Converging hydrostatic and hydromechanic concepts of preferential flow definitions

The boundary between preferential flow and Richards-type flow is a priori set at a volumetric soil water content θ at which soil water diffusivity D (θ) = η (= 10^− 6 m² s^− 1), where η is the kinematic viscosity. First we estimated with a hydrostatic approach from soil water retention curves the boundary, θ^K, between the structural pore domain, in which preferential flow occurs, and the matrix pore domain, in which Richards-type flow occurs. We then compared θ^K with θ that was derived from the respective soil hydrological property functions of same soil sample. Second, from in situ investigations we determined 96 values of θ^G as the terminal soil water contents that established themselves when the corresponding water-content waves of preferential flow have practically ceased. We compared the frequency distribution of θ^G with the one of θ that was calculated from the respective soil hydrological property functions of 32 soil samples that were determined with pressure plate apparatuses in the laboratory. There is support of the notion that θ^K ≈ θ^G ≈ θ, thus indicating the potential of θ to explain more generally what constitutes preferential flow. However, the support is assessed as working hypothesis on which to base further research rather than a procedure to a clear-cut identification of preferential flow and associated flow paths.     

Biodegradation potential of MTBE in a fractured chalk aquifer under aerobic conditions in long-term uncontaminated and contaminated aquifer microcosms

The potential for aerobic biodegradation of MTBE in a fractured chalk aquifer is assessed in microcosm experiments over 450 days, under in situ conditions for a groundwater temperature of 10 °C, MTBE concentration between 0.1 and 1.0 mg/L and dissolved O₂ concentration between 2 and 10 mg/L. Following a lag period of up to 120 days, MTBE was biodegraded in uncontaminated aquifer microcosms at concentrations up to 1.2 mg/L, demonstrating that the aquifer has an intrinsic potential to biodegrade MTBE aerobically. The MTBE biodegradation rate increased three-fold from a mean of 6.6 ± 1.6 μg/L/day in uncontaminated aquifer microcosms for subsequent additions of MTBE, suggesting an increasing biodegradation capability, due to microbial cell growth and increased biomass after repeated exposure to MTBE. In contaminated aquifer microcosms which also contained TAME, MTBE biodegradation occurred after a shorter lag of 15 or 33 days and MTBE biodegradation rates were higher (max. 27.5 μg/L/day), probably resulting from an acclimated microbial population due to previous exposure to MTBE in situ. The initial MTBE concentration did not affect the lag period but the biodegradation rate increased with the initial MTBE concentration, indicating that there was no inhibition of MTBE biodegradation related to MTBE concentration up to 1.2 mg/L. No minimum substrate concentration for MTBE biodegradation was observed, indicating that in the presence of dissolved O₂ (and absence of inhibitory factors) MTBE biodegradation would occur in the aquifer at MTBE concentrations (ca. 0.1 mg/L) found at the front of the ether oxygenate plume. MTBE biodegradation occurred with concomitant O₂ consumption but no other electron acceptor utilisation, indicating biodegradation by aerobic processes only. However, O₂ consumption was less than the stoichiometric requirement for complete MTBE mineralization, suggesting that only partial biodegradation of MTBE to intermediate organic metabolites occurred. The availability of dissolved O₂ did not affect MTBE biodegradation significantly, with similar MTBE biodegradation behaviour and rates down to ca. 0.7 mg/L dissolved O₂ concentration. The results indicate that aerobic MTBE biodegradation could be significant in the plume fringe, during mixing of the contaminant plume and uncontaminated groundwater and that, relative to the plume migration, aerobic biodegradation is important for MTBE attenuation. Moreover, should the groundwater dissolved O₂ concentration fall to zero such that MTBE biodegradation was inhibited, an engineered approach to enhance in situ bioremediation could supply O₂ at relatively low levels (e.g. 2–3 mg/L) to effectively stimulate MTBE biodegradation, which has significant practical advantages. The study shows that aerobic MTBE biodegradation can occur at environmentally significant rates in this aquifer, and that long-term microcosm experiments (100s days) may be necessary to correctly interpret contaminant biodegradation potential in aquifers to support site management decisions.     

Impact of initial and boundary conditions on preferential flow

Preferential flow in soil is approached by a water-content wave, WCW, that proceeds downward from the ground surface. WCWs were obtained from sprinkler experiments with infiltration rates varying from 5 to 40 mm h^− 1. TDR-probes and tensiometers measured volumetric water contents θ(z,t) at seven depths, and capillary heads, h(z,t) at six depths in a column of an undisturbed soil. The wave is characterized by the velocity of the wetting front, c_W, the amplitude, w_S, and the final water content, θ. We tested with uni-variate and bi-variate linear regressions the impacts of initial volumetric water contents, θ_ini, and input rates, q_S, on c_W, w_S and θ.The test showed that θ_ini influenced θ and w_S and q_S effected c_W. The expected proportionality of w_S ≈ qs^1/3 was weak and c_W ≈ qs^2/3 was strong.     

A detailed field-based evaluation of naphthenic acid mobility in groundwater

An anaerobic plume of process-affected groundwater was characterized in a shallow sand aquifer adjacent to an oil sands tailings impoundment. Based on biological oxygen demand measurements, the reductive capacity of the plume is considered minimal. Major dissolved components associated with the plume include HCO₃, Na, Cl, SO₄, and naphthenic acids (NAs). Quantitative and qualitative NA analyses were performed on groundwater samples to investigate NA fate and transport in the subsurface. Despite subsurface residence times exceeding 20 years, significant attenuation of NAs by biodegradation was not observed based on screening techniques developed at the time of the investigation. Relative to conservative tracers (i.e., Cl), overall NA attenuation in the subsurface is limited, which is consistent with batch sorption and microcosm studies performed by other authors. Insignificant biological oxygen demand and low concentrations of dissolved As (< 10 µg L^− 1) in the plume suggest that the potential for secondary trace metal release, specifically As, via reductive dissolution reactions driven by ingress of process-affected water is minimal. It is also possible that readily leachable As is not present in significant quantities within the sediments of the study area. Thus, for similar plumes of process-affected groundwater in shallow sand aquifers which may occur as oil sands mining expands, a reasonable expectation is for NA persistence, but minimal trace metal mobilization.     

Degassing of H/He, CFCs and SF6 by denitrification: Measurements and two-phase transport simulations

The production of N₂ gas by denitrification may lead to the appearance of a gas phase below the water table prohibiting the conservative transport of tracer gases required for groundwater dating. We used a two-phase flow and transport model (STOMP) to study the reliability of ³H/³He, CFCs and SF₆ as groundwater age tracers under agricultural land where denitrification causes degassing. We were able to reproduce the amount of degassing (R² = 69%), as well as the ³H (R² = 79%) and ³He (R² = 76%) concentrations observed in a ³H/³He data set using simple 2D models. We found that the TDG correction of the ³H/³He age overestimated the control ³He/³He age by 2.1 years, due to the accumulation of ³He in the gas phase. The total uncertainty of degassed ³H/³He ages of 6 years (± 2 σ) is due to the correction of degassed ³He using the TDG method, but also due to the travel time in the unsaturated zone and the diffusion of bomb peak ³He. CFCs appear to be subject to significant degradation in anoxic groundwater and SF₆ is highly susceptible to degassing. We conclude that ³H/³He is the most reliable method to date degassed groundwater and that two-phase flow models such as STOMP are useful tools to assist in the interpretation of degassed groundwater age tracer data.     

Chemical and ecotoxicological analyses of sediments and elutriates of contaminated rivers due to e-waste recycling activities using a diverse battery of bioassays

A multi-trophic, multi-exposure phase assessment approach was applied to characterize the toxicity of sediments collected from two rivers in Guiyu, China, an e-waste recycling centre. Elutriate toxicity tests (bacterium Vibrio fischeri and microalga Selenastrum capricornutum) and whole sediment toxicity test (crustacean Heterocypris incongruens) showed that most sediments exhibited acute toxicity, due to elevated heavy metals and PAHs levels, and low pH caused by uncontrolled acid discharge. The survival rates of crustaceans were negatively (p < 0.05) correlated with total PAHs in sediments (411-1755 mg kg⁻¹); EC50s of V. fischeri on the elutriates were significantly correlated with elutriate pH (p < 0.01). Significant (p < 0.05) correlations between the induction of hepatic metallothionein in tilapia (Oreochromis mossambicus) and metal concentrations (Cu, Zn, Pb) in sediments were also observed, when fish were fed with diets containing sediment. The results showed that uncontrolled e-waste recycling activities may bring adverse effects to local aquatic ecosystem.     

Batch sorption dynamics and equilibrium for the removal of lead ions from aqueous phase using activated carbon developed from coffee residue activated with zinc chloride

Lignocellulosic materials are good precursors for the production of activated carbon. In this work, coffee residue has been used as raw material in the preparation of powder activated carbon by the method of chemical activation with zinc chloride for the sorption of Pb(II) from dilute aqueous solutions.The influence of impregnation ratio (ZnCl₂/coffee residue) on the physical and chemical properties of the prepared carbons was studied in order to optimize this parameter. The optimum experimental condition for preparing predominantly microporous activated carbons with high pore surface area (890 m²/g) and micropore volume (0.772 cm³/g) is an impregnation ratio of 100%. The developed activated carbon shows substantial capability to sorb lead(II) ions from aqueous solutions and for relative impregnation ratios of 75 and 100%, the maximum uptake is practically the same. Thus, 75% represents the optimal impregnation ratio.Batch experiments were conducted to study the effects of the main parameters such as contact time, initial concentration of Pb(II), solution pH, ionic strength and temperature. The maximum uptake of lead(II) at 25 °C was about 63 mg/g of adsorbent at pH 5.8, initial Pb(II) concentration of 10 mg/L, agitation speed of 200 rpm and ionic strength of 0.005 M. The kinetic data were fitted to the models of pseudo-first order and pseudo-second order, and follow closely the pseudo-second order model. Equilibrium sorption isotherms of Pb(II) were analyzed by the Langmuir, Freundlich and Temkin isotherm models. The Freundlich model gives a better fit than the others.Results from this study suggest that activated carbon produced from coffee residue is an effective adsorbent for the removal of lead from aqueous solutions and that ZnCl₂ is a suitable activating agent for the preparation of high-porosity carbons.     

Application of lime and calcium hypochlorite in the dephenolisation and discolouration of olive mill wastewater

The application of hypochlorite for the removal of soluble COD, phenolic and polyphenolic like compounds, and other organic compounds responsible for the olive mill wastewater (OOWW) colour has been experimentally studied. After the OOWW filtration on a sand column, the effluent was subjected to a fast liming under optimal conditions. Lime application reduced polyphenols, COD and SS contents to half of their initial values but an important blackening of the treated OOWW was observed, especially when adding high concentrations of lime (10% (W/V) and 15% (W/V)).A second stage of treatment was applied using calcium hypochlorite. In this stage, removal of the studied compounds reached as much as 95% at higher concentrations, and particularly the colouring of OOWW which is generally difficult to eliminate was greatly reduced. The OOWW hypochloration acted through coagulation–flocculation and a rapid oxidation of the organic matter proceeded from the first 5 min. The kinetic study of the degradation of the waste polluting compounds from liming showed that Ca(ClO)₂ reacts similarly in the elimination of organic compounds, polyphenols, SS and colouration. The analysis of the organochloride compounds generated by the reaction between hypochlorite and the organic compounds showed that DDD, DDT and the heptachlor contents exceeded the values recommended by the International and European drinking water standards.     

The whole relationship between environmental variables and firm performance: Competitive advantage and firm resources as mediator variables

The examination of the possible direct link between environmental protection and firm performance in the literature has generally produced mixed results. The present paper contributes to the literature by using the resource-based view as a mediating process in this relationship. The study specifically tests whether or not the resource-based view of the firm mediates the positive relationships of proactive environmental management and improved environmental performance with competitive advantage, which also has consequences for financial performance. We also check the possible link between the adoption of a pioneering approach and good environmental management practices. Our findings support that early investment timing and intensity in environmental issues impact on the adoption of a proactive environmental management, which in turn helps to improve environmental performance. The findings also show that a firm's resources and competitive advantage act as mediator variables for a positive relationship between environmental protection and financial performance. This contribution is original because the present paper develops a comprehensive whole picture of this path process, which has previously only been partially discussed in the literature. In addition, this study clarifies a relevant point in the literature, namely that the effect of environmental protection on firm performance is not direct and can vary depending on the sector considered. Whereas competitive advantage in relation to costs influences financial performance in the IPPC law sector, the relevant influence in the hotel sector comes from competitive advantage through differentiation.