CSMD1 regulates brain complement activity and circuit development.

Complement proteins facilitate synaptic elimination during neurodevelopmental pruning, but neural complement regulation is not well understood. CUB and Sushi Multiple Domains 1 (CSMD1) can regulate complement activity in vitro, is expressed in the brain, and is associated with increased schizophrenia risk. Beyond this, little is known about CSMD1 including whether it regulates complement activity in the brain or otherwise plays a role in neurodevelopment. We used biochemical, immunohistochemical, and proteomic techniques to examine the regional, cellular, and subcellular distribution as well as protein interactions of CSMD1 in the brain. To evaluate whether CSMD1 is involved in complement-mediated synapse elimination, we examined Csmd1-knockout mice and CSMD1-knockout human stem cell-derived neurons. We interrogated synapse and circuit development of the mouse visual thalamus, a process that involves complement pathway activity. We also quantified complement deposition on synapses in mouse visual thalamus and on cultured human neurons. Finally, we assessed uptake of synaptosomes by cultured microglia. We found that CSMD1 is present at synapses and interacts with complement proteins in the brain. Mice lacking Csmd1 displayed increased levels of complement component C3, an increased colocalization of C3 with presynaptic terminals, fewer retinogeniculate synapses, and aberrant segregation of eye-specific retinal inputs to the visual thalamus during the critical period of complement-dependent refinement of this circuit. Loss of CSMD1 in vivo enhanced synaptosome engulfment by microglia in vitro, and this effect was dependent on activity of the microglial complement receptor, CR3. Finally, human stem cell-derived neurons lacking CSMD1 were more vulnerable to complement deposition. These data suggest that CSMD1 can function as a regulator of complement-mediated synapse elimination in the brain during development.

Phosphorus recovery and recycling from model animal wastewaters using materials prepared from rice straw and corn cobs.

Anthropogenic loss of phosphorus to surface waters not only causes environmental problems but depletes valuable phosphorus reserves. In this study, magnesium amended biochars and magnesium silicate, synthesized from corn cobs and rice straw, respectively, were evaluated for phosphorus uptake including the effects of pH and alkalinity. The overall goal was to close the phosphorus loop by recovering phosphorus from animal waste and reusing it as fertilizer. After phosphorus uptake, spent materials were tested for phosphorus release using modified soil tests representing different soil pH and alkalinity conditions. In experiments using model animal wastewaters containing both ammonia and bicarbonate alkalinity, dissolved phosphorus was removed by struvite (MgNH4PO4·6H2O) formation, whereas in deionized water, dissolved phosphorus was removed by adsorption. Alkalinity in the model animal wastewaters competed with phosphate for dissolved or solid-associated magnesium, thereby reducing phosphorus uptake. Spent materials released significant phosphorus in waters with bicarbonate alkalinity. This work shows that abundant agricultural wastes can be used to synthesize solids for phosphorus uptake, with the spent materials having potential application as fertilizers.

Formulation of crude oil spill dispersants based on the HLD concept and using a lipopeptide biosurfactant.

Solvent-free dispersants for crude oil spills were formulated based on the hydrophilic-lipophilic deviation (HLD) concept and using lipopeptides from Bacillus sp. GY19. The lipopeptides were recovered and concentrated from cell-free broth by foam fractionation and freeze-drying. They had good surface activity under varying temperatures, pH and NaCl levels. Moreover, the lipopeptides had low toxicity to copepods (LC50 1174mg/L) and whiteleg shrimp (LC50 1050mg/L). The characteristic curvature (Cc) of the lipopeptides showed that they were more hydrophobic (Cc 4.93) than sodium dihexyl sulfosuccinate (SDHS, Cc -0.92). The HLD equation was used to calculate the lipopeptide and the SDHS fractions in the dispersant formulations according to the equivalent alkane carbon number (EACN) of hydrocarbons and seawater salinity. The molar fraction of lipopeptides increased with increasing EACN. The lipopeptide-SDHS mixtures formed microemulsion Type III with specific hydrocarbons and crude oils. Oil displacement and baffled flask tests showed that the formulations reduced the interfacial tension and solubilized crude oil in the water column at higher efficiency than commercial dispersants or lipopeptides alone. In summary, the effectiveness of the lipopeptide-based dispersant corresponded to the optimal HLD.

Transport and retention of TiO2 and polystyrene nanoparticles during drainage from tall heterogeneous layered columns.

Recent developments in nanotechnology have seen an increase in the use of manufactured nanomaterials. Although their unique physicochemical properties are desirable for many products and applications, concern continues to exist about their environmental fate and potential to cause risk to human and ecological health. The purpose of this work was to examine one aspect of nanomaterial environmental fate: transport and retention in the unsaturated zone during drainage. The work made use of tall segmented columns packed with layers of two different porous media, one medium sand and one fine sand. The use of tall columns allowed drainage experiments to be conducted where the water table remained within the height of the column, permitting control of final saturation profiles without the need for capillary barrier membranes which can potentially complicate analyses. Experiments were conducted with titanium dioxide (TiO2) and polystyrene nanomaterials. For the strongly negatively-charged polystyrene nanomaterials, little retention was observed under the conditions studied. For the TiO2 nanomaterials, results of the work suggest that while saturated fine sand layers may retain more nanomaterials than saturated coarse sand layers, significantly greater retention is possible in unsaturated media. Furthermore, unsaturated medium sand layers exhibited significantly greater retention than adjacent saturated fine sand layers when present at low saturations high above the water table. Retention by unsaturated media were found to correlate strongly with elevation. Free drainage experiments including both primary and secondary drainages in homogeneous columns showed evidence of redistribution during imbibition and secondary drainage, but still showed substantial unsaturated retention of TiO2 nanoparticles high in the column, despite re-saturation with- and drainage of nanoparticle-free water.

Arsenate adsorption onto iron oxide amended rice husk char.

In this study, rice husks were charred at 550 °C in a partially sealed ceramic vessel for 30minutes to create a high specific surface area (SSA) rice husk char (RHC). The RHC was then amended with iron oxides using dissolved ferric nitrate, Fe(NO3)3⋅9H2O, to provide a surface chemistry conducive to arsenic adsorption. The 550 °C iron oxide amended rice husk char's (550 IOA-RHC's) SSA was nearly 2.5 orders of magnitude higher and the arsenate adsorptive level was nearly 2 orders of magnitude higher than those reported for iron oxide amended sand, thus indicating a positive relationship between post-amendment SSA and arsenate adsorptive levels. Rice husks were then charred at temperatures ranging from 450 °C to 1050 °C to create an even higher SSA material, which might further increase arsenate adsorptive levels. The 950 °C RHC was chosen for amendment due to its high SSA and feasibility of being produced in the field. Once amended, the 950 °C iron oxide amended rice husk char (950 IOA-RHC) improved the arsenate adsorption capacity by thus confirming a positive relationship, though not a linear relationship, between post-amendment SSA and arsenic adsorptive capacity. Further study demonstrated that post-amendment mesoporous volume and mesoporous surface area appear to be better indicators of arsenic adsorptive capacity than SSA or iron content.

Practical considerations, column studies and natural organic material competition for fluoride removal with bone char and aluminum amended materials in the Main Ethiopian Rift Valley.

The fluoride removal capacities of three materials, bone char (BC), aluminum oxide coated bone char (ACBC) and aluminum oxide impregnated wood char (AIWC), along with activated alumina (AA) as a baseline material, were investigated in batch and column studies, including comparison between synthetic and natural groundwater. Results suggest that in all cases the laboratory column results exhibited higher fluoride removal efficiency than the field studies conducted in the Ethiopian Rift Valley. Further studies indicate that the reduced effectiveness in the field was likely due to a combination of the high pH of groundwater (8.2) and the presence of competing ions (sulfate). Batch studies testing potential competition from natural organic material (NOM) showed no statistical evidence of NOM competition with BC and minor evidence of competition with ACBC and AIWC. To provide evidence for using Rapid Scale Small Column Test (RSSCT) principles for BC two different column volume and particle sizes were used. The results indicate that RSSCT scaling equations, developed for activated carbon, are applicable for BC removal of fluoride. These results thus provide valuable insights for translating laboratory results of novel sorbents for mitigating fluoride tainted groundwater in the field.

Water-supply options in arsenic-affected regions in Cambodia: targeting the bottom income quintiles.

In arsenic-affected regions of Cambodia, rural water committees and planners can choose to promote various arsenic-avoidance and/or arsenic-removal water supply systems. Each of these has different costs of providing water, subsequently born by the consumer in order to be sustainable. On a volumetric basis ($/m3-yr) and of the arsenic-avoidance options considered, small-scale public water supply - e.g., treated water provided to a central tap stand - is the most expensive option on a life-cycle cost basis. Rainwater harvesting, protected hand dug wells, and vendor-supplied water are the cheapest with a normalized present worth value, ranging from $2 to $10 per cubic meter per year of water delivered. Subsidization of capital costs is needed to make even these options affordable to the lowest (Q5) quintile. The range of arsenic-removal systems considered here, using adsorptive media, is competitive with large-scale public water supply and deep tube well systems. Both community level and household-scale systems are in a range that is affordable to the Q4 quintile, though more research and field trials are needed. At a target cost of $5.00/m3, arsenic removal systems will compete with the OpEx costs for most of the arsenic-safe water systems that are currently available. The life-cycle cost approach is a valuable method for comparing alternatives and for assessing current water supply practices as these relate to equity and the ability to pay.

Synthesis, characterization, and evaluation of simple aluminum-based adsorbents for fluoride removal from drinking water.

Simple aluminum (hydr)oxides and layered double hydroxides were synthesized using common chemicals and equipment by varying synthesis temperature, concentrations of extra sulfate and citrate, and metal oxide amendments. Aluminum (hydr)oxide samples were aged at either 25 or 200°C during synthesis and, in some cases, calcined at 600 °C. Despite yielding increased crystallinity and mineral phase changes, higher temperatures had a generally negative effect on fluoride adsorption. Addition of extra sulfate during synthesis of aluminum (hydr)oxides led to significantly higher fluoride adsorption capacity compared to aluminum (hydr)oxides prepared with extra citrate or no extra ligands. X-ray diffraction results suggest that extra sulfate led to the formation of both pseudoboehmite (γ-AlOOH) and basaluminite (Al4SO4(OH)10⋅4H2O) at 200 °C; energy dispersive X-ray spectroscopy confirmed the presence of sulfur in this solid. Treatment of aluminum (hydr)oxides with magnesium, manganese, and iron oxides did not significantly impact fluoride adsorption. While layered double hydroxides exhibited high maximum fluoride adsorption capacities, their adsorption capacities at dissolved fluoride concentrations close to the World Health Organization drinking water guideline of 1.5 mg L(-1) were much lower than those for the aluminum (hydr)oxides.

Behavior of DNAPL mixture of organometallic and chlorinated solvent in the presence of surfactants and alcohols as density modifying agents.

This work evaluates the behavior of surfactant and alcohols in combination with a mixture of tributyltinchloride (TBT) and tetrachloroethylene (PCE) with the goal of modifying the mixed oil from being a dense non-aqueous phase liquid (DNAPL) to a light non-aqueous phase liquid (LNAPL). Phase behavior of the mixed oil was studied under various combinations of surfactant, alcohol, and salinity. Phase density conversion was examined using pseudo-ternary phase diagrams constructed between the mixed oil, surfactant solution (4 wt%), and two types of alcohols (n-butyl alcohol (BuOH) and tert-butyl alcohol (TBA)). Aqueous phase solubilization and oil phase density modification were studied at varying alcohol to surfactant (A/S) ratios. The results showed that the optimum surfactant system was sodium dihexylsulfosuccinate (SDHS) and hexadecyl diphenyloxidedisulfonate (C16DPDS) (3.6 wt% and 0.4 wt%, respectively) with salt (NaCl) of 3 wt%. From pseudo-ternary phase diagrams, BuOH was found to produce a larger LNAPL region than TBA. From solubilization studies, the surfactant system plus either TBA or BuOH caused PCE preferential solubilization and this preference was more pronounced at higher total surfactant concentration in the system with TBA addition. In terms of density modification, BuOH produced lower oil density than TBA at high A/S ratio. This phase behavior knowledge can be used to optimize site remediation of organometallic DNAPLs.

Transport and retention of fullerene (nC60) nanoparticles in unsaturated porous media: effects of solution chemistry and solid phase coating.

The retention and release of aqueous aggregates of fullerene nanoparticles (nC(60)) were studied under dynamic unsaturated conditions. Porous media containing nC(60) were taken through multiple drainage/imbibition (drying/wetting) cycles to explore the effects of solution conditions and solid surface modification on transport and ultimate fate in unsaturated porous media. In experiments conducted with NaCl as the background electrolyte, the retention of nC(60) during drainage was found to be negligibly small over a wide range of ionic strengths (I=0.2 to I=6 mM), significantly lower than the retention of titanium dioxide nanoparticles studied previously under similar conditions. In contrast, experiments conducted with CaCl(2) as the background electrolyte found that retention of nC(60) during drainage was significant at higher ionic strengths, particularly at the highest ionic strength studied (I=6 mM). Experiments examining the influence of dissolved natural organic matter on nC(60) retention in unsaturated media found no measurable impact on the transport. The effects of solid surface modification were examined by creating coatings that modified surface hydrophobicity and charge. Experiments found that a hydrophobic coating had no measurable impact on nC(60) retention, when compared with retention by unmodified media. In contrast, a porous medium with surfaces that were both hydrophobic and positively-charged retained 5-10 times more nC(60) during drainage than an unmodified porous medium. This result suggests that electrostatic interactions play a more important role than hydrophobic interactions in the transport and fate of nC(60) in the unsaturated zone. For all conditions where retention was observed, experiments found very little release or retained nC(60) after subsequent flushing with water, suggesting that once retained, the environmental mobility of nC(60) may be extremely limited.

Assessing the effect of grain-scale sorption rate limitations on the fate of hydrophobic organic groundwater pollutants.

Subsurface pollutant transport models accounting for sorption rate limitations are computationally more demanding than those assuming local sorption equilibrium. We combine batch and column tests with modeling for a comparative assessment of different sorption models. For the relatively hydrophobic compound naphthalene, a model assuming local sorption equilibrium was unable to reproduce breakthrough curves in column studies with Canadian River Alluvium sediment which contains carbonaceous particles. Fully calibrated independent forward predictions of a first-order kinetic and two diffusion kinetic sorption models were in much better agreement with the experimental data. Predictions using a diffusion-limited kinetic sorption model assuming concentration-independent sorption coefficients performed equally well as a model using the Freundlich isotherm. Both diffusion-based kinetic sorption models were superior to the first-order rate approach. In the present study, the validity of the local sorption equilibrium assumption is discussed based on a Damköhler number and thus, the compound's sorption properties, the aquifer properties, and the scale of the process. Relatively high groundwater velocities in combination with a low sorption coefficient K(d) and slow diffusion limited sorption kinetic rates are necessary conditions to justify the implementation of grain-scale sorption rate limitations in groundwater contaminant fate models. Such conditions exist when a low amount of carbonaceous particles is present in aquifers with high permeability.

Characterization and emulsification properties of rhamnolipid and sophorolipid biosurfactants and their applications.

Due to their non-toxic nature, biodegradability and production from renewable resources, research has shown an increasing interest in the use of biosurfactants in a wide variety of applications. This paper reviews the characterization of rhamnolipid and sophorolipid biosurfactants based on their hydrophilicity/hydrophobicity and their ability to form microemulsions with a range of oils without additives. The use of the biosurfactants in applications such as detergency and vegetable oil extraction for biodiesel application is also discussed. Rhamnolipid was found to be a hydrophilic surfactant while sophorolipid was found to be very hydrophobic. Therefore, rhamnolipid and sophorolipid biosurfactants in mixtures showed robust performance in these applications.

Remediation of NAPL source zones: lessons learned from field studies at Hill and Dover AFB.

Innovative remediation studies were conducted between 1994 and 2004 at sites contaminated by nonaqueous phase liquids (NAPLs) at Hill and Dover AFB, and included technologies that mobilize, solubilize, and volatilize NAPL: air sparging (AS), surfactant flushing, cosolvent flooding, and flushing with a complexing-sugar solution. The experiments proved that aggressive remedial efforts tailored to the contaminant can remove more than 90% of the NAPL-phase contaminant mass. Site-characterization methods were tested as part of these field efforts, including partitioning tracer tests, biotracer tests, and mass-flux measurements. A significant reduction in the groundwater contaminant mass flux was achieved despite incomplete removal of the source. The effectiveness of soil, groundwater, and tracer based characterization methods may be site and technology specific. Employing multiple methods can improve characterization. The studies elucidated the importance of small-scale heterogeneities on remediation effectiveness, and fomented research on enhanced-delivery methods. Most contaminant removal occurs in hydraulically accessible zones, and complete removal is limited by contaminant mass stored in inaccessible zones. These studies illustrated the importance of understanding the fluid dynamics and interfacial behavior of injected fluids on remediation design and implementation. The importance of understanding the dynamics of NAPL-mixture dissolution and removal was highlighted. The results from these studies helped researchers better understand what processes and scales are most important to include in mathematical models used for design and data analysis. Finally, the work at these sites emphasized the importance and feasibility of recycling and reusing chemical agents, and enabled the implementation and success of follow-on full-scale efforts.

Retention and release of TiO2 nanoparticles in unsaturated porous media during dynamic saturation change.

The retention and release of TiO(2) nanoparticles in porous media (packed glass beads) were studied under transient unsaturated conditions as the media were taken through multiple drainage/imbibition (drying/wetting) cycles at three different pH values. The focus of the work was to better understand the role of changing water table levels and rainfall infiltration events on the ultimate mobility of TiO(2) nanoparticles. Results indicate that retention during saturated transport varied considerably, from very strong retention at pH 5 (likely due to electrostatic interactions), to no measurable retention at pH 10. During primary drainage, additional retention (i.e., beyond what was retained during initial saturation) was observed at all pH values. During subsequent imbibition/drainage cycles where nanoparticle-free water was imbibed into the porous medium prior to drainage, the mass of retained TiO(2) remained nearly constant at all three pH values. Final imbibition/drainage and subsequent flushing, both using solution conditions adjusted to favor high mobility, showed very little additional nanoparticle release. These results indicate that the release of TiO(2) nanoparticles following retention by either saturated or unsaturated packed glass beads was difficult to achieve, regardless of the likely initial mechanisms of retention, even when solution conditions were changed to those that should favor high mobility.

Model stream channel testing of a UV-transparent polymer-based passive sampler for ultra-low-cost water screening applications.

Passive samplers are increasingly being considered for analyses of waters for screening applications, to monitor for the presence of unwanted chemical compounds. Passive samplers typically work by accumulating and concentrating chemicals from the surrounding water over time, allowing analyses to identify temporally short concentration surges that might be missed by water grab samples, and potentially reducing analysis and sample handling costs, allowing a greater number of sites to be monitored. The work described here tests a recently-developed passive sampling device which was designed to provide an ultra-low-cost screening method for organic chemicals in waters. The device was originally designed for detection of endocrine disrupting chemicals, but has the advantage that it is capable of simultaneously detecting a wide range of other aqueous organic contaminants as well. The device is based on a UV-transparent polymer which is used both to concentrate dissolved chemicals, and as an optical cell for absorbance detection and full-spectrum deconvolution to identify compounds. This paper describes the results of a test of the device conducted at the US EPA Experimental Stream Facility in Milford, Ohio. The test examined detection of triclosan and 4-nonylphenol in model stream channels using two different deployment methods. Results indicate that deployment method can significantly impact measured results due to differences in mass transfer. Passive samplers deployed in vials with permeable membrane septa showed no detection of either compound, likely due to lack of water motion in the vials. In contrast, passive samplers deployed directly in the flow were able to track concentrations of both compounds, and respond to temporal changes in concentration. The results of the work highlight the importance of using internal spiking standards (performance reference compounds) to avoid false non-detection results in passive sampler applications.

Biocompatible lecithin-based microemulsions with rhamnolipid and sophorolipid biosurfactants: formulation and potential applications.

The objectives of this research are first to evaluate the hydrophilicity/hydrophobicity of sophorolipid biosurfactants relative to conventional synthetic surfactants and then to formulate and evaluate microemulsions of lecithin/rhamnolipid/sophorolipid biosurfactants with a range of oils (varying EACN values and oil types). We found that sophorolipid biosurfactants are more hydrophobic than sodium bis(2-ethyl) dihexyl sulfosuccinate (SBDHS), which is more hydrophobic than sodium dihexyl sulfosuccinate (SDHS) and rhamnolipid biosurfactant. Sophorolipid thus played an important role as the hydrophobic component in lecithin/rhamnolipid/sophorolipid biosurfactant formulation. This biosurfactant formulation was able to produce Winsor Type I, III and II microemulsions and the corresponding ultralow IFT for limonene, decane, isopropyl myristate and hexadecane. The phase behavior of this formulation with isopropyl myristate did not change significantly with changing temperature (10, 25, 40 degrees C) and electrolyte concentration (0.9% and 4.0% w/v), making it desirable for cosmetic and drug delivery applications. The hexadecane detergency performance of our biocompatible formulation was higher than that of a commercial liquid detergent at the same surfactant active concentrations. This paper thus shows the ability and robustness of mixed biosurfactant systems in formulating microemulsions for a range of oils and their potential applications.

Adsorption and adsolubilization of polymerizable surfactants on aluminum oxide.

Surfactant-based adsorption processes have been widely investigated for environmental applications. A major problem facing surfactant-modified adsorbents is surfactant loss from the adsorbent due to loss of monomers from solution and subsequent surfactant desorption. For this study, a bilayer of anionic polymerizable surfactant (Hitenol BC 05, Hitenol BC 10 and Hitenol BC 20) and non-polymerizable surfactant (Hitenol N 08) was adsorbed onto alumina. The results of adsorption studies showed that as the number of ethylene oxide (EO) groups of the surfactants increased, the area per molecule increased and the maximum adsorption decreased. The lowest maximum adsorption onto alumina was for Hitenol BC 20 (20 EO groups) corresponding to 0.08 mmol/g or 0.34 molecule/nm(2) while the highest level of adsorption was 0.30 mmol/g or 1.28 molecule/nm(2) for Hitenol BC 05 (5 EO groups). This variation in adsorption was attributed to the increased bulkiness of the head group with increasing number of EO groups. Relative to the adsolubilization capacity of organic solutes, ethylcyclohexane adsolubilizes more than styrene. Styrene and ethylcyclohexane adsolubilization were both independent of the number of EO groups of the surfactant. For surfactant desorption studies, the polymerization of polymerizable surfactants increased the stability of surfactants adsorbed onto the alumina surface and reduced surfactant desorption from the alumina surface. These results provide useful information on surfactant-based surface modification to enhance contaminant remediation and industrial applications.

Multipass membrane air-stripping (MAS) for removing volatile organic compounds (VOCs) from surfactant micellar solutions.

Air-stripping is one of the most effective technologies for removing volatile organic compounds (VOCs) from surfactant solutions, although the presence of surfactant poses some unique challenges. This study evaluated the effect of a mixed surfactant system on the apparent Henry's law constant of tetrachloroethylene (PCE) and the efficiency of PCE removal from surfactant solutions using a lab-scale hollow fiber membrane contactor. Results show that the presence of surfactant significantly reduced the apparent Henry's law constant of PCE, and the reduction was proportional to the total surfactant concentration. PCE removal efficiency by membrane air-stripping (MAS) decreased as the surfactant system transitioned from solubilization to supersolubilization. Besides significantly reducing the apparent volatility of VOCs, the presence of surfactant brings additional mass transfer resistance in air-stripping, which makes it difficult to achieve high levels of contaminant removal, even at very high air/liquid (A/L) ratios. In contrast, multipass/multistage MAS operated at low A/L ratios could achieve near 100% contaminant removal because of less mass transfer limitation during each stripping pass/stage. Experimental results, together with model calculations demonstrate multipass (and multistage) air-stripping as a cost-effective alternative for removing VOCs from surfactant micellar solutions compared to the options of using large air strippers or operating at high A/L ratios.

A UV-transparent passive concentrator/spectrum deconvolution method for simultaneous detection of endocrine disrupting chemicals (EDCs) and related contaminants in natural waters.

Suspected endocrine disrupting chemicals (EDCs) have been widely detected in the environment, and are a source of increasing concern. One of the major challenges in assessing the risk associated with EDCs in the environment is that their environmental concentrations are typically extremely low - on the order of ngL(-1) to microgL(-1) - making them difficult to quantify without extensive pre-concentration procedures. Further complicating their detection is the fact that they are present in mixtures, sometimes with tens to hundreds of other compounds (pharmaceuticals, personal care products, detergents, natural organic matter). The objective of the work described here was to develop a method for rapid monitoring and detection of EDCs at trace concentrations in natural waters. The method makes use of a UV-transparent polymer-based concentrator to be used as a passive sampling device. The UV-transparent polymer-based concentrator serves both as a solid phase extraction medium to concentrate EDCs for analysis and exclude many compounds likely to interfere with detection (fines, macromolecules such as organic matter, ionic surfactants), and as an analytical optical cell, allowing rapid EDC quantification without labor-intensive pre-concentration procedures. A full-spectrum deconvolution technique is used to determine EDC concentrations from measured UV absorbance spectra in the polymer. Experiments were conducted to measure partitioning rate behavior and partition coefficients between the selected polymer (a functional polydimethylsiloxane) and water for seven compounds known or suspected of being endocrine disruptors: estrone, progesterone, estradiol, 2,6-di-tert-butyl-1,4-benzoquinone, phenanthrene, triclosan, and 4-nonylphenol. The method was tested for its ability to detect and quantify individual compounds in mixtures containing up to six components. Results show the method to have selectivity suitable for rapid screening applications at many sites where multiple compounds are present.

Role of the air-water interface in the retention of TiO2 nanoparticles in porous media during primary drainage.

The increasing use of nanomaterials in commercial products has resulted in increased concerns about their potential environmental impacts. The overall mobility of nanomaterials in the environment may depend in part on their mobility in the unsaturated zone of the subsurface, which may provide a sink for nanomaterials, preventing their spread, or a long-term contaminant source. The objective of this work was to study the dynamic unsaturated transport of titanium dioxide (TiO2) during primary drainage to examine the role of air-water interface formation on nanomaterial retention. A specialized automated system was used to track depletion of TiO2 in the pore solution of a porous medium during dynamic drainage, while simultaneously measuring capillary pressure (Pc) and saturation (S). A continuous mass balance was used to calculate the mass of retained TiO2 nanoparticles. Experiments were specifically designed to minimize TiO2 interactions with solid surfaces to allow direct assessment of the role of the air-water interface. Results indicate that the mass of retained TiO2 increases as saturation decreases at all drainage rates, with slower drainage rates corresponding to greater retention at a given saturation. Normalizing the retained mass (M) bythe measured air-water interfacial area (A) shows near-constant M/A values at high saturations (S > 0.4) and increasing M/A values with decreasing saturation as saturation drops below 0.4. This result may indicate air-water interfacial adsorption at high saturations, with increasing contributions from film straining at lower saturations.