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.     

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.     

Estimated Variability of National Atmospheric Deposition Program/Mercury Deposition Network Measurements Using Collocated Samplers

The National Atmospheric Deposition Program/Mercury Deposition Network (MDN) provides long-term, quality-assured records of mercury in wet deposition in the USA and Canada. Interpretation of spatial and temporal trends in the MDN data requires quantification of the variability of the MDN measurements. Variability is quantified for MDN data from collocated samplers at MDN sites in two states, one in Illinois and one in Washington. Median absolute differences in the collocated sampler data for total mercury concentration are approximately 11% of the median mercury concentration for all valid 1999–2004 MDN data. Median absolute differences are between 3.0% and 14% of the median MDN value for collector catch (sample volume) and between 6.0% and 15% of the median MDN value for mercury wet deposition. The overall measurement errors are sufficiently low to resolve between NADP/MDN measurements by ±2 ng·l⁻¹ and ±2 μg·m⁻²·year⁻¹, which are the contour intervals used to display the data on NADP isopleths maps for concentration and deposition, respectively.     

Using Spatial Pattern to Quantify Relationship Between Samples, Surroundings, and Populations

The need for accurate carbon budgeting, climate change modelling, and sustainable resource management has lead to an increase in the number of large area forest monitoring programs. Large area forest monitoring programs often utilize field and remotely sensed data sources. Sampling, via field or photo plots, enables the collection of data with the desired level of categorical detail in a timely and efficient manner. When sampling, the aim is to collect representative detailed data enabling the statistical reporting upon the characteristics of larger areas. As a consequence, approaches for investigating how well sample data represent larger areas (i.e., the sample neighbourhood and the population) are desired. Presented in this communication is a quantitative approach for assessing the nature of sampled areas in relation to surrounding areas and the overall population of interest. Classified Landsat data is converted to forest/non-forest categories to provide a consistent and uniform data set over a 130,000 km² study region in central British Columbia, Canada. From this larger study area 322 2 × 2 km photo plots on a 20 × 20 km systematic grid are populated with composition and configuration information for comparison to non-sampled areas. Results indicate that typically, within the study area, the spatial pattern of forest within a photo plot is representative of the forest patterns found within primary and secondary neighbourhoods and over the entire population of the study. These methods have implications for understanding the nature of data used in monitoring programs worldwide. The ability to audit photo and field plot information promotes an increased understanding of the results developed from sampling and provides tools identifying locations of possible bias.     

Still falling short: protection and partnerships in the Lebanon emergency response

The Israeli–Hezbollah conflict in the summer of 2006, although brief, had a lasting impact on the region and prompted an intense humanitarian response. The conflict raised challenging questions for the United Nations (UN) about how to assist a middle‐income yet extremely vulnerable population in a context where global and local relations are highly politicised. This paper focuses on two key questions that emerged from the humanitarian response. First, how can humanitarian agencies, and particularly the UN, improve the protection of civilians, and was what they did in Lebanon enough? Second, how can humanitarian agencies create partnerships with local actors and still remain true to core humanitarian principles when local actors are fiercely divided along confessional lines and influenced by external actors, and when some, such as Hezbollah, are parties to the conflict? This paper argues that despite the importance of protection and partnerships to the humanitarian response, their role in the UN emergency response still falls short.     

Refinery evaluation of optical imaging to locate fugitive emissions

Fugitive emissions account for approximately 50% of total hydrocarbon emissions from process plants. Federal and state regulations aiming at controlling these emissions require refineries and petrochemical plants in the United States to implement a Leak Detection and Repair Program (LDAR). The current regulatory work practice, U.S. Environment Protection Agency Method 21, requires designated components to be monitored individually at regular intervals. The annual costs of these LDAR programs in a typical refinery can exceed US$1,000,000. Previous studies have shown that a majority of controllable fugitive emissions come from a very small fraction of components. The Smart LDAR program aims to find cost-effective methods to monitor and reduce emissions from these large leakers. Optical gas imaging has been identified as one such technology that can help achieve this objective. This paper discusses a refinery evaluation of an instrument based on backscatter absorption gas imaging technology. This portable camera allows an operator to scan components more quickly and image gas leaks in real time. During the evaluation, the instrument was able to identify leaking components that were the source of 97% of the total mass emissions from leaks detected. More than 27,000 components were monitored. This was achieved in far less time than it would have taken using Method 21. In addition, the instrument was able to find leaks from components that are not required to be monitored by the current LDAR regulations. The technology principles and the parameters that affect instrument performance are also discussed in the paper.     

The effects of landscape-level disturbance on the composition of Minnesota caddisfly (Insecta: Trichoptera) trophic functional groups: evidence for ecosystem homogenization

Over 300,000 caddisfly specimens representing 249 species were collected from nearly 250 sites throughout Minnesota during 2000 and 2001 to determine the effects of human disturbance on the composition of caddisfly trophic functional groups at the landscape level. Canonical correspondence analysis determined that stream width was the most important variable influencing functional group composition in regions of the state with relatively low disturbance, and that differences in the caddisfly fauna between sizes of streams generally followed trends predicted by the river continuum concept. In regions of the state with moderate disturbance, both stream width and the percentage of disturbed habitat upstream of a site were important variables influencing functional group composition. In highly disturbed regions, no variables corresponded to changes in the composition of caddisfly functional groups. Instead, ecosystems were homogeneous: fine-particle filtering collectors dominated in all sizes of streams. The observed aquatic ecosystem homogenization is attributed mostly to input of fine-particle organic and inorganic sediment from extensive agriculture.     

Seasonal and Inter-Annual Variations in Methyl Mercury Concentrations in Zooplankton from Boreal Lakes Impacted by Deforestation or Natural Forest Fires

We compared the effects of natural and anthropogenic watershed disturbances on methyl mercury (MeHg) concentration in bulk zooplankton from boreal Shield lakes. MeHg in zooplankton was monitored for three years in nine lakes impacted by deforestation, in nine lakes impacted by wildfire, and in twenty lakes with undisturbed catchments. Lakes were sampled during spring, mid- and late summer. MeHg in zooplankton showed a seasonal trend: concentrations were the lowest in spring, then peaked in mid-summer and decreased in late summer. Over the three study years, MeHg concentrations observed in mid-summer in zooplankton from forest harvested lakes were significantly higher than in reference and fire-impacted lakes, whereas differences between these two groups of lakes were not significant. The pattern of distribution of MeHg in zooplankton during the different seasons paralleled that of dissolved organic carbon (DOC), which is known as a vector of Hg from watershed soils to lake water. Besides DOC, MeHg in zooplankton also showed a positive significant correlation with epilimnetic temperature and sulfate concentrations. An inter-annual decreasing trend in MeHg was observed in zooplankton from reference and fire-impacted lakes. In forest harvested lakes, however, MeHg concentrations remained higher and nearly constant over three years following the impact. Overall these results indicate that the MeHg pulse observed in zooplankton following deforestation by harvesting is relatively long-lived, and may have repercussions to the accumulation of MeHg along the food chain. Therefore, potential effects of deforestation on the Hg contamination of fish should be taken into account in forest management practices.     

Preparation and evaluation of candidate certified reference materials (CRMs) for nutrients in seawater

Certified reference materials (CRMs) are an essential part of the quality assurance (QA) necessary for the reliable analytical measurement of nutrients in seawater. The CRMs currently available for these analyses are not matrix matched to marine samples. QUASIMEME routinely produces test materials for the nutrients in seawater and nutrients in estuarine water and low-salinity open water Laboratory Performance Studies (LPS) that are both homogeneous and stable. QUASIMEME, in conjunction with Eurofins Scientific, Denmark have produced two reference materials (RMs). The homogeneity testing and preliminary stability studies were carried out by QUASIMEME, and the results are presented in this article. Participants of the QUASIMEME LPS who demonstrated satisfactory long-term performance for the analysis of nutrients in seawater and nutrients in estuarine water and low-salinity open water were invited to take part in the certification exercise. Twenty laboratories returned data, a summary of which is also presented. The certification and long-term stability testing and additional data analysis were carried out by Eurofins Scientific, Denmark, and are outwith the scope of this article and not reported here. Eurofins Scientific, Denmark have marketed these RMs as part of their range of VKI Reference Materials (further information is available from eurofins@eurofins.dk).     

A near real-time system for continuously monitoring airborne subtilisin-type enzymes in the industrial atmosphere

We describe the development and validation of a portable system comprising an air sampler coupled to an automated flow injection analysis device. The system is able to monitor airborne concentrations of subtilisin-type enzymes in the workplace atmosphere on a continuous basis. Sampling is in two stages: using a sampling head that is designed to mimic human respiration at approx. 1 m s(-1) at a sampling rate of 600 l min(-1). In the second stage, the captured particles are deposited by impaction from the air stream onto the inner surface of a cyclone that is continuously washed with a jet of buffer solution. Deposited particles are then washed into a reservoir from which samples are taken every 5-6 min and injected automatically into a continuous flow injection analysis system. Proteolytic enzyme in the sample passes through a bioreactor maintained at about 40 degrees C. This contains a cellulose solid phase matrix on which is covalently immobilised Texas Red-labelled gelatin as substrate. The passing enzyme partially digests the substrate releasing fluorophore that is detected down stream in a flow cell coupled to a fluorimeter. The system is calibrated using enzyme standards and the intensity of the resulting peaks from the ex-air samples is converted to airborne concentrations using a mathematical model programmed into a PC. The system has a limit of detection of 4.8 ng m(-3) and a dynamic range of 5-60 ng m(-3). The within assay precision (RSD) is 6.3-9.6% over this range. The within batch precision is 20.3% at 20 ng m(-3) and the corresponding between batch value is 19.5%. The system has been run for periods up to 8 h in the laboratory and for up to 4 h at a factory site and the values obtained compared with time-averaged values obtained from a conventional Galley sampler and in-house analysis when reasonable agreement of the results was observed. The stability of the system over 21 days of continuous use with standards injected periodically was studied. Linearity was observed for all the standard plots throughout. At the end of 21 days, after a total exposure equivalent to 2395 ng ml(-1) of Savinase, the signal due to the 5.0 ng ml(-1) standard was still easily detectable.