Photo-oxidation of cork manufacturing wastewater

Several photo-activated processes have been investigated for oxidation of a cork manufacturing wastewater. A comparative activity study is made between different homogeneous (H2O2/UV-Vis and H2O2/Fe2+/UV-Vis) and heterogeneous (TiO2/UV-Vis and TiO2/H2O2/UV-Vis) systems, with degradation performances being evaluated in terms of total organic carbon (TOC) removal. Results obtained in a batch photo-reactor show that photo-catalysis with TiO2 is not suitable for this kind of wastewater while the H2O2/UV-Vis oxidation process, for which the effect of some operating conditions was investigated, allows to remove 39% of TOC after 4 h of operation (for C(H2O2)=0.59 M, pH=10 and T=35 degrees C). The combined photo-activated process, i.e., using both TiO2 and H2O2, yields an overall TOC decrease of 46% (for C(TiO2)=1.0 gl(-1)). The photo-Fenton process proved to be the most efficient, proceeds at a much higher oxidation rate and allows to achieve 66% mineralization in just 10 min of reaction time (for C(H2O2)=0.31 M, T=30 degrees C, Fe2+:H2O2=0.12 (mol) and pH=3.2).     

Effect of landfill leachate irrigation on red maple (Acer rubrum L.) and sugar maple (Acer saccharum Marsh.) seedling growth and on foliar nutrient concentrations

Greenhouse experiments were conducted to investigate the nature and severity of stresses imposed on northern hardwood tree species (red maple (Acer rubrum L.) and sugar maple (Acer saccharum Marsh.)) by the application of municipal landfill leachate. Red maple seedlings received applications of untreated and pretreated (lime, activated carbon) leachate, to both leaves and soil, at irrigation rates consistent with evapotranspirational demands. Plant height measurements indicated no significant growth effects arising from leachate application over a 7-week period. Stem diameter, however, was positively affected by applications of both untreated and lime-treated leachate diluted to 75% with deionized water. Iron foliar concentrations were significantly higher in seedlings irrigated with untreated leachate applied to leaves and soil, but not in seedlings where leachate was applied to soil only. Nitrogen foliar concentrations were substantially higher in seedlings receiving undiluted and untreated leachate applied to the soil only. The Cu concentration of the red maple foliage decreased appreciably in plants receiving moderate applications of leachate. Foliar Ca concentrations decreased notably in seedlings irrigated with untreated leachate applied to the soil and with diluted, carbon-treated leachate. The Cu concentration of the red maple foliage decreased appreciably in plants receiving applications of undiluted and 50% water-diluted lime-treated leachate while Mn levels were consistently high across all treatments. Leachate application did not cause any discernable changes in foliar concentrations of P, K, Mg, B or Zn. In an ancillary experiment, sugar maple seedlings were subjected to saturation/ drainage treatment cycles with undiluted and untreated leachate. Severe visible symptoms of vegetative stress were apparent within 24 h and 100% seedling mortality occurred after five such waterlogging cycles. Fe assimilation was apparent in both leachate treatments relative to the 24 h water treatment. Despite the short-term nature of the experiments, the results indicate how quickly forest vegetation may respond to altered chemical environments. This underscores the need for correct installation and control of leachate irrigation systems.     

Nitric oxide formation in an iron oxide pellet rotary kiln furnace

A one-dimensional numerical model was developed to simulate the effects of heat and mass transfer on the formation of oxides of nitrogen (NOx) in a rotary kiln furnace for iron oxide pellet induration. The modeled kiln has a length-to-diameter ratio of approximately seven. The principal mechanism of heat transfer is radiation from the flame, which was described by the net radiation method. The well known Zeldovich mechanism was used to predict thermal NOx generation. Temperature fluctuations in the vicinity of the flame were estimated with a clipped Gaussian probability density function. The thermal energy and mass balance model equations were solved numerically. The model is capable of predicting temperature profiles and NOx production rates in agreement with observed plant performance. The model was used to explore the effects of process changes on the total NOx formation in the kiln. It was concluded that the gas temperature as well as the partial pressure of oxygen in the process gases controls the rate of NOx formation. Lowering the temperature of the kiln gases by increasing the secondary air flow rates requires simultaneously decreasing the pellet production rate in order to maintain the pellet temperatures needed for blast furnace conditions.     

Environmental cadium exposure and metabolic responses of the Nile tilapia, Oreochromis niloticus

The contamination of water by metal compounds is a worldwide environmental problem. This study was undertaken to evaluate the impact of short-term cadmium exposure on metabolic patterns of the freshwater fish Oreochromis niloticus. The fish were exposed to 320, 640, 1,280 and 2,560 microg/l sublethal concentrations of Cd++ (CdCl2) in water for 7 days. The specific activities of the enzymes phosphofructo kinase (PFK-E.C.2.7.1.11.), lactate dehydrogenase (LDH-E.C.1.1.1.27.) and creatine kinase (CKE.C.2.7.3.2.) were decreased in white muscle after cadmium treatments, indicating decreases in the capacity of glycolysis in this tissue. Cadmium exposure induced increased glucose concentration in white muscle of fish. On the other hand, cadmium exposure at sublethal concentrations increased phosphofructo kinase and LDH in red muscle of fish. Cadmium significantly decreased total protein concentrations in liver and white muscle regardless of tissue glycogen levels. The data suggest that cadmium acts as a stressor, leading to metabolic alterations similar to those observed in starvation.     

Effect of pH on the aggregation of a gray humic acid in colloidal and solid states

The potential of triethylenetetramine (TETA) to inhibit the oxidation of three pyrrhotites, Garson, McCreedy and Po-97 has been studied systematically and confirmed by comparing the release of Fe and SO4(2-) from samples with and without coating treatment. Each sample, original or coated by TETA, was exposed to oxygen, 1 x 10(-3) M FeCl3, and Acidithiobacillus ferrooxidans, respectively, for specific oxidation periods. Both abiotic and biotic oxidation of samples treated by this passivating agent has been reduced significantly in this study. Under the aerobic condition, lower concentrations of ferric, total Fe or SO4(2-) were obtained from the coated samples than those from the uncoated samples. In the presence of 1 x 10(-3) M FeCl3 at 30 degrees C, TETA was able to reduce oxidation rates of Garson, McCreedy and Po-97 by 83%, 79%, and 81% (based on Fe release), respectively. A higher pH, lower Eh, and lower concentrations of total Fe and SO4(2-) were also observed in the biotic oxidation of coated Garson by Acidithiobacillus ferrooxidans. The protection of pyrrhotite surface from oxidant attack by TETA barrier and the alkaline property of this coating agent can be used to interpret the inhibition of oxidation.     

Hazard identification and risk assessment procedure for genetically modified plants in the field--GMHAZID

The safe application of genetically modified organisms (GMOs) requires a risk assessment prior to their proposed use. Based on methods from the chemical industry, we developed a hazard identification procedure for the risk assessment of field tests with genetically modified plants. This risk assessment method, GMHAZID, is carried out in the form of guided brainstorm sessions. GMHAZID was tested with a case study for which a risk assessment had previously been made, and the results of the assessments were compared. The results showed that some new hazards potentially leading to uncontrolled spreading, in addition to those from the previous assessment, were identified using GMHAZID. GMHAZID also recognised some hazards leading to failures in the field experiments. We suggest that GMHAZID provides systematics, reliability, and transparency to the risk assessment procedure.     

Isotopic fractionation during reductive dechlorination of trichloroethene by zero-valent iron: influence of surface treatment

During reductive dechlorination of trichloroethene (TCE) by zero-valent iron, stable carbon isotopic values of residual TCE fractionate significantly and can be described by a Rayleigh model. This study investigated the effect of observed reaction rate, surface oxidation and iron type on isotopic fractionation of TCE during reductive dechlorination. Variation of observed reaction rate did not produce significant differences in isotopic fractionation in degradation experiments. However, a small influence on isotopic fractionation was observed for experiments using acid-cleaned electrolytic iron versus experiments using autoclaved electrolytic iron, acid-cleaned Peerless cast iron or autoclaved Peerless cast iron. A consistent isotopic enrichment factor of epsilon = -16.7/1000 was determined for all experiments using cast iron, and for the experiments with autoclaved electrolytic iron. Column experiments using 100% cast iron and a 28% cast iron/72% aquifer matrix mixture also resulted in an enrichment factor of -16.9/1000. The consistency in enrichment factors between batch and column systems suggests that isotopic trends observed in batch systems may be extrapolated to flowing systems such as field sites. The fact that significant isotopic fractionation was observed in all experiments implies that isotopic analysis can provide a direct qualitative indication of whether or not reductive dechlorination of TCE by Fe0 is occurring. This evidence may be useful in answering questions which arise at field sites, such as determining whether TCE observed down-gradient of an iron wall remediation scheme is the result of incomplete degradation within the wall, or of the dissolved TCE plume by passing the wall.     

Column study of the influence of air humidity on the retention of hydrocarbons on soil

Inverse gas chromatography (IGC) is used for the analysis of the influence of air relative humidity on the retention of hexane, benzene, toluene and p-xylene in a sandy soil under experimental conditions similar to those typical of soil vapor extraction (SVE). The advantages of IGC over other techniques, are (a) an efficient use of lab resources, (b) a high sensitivity to low partitioning coefficients and (c) a closer reproduction of field conditions. In our procedure, experiments with only two samples of different mass are necessary to establish if linear isotherms can be used to describe the retention of the contaminants. This approach gives information necessary for analyzing the feasibility and design of remediation technologies with a laboratory effort significantly smaller than the adsorption/desorption cycle for isotherm determination. The retention coefficients of the contaminants decrease as humidity increases in a similar fashion for all of them, probably because the reduction in the number of the adsorption sites available for the organic compounds due to the presence of water is quite similar for all the contaminants studied. These retention coefficients may be related to those obtained for dry air conditions for all the contaminants through (R - 1)RH% = A(R - 1)dry air(B), where the parameter B is found to remain approximately constant (0.90), while the parameter A decreases linearly with the relative moisture.     

Effects of ozone on three open-pollinated families of Pinus taeda L. grown in two substrates

Seedlings from three open-pollinated loblolly pine (Pinus taeda L.) families grown in a mixture of commercial peat moss and grade 3 vermiculite (1:3 by volume) or a mixture of mineral soil and peat (1:1 by volume) were exposed to 0, 160 or 320 ppb ozone (O3) for 6h/day, 4 days/week for 8 weeks beginning 12 weeks after transplanting. Before exposures began, seedlings grown in the vermiculite-peat substrate were taller but smaller in diameter than those grown in the mineral soil-peat substrate. After 8 weeks of exposure, seedlings grown in the mineral soil-peat substrate were significantly larger in diameter and total biomass than those grown in the vermiculite-peat substrate. Primary needle and secondary needle injury increased with increasing O3 concentrations. Suppression of diameter growth, shoot weight and root weight was linear as O3 concentration increased. The effect of O3 on height or diameter growth or shoot biomass was not influenced by substrate type; but the suppression of root biomass due to O3 was dependent on substrate, with greater suppression in biomass occurring in the vermiculite-peat substrate. Foliar injury due to O3 was slightly greater in family 8-103, but growth suppression due to O3 was not significantly different among the families. Based on root biomass, response of seedlings to O3 was substrate-dependent.     

Separate dissolved and particulate trace metal budgets for an estuarine system: an aid for management decisions

The sources and sinks of dissolved and particulate Pb, Cu and Zn were determined for the main basin of Puget Sound to understand the effect man has had on metal concentrations in both the water column and in the sediments. Municipal, industrial and atmospheric sources contributed about 66% of the total Pb added to the main basin of Puget Sound during the early 1980s. Advective inputs were the major sources of total Cu and Zn (approximately 40%) while riverine and erosional sources contributed about 30%. The discharge of the particle-bound trace metals from rivers minimized the influence of particulate anthropogenic sources, which constituted 50%, 23% and 18% of the total particulate Pb, Cu and Zn inputs, respectively. While advective transport was the major source of dissolved Cu and Zn (approximately 60% of all dissolved inputs), industrial, municipal and atmospheric inputs contributed about 85%, 30% and 38% of the dissolved Pb, Cu and Zn inputs, respectively. The sources of dissolved and particulate Cu and Zn were comparable with the sinks within the errors of the analyses indicating their quasi-conservative nature. Advection removed about 60% of the total Cu and Zn added to the main basin while 40% was deposited in the sediments of Puget Sound. Because of this quasi-conservative nature of Cu and Zn, anthropogenic inputs of Cu and Zn were dispersed from the system more than they were contained within main basin sediments. About 75% of the dissolved Pb discharged into the main basin of Puget Sound was lost from the dissolved phase and was balanced by a similar gain in the particulate phase. Because of this extensive scavenging and the effective retention of particles within the main basin, about 70% of the total Pb added to the main basin was retained within its sediments. These separate mass balances have utility in management decisions because they show the relative contributions from different sources and demonstrate whether the influences of dissolved and particulate inputs are reflected solely in the water column or the sediments, respectively.