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A major area of growth for “nano-enabled” products has been the addition of nanoparticles (NPs) to surface coatings including paints, stains and sealants. Zinc oxide (ZnO) NPs, long used in sunscreens and sunblocks, have found growing use in surface coating formulations to increase their UV resistance, especially on outdoor products. In this work, ZnO NPs, marketed as an additive to paints and stains, were dispersed in Milli-Q water and a commercial deck stain. Resulting solutions were applied to either Micronized-Copper Azole (MCA) pressure treated lumber or a commercially available composite decking. A portion of coated surfaces were placed outdoors to undergo environmental weathering, while the remaining samples were stored indoors to function as experimental controls. Weathered and control treatments were subsequently sampled periodically for 6 months using a simulated dermal contact method developed by the Consumer Product Safety Commission (CPSC). The release of ZnO NPs, and their associated degradation products, was determined through sequential filtration, atomic spectroscopy, X-Ray Absorption Fine Structure Spectroscopy, and electron microscopy. Across all treatments, the percentage of applied zinc released through simulated dermal contact did not exceed 4%, although transformation and release of zinc was highly dependent on dispersion medium. For MCA samples weathered outdoors, water-based applications released significantly more zinc than stain-based, 180 ± 28, and 65 ± 9 mg/m2 respectively. Moreover, results indicate that the number of contact events drives material release.

The biomass concentrator reactor (BCR), a gravity flow membrane bioreactor (MBR) design, was evaluated for use in treating a municipal wastewater stream. The BCR operates with less than 2.5 cm of pressure head and uses a 3 to 4 mm thick tortuous path membrane with pore size ranging from 18 to 28 μm to achieve solids separation. A two-stage, aerobic/anoxic reactor was evaluated for the removal of chemical oxygen demand (COD), ammonia, total nitrogen, and solids separation. The reactor was fed 72 L/day, with a hydraulic retention time of 9.3 hours, and had a solids retention time of 20 days. The influent COD was reduced by 93%, whereas, influent ammonia was reduced below 0.1 mg/L and total nitrogen was reduced by 53.7%. A lack of readily biodegradable COD limited denitrification and thus total nitrogen removal. The reactor solids were retained completely in the reactor by the membrane for the duration of testing.

Micronized copper azole (MCA) and micronized copper quaternary (MCQ) are the latest wood preservatives to replace the liquid alkaline copper and chromated copper arsenate preservatives due to concerns over the toxicity or lack of effectiveness of the earlier formulations. Today, the use of MCA has become abundant in the wood preservative industry with approximately 38millionlbs of copper carbonate being used to treat lumber each year. Despite this widespread usage, little information is available on the bioaccessibility of this preservative upon gastrointestinal exposure. Using a simulated hand-to-mouth/gastric system exposure study we investigated several types of commercially available copper-treated lumber products as-purchased and after exposure to outdoor weathering conditions. Soluble and particulate fractions of copper were measured after transfer to and release from surface wipes passed along copper-treated lumber and exposed to synthetic stomach fluid (SSF, pH1.5) or deionized (DI) water. Wipes passed along new boards contained greater amounts of copper than wipes from weathered boards. The total copper recovered from the wipes after microwave extraction varied among the different wood types. For all wood types the copper released into SSF was more soluble than what was soluble in DI water. The data suggest that copper from treated wood is highly bioaccessible in SSF regardless of wood type and weathering condition.

Real-time monitoring of water reuse systems ensures the production of high quality water to protect human health at the point-of-use. In this study, several online real-time sensors were utilized to monitor effluent from a wastewater fed laboratory-scale membrane bioreactor (MBR) under natural and simulated failure conditions. These simulated failures included adding reactor mixed liquor to emulate a membrane breach, and spiking MS2 bacteriophage into the reactor to create a high viral load, which might be observed during an outbreak. The CANARY event detection software was used to analyze sensor data and report changes in water quality that might be indicative of poor system behavior. During simulated failure conditions, CANARY reported 20 alarms, accurately detecting each failure. During natural operating conditions, 219 alarms were produced and 189 were attributed to known events (e.g., system and sensor maintenance). The remaining alarms (23) during natural operating conditions were considered to have an unknown cause. However, 13 of those had signal deviations similar to known events, but could not be definitively linked to a source. The results of this study suggest that real-time monitoring in conjunction with CANARY analysis may be useful as an early warning system for monitoring the effluent of water reuse systems, and may help to quickly identify treatment malfunctions or other abnormal conditions.

Production and marketing of “nano-enabled” products for consumer purchase has continued to expand. However, many questions remain about the potential release and transformation of these nanoparticle (NP) additives from products throughout their lifecycle. In this work, two surface coating products advertised as containing ZnO NPs as active ingredients, were applied to micronized copper azol (MCA) and aqueous copper azol (ACA) pressure treated lumber. Coated lumber was weathered outdoors for a period of six months and the surface was sampled using a method developed by the Consumer Product Safety Commission (CPSC) to track potential human exposure to ZnO NPs and byproducts through simulated dermal contact. Using this method, the total amount of zinc extracted during a single sampling event was

Lumber pressure-treated with micronized copper was examined for the release of copper and copper micro/nanoparticles using a surface wipe method to simulate dermal transfer. In 2003, the wood industry began replacing CCA treated lumber products for residential use with copper based formulations. Micronized copper (nano to micron sized particles) has become the preferred treatment formulation. There is a lack of information on the release of copper, the fate of the particles during dermal contact, and the copper exposure level to children from hand-to-mouth transfer. For the current study, three treated lumber products, two micronized copper and one ionic copper, were purchased from commercial retailers. The boards were left to weather outdoors for approximately 1year. Over the year time period, hand wipe samples were collected periodically to determine copper transfer from the wood surfaces. The two micronized formulations and the ionic formulation released similar levels of total copper. The amount of copper released was high initially, but decreased to a constant level (~1.5mgm(-2)) after the first month of outdoor exposure. Copper particles were identified on the sampling cloths during the first two months of the experiment, after which the levels of copper were insufficient to collect interpretable data. After 1month, the particles exhibited minimal changes in shape and size. At the end of 2-months, significant deterioration of the particles was evident. Based on the wipe sample data, a playground visit may result in a potential exposure to 2.58mg of copper, which is near or exceeds the daily tolerable upper intake limits for children under the age of 8, if completely ingested through hand-to-mouth transfer. While nanoparticles were found, there is not enough information to estimate the exposure from the released particles due to a lack of published literature on copper carbonate.

This article reports biodegradation rates for a commercial dispersant, JD-2000, South Louisiana crude oil (SLC) alone, and SLC dispersed with JD-2000 at 5 and 25 °C. Results from the biodegradation experiments revealed that Component X, a chemical marker for JD-2000, rapidly degraded at both temperatures. The application of JD-2000 decreased by half the overall biodegradation rate of aliphatic compounds at 25 °C. At 5 °C, a residual fraction consisting of iso- and n-alkanes (C29-C35) persisted after 56 d. The combination of dispersant and higher temperature resulted in faster removal rates for 2- and 3-ring polycyclic aromatic hydrocarbons. When compared with Corexit 9500, our results suggest that the chemistry of the surfactant (or surfactants) in JD-2000 might have favored oil dissolution (substrate transport to the aqueous phase) as an uptake mechanism over adhesion, which requires direct contact of the biomass with the oil.

The widespread use of copper in treated lumber may result in a potential for human exposure. Due to a lack of information concerning the release of copper from treated wood particles following oral ingestion, the in vitro bioaccessibility of copper from copper-treated wood dust in synthetic stomach fluid (SSF) and DI water was investigated. Copper-containing particles ranging in size from nano-scale to micron-scale were observed by transmission electron microscopy (TEM) in thin sections of these micronized copper-treated wood products. Three copper-treated wood products (liquid alkali copper quaternary and two micronized copper quarternary products) from different manufacturers were incubated in the extraction media. The released copper was then fractionated by centrifugation and filtration through 0.45 μm and 10 kDa filters, respectively. Soluble copper released into isolated fractions was measured using Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES). Total copper from each wood product was also determined using microwave-assisted acid digestion of dried wood samples and ICP-OES. The bioaccessible copper released into SSF was between 83 and 90% for all wood types. However, the percent of copper released in DI water was between 14 and 25% for all wood products. These data suggest that copper is highly bioaccessible at the low pH values present in the stomach and may pose a potential exposure risk upon ingestion.

The U.S. Army is seeking to produce safer, less sensitive munitions through the addition of two new energetics, 2,4-dinitroanisole (DNAN) and N-methyl paranitro aniline (MNA), to the munitions’ formula. Production of these munitions would add them to the waste stream. The use of an anaerobic fluidized-bed bioreactor (AFBB) was studied for treating these compounds in a simulated wastewater with ethanol as the electron donor. The reactor degraded both of the compounds to below detection limits over a wide range of ethanol concentrations. The degradation was found to be a transformation into secondary products for both energetics: diaminoanisole (for DNAN) and N-methyl-p-phenylenediamine (for MNA). Both of these by-products reacted upon exposure to air, forming azobond dimers. Potassium perchlorate was added to the feed stream to test if additional energetics would disrupt the transformation. The AFBB continued transformation and was able to remove the perchlorate after a two week acclimation period....

The treatment of hypersaline wastewaters represents a challenge since high salt concentrations disrupt bacteria present in normal biological treatments. This study was conducted to determine the fate of amines in two hypersaline wastewaters obtained from an industrial treatment plant processing influents with 3% and 7% of NaCl. The compounds were aniline (ANL), 4,4'-methylenedianiline (4,4'-MDA), cyclohexylamine (CHA), N-(2-aminoethyl)ethanolamine (AEA), N,N-diethylethanolamine (DEA), N,N-bis(2-hydroxyethyl)methylamine (MDEA), and tris(2-hydroxyethyl)amine (TEA). Mixtures of these chemicals with a mixed liquor suspended solids concentration of 1000 mg L(-1) were prepared at two salinities (3% and 7% NaCl). Ethanolamines were readily biodegraded at both salinities, following first-order kinetics with half-lives ranging between 10 and 58 h. Hydroxyl groups present in the ethanolamines had a positive impact on the biodegradation. Salinity did not affect the biodegradation rate of TEA and MDEA, whereas AEA and DEA degraded faster in 3% NaCl. After 48h, CHA was metabolized within a 24-h period in 3% NaCl, while no degradation was observed in 7% NaCl. ANL exhibited lag phases in both salinities and, in the following 24-h period, ANL concentrations dropped 40% and disappeared after 48 h. 4,4'-MDA degraded in 3% NaCl (half-life of 123 h) and remained unaltered after 120 h in 7% NaCl.

This study reports the synthesis and characterization of composite nitrogen and fluorine co-doped titanium dioxide (NF-TiO(2)) for the removal of contaminants of concern in wastewater under visible and solar light. Monodisperse anatase TiO(2) nanoparticles of different sizes and Evonik P25 were assembled to immobilized NF-TiO(2) by direct incorporation into the sol-gel or by the layer-by-layer technique. The composite films were characterized with X-ray diffraction, high-resolution transmission electron microscopy, environmental scanning electron microscopy, and porosimetry analysis. The photocatalytic degradation of atrazine, carbamazepine, and caffeine was evaluated in a synthetic water solution and in an effluent from a hybrid biological concentrator reactor (BCR). Minor aggregation and improved distribution of monodisperse titania particles was obtained with NF-TiO(2)-monodisperse (10 and 50 nm) from the layer-by-layer technique than with NF-TiO(2) +monodisperse TiO(2) (300 nm) directly incorporated into the sol. The photocatalysts synthesized with the layer-by-layer method achieved significantly higher degradation rates in contrast with NF-TiO(2)-monodisperse titania (300 nm) and slightly faster values when compared with NF-TiO(2)-P25. Using NF-TiO(2) layer-by-layer with monodisperse TiO(2) (50 nm) under solar light irradiation, the respective degradation rates in synthetic water and BCR effluent were 14.6 and 9.5 × 10(-3) min(-1) for caffeine, 12.5 and 9.0 × 10(-3) min(-1) for carbamazepine, and 10.9 and 5.8 × 10(-3) min(-1) for atrazine. These results suggest that the layer-by-layer technique is a promising method for the synthesis of composite TiO(2)-based films compared to the direct addition of nanoparticles into the sol.

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