement of the service level. Performance evaluation of the existing system is based on meeting 25 liters per person per day while maintaining positive pressure at all nodes in the network. The future performance is based on meeting a minimum pressure of 20 psi in the main line, as proposed by Chase (2000). The EPANET model results yield an average nodal pressure for all communities of 71 psi, with a range from 1.3 – 160 psi. Thus, if the current water delivery schedule obtained from the local municipality is followed, all communities should have sufficient pressure to deliver 25 l/p/d, with the exception of Los Rosales, which can only supply 3.25 l/p/d. However, if the line to Los Rosales were increased from one to four inches, the system could supply this community with 25 l/p/d. The district of Independencia could greatly benefit from increasing the service level to 24-hour water delivery and a minimum of 50 l/p/d, so that communities without reliable access due to insufficient pressure would become equal beneficiaries of this invaluable resource. To evaluate the feasibility of this, EPANET was used to model the system with a range of population growth rates, system lifetimes, and demands. In order to meet a minimum pressure of 20 psi in the main line, the 6-inch diameter main line must be increased and approximately two miles of trench must be excavated up to 30 feet deep. The sections of the main line that must be excavated are mile 0-1 and 1.5-2.5, and the first 3.4 miles of the main line must be increased from 6 to 16 inches, contracting to 10 inches for the remaining 5.8 miles. Doing this would allow 24-hour water delivery and provide 50 l/p/d for a range of population growth rates and system lifetimes. It is expected that improving the water delivery service would reduce the morbidity and mortality from diarrheal diseases by decreasing the recontamination of the water due to transport and household storage, as well as by maintaining continuous pressure in the system to prevent infiltration of contaminated groundwater. However, this expansion must be carefully planned so as not to affect aquatic ecosystems or other districts utilizing water from the Pisco River. It is recommended that stream gaging of the Pisco River and precipitation monitoring of the surrounding watershed is initiated in order to begin a hydrological study that would be integrated into the district’s water resource planning. It is also recommended that the district begin routine water quality testing, with the results available to the public.

Cylinder wall waste heat recovery from liquid-cooled internal combustion engines utilizing thermoelectric generators

This report is a dissertation proposal that focuses on the energy balance within an internal combustion engine with a unique coolant-based waste heat recovery system. It has been predicted by the U.S. Energy Information Administration that the transportation sector in the United States will consume approximately 15 million barrels per day in liquid fuels by the year 2025. The proposed coolant-based waste heat recovery technique has the potential to reduce the yearly usage of those liquid fuels by nearly 50 million barrels by only recovering even a modest 1% of the wasted energy within the coolant system. The proposed waste heat recovery technique implements thermoelectric generators on the outside cylinder walls of an internal combustion engine. For this research, one outside cylinder wall of a twin cylinder 26 horsepower water-cooled gasoline engine will be implemented with a thermoelectric generator surrogate material. The vertical location of these TEG surrogates along the water jacket will be varied along with the TEG surrogate thermal conductivity. The aim of this proposed dissertation is to attain empirical evidence of the impact, including energy distribution and cylinder wall temperatures, of installing TEGs in the water jacket area. The results can be used for future research on larger engines and will also assist with proper TEG selection to maximize energy recovery efficiencies.

MATURE FINE TAILINGS (MFTs): A STUDY OF COMPRESSIVE STRENGTH AND RHEOLOGICAL PROPERTIES OF ATHABASCA OIL SANDS PETROLEUM MINING WASTE APPLIED IN CONCRETE MIXTURES

This study investigates the compressive properties of concrete incorporating Mature Fine Tailings (MFTs) waste stream from a tar sands mining operation. The objectives of this study are to investigate material properties of the MFT material itself, as well as establish general feasibility of the utilization of MFT material in concrete mixtures through empirical data and visual observations. Investigations undertaken in this study consist of moisture content, materials finer than No. 200 sieve, Atterburg Limits as well as visual observations performed on MFT material as obtained. Control concrete mixtures as well as MFT replacement mixture designs (% by wt. of water) were guided by properties of the MFT material that were experimentally established. The experimental design consists of compression testing of 4”-diameter concrete cylinders of a control mixture, 30% MFT, 50% MFT and 70% MFT replacement mixtures with air-entrainer additive, as well as a control mixture and 30% MFT replacement mixture with no air-entrainer. A total of 6 mixtures (2 control mixtures, 4 replacement mixtures) moist-cured in lime water after 24 hours initial curing were tested for ultimate compressive strength at 7 days and 28 days in accordance to ASTM C39. The test results of fresh concrete material show that the addition of air-entrainer to the control mixture increases slump from 4” to 5.5”. However, the use of MFT material in concrete mixtures significantly decreases slump as compared to controls. All MFT replacement mixtures (30%, 50%, and 70%) with air-entrainer present slumps of 1”. 30% MFT with no air-entrainer presents a slump of 1.5”. It was found that 7-day ultimate compressive stress was not a good predictor of 28-day ultimate compressive stress. 28-day results indicate that the use of MFT material in concrete with air-entrainer decreases ultimate compressive stress for 30%, 50% and 70% MFT replacement amounts by 14.2%, 17.3% and 25.1% respectively.

LIFE CYCLE ASSESSMENTS (LCAs) OF PYROLYSIS-BASED GASOLINE AND DIESEL FROM DIFFERENT REGIONAL FEEDSTOCKS: CORN STOVER, SWITCHGRASS, SUGAR CANE BAGASSE, WASTE WOOD, GUINEA GRASS, ALGAE, AND ALBIZIA

Renewable hydrocarbon biofuels are being investigated as possible alternatives to conventional liquid transportation fossil fuels like gasoline, kerosene (aviation fuel), and diesel. A diverse range of biomass feedstocks such as corn stover, sugarcane bagasse, switchgrass, waste wood, and algae, are being evaluated as candidates for pyrolysis and catalytic upgrading to produce drop-in hydrocarbon fuels. This research has developed preliminary life cycle assessments (LCA) for each feedstock-specific pathway and compared the greenhouse gas (GHG) emissions of the hydrocarbon biofuels to current fossil fuels. As a comprehensive study, this analysis attempts to account for all of the GHG emissions associated with each feedstock pathway through the entire life cycle. Emissions from all stages including feedstock production, land use change, pyrolysis, stabilizing the pyrolysis oil for transport and storage, and upgrading the stabilized pyrolysis oil to a hydrocarbon fuel are included. In addition to GHG emissions, the energy requirements and water use have been evaluated over the entire life cycle. The goal of this research is to help understand the relative advantages and disadvantages of the feedstocks and the resultant hydrocarbon biofuels based on three environmental indicators; GHG emissions, energy demand, and water utilization. Results indicate that liquid hydrocarbon biofuels produced through this pyrolysis-based pathway can achieve greenhouse gas emission savings of greater than 50% compared to petroleum fuels, thus potentially qualifying these biofuels under the US EPA RFS2 program. GHG emissions from biofuels ranged from 10.7-74.3 g/MJ from biofuels derived from sugarcane bagasse and wild algae at the extremes of this range, respectively. The cumulative energy demand (CED) shows that energy in every biofuel process is primarily from renewable biomass and the remaining energy demand is mostly from fossil fuels. The CED for biofuel range from 1.25-3.25 MJ/MJ from biofuels derived from sugarcane bagasse to wild algae respectively, while the other feedstock-derived biofuels are around 2 MJ/MJ. Water utilization is primarily from cooling water use during the pyrolysis stage if irrigation is not used during the feedstock production stage. Water use ranges from 1.7 - 17.2 gallons of water per kg of biofuel from sugarcane bagasse to open pond algae, respectively.

Presence of UV filters in surface water and the effects of phenylbenzimidazole sulfonic acid on rainbow trout (Oncorhynchus mykiss) following a chronic toxicity test

UV filters belong to a group of compounds that are used by humans and are present in municipal waste-waters, effluents from sewage treatment plants and surface waters. Current information regarding UV filters and their effects on fish is limited. In this study, the occurrence of three commonly used UV filters - 2-phenylbenzimidazole-5-sulfonic acid (PBSA), 2-hydroxy-4-methoxybenzophenone (benzophenone-3, BP-3) and 5-benzoyl-4-hydroxy-2-methoxy-benzenesulfonic acid (benzophenone-4, BP-4) - in South Bohemia (Czech Republic) surface waters is presented. PBSA concentrations (up to 13μgL(-1)) were significantly greater than BP-3 or BP-4 concentrations (up to 620 and 390ngL(-1), respectively). On the basis of these results, PBSA was selected for use in a toxicity test utilizing the common model organism rainbow trout (Oncorhynchus mykiss). Fish were exposed to three concentrations of PBSA (1, 10 and 1000µgL(-1)) for 21 and 42 days. The PBSA concentrations in the fish plasma, liver and kidneys were elevated after 21 and 42 days of exposure. PBSA increased activity of certain P450 cytochromes. Exposure to PBSA also changed various biochemical parameters and enzyme activities in the fish plasma. However, no pathological changes were obvious in the liver or gonads.

Squeezing of Pore-water from Core Samples of DGR Boreholes: Feasibility Study

Three archived core samples from boreholes DGR-4, DGR-5 and DGR-6 from the Salina F Unit, Queenston Formation and the Georgian Bay Formation were subjected to squeezing tests at pressures of up to 500 MPa. Two samples did not yield any water, while a total of 0.88 g pore water was obtained from a clay-rich sample from the Blue Mountain Formation (water content = 2.8 wt.%, porosity = 8 %). This water mass was sufficient for a full chemical and water-isotope analysis – the first direct determination of pore-water composition in rocks from the DGR boreholes. The results are generally in reasonable agreement with those of independent methods, or the observed differences can be explained. Ancillary investigations included the determination of water content, densities and mineralogy, aqueous extraction of squeezed cores, and SEM investigations to characterise the microtexture of unsqueezed and squeezed rock materials. It is concluded that squeezing is a promising method of pore-water extraction and characterisation and is recommended as an alternative method for future studies. Selection criteria for potentially squeezable samples include high clay-mineral content (correlating in a high water content) and low carbonate content (low stiffness, limited cementation). Potential artefacts of the method, such as ion filtration or pressure solution, should be explored and quantified in future efforts.

Assessing the Environmental Hazard of Using Seawater for Ore Processing at the Lasail Mine Site in the Sultanate of Oman

The Lasail mining area (Sultanate of Oman) was contaminated by acid mine drainage during the exploitation and processing of local and imported copper ore and the subsequent deposition of sulphide-bearing waste material into an unsealed tailings dump. In this arid environment, the use of seawater in the initial stages of ore processing caused saline contamination of the fresh groundwater downstream of the tailings dump. After detection of the contamination in the 1980s, different source-controlled remediation activities were conducted including a seepage water collection system and, in 2005, surface sealing of the tailings dump using an HDPE-liner to prevent further infiltration of meteoric water. We have been assessing the benefits of the remediation actions undertaken so far. We present chemical and isotopic (δ18O, δ 2H, 3H) groundwater data from a long-term survey (8–16 years) of the Wadi Suq aquifer along a 28 km profile from the tailings dump to the Gulf of Oman. Over this period, most metal concentrations in the Wadi Suq groundwater decreased below detection limits. In addition, in the first boreholes downstream of the tailings pond, the salinity contamination has decreased by 30 % since 2005. This decrease appears to be related to the surface coverage of the tailings pond, which reduces flushing of the tailings by the sporadic, but commonly heavy, precipitation events. Despite generally low metal concentrations and the decreased salinity, groundwater quality still does not meet the WHO drinking water guidelines in more than 90 % of the Wadi Suq aquifer area. The observations show that under arid conditions, use of seawater for ore processing or any other industrial activity has the potential to contaminate aquifers for decades.

Tracking water pathways in steep hillslopes by d18O depth profiles of soil water

Assessing temporal variations in soil water flow is important, especially at the hillslope scale, to identify mechanisms of runoff and flood generation and pathways for nutrients and pollutants in soils. While surface processes are well considered and parameterized, the assessment of subsurface processes at the hillslope scale is still challenging since measurement of hydrological pathways is connected to high efforts in time, money and personnel work. The latter might not even be possible in alpine environments with harsh winter processes. Soil water stable isotope profiles may offer a time-integrating fingerprint of subsurface water pathways. In this study, we investigated the suitability of soil water stable isotope (d18O) depth profiles to identify water flow paths along two transects of steep subalpine hillslopes in the Swiss Alps. We applied a one-dimensional advection–dispersion model using d18O values of precipitation (ranging from _24.7 to _2.9‰) as input data to simulate the d18O profiles of soil water. The variability of d18O values with depth within each soil profile and a comparison of the simulated and measured d18O profiles were used to infer information about subsurface hydrological pathways. The temporal pattern of d18O in precipitation was found in several profiles, ranging from _14.5 to _4.0‰. This suggests that vertical percolation plays an important role even at slope angles of up to 46_. Lateral subsurface flow and/or mixing of soil water at lower slope angles might occur in deeper soil layers and at sites near a small stream. The difference between several observed and simulated d18O profiles revealed spatially highly variable infiltration patterns during the snowmelt periods: The d18O value of snow (_17.7 ± 1.9‰) was absent in several measured d18O profiles but present in the respective simulated d18O profiles. This indicated overland flow and/or preferential flow through the soil profile during the melt period. The applied methods proved to be a fast and promising tool to obtain time-integrated information on soil water flow paths at the hillslope scale in steep subalpine slopes.

Mineralogical and isotopic record of diagenesis from the Opalinus Clay formation at Benken, Switzerland: Implications for the modeling of pore-water chemistry in a clay formation

Argillaceous rocks are considered to be a suitable geological barrier for the long-term containment of wastes. Their efficiency at retarding contaminant migration is assessed using reactive-transport experiments and modeling, the latter requiring a sound understanding of pore-water chemistry. The building of a pore-water model, which is mandatory for laboratory experiments mimicking in situ conditions, requires a detailed knowledge of the rock mineralogy and of minerals at equilibrium with present-day pore waters. Using a combination of petrological, mineralogical, and isotopic studies, the present study focused on the reduced Opalinus Clay formation (Fm) of the Benken borehole (30 km north of Zurich) which is intended for nuclear-waste disposal in Switzerland. A diagenetic sequence is proposed, which serves as a basis for determining the minerals stable in the formation and their textural relationships. Early cementation of dominant calcite, rare dolomite, and pyrite formed by bacterial sulfate reduction, was followed by formation of iron-rich calcite, ankerite, siderite, glauconite, (Ba, Sr) sulfates, and traces of sphalerite and galena. The distribution and abundance of siderite depends heavily on the depositional environment (and consequently on the water column). Benken sediment deposition during Aalenian times corresponds to an offshore environment with the early formation of siderite concretions at the water/sediment interface at the fluctuating boundary between the suboxic iron reduction and the sulfate reduction zones. Diagenetic minerals (carbonates except dolomite, sulfates, silicates) remained stable from their formation to the present. Based on these mineralogical and geochemical data, the mineral assemblage previously used for the geochemical model of the pore waters at Mont Terri may be applied to Benken without significant changes. These further investigations demonstrate the need for detailed mineralogical and geochemical study to refine the model of pore-water chemistry in a clay formation.

Quantification of water content across a cement-clay interface using high resolution neutron radiography

In many designs for radioactive waste repositories, cement and clay will come into direct contact. The geochemical contrast between cement and clay will lead to mass fluxes across the interface, which consequently results in alteration of structural and transport properties of both materials that may affect the performance of the multi-barrier system. We present an experimental approach to study cement-clay interactions with a cell to accommodate small samples of cement and clay. The cell design allows both in situ measurement of water content across the sample using neutron radiography and measurement of transport parameters using through-diffusion tracer experiments. The aim of the high- resolution neutron radiography experiments was to monitor changes in water content (porosity) and their spatial extent. Neutron radiographs of several evolving cement-clay interfaces delivered quantitative data which allow resolving local water contents within the sample domain. In the present work we explored the uncertainties of the derived water contents with regard to various input parameters and with regard to the applied image correction procedures. Temporal variation of measurement conditions created absolute uncertainty of the water content in the order of ±0.1 (m3/m3), which could not be fully accounted for by correction procedures. Smaller relative changes in water content between two images can be derived by specific calibrations to two sample regions with different, invariant water contents.