The removal of lignin and phenol from paper mill effluents by electrocoagulation

This study aims to investigate the treatment of paper mill effluents using electrocoagulation. Removal of lignin, phenol, chemical oxygen demand (COD) and biological oxygen demand (BOD) from paper mill effluents was investigated at various current intensities by using different electrodes (Al and Fe) and at various electrolysis times (1.0, 2.5, 5.0 and 7.5min). It was observed that the experiments carried out at 12V, an electrolysis time of 2min and a current intensity of 77.13mA were sufficient for the removal of these pollutants with each electrode. The removal capacities of the process using an Al electrode were 80% of lignin, 98% of phenol, 70% of BOD, and 75% of COD after 7.5min. Using an Fe electrode the removal capacities were 92%, 93%, 80% and 55%, respectively. In addition, it was found that removal of lignin, phenol, BOD and COD increased with increasing current intensity. In the experiments carried out at different current intensities, higher removal can be explained through a decrease in intra-resistance of solution and consequently an increase at the transfer speed of organic species to electrodes. It was also found that Al electrode performs higher efficiency than Fe electrode except for COD removal. However, the time required for removal of BOD was more than that of COD. The results suggest that electrocoagulation could be considered as an effective alternative to paper mill effluents treatment.     

Invasion of Pinus halepensis Mill. following a wildfire in an Argentine grassland nature reserve

The Ernesto Tornquist nature reserve is a relict of native Pampas vegetation in Argentina. Alien trees were introduced to the reserve in the 1950s, mainly to "improve" the natural landscape, resulting in the arrival of a totally new life form. In 1987, a fire affected an area planted with Pinus halepensis resulting in its massive expansion. In 1999, we removed trees from 17 circular plots of 10 m diameter placed systematically within the area that was colonized after the fire. Trunks were cut 20 cm from the ground and growth rings were counted. We studied the age structure of the population in order to reconstruct the colonizing events after the fire. We found that recruitment occurred throughout this period, except in the three years after the disturbance. We suggest that this delay in recruitment might be caused by low seedling survival under water stress conditions due to low rainfall, combined with scarce vegetation cover after fire. This could have been associated with an initial reduction in propagule pressure due to the scarcity of surviving trees in the vicinity and with the fact that fire occurred after the peak of seed release, during an extremely dry summer, probably killing a great number of seeds that were already in the soil. In the following years, recruitment was probably aided by pioneer trees and later by seeds shed from established pines. Alien trees had been allowed to reach maturity due to wildfire prevention and control in the years preceding the fire and the accumulated dry matter resulted in increased fire intensity that reduced the ability of grasses to re-sprout. As a consequence, the invasion window that allowed the expansion of pines remained open for at least 12 years.     

Coupling a 3D patch model and a rockfall module to assess rockfall protection in mountain forests

Many forests in the Alps are acknowledged for protecting objects, such as (rail) roads, against rockfall. However, there is a lack of knowledge on efficient silvicultural strategies and interventions to maintain these forests at optimal protection level. Therefore, assessment tools are required that quantify the rockfall protection effect of forest stands over time, and thereby provide the ability to evaluate the necessity and effect of management interventions. This paper introduces such a tool that consists of a 3D rockfall module embedded in the patch based forest simulator PICUS. The latter is extended for this study with a new regeneration module. In a series of experiments the new combined simulation tool is evaluated with regard to parameter sensitivity, model intercomparison experiments with recently proposed algorithms from the literature, and the ability to respond realistically to different management regimes in rockfall protection forests. Results confirm the potential of the new tool for realistic simulation of rockfall activity in heterogeneous mountain forests, but point at the urgent need to improve the knowledge base on the interaction of understory and rockfall activity. Further work will focus on model validation against empirical rockfall data, and include reduced tree vitality due to damage from boulder collisions as well as the explicit consideration of downed dead wood.     

Baseline assessment for environmental services payments from satellite imagery: a case study from Costa Rica and Mexico

In this study we evaluate the accuracy of four global and regional forest cover assessments (MODIS, IGBP, GLC2000, PROARCA) as tools for baseline estimation. We conduct this research at the national scale for Costa Rica and for two tropical dry forest study sites in Costa Rica (Santa Rosa) and Mexico (Chamela-Cuixmala). We found that at the national level, the total forest cover accuracy of the four land cover maps was inflated due to an overestimation of forest in areas with an evergreen canopy. However, the four maps greatly underestimated the extent of the deciduous forest (dry forest); an ecosystem that faces high deforestation pressure and poses complications to the mapping of its extent from remotely sensed data. For the tropical dry forest sites, all maps have low forest cover accuracies (mean for Santa Rosa: 27%; mean for Chamela-Cuixmala: 56%). This has implications for policy implementation.     

The Contribution of Marsh Zones to Water Quality in Dutch Shallow Lakes: A Modeling Study

Many lakes have experienced a transition from a clear into a turbid state without macrophyte growth due to eutrophication. There are several measures by which nitrogen (N) and phosphorus (P) concentrations in the surface water can be reduced. We used the shallow lake model PCLake to evaluate the effects of three measures (reducing external nutrient loading, increasing relative marsh area, and increasing exchange rate between open water and marsh) on water quality improvement. Furthermore, the contribution of different retention processes was calculated. Settling and burial contributed more to nutrient retention than denitrification. The model runs for a typical shallow lake in The Netherlands showed that after increasing relative marsh area to 50%, total phosphorous (TP) concentration in the surface water was lower than the Maximum Admissible Risk (MAR, a Dutch government water quality standard) level, in contrast to total nitrogen (TN) concentration. The MAR levels could also be achieved by reducing N and P load. However, reduction of nutrient concentrations to MAR levels did not result in a clear lake state with submerged vegetation. Only a combination of a more drastic reduction of the present nutrient loading, in combination with a relatively large marsh cover (approximately 50%) would lead to such a clear state. We therefore concluded that littoral marsh areas can make a small but significant contribution to lake recovery.     

Field scale characterization and modeling of contaminant release from a coal tar source zone

A coal tar contaminated site was characterized using traditional and innovative investigation methods. A careful interpretation of hydrogeological and hydrogeochemical data allowed for the conceptualization of the heterogeneous coal tar distribution in the subsurface. Past and future contaminant release from the source zone was calculated using a modeling framework consisting of a three-dimensional steady-state groundwater flow model (MODFLOW) and two hydrogeochemical models (MIN3P). Computational time of long-term simulations was reduced by simplifying the coal tar composition using 3 composite and 2 individual constituents and sequential application of a 2D centerline model (for calibration and predictions) and a 3D model (only for predictions). Predictions were carried out for a period of 1000 years. The results reveal that contaminant mass flux is governed by the geometry of zones containing residual coal tar, amount of coal tar, its composition and the physicochemical properties of the constituents. The long-term predictions made using the 2D model show that even after 1000 years, source depletion will be small with respect to phenanthrene, 89% of initial mass will be still available, and for the moderately and sparingly soluble composite constituents, 60% and 98%, respectively.     

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.     

Non-Fickian dispersion in a single fracture

Solute transport in fractured rocks is of major interest in many applications, from the petroleum industry to ground water management. This work focuses on the dispersion process in a transparent replica of a real single fracture. The fracture exhibits strong changes in heterogeneity, with the first half very heterogeneous and the second half fairly homogeneous. Three models have been used to interpret the tracer experiments: the classical advection-dispersion equation (ADE), the continuous time random walk (CTRW), and the stratified model. The main goals were to test these models and to study possible correlations between fitting parameters and heterogeneities. As expected, the solution derived from the ADE equation appears to be unable to model long-time tailing behavior. On the other hand, the results confirm the CTRW robustness and the coefficient beta seems well correlated to heterogeneities. Finally, the stratified model is also able to describe non-Fickian dispersion. The parameters defined by this model are correlated to the heterogeneities of the fracture.     

Long-term oxygen depletion from infiltrating groundwaters: model development and application to intra-glaciation and glaciation conditions

Processes that control the redox conditions in deep groundwaters have been studied. The understanding of such processes in a long-term perspective is important for the safety assessment of a deep geological repository for high-level nuclear waste. An oxidising environment at the depth of the repository would increase the solubility and mobility of many radionuclides, and increase the potential risk for radioactive contamination at the ground surface. Proposed repository concepts also include engineered barriers such as copper canisters, the corrosion of which increases considerably in an oxidising environment compared to prevailing reducing conditions. Swedish granitic rocks are typically relatively sparsely fractured and are best treated as a dual-porosity medium with fast flowing channels through fractures in the rock with a surrounding porous matrix, the pores of which are accessible from the fracture by diffusive transport. Highly simplified problems have been explored with the aim to gain understanding of the underlying transport processes, thermodynamics and chemical reaction kinetics. The degree of complexity is increased successively, and mechanisms and processes identified as of key importance are included in a model framework. For highly complex models, analytical expressions are not fully capable of describing the processes involved, and in such cases the solutions are obtained by numerical calculations. Deep in the rock the main source for reducing capacity is identified as reducing minerals. Such minerals are found inside the porous rock matrix and as infill particles or coatings in fractures in the rock. The model formulation also allows for different flow modes such as flow along discrete fractures in sparsely fractured rocks and along flowpaths in a fracture network. The scavenging of oxygen is exemplified for these cases as well as for more comprehensive applications, including glaciation considerations. Results show that chemical reaction kinetics control the scavenging of oxygen during a relatively short time with respect to the lifetime of the repository. For longer times the scavenging of oxygen is controlled by transport processes in the porous rock matrix. The penetration depth of oxygen along the flowpath depends largely on the hydraulic properties, which may vary significantly between different locations and situations. The results indicate that oxygen, in the absence of easily degradable organic matter, may reach long distances along a flow path during the life-time of the repository (hundreds to thousands of metres in a million years depending on e.g. hydraulic properties of the flow path and the availability of reducing capacity). However, large uncertainties regarding key input parameters exist leading to the conclusion that the results from the model must be treated with caution pending more accurate and validated data. Ongoing and planned experiments are expected to reduce these uncertainties, which are required in order to make more reliable predictions for a safety assessment of a nuclear waste repository.     

Degradation rates of CFC-11, CFC-12 and CFC-113 in anoxic shallow aquifers of Araihazar, Bangladesh

Chlorofluorocarbons CFC-11 (CCl(3)F), CFC-12 (CCl(2)F(2)), and CFC-113 (CCl(2)F-CClF(2)) are used in hydrology as transient tracers under the assumption of conservative behavior in the unsaturated and saturated soil zones. However, laboratory and field studies have shown that these compounds are not stable under anaerobic conditions. To determine the degradation rates of CFCs in a tropical environment, atmospheric air, unsaturated zone soil gas, and anoxic groundwater samples were collected in Araihazar upazila, Bangladesh. Observed CFC concentrations in both soil gas and groundwater were significantly below those expected from atmospheric levels. The CFC deficits in the unsaturated zone can be explained by gas exchange with groundwater undersaturated in CFCs. The CFC deficits observed in (3)H/(3)He dated groundwater were used to estimate degradation rates in the saturated zone. The results show that CFCs are degraded to the point where practically no (<5%) CFC-11, CFC-12, or CFC-113 remains in groundwater with (3)H/(3)He ages above 10 yr. In groundwater sampled at our site CFC-11 and CFC-12 appear to degrade at similar rates with estimated degradation rates ranging from approximately 0.25 yr(-1) to approximately 6 yr(-1). Degradation rates increased as a function of reducing conditions. This indicates that CFC dating of groundwater in regions of humid tropical climate has to be carried out with great caution.