MULTICOMPONENT GEOCHEMICAL TRANSPORT MODELING USING HYDRUS-1D AND HP11

Abstract: The transport of reactive contaminants in the subsurface is generally affected by a large number of nonlinear and often interactive physical, chemical, and biological processes. Simulating these processes requires a comprehensive reactive transport code that couples the physical processes of water flow and advective-dispersive transport with a range of biogeochemical processes. Two recently developed coupled geochemical models that are both based on the HYDRUS-1D software package for variably saturated flow and transport are summarized in this paper. One model resulted from coupling HYDRUS-1D with the UNSATCHEM module. While restricted to major ion chemistry, this program enables quantitative predictions of such problems as analyzing the effects of salinity on plant growth and the amount of water and amendments required to reclaim salt-affected soil profiles. The second model, HPI, resulted from coupling HYDRUS-1D with the PHREEQC biogeochemical code. The latter program accounts for a wide range of instantaneous or kinetic chemical and biological reactions, including complexation, cation exchange, surface complexation, precipitation dissolution and/or redox reactions. The versatility of HP1 is illustrated in this paper by means of two examples: the leaching of toxic trace elements and the transport of the explosive TNT and its degradation products.     

Immobilization of iodide on copper(I) sulfide minerals

In the goal of finding efficient scavengers for radioiodide in conditions (pH, pE) close to those encountered in deep geological sites, sorption of iodide ions on cuprous sulfide minerals (especially roxbyite, Cu(1.75)S) has been studied. Surface analysis by X-ray photoelectron spectroscopy has shown that commercial cuprous sulfides are covered by an oxidized overlayer (mainly in the form of CuSO(4)). Therefore, a synthetic procedure to get roxbyite (typically by mixing Na(2)S with an aqueous suspension of commercial Cu(2)O) was applied to produce pure samples with clean surfaces. Batch equilibration of cuprous sulfide particles suspended in aqueous solutions containing iodide species has revealed significant consumption of iodide. The sorption mechanism involves the formation of a surface complex via the exchange of surface hydroxyl groups by iodide anions, as highlighted by a transient pH increase during the immobilization process. Other copper and mixed copper-iron sulfides (e.g. CuS, CuFeS(2)), which are stable over wide pH and potential ranges are also likely to accumulate iodide species. Because of the specific interaction between iodide and copper(I) centers on the minerals, high distribution coefficients (>1000 ml/g) were observed.     

Behavior of a hammerhead ribozyme in aqueous solution at medium to high temperatures

The “RNA world” hypothesis proposes that—early in the evolution of life—RNA molecules played important roles both in information storage and in enzymatic functions. However, this hypothesis seems to be inconsistent with the concept that life may have emerged under hydrothermal conditions since RNA molecules are considered to be labile under such extreme conditions. Presently, the possibility that the last common ancestor of the present organisms was a hyperthermophilic organism which is important to support the hypothesis of the hydrothermal origin of life has been subject of strong discussions. Consequently, it is of importance to study the behavior of RNA molecules under hydrothermal conditions from the viewpoints of stability, catalytic functions, and storage of genetic information of RNA molecules and determination of the upper limit of temperature where life could have emerged. In the present work, self-cleavage of a natural hammerhead ribozyme was examined at temperatures 10–200?°C. Self-cleavage was investigated in the presence of Mg²⁺, which facilitates and accelerates this reaction. Self-cleavage of the hammerhead ribozyme was clearly observed at temperatures up to 60?°C, but at higher temperatures self-cleavage occurs together with hydrolysis and with increasing temperature hydrolysis becomes dominant. The influence of the amount of Mg²⁺ on the reaction rate was also investigated. In addition, we discovered that the reaction proceeds in the presence of high concentrations of monovalent cations (Na⁺ or K⁺), although very slowly. Furthermore, at high temperatures (above 60?°C), monovalent cations protect the ribozyme against degradation.     

Leaching behaviour of hazardous demolition waste

Demolition wastes are generally disposed of in unlined landfills for inert waste. However, demolition wastes are not just inert wastes. Indeed, a small fraction of demolition waste contains components that are hazardous to human health and the environment, e.g., lead-based paint, mercury-contained in fluorescent lamps, treated wood, and asbestos. The objective of this study is to evaluate the release potential of pollutants contained in these hazardous components when they are mixed with inert wastes in unlined landfills. After identification of the different building products which can contain hazardous elements and which can be potentially pollutant in landfill scenario, we performed leaching tests using three different lysimeters: one lysimeter containing only inert wastes and two lysimeters containing inert wastes mixed with hazardous demolition wastes. The leachates from these lysimeters were analysed (heavy metals, chlorides, sulphates fluoride, DOC (Dissolved Organic Carbon), phenol index, and PAH). Finally, we compared concentrations and cumulative releases of elements in leachates with the limits values of European regulation for the acceptance of inert wastes at landfill. Results indicate that limit values are exceeded for some elements. We also performed a percolation column test with only demolition hazardous wastes to evaluate the specific contribution of these wastes in the observed releases.     

Environmental impacts of residual Municipal Solid Waste incineration: A comparison of 110 French incinerators using a life cycle approach

Incineration is the main option for residual Municipal Solid Waste treatment in France. This study compares the environmental performances of 110 French incinerators (i.e. 85% of the total number of plants currently in activity in France) in a Life Cycle Assessment perspective, considering 5 non-toxic impact categories: climate change, photochemical oxidant formation, particulate matter formation, terrestrial acidification and marine eutrophication. Mean, median and lower/upper impact potentials are determined considering the incineration of 1 tonne of French residual Municipal Solid Waste. The results highlight the relatively large variability of the impact potentials as a function of the plant technical performances. In particular, the climate change impact potential of the incineration of 1 tonne of waste ranges from a benefit of ?58 kg CO₂-eq to a relatively large burden of 408 kg CO₂-eq, with 294 kg CO₂-eq as the average impact. Two main plant-specific parameters drive the impact potentials regarding the 5 non-toxic impact categories under study: the energy recovery and delivery rate and the NO_x process-specific emissions. The variability of the impact potentials as a function of incinerator characteristics therefore calls for the use of site-specific data when required by the LCA goal and scope definition phase, in particular when the study focuses on a specific incinerator or on a local waste management plan, and when these data are available.     

Larval chemical defence and evolution of host shifts in Chrysomela leaf beetles

Summary. Larvae of Chrysomela leaf beetles release for defence volatile compounds belonging to various chemical families. This study focuses on the defensive strategy based on the esterification of isobutyric acid and 2-methylbutyric acid with a wide variety of alcohols taken up from the host plant. To date, only two species are known to produce these repellents C. interrupta, which is associated with Betulaceae and C. lapponica which occurs either on Betulaceae or Salicaceae.? In order to know if other species have developed this chemical defence and how the food plant influences the secretion of these toxins, we targeted by mass spectrometry the presence of iso- and 2-methylbutyric acids and esters of them in the defensive secretions of Chrysomela larvae exclusively associated with Betulaceae or Salicaceae. ?Screening analyses reveal that the synthesis of these compounds is a common character restricted to all the members belonging to the C. interrupta group sensu Brown (1956) regardless of the host-plant family. These results suggest that the biochemical mechanism leading to the synthesis of these compounds could be considered as a synapomorphy meaning that the group is probably monophyletic. ?Defensive secretions of the members of the interrupta group are quantitatively assayed for iso- and 2-methylbutyric acids and their (Z)-3-hexenyl esters. Results reveal a chemical plasticity developed by Chrysomela species associated with Salicaceae. The amounts of iso- and 2-methylbutyric acids derivatives and of salicylaldehyde in their larval secretions depend on the food plant and on its content in phenolglucosides. Received 5 October 1998; accepted 25 November 1998.     

Intestinal absorption of the acetamiprid neonicotinoid by Caco-2 cells: Transepithelial transport,cellular uptake and efflux

The human intestinal absorption of acetamiprid (AAP) using the Caco-2 cell line reveals that AAP flux was active in a bidirectional mode with an apparent permeability coefficient of 26^.10^?6 cm·s^?1 at 37°C. Apical uptake was concentration-dependent and unsaturated for AAP concentrations up to 200 μ M. AAP cell preloading demonstrated the involvement of active transport mechanisms. Arrhenius plot analysis revealed an unusual profile with two apparent activation energies suggesting two transport processes. Uptake Vi studies indicated the involvement of a sodium-dependent transporter, the presence of a common transporter of AAP and nicotine and the involvement of Ti-sensitive ATP-dependent efflux transporters. Apical efflux investigations showed the involvement of inward active transporter(s). Whereas vincristine had no effect on intracellular accumulation, taxol and daunorubicin treatments unexpectedly led to 10% and 23% reductions respectively, suggesting that the latter shared a common inward transporter with AAP. All these results suggest full and express AAP absorption in vivo with transport involving both inward and outward, passive and active mechanisms. Thus, AAP or its metabolites could be representative of a risk for human health after its ingestion in food.     

Identification of odour sources in an industrial park from resident diaries statistics

A methodology based on social participation through the use of resident diaries was applied to evaluate the odour annoyance in the surroundings of an industrial park in Belgium during one year. The studied area covers about 8 km² and includes13 potential odour emitting facilities. The network involved 44 residents in the survey, among whom 19 were particularly considered for a detailed analysis. The questionnaire aimed at providing an odour rating twice-daily on a 6-level scale together with an odour type.The fact that the response rate corresponding to “no-odour” was high (79%) is particularly discussed. Some tests are proposed to check the plausibility of the answers, the coherence within clusters of residents and the individual performance of respondents to discriminate among odour ratings. The odour rose is presented as an attractive and visual tool, particularly suited in the case of multi-source areas, to map the different odour emissions, to point out the most worrying ones, to identify others creating less annoyance and possibly new unpredicted ones. The resident diary method has proven to be particularly useful, conjointly to other ones, to the case of multi-sources facilities in large areas, when the purpose is the assessment of the long-term evolution of odour annoyance.