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The amount of antibiotics and personal care products entering local sewage systems and ultimately natural waters is increasing and raising concerns about long-term human health effects. We developed an adsorptive photocatalyst, Cu0.5Mn0.5Fe2O4 nanoparticles, utilizing co-precipitation and calcination with melamine, and quantified its efficacy in removing paraben and oxytetracycline (OTC). During melamine calcination, Cu0.5Mn0.5Fe2O4 recrystallized, improving material crystallinity and purity for the adsorptive–photocatalytic reaction. Kinetic experiments showed that all four parabens and OTC were removed within 120 and 45 min. We found that contaminant adsorption and reaction with active radicals occurred almost simultaneously with the photocatalyst. OTC adsorption could be adequately described by the Brouers–Sotolongo kinetic and Freundlich isotherm models. OTC photocatalytic degradation started with a series of reactions at different carbon locations (i.e., decarboxamidation, deamination, dehydroxylation, demethylation, and tautomerization). Further toxicity testing showed that Zea mays L. and Vigna radiata L. shoot indexes were less affected by treated water than root indexes. The Zea mays L. endodermis thickness and area decreased considerably after exposure to the 25% (v/v)-treated water. Overall, Cu0.5Mn0.5Fe2O4 nanoparticles exhibit a remarkable adsorptive–photocatalytic performance for the degradation of tested antibiotics and personal care products.

One of the biggest challenges to treating contaminated aquifers with chemical oxidants is achieving uniform coverage of the target zone. In an effort to maximize coverage, we report the design and installation of a novel aerated, slow-release oxidant delivery system that can be installed by direct-push equipment. By continuously bubbling air beneath a slow-release oxidant in situ, an airlift pump is created that causes water and oxidant to be dispersed from the top of the outer screen and drawn in at the bottom. This continuous circulation pattern around each drive point greatly facilitates the spreading of the oxidant as it slowly dissolves from the wax matrix (i.e., oxidant candle). Given that the aeration rate controls the outward flow of oxidant from the outer screen in all directions, the radius of influence around each drive point is largely a function of the outward velocity of the oxidant exiting the screen and the advection rate opposing the upgradient and lateral spreading. Temporal sampling from three field sites treated with the aerated oxidant system are presented and results show that contaminant concentrations typically decreased 50&ndash, 99% within 6&ndash, 9 months after installation. Supporting flow tank experiments that demonstrate oxidant flow patterns and treatment efficacy are also presented.

The water quality of lakes, rivers and streams associated with metropolitan areas is declining from increased inputs of urban runoff that contain polycyclic aromatic hydrocarbons (PAHs). Our objective was to transform and mineralize PAHs in runoff using a combined chemical and biological approach. Using (14)C-labeled phenanthrene, (14)C-benzo(a)pyrene and a mixture of 16 PAHs, we found that ozone transformed all PAHs in a H2O matrix within minutes but complete mineralization to CO2 took several weeks. When urban runoff water (7.6 mg CL(-1)) replaced H2O as the background matrix, some delays in degradation rates were observed but transforming a mixture of PAHs was still complete within 10 min. Comparing the biodegradability of the ozonated products to the parent structures in unsaturated soil microcosms showed that the 3-ring phenanthrene was more biodegradable (as evidence by (14)CO2 released) than its ozonated products but for the 5-ring benzo(a)pyrene, the products produced by ozone were much more biodegradable (22% vs. 3% mineralized). For phenanthrene, we identified diphenaldehyde as the initial degradation product produced from ozonation. By continuing to pump the ozonated products ((14)C-labeled diphenaldehyde or ozone-treated benzo(a)pyrene) onto glass beads coated with microorganisms, we verified that biological mineralization could be achieved in a flow-through system and mineralization rates improved with acclimation of the microbial population (i.e., time and exposure to the substrate). These results support a combined ozone and biological approach to treating PAHs in urban runoff water.

1,4-dioxane is an emerging contaminant that was used as a corrosion inhibitor with chlorinated solvents. Metal-activated persulfate can degrade dioxane but reaction kinetics have typically been characterized by a rapid decrease during the first 30 min followed by either a slower decrease or no further change (i.e., plateau). Our objective was to identify the factors responsible for this plateau and then determine if slow-release formulations of sodium persulfate and Fe 0 could provide a more sustainable degradation treatment. We accomplished this by conducting batch experiments where Fe 0 -activated persulfate was used to treat dioxane. Treatment variables included the timing at which the dioxane was added to the Fe 0 -persulfate reaction (T = 0 and 30 min) and including various products of the Fe 0 -persulfate reaction at T = 0 min (Fe 2+ , Fe 3+ , and SO 4 2− ). Results showed that when dioxane was spiked into the reaction at 30 min, no degradation occurred; this is in stark contrast to the 60% decrease observed when added at T = 0 min. Adding Fe 2+ at the onset (T = 0 min) also severely halted the reaction and caused a plateau. This indicates that excess ferrous iron produced from the Fe 0 -persulfate reaction scavenges sulfate radicals and prevents further dioxane degradation. By limiting the release of Fe 0 in a slow-release wax formulation, degradation plateaus were avoided and 100% removal of dioxane observed. By using 14 C-labeled dioxane, we show that ∼40% of the dioxane carbon is mineralized within 6 d. These data support the use of slow-release persulfate and zerovalent iron to treat dioxane-contaminated water.

The chemical oxidant permanganate (MnO(4)(-)) has been shown to effectively transform hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) at both the laboratory and field scales. We treated RDX with MnO(4)(-) with the objective of quantifying the effects of pH and temperature on destruction kinetics and determining reaction rates. A nitrogen mass balance and the distribution of reaction products were used to provide insight into reaction mechanisms. Kinetic experiments (at pH ∼ 7, 25 °C) verified that RDX-MnO(4)(-) reaction was first-order with respect to MnO(4)(-) and initial RDX concentration (second-order rate: 4.2 × 10(-5) M(-1) s(-1)). Batch experiments showed that choice of quenching agents (MnSO(4), MnCO(3), and H(2)O(2)) influenced sample pH and product distribution. When MnCO(3) was used as a quenching agent, the pH of the RDX-MnO(4)(-) solution was relatively unchanged and N(2)O and NO(3)(-) constituted 94% of the N-containing products after 80% of the RDX was transformed. On the basis of the preponderance of N(2)O produced under neutral pH (molar ratio N(2)O/NO(3) ∼ 5:1), no strong pH effect on RDX-MnO(4)(-) reaction rates, a lower activation energy than the hydrolysis pathway, and previous literature on MnO(4)(-) oxidation of amines, we propose that RDX-MnO(4)(-) reaction involves direct oxidation of the methylene group (hydride abstraction), followed by hydrolysis of the resulting imides, and decarboxylation of the resulting carboxylic acids to form N(2)O, CO(2), and H(2)O.

A former agrichemical dealership in western Nebraska was suspected of having contaminated soil. Our objective was to characterize and remediate the contaminated site by a combined chemical-biological approach. This was accomplished by creating contour maps of the on-site contamination, placing the top 60 cm of contaminated soil in windrows and mixing with a mechanical high-speed mixer. Homogenized soil containing both atrazine [6-chloro-N-ethyl-N'-isopropyl-1,3,5-triazine-2,4-diamine] and cyanazine {2-[[4-chloro-6-(ethylamino)-1,3,5-triazin-2-yl] amino]-2-methylpropanenitrile} was then used in laboratory investigations to determine optimum treatments for pesticide destruction. Iron suspension experiments verified that zerovalent iron (Fe(0)) plus ferrous sulfate (FeSO(4).7H(2)O) removed more than 90% of both atrazine and cyanazine within 14 d. Liquid chromatography/mass spectrometry (LC/MS) analysis of the atrazine solution after treating with Fe(0) and ferrous sulfate identified several degradation products commonly associated with biodegradation (i.e., deethlyatrazine (DEA), deisopropylatrazine (DIA), hydroxyatrazine (HA), and ammelines). Biological treatment evaluated emulsified soybean [Glycine max (L.) Merr.] oil (EOS) as a carbon source to stimulate biodegradation in static soil microcosms. Combining emulsified soybean oil with the chemical amendments resulted in higher destruction efficiencies (80-85%) and reduced the percentage of FeSO(4) needed. This chemical-biological treatment (Fe(0) + FeSO(4) + EOS, EOS Remediation, Raleigh, NC) was then applied with water to 275 m(3) of contaminated soil in the field. Windrows were tightly covered with clear plastic to increase soil temperature and maintain soil water content. Temporal sampling (0-342 d) revealed atrazine and cyanazine concentrations decreased by 79 to 91%. These results provide evidence that a combined chemical-biological approach can be used for on-site, field-scale treatment of pesticide-contaminated soil.

Dinoseb, a dinitroherbicide, was once commonly used in aerial crop dusting of agronomic crops in the western United States. Widespread use combined with improper disposal practices at rural air strips has contaminated numerous sites. Our objective was to determine if zerovalent iron (Fe(0)) could remediate dinoseb-contaminated soil. This was accomplished by conducting a series of batch experiments where we first determined if Fe(0) could remove dinoseb in aqueous solutions, then in contaminated soil slurries, and finally, in unsaturated soil microcosms (25 degrees C, theta(g)=0.30 kg H(2)O kg(-1)). Results showed quantitative dinoseb removal in the presence of Fe(0) in all three media (aqueous solutions, soil slurries, moist soils) and that removal increased by including either ferrous or aluminum sulfate with the iron treatment. Incubating contaminated soils with Fe(0) or Fe(0) plus salts (FeSO(4) or Al(2)(SO(4))(3)) resulted in 100% removal of dinoseb within 7 d. Liquid chromatography/mass spectrometry (LC/MS) analysis of degradation products showed the transformations imposed by the iron treatments were reduction of one or both nitro groups to amino groups. These amino degradation products were further transformed to quinonimine and benzoquinone and did not persist. These results support the use of zerovalent iron for on-site treatment of dinoseb-contaminated soil.

Potassium permanganate absorbed on alumina is used to oxidize 1,4-cyclohexadienes to the corresponding aromatic compounds. Intermolecular Diels-Alder reactions followed by dehydrogenation of the products with potassium permanganate supported on alumina gives an efficient two step synthesis of highly substituted aromatic compounds from acyclic precursors.

Treatment of β,β-disubstituted enamines with potassium permanganste supported on neutral alumina leads to a mild and selective oxidative cleavage reaction which produces ketones and formamides. The ketones can be isolated in high yield and purity by a simple workup procedure. The oxidizing agent is selective and preferentially oxidizes an enamine carbon-carbon double bond in the presence of a distal carbon-carbon double bond. Other functional groups unaffected by this reagent include nitriles, secondary alcohols, and alkynes allowing a wide range of potentially selective oxidations.

A systematic study has been completed demonstrating the utility and scope of the potassium dichromate-mediated oxidative cleavage of enamines. Among the methods studied, the biphasic, chromic acid-diethyl ether conditions gave the best results and prevented over-oxidation of the carbonyl products. This method is general for β,β-disubstituted enamines, such as (1E)-1-(4-morpholino)-2-phenyl-2-methyl-1-propene, and gave the corresponding dehomologated ketones in good yield in one hour at 25 °C.

Ketoximes are converted to the parent ketones in good yields when treated with potassium permanganate supported on neutral alumina (ASPP). An optimized procedure has been developed, the simple work-up minimizes loss of product and oximes have been selectively oxidized in the presence of alkenes.

A systematic study has been completed demonstrating the utility and scope of the potassium dichromate-mediated oxidative cleavage of enamines. Among the methods studied, the biphasic, chromic acid-diethyl ether conditions gave the best results and prevented over-oxidation of the carbonyl products. This method is general for β,β-disubstituted enamines, such as (1E)-1-(4-morpholino)-2-phenyl-2-methyl-1-propene, and gave the corresponding dehomologated ketones in good yield in one hour at 25 °C.

Potassium permanganate absorbed on alumina is used to oxidize 1,4-cyclohexadienes to the corresponding aromatic compounds. Intermolecular Diels-Alder reactions followed by dehydrogenation of the products with potassium permanganate supported on alumina gives an efficient two step synthesis of highly substituted aromatic compounds from acyclic precursors.

Ketoximes are converted to the parent ketones in good yields when treated with potassium permanganate supported on neutral alumina (ASPP). An optimized procedure has been developed, the simple work-up minimizes loss of product and oximes have been selectively oxidized in the presence of alkenes.