Influence of the zeta potential on the sorption and toxicity of iron oxide nanoparticles on S. cerevisiae and E. coli.

The influence of the zeta potential on the sorption between microorganisms (Saccharomyces cerevisiae and Escherichia coli) and iron oxide nanoparticles is demonstrated in a model salt solution at two different pH-values. There was only a 1% survival rate of E. coli (4.5 x 10(7)cells/mL) in the presence of 24 mg/L nanoparticulate iron oxide at pH 4. S. cerevisiae were less affected by the presence of the nanoparticulate iron oxide. The extent of iron oxide nanoparticle coverage on the surface of the microorganisms appears to be related to electrostatic interaction forces. Furthermore, the toxic effect of the nanoparticle concentration follows the sorption isotherm for E. coli. Based on the resulting hydrodynamic size distributions in the supernatant after sorption experiments, it could be shown that predominantly smaller particle aggregates oxide were sorbed onto E. coli. This was evident by a shift in the particle size distribution towards a larger mean particle size. The effect was observed to a lower extent for S. cerevisiae. The extent of iron oxide nanoparticle sorption on E. coli quickly reached a maximum and remained constant during a 24 h period compared to S. cerevisiae where sorption increased over time.

Fate of steroid estrogens in Australian inland and coastal wastewater treatment plants.

A comparison of estrone (E1), 17beta-estradiol (E2), and 17alpha-ethinylestradiol (EE2) removal at a coastal enhanced primary and inland advanced sewage treatment plant (STP) is reported. The average concentration of estrogens in the raw sewage is similar to that reported in other studies. The sequential batch reactor at the advanced STP removed on average 85% of the incoming E1 and 96% of the E2. Further removal was observed during later microfiltration with the estrogen concentration below detection (<0.1 ng x L(-1)) after reverse osmosis. Some 6% of the influent E1+E2 was removed in the waste activated sludge. The detection of EE2 in the waste activated sludge (0.42 ng x g(-1) solids dry weight), undetectable in the raw sewage, suggests that EE2 is resistant to biological treatment in the sequential batch reactor and is primarily removed due to sorption. Little estrogen removal was observed at the enhanced primary with only 7% of E1 and 0% of E2 removed. Low removal is expected based on the degree of estrogens partitioning in the organic fraction given the relatively low solids concentration, but surprisingly, some 43% of E2, 24% of E1, and 100% of EE2 remains associated with the solids fraction in the treated effluent. Further research is necessary to determine whether the low level of estrogen removal for the coastal treatment plant will adversely affect the receiving marine environment.

Quantification of the oxidizing capacity of nanoparticulate zero-valent iron.

Addition of nanoparticulate zero-valent iron (nZVI) to oxygen-containing water results in oxidation of organic compounds. To assess the potential application of nZVI for oxidative transformation of organic contaminants, the conversion of benzoic acid (BA) to p-hydroxybenzoic acid (p-HBA) was used as a probe reaction. When nZVI was added to BA-containing water, an initial pulse of p-HBA was detected during the first 30 min, followed by the slow generation of additional p-HBA over periods of at least 24 h. The yield of p-HBA increased with increasing BA concentration, presumably due to the increasing 'ability of BA to compete with alternate oxidant sinks, such as ferrous iron. At pH 3, maximum yields of p-HBA during the initial phase of the reaction of up to 25% were observed. The initial rate of nZVI-mediated oxidation of BA exhibited a marked reduction at pH values above 3. Despite the decrease in oxidant production rate, p-HBA was observed during the initial reaction phase at pH values up to 8. Competition experiments with probe compounds expected to exhibit different affinities for the nZVI surface (phenol, aniline, o-hydroxybenzoic acid, and synthetic humic acids) indicated relative rates of reaction that were similar to those observed in competition experiments in which hydroxyl radicals were generated in solution. Examination of the oxidizing capacity of a range of Fe0 particles reveals a capacity in all cases to induce oxidative transformation of benzoic acid, but the high surface areas that can be achieved with nanosized particles renders such particles particularly effective oxidants.

Oxidative degradation of the carbothioate herbicide, molinate, using nanoscale zero-valent iron.

Degradation of the carbothiolate herbicide, molinate, has been investigated in oxic solutions containing nanoscale zero-valent iron particles and found to be effectively degraded by an oxidative pathway. Both ferrous iron and superoxide (or, at pH < 4.8, hydroperoxy) radicals appearto be generated on corrosion of the zero-valent iron with resultant production of strongly oxidizing entities capable of degrading the trace contaminant.

Household dust metal levels in the Sydney metropolitan area.

Household dust was collected from 82 residential homes within the Sydney metropolitan area. The geometric mean concentrations of metals in the household dust were Cd, 1.9 microg/g; Cr, 64.3 microg/g; Cu, 103 microg/g; Fe, 2740 microg/g; Mn, 54 microg/g; Ni, 15.6 microg/g; Pb, 85.2 microg/g; and Zn, 437 microg/g. Differences in household income level, dwelling type, or the number of occupants were not statistically significant for the majority of metals. The exceptions were higher amounts of Zn (P=0.033) and Fe (P=0.047) found in households with only 1-2 residents compared to those with 3-4 or >4 residents, and slightly higher Mn levels (P=0.033) were found in low-income households (AUD 0-30,000 dollars/year). Region was highly significant for Pb levels in Sydney but not significant for other metals. Large variations in Pb levels were found in household dust (16-16,600 microg/g), with the inner-west region associated with significantly higher Pb levels (P<0.001). Comparisons with a study from a decade earlier have revealed that the household dust Pb levels have remained constant despite substantial improvements in air quality in the inner-west area of Sydney. New epidemiological studies are required to determine whether Pb blood levels have also remained unchanged and whether accumulated Pb in household dust represents a significant health risk to children in this region.

Kinetic modeling of TiO2-catalyzed photodegradation of trace levels of microcystin-LR.

A kinetic model has been developed to investigate the relative importance of major pathways for the photocatalytic degradation of trace levels of the cyanobacterial toxin microcystin-LR (MLR) in solutions containing a complex suite of dissolved organic matter and to test the sensitivity of MLR degradation to rate constants of the key processes. The kinetic model incorporates adsorption of the trace contaminant, other organics and oxygen on the particle surface, surface reactions between adsorbed radical and nonradical species, desorption of surface radical species, solution phase radical reactions, and radical termination pathways. Under conditions where the contaminant adsorbs strongly to semiconductor surface sites, rapid degradation is observed, and a primary degradation step appears to involve reaction between surface-located long-lived organic radicals (formed from hydroxyl radical scavenging by the bulk organic) and adsorbed trace contaminant. MLR degradation is relatively insensitive to changes in light intensity under these strongly adsorbing conditions but highly dependent under weakly adsorbing conditions and when solution phase degradation is important. While not verified independently, desorption of surface bound superoxide appears to lead to the production of organic peroxyl radicals through reaction of superoxide with the bulk organic. These solution phase organic peroxyl radicals are highly reactive and appear to be the primary source of trace contaminant degradation under conditions where the trace contaminant shows no observable adsorption and surface degradation is negligible. Under alkaline conditions, adsorption of carbonate onto the particle surface results in scavenging of surface hydroxyl radicals to form surface carbonate radicals that rapidly quench surface bound superoxide. This prevents organic peroxyl production, the primary agent of solution-phase trace contaminant degradation.

Photo-Fenton degradation of dichloromethane for gas phase treatment.

A continuous photo-Fenton process has been used for the degradation of gaseous dichloromethane (DCM). By absorbing gaseous DCM into a reactive Fenton mixture, the scrubbing and degradation processes could be completed in the one reactor. Operating with a Dark Fenton solution did not result in removal of DCM any better than simply using MilliQ water. This was because the Fe(II) quickly converted to Fe(III) but was unable to regenerate. After a short time, the Fenton process was no longer operating and the DCM quickly accumulated in the reaction solution, preventing further accumulation due to a decreasing concentration gradient in the reactive solution. However, by using UV light and increasing the retention time from 20 to 50 s, there was sufficient time for the reactive solution to regenerate and continuous operation could achieve at least 65% removal of DCM from the gaseous phase at ambient temperature.

Absence of detectable levels of the cyanobacterial toxin (microcystin-LR) carry-over into milk.

The potential for the carry-over of the cyanobacterial toxin, microcystin-LR, from feed to milk was assessed using four Holstein-Friesian cows in a 4 week feeding trial. Two cows were used as control and the other two dosed daily at increasing weekly concentrations of microcystins from zero to a maximum dosage of 13 microg toxin kg x (-1) d x (-1) (or 7.4 mg toxin day(-1)). The absence of any deviation from the control in terms of physiological response and plasma indicators (total bilirubin, gamma-glutamyl transpeptidase and alkaline phosphatase) suggests that the microcystin-LR dosage did not have a detrimental effect on cattle liver function or milk yield during the course of the study. While the milk production did decrease over the period of the trial, no difference was observed between control and dosed cattle. Protein phosphatase inhibition assays were successfully used to determine the presence of microcystin-LR in prepared milk samples with an average recovery of 88% for samples spiked with 0.6 microg x l(-1) microcystin-LR. The level of microcystin-LR in all milk samples during the trial was less than 0.2 microg x l(-1). This suggests that after digestion, microcystin--LR is either not present in milk or sufficiently modified to render it non-toxic.