Modified Fenton reaction for trichlorophenol dechlorination by enzymatically generated H2O2 and gluconic acid chelate

Glucose oxidase is a well-known enzyme that catalyzes the oxidation of β-d-glucose to produce gluconic acid and hydrogen peroxide. Fenton reaction is a powerful oxidation technology used for the oxidation of groundwater pollutants. For the application of Fenton reaction in groundwater remediation, successful operation of Fenton reaction near neutral pH, and on-site generation of both H₂O₂ and chelate will be beneficial. The focus of this experimental study was to couple the glucose oxidation reaction with chelate-based Fenton reaction. The idea was to use the hydrogen peroxide and chelate gluconic acid generated during glucose oxidation for the dechlorination of 2,4,6-trichlorophenol (TCP) by Fenton reaction. The oxidation of glucose was achieved using the enzyme in free and immobilized forms. The rate of production of hydrogen peroxide was determined for each system, and was used to estimate the time required for complete consumption of glucose during the process, thus avoiding any traces of glucose in the Fenton reaction. In the case of free enzyme reaction, separation of the enzyme was achieved using an ultrafiltration membrane before initiating the Fenton reaction. The oxidation of TCP by Fenton reaction was performed at varying ratios of gluconic acid/Fe, and its effect on the decomposition of TCP and H₂O₂ was studied. TCP degradation was studied both in terms of parent compound degradation and free chloride generation.     

The impact of agroforestry combined with water harvesting on soil carbon and nitrogen stocks in central Chile evaluated using the ICBM/N model

Soil organic carbon (SOC) and total nitrogen (N) stocks in an agroforestry system with water harvesting were analysed in a field experiment and the results compared with those of other crop management systems in the Mediterranean zone of central Chile. Agroforestry with water harvesting showed higher positive effects on N stocks, mainly in the upper soil layer, than the other crop management systems. However, soil analysis revealed a lack of differences between treatments, a fact that might be related mainly to the short study time (12 years) and the high spatial variability in these soil properties at the experimental site. In addition, the Introductory Carbon Balance Model that simulates N processes (ICBM/N) was evaluated for simulating trends in SOC and N stocks in the field experiment. Soil data collected between 1996 and 2008 in the field experiment and primarily literature data sets were used to test ICBM/N and its performance was evaluated by considering uncertainty in model inputs using Generalised Likelihood Uncertainty Estimation (GLUE) methodology. The GLUE estimates (5% and 95%) and measured SOC and N stocks were in satisfactory agreement. The observed SOC and N stocks were bracketed by the uncertainty bands in 70% and 80% of the simulations, respectively. Sensitivity analysis showed the model to be most sensitive to C parameters, such as the humification coefficient (h). The results of this study show that ICBM/N can be an effective tool for estimating SOC and N stocks from agroforestry combined with water harvesting systems in the Mediterranean zone of central Chile over the medium term. However, they also indicate that additional data sets are needed to redefine the parameter distributions in the model and thus to predict trends in SOC and N stocks in the future.     

Effect of variations in the redox potential of Gleysol on barium mobility and absorption in rice plants

Two assays were designed to obtain information about the influence of redox potential variations on barium mobility and bioavailability in soil. One assay was undertaken in leaching columns, and the other was conducted in pots cultivated with rice (Oryza sativa) using soil samples collected from the surface of Gleysol in both assays. Three doses of barium (100,300 mg kg⁻¹ and 3000 mg kg⁻¹-soil dry weight) and two redox potential values (oxidizing and reducing) were evaluated. During the incubation period, the redox potential (Eh) was monitored in columns and pots until values of −250 mV were reached. After the incubation period, geochemical partitioning was conducted on the barium using the European Communities Bureau of Reference (BCR) method. Rainfall of 200 mm d⁻¹ was simulated in the columns and in the planting of rice seedlings in the pots. The results of the geochemical partitioning demonstrated that the condition of reduction favors increased barium concentrations in the more labile chemical forms and decreased levels in the chemical forms related to oxides. The highest barium concentrations in leached extracts (3.36 mg L⁻¹) were observed at the highest dose and condition of reduction at approximately five times above the drinking water standard. The high concentrations of barium in the soil did not affect plant dry matter production. The highest levels and accumulation of barium in roots, leaves, and grains of rice were found at the highest dose and condition of reduction. These results demonstrate that reduction leads to solubilization of barium sulfate, thereby favoring greater mobility and bioavailability of this element.     

An investigation on the physical,chemical and ecotoxicological characteristics of particulate matter emitted from light-duty vehicles

Particulate matter (PM) emitted from three light-duty vehicles was studied in terms of its physicochemical and ecotoxicological character using Microtox^® bioassay tests. A diesel vehicle equipped with an oxidation catalyst emitted PM which consisted of carbon species at over 97%. PM from a diesel vehicle with a particle filter (DPF) consisted of almost equal amounts of carbon species and ions, while a gasoline vehicle emitted PM consisting of ～90% carbon and ～10% ions. Both the DPF and the gasoline vehicles produced a distinct nucleation mode at 120 km/h. The PM emitted from the DPF and the gasoline vehicles was less ecotoxic than that of conventional diesel, but not in direct proportion to the emission levels of the different vehicles. These results indicate that PM emission reductions are not equally translated into ecotoxicity reductions, implying some deficiencies on the actual environmental impact of emission control technologies and regulations.     

Past and future changes in Canadian boreal wildfire activity

Climate change in Canadian boreal forests is usually associated with increased drought severity and fire activity. However, future fire activity could well be within the range of values experienced during the preindustrial period. In this study, we contrast 21st century forecasts of fire occurrence (FireOcc, number of large forest fires per year) in the southern part of the Boreal Shield, Canada, with the historical range of the past 240 years statistically reconstructed from tree-ring width data. First, a historical relationship between drought indices and FireOcc is developed over the calibration period 1959-1998. Next, together with seven tree-ring based drought reconstructions covering the last 240 years and simulations from the CGCM3 and ECHAM4 global climate models, the calibration model is used to estimate past (prior to 1959) and future (post 1999) FireOcc. Last, time-dependent changes in mean FireOcc and in the occurrence rate of extreme fire years are evaluated with the aid of advanced methods of statistical time series analysis. Results suggest that the increase in precipitation projected toward the end of the 21st century will be insufficient to compensate for increasing temperatures and will be insufficient to maintain potential evapotranspiration at current levels. Limited moisture availability would cause FireOcc to increase as well. But will future FireOcc exceed its historical range? The results obtained from our approach suggest high probabilities of seeing future FireOcc reach the upper limit of the historical range. Predictions, which are essentially weighed on northwestern Ontario and eastern boreal Manitoba, indicate that, by 2061-2100, typical FireOcc could increase by more than 34% when compared with the past two centuries. Increases in fire activity as projected by this study could negatively affect the implementation in the next century of forest management inspired by historical or natural disturbance dynamics. This approach is indeed feasible only if current and future fire activities are sufficiently low compared with the preindustrial fire activity, so a substitution of fire by forest management could occur without elevating the overall frequency of disturbance. Conceivable management options will likely have to be directed toward minimizing the adverse impacts of the increasing fire activity.     

Assessment of the contribution of land use pattern and intensity to landscape quality: use of a landscape indicator

The objective of this research work is the evaluation of the impact of landuse pattern and intensity on landscape by means of an indicator. The method used to calculate a ‘landscape indicator’ (I_land) allows to take into account the objective as well as the subjective approach of landscape. I_land corresponds to the degree of agreement between landscape supply by farmers and landscape demand by the social groups. The supply and the demand are evaluated through four criteria: ‘diversity’, ‘upkeep’, ‘openness’ and ‘heritage’. The landscape supply is calculated from data of landscape objects (punctual, linear and spatial) for each criterion recorded at the field level. The values of the four criteria for the landscape demand are allocated by the user(s) of the indicator (decision makers, regional council, social groups…) into five classes (0–4). The value of the landscape indicator is the least favourable difference between supply and demand for the four criteria. An example of calculation of the ‘landscape indicator’ for an arable farm is given. The collection of data needs 2 h with the farmer and 2 h for a survey of the farm land.     

Catalytic combustion of soot over ceria-zinc mixed oxides catalysts supported onto cordierite

Modified substrates as outer heterogeneous catalysts was employed to reduce the soot generated from incomplete combustion of diesel or diesel/biodiesel blends, a process that harms the environment and public health. The unique storage properties of ceria(CeO2) makes it one of the most efficient catalysts available to date. Here, we proposed that ceria-based catalysts can lower the temperature at which soot combustion occurs; more specifically, from 610℃ to values included in the diesel exhausts operation range(300–450℃). The sol-gel method was used to synthesize mixed oxide-based catalysts(CeO2:ZnO); the resulting catalysts were deposited onto cordierite substrates. In addition, the morphological and structural properties of the material were evaluated by XRD, BET, TPR-H2, and SEM. Thermogravimetric(TG/DTA) analysis revealed that the presence of the catalyst decreased the soot combustion temperature by 200℃ on average, indicating that the oxygen species arise at low temperatures in this situation, promoting highly reactive oxidation reactions. Comparative analysis of soot emission by diffuse reflectance spectroscopy(DRS) showed that catalyst-impregnated cordierite samples efficiently oxidized soot in a diesel/biodiesel stationary motor: soot emission decreased by more than 70%.     

Vegetation structure constrains primary production response to water availability in the Patagonian steppe

Grassland aboveground net primary production (ANPP) increases linearly with precipitation in space and time, but temporal models relating time series of ANPP and annual precipitation for single sites show lower slopes and regression coefficients than are shown by spatial models. The analysis of several ANPP time series showed lags in the ecosystem response to increased water availability, which may explain the difference between spatial and temporal models. The lags may result from constraints that ecosystems experience after drought. Our objective was to explore the structural constraints of the ANPP response to rainfall variability in a semiarid ecosystem, the Patagonian steppe, in southern Argentina. We designed a 3-yr rainfall manipulation experiment where we decreased water input with rainout shelters during two consecutive years, which included three levels of rainfall interception (30%, 55%, and 80%) and a control. In the third year, we irrigated one-half of the plots of each rainfall-interception treatment. We evaluated the immediate effects of drought on current-year ANPP and the effects of previous-year drought on vegetation recovery after water supplementation. ANPP (g x m(-2) x yr(-1)) was linearly related to annual precipitation input (APPT; mm/yr) along the experimental precipitation gradient (ANPP = 0.13 x APPT + 58.3; r2 = 0.34, P < 0.01), and this relationship was mostly accounted for by changes in the ANPP of grasses. Plant density (D; no. individuals/mm2) was related to the precipitation received during the drought period (D = 0.11 x APPT + 18; r2 = 0.39, P < 0.05). The recovery of plants after irrigation was lower for those plots that had experienced experimental drought the previous years relative to controls, and the lags were proportional to the intensity of drought. Therefore, our results suggest that the density of plants may constrain the recovery of vegetation after drought, and these constraints may determine lags that limit the capacity of the ecosystem to take advantage of wet years after dry years.     

Analysis of Cleaner Production Practices in a Printing Company in Brazil

This article presents an analysis of the application of a cleaner production program within a Brazilian printing company and describes its specific characteristics to propose a benchmark for similar efforts at other companies. As a result, a very number of improvement opportunities (136) were identified, indicating that the printing industry needs to make reasonable, collective efforts to ensure that companies' environmental systems reach international marks.