Sorption of polycyclic aromatic compounds to humic and fulvic acid HPLC column materials

Two different humic acids (HA) and a fulvic acid (FA) were chemically immobilized to a high performance liquid chromatography (HPLC) silica column material. The immobilization was performed by binding amino groups in HA/FA to the free aldehyde group in glutardialdehyde attached to the silica gel. The HPLC column materials were compared with a blank column material made by applying the same procedure but without immobilizing HA or FA. Also, a column was made by binding carbonyl groups in HA to amino groups attached to the silica gel. The humic substances were selected to secure appropriate variation of their structural features. The retention factors of 45 polycyclic aromatic compounds (PAC) to the four columns were determined by HPLC. The advantage of the technique is a large number of compounds can easily be studied. The binding procedure does not appear to cause a drastic selection between the HA molecules. The k' values obtained for the two Aldrich HA columns agree in general reasonably. The retention or sorption of the compounds increased with the size of the PAC and the number of lipophilic substituents, but decreased when polar substituents were present. The PAC retention was much stronger to the two HA columns than to the FA and blank column, both for hydrophobic polycyclic aromatic hydrocarbons (PAH) and the polar PAC. Other factors impacting the PAC binding may be specific interactions with HA and the ionic strength of the aqueous phase. The technique has been applied to do direct determinations of Koc.     

Heavy metal anomalies in lagoon sediments related to intensive agriculture in Altata-Ensenada del Pabellón coastal system (SE Gulf of California)

Heavy metal concentrations were examined in surface sediments from 79 sites within the Altata-Ensenada del Pabellon lagoon system. Data were normalized to separate natural from anthropogenic factors using aluminum and lithium as conservative elements and following two different discriminating criteria. For the normalization process, the natural metal concentrations were assumed to vary consistently with aluminum and lithium, unless the metal contents were of human origin. Strong linear correlations (P < .001) were observed between the conservative elements and the metals measured. According to Szefer's normalizing criteria, about 90% of the polluted sites, for at least one metal, occurred near agricultural discharge drains. In accordance with the Muller [Umschau 79 (1979) 778.] scale, this lagoon system is subject to pollutant effects only with regard to Pb (moderately to strongly polluted). It was concluded that either Al and Li could be useful to normalize granulometric variability in heavy metal studies of these lagoon sediments, and that Summers' normalization criterion proved more rigorous than Szefer's for these types of sediments.     

Lightning Fires in a Brazilian Savanna National Park: Rethinking Management Strategies

Fire occurrences and their sources were monitored in Emas National Park, Brazil (17°49′–18°28′S; 52°39′–53°10′W) from June 1995 to May 1999. The extent of burned area and weather conditions were registered. Forty-five fires were recorded and mapped on a GIS during this study. Four fires occurred in the dry winter season (June–August; 7,942 ha burned), all caused by humans; 10 fires occurred in the seasonally transitional months (May and September) (33,386 ha burned); 31 fires occurred in the wet season, of which 30 were caused by lightning inside the park (29,326 ha burned), and one started outside the park (866 ha burned). Wet season lightning fires started in the open vegetation (wet field or grassy savanna) at a flat plateau, an area that showed significantly higher fire incidence. On average, winter fires burned larger areas and spread more quickly, compared to lightning fires, and fire suppression was necessary to extinguish them. Most lightning fires were patchy and extinguished primarily by rain. Lightning fires in the wet season, previously considered unimportant episodes, were shown to be very frequent and probably represent the natural fire pattern in the region. Lightning fires should be regarded as ecologically beneficial, as they create natural barriers to the spread of winter fires. The present fire management in the park is based on the burning of preventive firebreaks in the dry season and exclusion of any other fire. This policy does not take advantage of the beneficial effects of the natural fire regime and may in fact reduce biodiversity. The results presented here stress the need for reevaluating present policies and management procedures concerning fire in cerrado conservation areas.     

Pilot‐scale evaluation using bioaugmentation to enhance PCE dissolution at dover AFB national test site

An Interstate Technology and Regulatory Council (ITRC) forum was recently held that focused on six case studies in which bioremediation of dense nonaqueous‐phase liquids (DNAPLs) was performed; the objective was to demonstrate that there is credible evidence for bioremediation as a viable environmental remediation technology. The first two case studies from the forum have been previously published; this third case study involves a pilot‐scale demonstration that investigated the effects of biological activity on enhancing dissolution of an emplaced tetrachloroethene (PCE) DNAPL source. It used a controlled‐release test cell with PCE as the primary DNAPL in a porous media groundwater system. Both laboratory tests and a field‐scale pilot test demonstrated that bioaugmentation can stimulate complete dechlorination to a nontoxic end product and that the mass flux from a source zone increases when biological dehalorespiration activity is enhanced through nutrient (electron donor) addition and bioaugmentation. All project goals were met. Important achievements include demonstrating the ability to degrade a PCE DNAPL source to ethene and obtaining significant information on the impacts to the microbial populations and corresponding isotope enrichments during biodegradation of a source area. © 2007 Wiley Periodicals, Inc.     

Remediation with cyclodextrin: Recovery of the remedial agent by membrane filtration

Cyclodextrin‐enhanced flushing of contaminants from the subsurface is a promising innovative remediation technology. It will become more economically viable at more sites if methods can be developed to recover and reconcentrate the cyclodextrin solution after it has been flushed through an aquifer. The goal of this study was to determine if membrane technology is capable of meeting that need. Five membranes with different material properties were tested for this purpose in the laboratory. The results of these tests indicate that there are large differences both in the efficiency of these membranes to extract hydroxpropyl‐β‐cyclodextrin (HPCD) and their stability when exposed to trichloroethylene (TCE) at concentrations near aqueous solubility. Not only does the molecular weigh cutoff (MWCO) of a membrane determine if HPCD can be retained, but crucial selection criteria are the membrane's resistance and compatibility with TCE. Of the five membrane materials tested, only two (polymer composite membrane and polysulfone) met both these requirements. The polymer composite membrane (MPF‐44) showed reliable and stable HPCD recoveries (>95 percent) even when exposed to high TCE concentrations. The polysulfone membrane showed high HPCD recoveries, 88.5 ± 0.4 percent to 97 percent ±1 percent for ultrafiltration and nanofiltration membranes, respectively. However, membrane swelling and deterioration became a problem at high TCE concentrations (>1,000 mg/L). These problems diminished when the TCE concentration was less than 1 mg/L. Field tests demonstrated that batch mode treatment by ultrafiltration doubled the cyclodextrin concentration from 5 to 10 percent within three hours at a constant operating pressure of 13 psi. Under continuous single‐pass treatment conditions, cyclodextrin concentration also increased, although the rate of increase was much smaller than in batch mode. Overall, these tests showed that cyclodextrin recovery is possible under field conditions. © 2007 Wiley Periodicals, Inc.     

Thermal and hydrometallurgical recovery methods of heavy metals from municipal solid waste fly ash

Heavy metals in fly ash from municipal solid waste incinerators are present in high concentrations. Therefore fly ash must be treated as a hazardous material. On the other hand, it may be a potential source of heavy metals. Zinc, lead, cadmium, and copper can be relatively easily removed during the thermal treatment of fly ash, e.g. in the form of chlorides. In return, wet extraction methods could provide promising results for these elements including chromium and nickel. The aim of this study was to investigate and compare thermal and hydrometallurgical treatment of municipal solid waste fly ash. Thermal treatment of fly ash was performed in a rotary reactor at temperatures between 950 and 1050 °C and in a muffle oven at temperatures from 500 to 1200 °C. The removal more than 90% was reached by easy volatile heavy metals such as cadmium and lead and also by copper, however at higher temperature in the muffle oven. The alkaline (sodium hydroxide) and acid (sulphuric acid) leaching of the fly ash was carried out while the influence of temperature, time, concentration, and liquid/solid ratio were investigated. The combination of alkaline-acidic leaching enhanced the removal of, namely, zinc, chromium and nickel.     

The liver but not the skin is the site for conversion of a red carotenoid in a passerine bird

Carotenoids may provide numerous health benefits and are also responsible for the integumentary coloration of many bird species. Despite their importance, many aspects of their metabolism are still poorly known, and even basic issues such as the anatomical sites of conversion remain controversial. Recent studies suggest that the transformation of carotenoid pigments takes place directly in the follicles during feather growth, even though the liver has been previously recognised as a storing organ for these pigments with a certain potential for conversion. In this context, we analysed the carotenoid profile of plasma, liver, skin and feathers of male Common Crossbills (Loxia curvirostra). Interestingly, the derivative feather pigment 3-hydroxy-echinenone was detected in the liver and in the bloodstream (i.e. the necessary vehicle to transport metabolites to colourful peripheral tissues). Our results demonstrate for the first time with empirical data that the liver may act as the main site for the synthesis of integumentary carotenoids. This finding contradicts previous assumptions and raises the question of possible inter-specific differences in the site of carotenoid conversion in birds.     

Shifts in Microbial Communities, Microbial Biomass and Organic Matter Mineralization for Three Mediterranean Soils Contaminated By Metals

Microbial communities (phospholipid fatty acid pattern, bacterial growing strategies, eco-physiological index (EPI) and total bacteria counts, as a number of heterotrophic cuhurable bacteria), substrate-induced respiration (SIR), and nitrogen mineralization were studied in three Mediterranean soils at three different depth levels (A, B and C). Soils were experimentally treated with a final concentration of 1000 ppm of trace metals (Cu²⁺, Zn²⁺, Al³⁺, Fe²⁺, Pb²⁺, Ni²⁺, Mn²⁺, Cr³⁺ and Cd²⁺). Soils were stored in 571 plastic containers for one year, and watered with 1001 during this period. Leachate was recovered through a bottom tap. Samples of the three depths were studied. Soil microbial communities showed different effects to other studies presented in the literature, but carried out on non-Mediterranean soils. Dramatic differences were found between treated soils and untreated ones, but not between soils or horizons. the treated soil displayed a decrease in CFUs, SIR N-mineralization and EPI together with a dominance of r-growing strategists. the relative moles percent of several PLFAs, especially 15:0, 16: 1ω7, cy17: 0, br18:0 and 18: 1ω7 decreased because of the pollution of soils, whereas 10Me16, 18:2ω6, cy19:0, i16:0 and br17:0 showed higher values than in untreated soils.