Uranium sorption on various forms of titanium dioxide--influence of surface area, surface charge, and impurities

Titanium dioxide (TiO(2)) has often served as a model substrate for experimental sorption studies of environmental contaminants. However, various forms of Ti-oxide have been used, and the different sorption properties of these materials have not been thoroughly studied. We investigated uranium sorption on some thoroughly characterized TiO(2) surfaces with particular attention to the influence of surface area, surface charge, and impurities. The sorption of U(VI) differed significantly between samples. Aggressive pretreatment of one material to remove impurities significantly altered the isoelectric point, determined by an electroacoustic method, but did not significantly impact U sorption. Differences in sorption properties between the various TiO(2) materials were related to the crystallographic form, morphology, surface area, and grain size, rather than to surface impurities or surface charge. In-situ attenuated total reflection Fourier-transform infrared (ATR FT-IR) spectroscopic studies showed that the spectra of the surface species of the TiO(2) samples are not significantly different, suggesting the formation of similar surface complexes. The data provide insights into the effect of different source materials and surface properties on radionuclide sorption.     

Tertiary-treated municipal wastewater is a significant point source of antibiotic resistance genes into Duluth-Superior Harbor

In this study, the impact of tertiary-treated municipal wastewater on the quantity of several antibiotic resistance determinants in Duluth-Superior Harbor was investigated by collecting surface water and sediment samples from 13 locations in Duluth-Superior Harbor, the St. Louis River, and Lake Superior. Quantitative PCR (qPCR) was used to target three different genes encoding resistance to tetracycline (tet(A), tet(X), and tet(W)), the gene encoding the integrase of class 1 integrons (intI1), and total bacterial abundance (16S rRNA genes) as well as total and human fecal contamination levels (16S rRNA genes specific to the genus Bacteroides ). The quantities of tet(A), tet(X), tet(W), intI1, total Bacteroides , and human-specific Bacteroides were typically 20-fold higher in the tertiary-treated wastewater than in nearby surface water samples. In contrast, the quantities of these genes in the St. Louis River and Lake Superior were typically below detection. Analysis of sequences of tet(W) gene fragments from four different samples collected throughout the study site supported the conclusion that tertiary-treated municipal wastewater is a point source of resistance genes into Duluth-Superior Harbor. This study demonstrates that the discharge of exceptionally treated municipal wastewater can have a statistically significant effect on the quantities of antibiotic resistance genes in otherwise pristine surface waters.     

Glucose prevents citrate metabolism by enterococci

Enterococcus faecalis FAIR E-239, growing on glucose plus citrate, metabolized citrate at pH 6.5 or 7.5, but only when glucose had been exhausted; it did not metabolize citrate at pH 5.5 or 8.5. When grown on citrate only, the strain metabolized citrate at all pH values, and two growth rates were apparent. Citrate was mainly metabolized during the second, much slower growth rate. Glucose also inhibited citrate metabolism by E. faecalis FAIR E-237 and FAIR E-259 and Enterococcus faecium FAIR E-338 and FAIR E-371. Glucose-grown resting cells were unable to metabolize citrate. Citrate-grown resting cells had a pH optimum of 4.7 for citrate metabolism but also metabolized significant amounts of citrate at pH 4.2 and 6.5. Resting stationary phase cells used citrate more rapidly than resting log phase cells. Citrate metabolism was faster at citrate levels <10 mM than above 10 mM. These results suggest that some form of catabolite repression is occurring.     

Role of soil freezing events in interannual patterns of stream chemistry at the Hubbard Brook Experimental Forest,New Hampshire

Soil freezing is a disturbance of the below ground environment, potentially resulting in increased losses of NO3- and surface water acidification. Here, we report the effects of soil freezing on interannual variation in stream chemistry at the Hubbard Brook Experimental Forest, New Hampshire. Data from 1970 to 1997 of soil frost depth, snow cover, precipitation, air temperature, and stream discharge and chemistry were used in a stepwise linear regression model to select the variables that best predicted deviations of annual stream concentrations from 4-year running averages. Variables quantifying soil freezing severity were selected as significant predictors of short-term fluctuations in stream K+, NO3-, Ca2+, and Mg2+ concentrations from 1970 to 1989, explaining 59 and 47% of the short-term variability in K+ and NO3-, respectively. Fine-root mortality and disturbance of root-soil-microbe interactions, with subsequent effects on decomposition and nutrient uptake, likely contributed to the mobilization of K+ and NO3- to streamwater following severe soil freezing events. The relationship between soil freezing and stream chemistry, however, weakened during the period 1990-1997. Because soil freezing has had inconsistent effects on stream chemistry during the period 1970-1997, it is unclear whether future changes in the frequency, duration, and depth of soil freezing events as the result of changes in the snow cover regime under a warmer climate will have significant impacts on the losses of NO3- and nutrient-base cations from temperate northern ecosystems.     

Demonstration of a method for the direct determination of polycyclic aromatic hydrocarbons in submerged sediments

We describe the development of a novel method for real-time in situ characterization of polycyclic aromatic hydrocarbons (PAHs) in submerged freshwater sediments. Laser-induced fluorescence (LIF) spectroscopy, a mature technique for PAH characterization in terrestrial sediments, was adapted for shipboard use. A cone penetrometer-type apparatus was designed for probe penetration at a constant rate (1 cm/s) to a depth of 3 m. A field-portable LIF system was used for in situ measurements in which the output of a pulsed excimer laser was transmitted by optical fiber to a sapphire window (6.4-mm o.d.) in the probe wall; fluorescent emission was collected by a separate optical fiber for transmission to the spectrometer on deck. Four wavelengths (340, 390, 440, 490 nm) were selected via optical delay lines, and multiple-wavelength waveforms were created. These multiple-wavelength waveforms contain information on the fluorescence frequency, intensity, and emission decay rate. Field testing was conducted at 10 sites in Milwaukee Harbor (total PAH concentrations ranged from approximately 10 to 650 microg/g); conventional sediment core samples were collected concurrently. The core samples were analyzed by EPA methods 3545 (pressurized fluid extraction, PFE) and 8270C (gas chromatography-mass spectrometry, GC-MS) for PAHs. A partial least-squares regression (PLSR) model wasthen created based on laboratory LIF measurements and PFE-GC-MS of the core samples. The PLSR model was applied to the in situ field test data, and 13 of the 16 EPA-regulated PAHs were quantified with a relative error of <30% overall (the remaining three PAHs were found at levels insufficient to quantify). We additionally describe preliminary source apportionment relationships that were revealed by the PLSR model for the in situ LIF measurements.     

Reductive debromination of polybrominated diphenyl ethers in anaerobic sediment and a biomimetic system

Because of the bioaccumulation of penta- and tetrapolybrominated diphenyl ether (PBDE) flame retardants in biota,the environmental biotransformation of decabromodiphenyl ether (BDE-209) is of interest. BDE-209 accounts for more than 80% by mass of PBDE production and is the dominant PBDE in sediments. Most sediments are anaerobic and reports of microbial reductive dehalogenation of hydrophobic persistent organohalogen pollutants are numerous. Reductive debromination of BDE-209 in the environment could provide a significant source of lesser-brominated PBDEs to biota. Moreover, a recent study showed that BDE-209 debrominates in sewage sludge, and another demonstrated that some halorespiring bacteria will debrominate BDE-209. To determine whether reductive debromination of BDE-209 occurs in sediments, parallel experiments were conducted using anaerobic sediment microcosms and a cosolvent-enhanced biomimetic system. In the biomimetic system, reductive debromination occurred at rates corresponding to bromine substitution levels with a BDE-209 half-life of only 18 s compared with a halflife of almost 60 days for 2,2',4,4'-tetrabromodiphenyl ether. In sediment, the measured debromination half-life of BDE-209 was well over a decade and was in good agreement with the predicted value obtained from the biomimetic experiment. Product congeners were predominantly double para-substituted. BDE-209 debrominated in sediment with a corresponding increase in nona-, octa-, hepta-, and hexa-PBDEs. Nine new PBDE congeners appeared in sediment from reductive debromination. Given the very large BDE-209 burden already in sediments globally, it is important to determine whether this transformation is a significant source of lesser-brominated PBDEs to the environment.     

Impact of electronic waste disposal on lead concentrations in landfill leachate

Lead is the element most likely to cause discarded electronic devices to be characterized as hazardous waste. To examine the fate of lead from discarded electronics in landfills, five columns were filled with synthetic municipal solid waste (MSW). A mix of electronic devices was added to three columns (6% by weight), while two columns served as controls. A sixth column contained waste excavated from an existing MSW landfill. Leachate quality was monitored for 440 days. In columns with the synthetic waste, leachate pH indicated that the simulated landfill environment was characteristic of the acid phase of waste decomposition; lead leachability should be greater in the acid phase of landfill degradation as compared to the methanogenic phase. Lead concentrations ranged from 7 to 66 microg/L in the columns containing electronic waste and ranged from < 2 to 54 microg/L in the control columns. Although the mean lead concentrations in the columns containing electronic devices were greater than those in the controls, the difference was not found to be statistically significant when comparing the data sets over the entire monitoring period. Lead results from the excavated waste column suggest that lead concentrations in all columns will decrease as the pH increases toward more neutral methanogenic conditions.     

Curcumin and the cellular stress response in free radical-related diseases

Free radicals play a main pathogenic role in several human diseases such as neurodegenerative disorders, diabetes, and cancer. Although there has been progress in treatment of these diseases, the development of important side effects may complicate the therapeutic course. Curcumin, a well known spice commonly used in India to make foods colored and flavored, is also used in traditional medicine to treat mild or moderate human diseases. In the recent years, a growing body of literature has unraveled the antioxidant, anticarcinogenic, and antinfectious activity of curcumin based on the ability of this compound to regulate a number of cellular signal transduction pathways. These promising data obtained in vitro are now being translated to the clinic and more than ten clinical trials are currently ongoing worldwide. This review outlines the biological activities of curcumin and discusses its potential use in the prevention and treatment of human diseases.     

Selenoprotein deficiency enhances radiation-induced micronuclei formation

The availability of selenium and the levels of specific selenoproteins might affect cancer risk by influencing the ability of DNA damaging agents to cause genomic instability and mutations. Transgenic mice that express reduced levels of selenoproteins and previously shown to be more susceptible to pathology associated with cancer development were used to study this possibility. These mice were exposed to X-rays and DNA damage assessed in the erythrocytes, where micronuclei formation was higher compared to the same cells obtained from irradiated wild-type controls. To determine whether the selenoprotein glutathione peroxidase-1 (GPx-1) might be involved in this protection, its levels were reduced by siRNA targeting in LNCaP human prostate cells. UV-induced micronuclei frequency was higher in these cells compared to control-transfected cells. These results indicate a role for selenoproteins in protecting DNA from damage and support human data implicating GPx-1 as a possible target of the chemoprotective effect of selenium.