Diffusion of HTO, Cl and I in Opalinus Clay samples from Mont Terri: Effect of confining pressure

Diffusion coefficients (T=23±2 °C) and accessible porosities for HTO, ³⁶Cl⁻ and ¹²⁵I⁻ were measured on Opalinus Clay (OPA) samples from the Mont Terri Underground Rock Laboratory (URL) using the through-diffusion technique. The direction of transport (diffusion) was perpendicular to bedding. Special cells that allowed the application of confining pressure were designed and constructed. The pressures ranged from 1 to 5 MPa, the latter value simulating the overburden at the Mont Terri URL (about 200 m). The test solution used in the experiments was a synthetic version of the Opalinus Clay pore water, which has Na⁺ and Cl⁻ as the main components (I=0.42 M).The measured values of the effective diffusion coefficients (D_e) and rock capacity factors (α) are: D_e=1.2–1.5×10⁻¹¹ m² s⁻¹ and α=0.09–0.11 for HTO, D_e=4.0–5.5×10⁻¹² m² s⁻¹ and α=0.05 for ³⁶Cl⁻ and D_e=3.2–4.6×10⁻¹² m² s⁻¹ and α=0.07–0.10 for ¹²⁵I⁻. For non-sorbing tracers (HTO, ³⁶Cl) the rock capacity factor α is equal to the diffusion-accessible porosity . The experimental results showed that pressure only had a small effect on the value of the diffusion coefficients. Increasing the pressure from 1 to 5 MPa resulted in a decrease of the diffusion coefficient of 17% for HTO, 28% for ³⁶Cl⁻ and 30% for ¹²⁵I⁻. Moreover, the diffusion coefficients for ³⁶Cl⁻ and ¹²⁵I⁻ are smaller than for HTO, which is consistent with an effect arising from anion exclusion.The diffusion coefficients of HTO and ¹²⁵I⁻ measured in this study are in good agreement with recent measurements at three other laboratories performed within the framework of a laboratory comparison exercise. The values of the diffusion-accessible porosities show a larger degree of scatter.     

Halogenated compounds and climate change: future emission levels and reduction costs

OBJECTIVES: This work assesses the contribution to climate change resulting from emissions of the group of halogenated greenhouse gases. METHODS: A bottom-up emission model covering 22 technological sectors in four major regions is described. Emission estimates for 1996 and projection for 2010 and 2020 are presented. The costs for deep cuts into projected emission levels are calculated. RESULTS: The substances covered by this study have contributed emissions of 1100 +/- 800 MT CO2 equivalents per year in 1996. In terms of their relative contribution to emissions of CO2 equivalents, this corresponds to 3 +/- 2% of global emissions of all anthropogenic greenhouse gases. The wide range of uncertainty is due to the poorly quantified net global warming potential of the ozone depleting substances, which have an indirect cooling effect on climate through the destruction of stratospheric ozone. For annual emissions of HFCs, PFCs and SF6 (which are regulated under the Kyoto Protocol and for which global warming potentials are well defined), the relative contribution is projected to increase to 2% (600 MT CO2 eq.) of global greenhouse gas emissions by 2010. This trend is expected to continue, emissions are projected to grow to a contribution of roughly 3% (870 MT CO2 eq.) in 2020 compared to 0.9% (300 MT CO2 eq.) in 1996. For HFCs, PFCs and SF6, this study identifies global emission reduction potentials of 260 MT CO2 eq. per year in 2010 and 640 MT CO2 eq. per year in 2020 at below US$ 50 per ton. These values correspond to roughly 40% and 75% of projected emissions in 2010 and 2020, respectively.     

Mobility of heavy metals as related to soil chemical and mineralogical characteristics of Brazilian soils

In order to better understand the relationship between soil characteristics and mobility of some heavy metals, correlation studies were conducted in samples of unlimed and limed A, B and C horizons of three Brazilian soils, representative of the majority of the tropical soils. A number of chemical and mineralogical characteristics of one Oxisol and two Ultisols were related to the retardation factors (Rf) for zinc (Zn), cadmium (Cd), copper (Cu) and lead (Pb). The retardation factors, obtained in leaching column experiments, were used as an estimate of solute movement in the profile. Soil types and soil horizons were found to influence metal retardation factors which, in turn, correlated better with the chemical than the mineralogical soil characteristics. For the unlimed soil samples, the soil characteristics that significantly correlated with Zn-Rf and Cd-Rf were the sum of exchangeable bases (SB), and soil exchangeable (Ca-KCl) and non-exchangeable (Ca-HCl) calcium contents. These results showed the strong influence of the cation exchange phenomenon on the retention and mobility of these two metals. For Cu and Pb, not only SB, cation exchange capacity (CEC) and Ca-KCl and Ca-HCl but also the organic matter correlated well with the Rf, showing that complex or chelate formation may play an important role in the movement of these elements. The important soil chemical characteristics related to the retardation factors in the limed soil samples were SB for Cd, and Ca-HCl for Cu and Pb, suggesting that precipitation may also influence the mobility and retention of the latter two heavy metals in these soil samples. Soil pH influenced the heavy metals adsorption and movement as shown by the significant correlation with the retardation factors when the combined data for the unlimed and limed soil samples was considered.     

Preparation and certification of a reference material on PCBs in pig fat and its application in quality control in monitoring laboratories during the Belgian "PCB-crisis"

In this article, the production and validation of a new certified reference material "PCBs in animal fat" for the control of the maximum level of 200 ng/g setup by the European Communities for veterinary products from Belgium is described. Three materials are established: a blank, one material with about 100 ng/g and one with about 200 ng/g (sum of seven PCBs). Data on the production and certification are given. Additionally, this material was used as an unknown test material in the quality assurance program of the Belgium meat monitoring system (before the certification of the material). While the certification was performed with an uncertainty of less than 10%, the round robin exhibited larger deviations. However, these deviations were less than 20% for most of the 30 participating laboratories. Only two had significantly higher deviations.     

Removal of hydrocarbons from wastewater using treated bark

This paper explores the possibility of removing hydrocarbons (HCs) and trace elements from synthetic and industrial effluents using treated bark as biosorbent. Coniferous bark was treated either chemically (Tc) or biologically (Tb) to eliminate soluble organic compounds of bark. The removal efficiency (RE) of the HCs from a synthetic oil-water mixture containing spent diesel motor oil exceeds 95% using 2 g/L of treated bark mixed with a synthetic oil-water mixture containing 2 g/L of spent oil. Under these conditions, the retention capacity (RC) was approximately 1 g HC/g dry substrate. The sorption reaction seems to be quasi-instantaneous, and the retention capacity of spent oil on treated bark increases as the temperature augments. This implies that the retention mechanism is related to the capillary action. Results of Fourier transform infrared (FTIR) spectroscopy indicate that spent oil is mainly composed of alkanes. They also suggest that no chemical bonds between Tc and spent oil were established. Measurement of the surface tension of spent oil and the wetting index of the bark suggests that only spent oil will be retained by the substrate. Treatment of an industrial effluent containing 14.4 g/L of total HCs was performed using Tc. It was possible to remove 97% of HCs and retain some trace elements such as Al, Ca, Fe, Mg, S, and so on.     

Personal exposure to fine particulate matter in elderly subjects: relation between personal, indoor, and outdoor concentrations

The time-series correlation between ambient levels, indoor levels, and personal exposure to PM2.5 was assessed in panels of elderly subjects with cardiovascular disease in Amsterdam, the Netherlands, and Helsinki, Finland. Subjects were followed for 6 months with biweekly clinical visits. Each subject's indoor and personal exposure to PM2.5 was measured biweekly, during the 24-hr period preceding the clinical visits. Outdoor PM2.5 concentrations were measured at fixed sites. The absorption coefficients of all PM2.5 filters were measured as a marker for elemental carbon (EC). Regression analyses were conducted for each subject separately, and the distribution of the individual regression and correlation coefficients was investigated. Personal, indoor, and ambient concentrations were highly correlated within subjects over time. Median Pearson's R between personal and outdoor PM2.5 was 0.79 in Amsterdam and 0.76 in Helsinki. For absorption, these values were 0.93 and 0.81 for Amsterdam and Helsinki, respectively. The findings of this study provide further support for using fixed-site measurements as a measure of exposure to PM2.5 in epidemiological time-series studies.     

Base cation deposition in europe-part I. Model description, results and uncertainties

Deposition of base cations (Na⁺, Mg²⁺, Ca²⁺, K⁺) in Europe was mapped for 1989 with a spatial resolution of 10 x 20 km using the so-called inferential modeling technique. Deposition fields resembled the geographic variability of sources, land-use and climate. Dry deposition constituted on average 45% of the total base cation deposition in Europe. Modeled deposition estimates compared reasonably well with deposition estimates derived from throughfall and bulk-precipitation measurements made at 174 sites scattered over Europe. Using error propagation, the random and systematic error in total deposition for an average grid cell of 10 x 20 km was estimated to equal 35–50% and 25–40%, respectively. Within individual grids a relatively large variability in deposition is expected.     

Discrimination of factors influencing biota of a stream receiving multiple-source perturbations

Blaine Creek is a fifth-order stream located in eastern Kentucky that has been subject to contamination by oil brines, surface mining, and a coal fly ash settling pond discharge. Toxicity tests, effluent and receiving water chemical monitoring, and Blaine Creek benthic sampling were used to evaluate the effect of the ash pond effluent on the creek. Reproductive impairment of Ceriodaphnia was demonstrated at effluent concentrations ranging from 30 to 100%, but no instream impact on benthic invertebrates could be found at effluent flows that provided up to 65% of the creek's discharge. Correlation and regression analysis of physicochemical versus benthic monitoring data indicated that upstream oil brine contamination and scouring of the creek's predominately shifting sand substrate during rainfall events were the primary factors affecting the benthic fauna, and appeared to override potential effects from other sources. These results demonstrated the value of integrated field/laboratory investigations for effluent impact assessments.     

Comparative study on the susceptibility of freshwater species to copper-based pesticides

Copper compounds have been intentionally introduced into water bodies as aquatic plant herbicides, algicides and molluscicides. Copper-based fertilizers and fungicides have been widely used in agriculture as well. Despite the fact that copper is an essential element for all biota, elevated concentrations of this metal have been shown to affect a variety of aquatic organisms. Nonetheless, comparative studies on the susceptibility of different freshwater species to copper compounds have seldom been performed. This study was conducted to compare toxicity of copper-based pesticides (copper oxychloride, cuprous oxide and copper sulfate) to different freshwater target (Raphidocelis subcapitata, a planktonic alga and Biomphalaria glabrata, a snail) and non-target (Daphnia similis, a planktonic crustacean and Danio rerio, a fish) organisms. Test water parameters were as follows: pH = 7.4 +/- 0.1; hardness 44 +/- 1 mg/l as CaCO3; DO 8-9 mg/l at the beginning and > 4 mg/l at the end; temperature, fish and snails 25 +/- 1 degrees C, Daphnia 20 +/- 2 degrees C, algae 24 +/- 1 degrees C. D. similis (immobilization), 48-h EC50s (95% CLs) ranging from 0.013 (0.011-0.016) to 0.043 (0.033-0.057) mg Cu/l, and R. subcapitata (growth inhibition), 96-h IC50s from 0.071 (0.045-0.099) to 0.137 (0.090-0.174) mg Cu/l, were the most susceptible species. B. glabrata (lethality), 48-h LC50s from 0.179 (0.102-0.270) to 0.854 (0.553-1.457) mg Cu/l, and D. rerio (lethality), 48-h LC50s 0.063 (0.045-0.089), 0.192 (0.133-0.272) and 0.714 (0.494-1.016) mg Cu/l, were less susceptible than Daphnia to copper-based pesticides. Findings from the present study therefore suggest that increased levels of copper in water bodies is likely to adversely affect a variety of aquatic species.