Removal of PCB-DNAPL from a rough-walled fracture using alcohol/polymer flooding

Phase behaviour experiments employing PCB (Aroclor 1242)/alcohol/water systems were conducted with ethanol (EtOH) and n-propanol (nPA). Both exhibited an affinity for the aqueous phase within the entire two-phase region. As much as 88% by volume (88% vol.) EtOH and 80% vol. nPA were necessary to achieve full miscibility of the PCB in the aqueous phase. DNAPL-water interfacial tension (IFT) was reduced from 38.9 dyn/cm to 4.7 dyn/cm and 2.4 dyn/cm with 80% vol. EtOH and 76% vol. nPA. The addition of alcohol brought about 41% and 54% reductions in DNAPL viscosity at maximal concentrations of EtOH and nPA. Density of the PCB-DNAPL was relatively unaffected by the presence of alcohol. A series of seven experiments were conducted where successive slugs of nPA and xanthan gum polymer solutions were injected into a fractured shale sample. A 30% vol. nPA solution injected under a hydraulic gradient of 0.36 allowed enhanced PCB removal primarily through reduction of IFT and resulted in 72% DNAPL recovery. Several pore volumes of alcohol solution were necessary to displace all the potentially mobile non-wetting phase since the high-viscosity DNAPL was mobilized at a lower flow rate than the overall fluid velocity, illustrating non-piston displacement. The injection of a 95% vol. nPA alcohol solution, theoretically at a sufficient concentration to produce fully miscible displacement of the residual DNAPL at equilibrium, resulted in non-equilibrium partitioning of the PCB into the flushing solution, likely due to the high fluid velocities in the fracture. The injection of 200 pore volumes of 95% vol. nPA solution resulted in 94% DNAPL recovery. Alcohol floods operated below the miscibility envelope appear to be a valuable source zone remedial alternative where the objective is to reduce DNAPL mobility to zero, but it should be noted that DNAPL mobility is increased during the application of the technology and steps may need to be taken to prevent unwanted vertical mobilization.     

In situ and laboratory bioassays using Poecilia reticulata Peters, 1859 in the biomonitoring of an acidic lake at Camaçari, BA, Brazil

The suitability and viability of acute in situ bioassays were investigated in the biomonitoring program of an acidic lake contaminated with sulphur residues. Responses of organisms observed in laboratory and in situ bioassays were also assessed to determine whether or not they were similar and comparable, regarding accuracy and precision. Newborn Poecilia reticulata were employed as test organisms and exposed to the same water samples under in situ and laboratory conditions. Mortality/immobility was the endpoint assessed and dead/immobile organisms were counted at various time intervals during exposure. The mean calculated LT50 values and 95% confidence intervals were 1.61 (1.36-1.87) h in the laboratory bioassays and 0.72 (0.55-0.89) h in the in situ bioassays. Statistical comparison of these values revealed a significant difference (p<0.05). In situ bioassays were more accurate than those carried out in the laboratory, demonstrating higher sensitivity and better reproduction of what occurs in nature, while laboratory bioassays were more precise.     

Genotypic variations in the accumulation of Cd, Cu, Pb and Zn exhibited by six commonly grown vegetables

Metal contaminants in garden and allotment soils could possibly affect human health through a variety of pathways. This study focused on the potential pathway of consumption of vegetables grown on contaminated soil. Five cultivars each of six common vegetables were grown in a control and in a soil spiked with Cd, Cu, Pb and Zn. Highly significant differences in metal content were evident between cultivars of a number of vegetables for several of the contaminants. Carrot and pea cultivars exhibited significant differences in accumulated concentrations of Cd and Cu with carrot cultivars also exhibiting significant differences in Zn. Distinctive differences were also identified when comparing one vegetable to another, legumes (Leguminosae) tending to be low accumulators, root vegetables (Umbelliferae and Liliaceae) tending to be moderate accumulators and leafy vegetables (Compositae and Chenopodiaceae) being high accumulators.     

Bagasse-assisted bioremediation of ammonia from shrimp farm wastewater.

Development of new economically feasible ecofriendly products from agricultural wastes or byproducts for shrimp farm wastewater treatment is the objective of our continued research. Ammonia is a nitrogenous toxicant, which is commonly found in wastewater from shrimp farms. In the present study, we explored the possibility of the use of simply and inexpensively prepared bagasse products so that this abundant crop byproduct could be used to remove ammonia from shrimp farm wastewater. Bagasse, a natural highly fibrous lignocellulosic byproduct of sugarcane, was converted into five different products. Experimental results have shown that ammonia is efficiently removed from wastewater by four bagasse products with a dose of 1 to 6 g/L within 24 hours. The effect of bagasse products on other water quality parameters and growth kinetics of biofilm bacteria onto bagasse fiber have also been studied. Efficacies of products were compared by using statistical analysis. Products developed from bagasse are useful and economical.     

Quality assured measurements of animal building emissions: gas concentrations

Comprehensive field studies were initiated in 2002 to measure emissions of ammonia (NH3), hydrogen sulfide (H2S), carbon dioxide (CO2), methane (CH4), nonmethane hydrocarbons (NMHC), particulate matter <10 microm in diameter, and total suspended particulate from swine and poultry production buildings in the United States. This paper focuses on the quasicontinuous gas concentration measurement at multiple locations among paired barns in seven states. Documented principles, used in air pollution monitoring at industrial sources, were applied in developing quality assurance (QA) project plans for these studies. Air was sampled from multiple locations with each gas analyzed with one high quality commercial gas analyzer that was located in an environmentally controlled on-farm instrument shelter. A nominal 4 L/min gas sampling system was designed and constructed with Teflon wetted surfaces, bypass pumping, and sample line flow and pressure sensors. Three-way solenoids were used to automatically switch between multiple gas sampling lines with > or =10 min sampling intervals. Inside and outside gas sampling probes were between 10 and 115 m away from the analyzers. Analyzers used chemiluminescence, fluorescence, photoacoustic infrared, and photoionization detectors for NH3, H2S, CO2, CH4, and NMHC, respectively. Data were collected using personal computer-based data acquisition hardware and software. This paper discusses the methodology of gas concentration measurements and the unique challenges that livestock barns pose for achieving desired accuracy and precision, data representativeness, comparability and completeness, and instrument calibration and maintenance.     

Long-term comparison of trace organics removal performances between conventional and membrane activated sludge processes.

The removal of trace organic compounds through membrane bioreactors (MBR) compared with a conventional wastewater treatment plant (WWTP) in a long-term study was investigated. Two MBR pilot plants were operated in parallel to a full-scale WWTP fed with the same municipal raw wastewater. Polar compounds (phenazone-type pharmaceuticals, their metabolites, and carbamazepine) and less polar estrogenic steroids (estradiol, estrone, and ethinylestradiol) were quantified. The removal rate of phenazone, propyphenazone, and formylaminoantipyrine by the conventional WWTP was less than 15%. Significantly higher removal rates (60 to 70%) started to be clearly monitored in the pilot plants after approximately 5 months. Higher removal rates coincided with higher temperatures in the summer. The conventional WWTP removed, on average, more than 90% of the natural steroids estrone and estradiol and approximately 80% of the synthetic ethinylestradiol. Approximately 99% of estradiol and estrone and approximately 95% of ethinylestradiol was eliminated by the MBR processes.     

Fine route for an efficient removal of 2,4-dichlorophenoxyacetic acid (2,4-D) by zeolite-supported TiO2

Zeolites HY, Hbeta and HZSM-5 with different physico-chemical properties were chosen as support for TiO2 to illustrate their adsorption, dispersion and electronic structure in photocatalysis. The extent of TiO2 loading was monitored by XRD and BET surface area measurements. The adsorption capacity of HY zeolite was found to be high and hence chosen for further modification to continue the investigation. Photodegradation kinetics were carried out with 2,4-dichlorophenoxyacetic acid (2,4-D) in aqueous solution. The extent of 2,4-D degradation on TiO2/HY loading revealed the importance of adsorption in photocatalysis. Mineralisation studies on all three zeolites with 1 wt.% TiO2 loading demonstrated the good dispersion properties of TiO2/HY. Its photocatalytic activity was found to be excellent with formulated 2,4-D. Comparison of relative photonic efficiencies demonstrated that supported photocatalysts exhibited higher activity than some of the commercial photocatalysts. The high activity of supported TiO2 is due to synergistic effects of improved adsorption of 2,4-D and efficient delocalisation of photogenerated electrons by zeolite support.     

Histological examination of sublethal effects of diazinon on ovary of bluegill,Lepomis macrochirus

The effects of the insecticide, diazinon (an organophosphorous compound), on the ovaries of bluegill (Lepomis macrohirus) were studied. Histological preparations of bluegill ovarian tissue was examined at 24, 48, 72 and 96 h and 1, 2 and 3 weeks following exposure to sublethal doses of diazinon (60 microg/l). The control contained primary follicles with an intact ovigerous lamellae and tunica albuginea. The control also revealed well developed stage IV oocytes with properly distributed provitelline nucleoli. After 24 h of exposure to diazinon, primary follicles began to show adhesion and cytoplasmic retraction in oocyte II occured. Cytoplasmic degeneration and additional adhesion and more retraction were visible at 48 h in oocyte II; 72 h brought forth adhesion, retraction and cytoplamic expulsion from oocyte IV. The number of atretic oocytes increased. Damages to the oocyte IV started to occur after 72 h of exposure. Cytoplasmic retraction and clumping was more visible at 96 h in oocyte IV. Partial destruction of the ovigerous lamellae and vitellogenic membrane occurred after 1 week. Two weeks continued to reveal destruction of follicles. Severe damage of the ovigerous lamellae, increased intrafollicular spaces, vacuolated cytoplasm, extrusion of karyoplasm and necrosis in the cytoplasm were most evident following 3 weeks of exposure. The ovarian wall became frayed and broken. Additionally, a marked increase of atretic follicles, shrinkage, and embedded nucleoli into the surrounding cytoplasm in oocyte II, III and IV were observed at week 3. This study revealed that oocytes at their different stages of maturation get affected differently at various exposure. Based on observations of the ovarian tissue compositional and structural changes following given exposure times, it becomes evident that consistent sublethal doses of diazinon can and will alter microscopic anatomy of the fish ovary.     

Changes of copper speciation in maize rhizosphere soil

Chemical forms of copper in the rhizosphere and bulk soil of maize were investigated using rhizobox cultivation and sequential extraction techniques. The copper accumulations were also determined. The results demonstrated that there were continuous changes in copper fractionation within the maize rhizosphere. Initially, the amount of exchangeable copper increased before dropping below the initial level after 40 days or so. Carbonate associated copper followed a similar trend of change, but with a slower pace than the exchangeable copper. The increase in carbonate associated copper only become evident after 30 days, with the net loss occurring after 60 days. There were also initial increases in oxide bound copper as well as decreases in the organic matter associated copper, both followed by a turnover after 40-50 days. The accumulation of copper in the maize plant was found to be biomass dependent. The amount of accumulated copper absorbed in the plant material exceeded the initial quantity of the exchangeable copper in the soil, revealing a transformation from less bioavailable to more bioavailable fractions. During cultivation, decreases in redox potential and increases in pH, dissolved organic carbon (DOC), and microbial activity in the maize rhizosphere were observed. The change in copper speciation may result from root-induced changes in DOC, redox potential, and microbial activity in the rhizosphere.     

Uranium transport around the reactor zone at Bangombé and Okélobondo (Oklo): examples of hydrogeological and geochemical model integration and data evaluation

The sites at Bangombé and Okélobondo (Oklo) in Gabon provide a unique opportunity to study the behaviour of products from natural nuclear reactions in the vicinity of reactor zones which were active around two billion years ago. The Commission of the European Communities initiated the Oklo Natural Analogue Programme. One of the principal aims was to study indications of present time migration of elements from the reactor zones under ambient conditions. The hydrogeological and hydrochemical data from the Oklo sites were modelled in order to better understand the geochemical behaviour of radionuclides in the natural system, by using independent models and by comparing the modelling outcome. Two modelling approaches were used: M3 code (hydrochemical mixing and mass balance model), developed by the Swedish Nuclear Fuel and Waste Management Company (SKB) and HYTEC (reactive transport model) developed by Ecole des Mines de Paris. Two different reactor zones were studied: Bangombé, a shallow site, the reactor being at 11 m depth, and OK84 at Okélobondo, situated at about 450 m depth, more comparable with a real repository location. This allowed the validation of modelling tools in two different sedimentary environments: one shallow, with a more homogeneous layering situated in an area of meteoric alteration, and the other offering the opportunity to study radionuclide migration from the reaction zone over a distance of 450 m through very heterogeneous sedimentary layers. The modeling results indicate that the chemical reactions retarding radionuclide transport are very different at the two sites. At Bangombé, the decomposition of organic material consumes oxygen and at Okélobondo the oxygen is consumed by inorganic reactions resulting, in both cases, in uranium retardation. Both modelling approaches (statistic with M3 code and deterministic with HYTEC code) could describe this situation. The goal of this exercise is to test codes which can help to describe and understand the processes taking place at the sites, validate the models with in situ data, and thus build confidence in the tools used for future site characterization. Ultimately, this allows identifying and selecting processes and parameters that can be used as input into repository performance assessment calculations and modelling exercises.