Quantification and Analysis of Micro-Level Activities Data from Children Aged 1-12 Years Old for Use in the Assessments of Exposure to Recycled Tire on Turf and Playgrounds.

BACKGROUND: There are growing health concerns about exposure to toxicants released from recycled tire rubber, which is commonly used in synthetic turf and playground mats. To better estimate children's exposure and risk from recycled tire rubber used in synthetic turf and playground mats, there is a need to collect detailed accurate information on mouthing activity and dermal contact behaviors. The objective of this study was to quantify and analyze micro-level activity time series (MLATS) data from children aged 1-12 years old while playing (non-sport-related games) at turf-like locations and playgrounds. Another objective was to estimate the incidental ingestion rate of rubber crumb among children. METHODS: Hand and mouth contact frequency, hourly duration, and median contact duration with different objects were calculated for children playing on turf (i.e., parks, lawns, and gardens) (n = 56) and for children playing on playground structures (n = 24). Statistically significant differences between males and females as well as children's age groups were evaluated. The daily incidental ingestion rate of rubber crumb was calculated. RESULTS: For children playing on turf, there were significant differences between younger (1-6 y) and older (7-12 y) children for the mouthing median duration with non-dietary objects and all objects. For children playing on playground structures, we found significant mouthing frequency differences between younger (1-6 y) and older children (7-12 y) with all objects, and for mouthing median duration with non-dietary objects. There were no significant differences between males and females playing on artificial turf-like surfaces or playground mats. Our estimated mean incidental ingestion rate was 0.08, 0.07, and 0.08 g rubber crumb/day for children <2, 2-6, and 6-11 years old, respectively. DISCUSSION: our results suggest that age and contact duration should be considered in risk assessment models to evaluate mouthing activities when children are playing on artificial turf surfaces or playground mats.

Soil ingestion among young children in rural Bangladesh.

Ingestion of soil and dust is a pathway of children's exposure to several environmental contaminants, including lead, pesticides, and fecal contamination. Empirically based estimates of central tendency for soil consumption by children in high-income countries range from 9 to 135 dry mg/day. Using a Monte Carlo simulation, we modeled the mass of soil directly and indirectly ingested per day by rural Bangladeshi children and identified the parameters that influence the mass ingested. We combined data from observations of direct and indirect ingestion among children with measurements of soil mass on the children's hands, mother's hands, and objects to quantify soil ingestion/day. Estimated geometric mean soil ingestion was 162 dry mg/day for children 3-5 months, 224 dry mg/day for children 6-11 months, 234 dry mg/day for children 12-23 months, 168 dry mg/day for children 24-35 months, and 178 dry mg/day for children 36-47 months old. Across all age groups, children placing their hands in their mouths accounted for 46-78% of total ingestion and mouthing objects contributed 8-12%. Direct ingestion of soil accounted for nearly 40% of soil ingested among children 6-23 months old. Sensitivity analyses identified that the parameters most affecting the estimates were the load of soil on the child's hand, the frequency of hand-to-mouth contacts while not eating, and, for children 6-23 months old, the frequency of direct soil ingestion. In a rural, low-income setting, children's soil consumption was substantially more than the estimates for children in high-income countries. Further characterizing soil ingestion of children in low-income contexts would improve assessments of the risks they face from soil-associated contaminants.

Stochastic Collision-Attachment-Based Monte Carlo Simulation of Colloidal Fouling: Transition from Foulant-Clean-Membrane Interaction to Foulant-Fouled-Membrane Interaction.

The initial behavior of colloidal fouling is governed by foulant-clean-membrane interaction (F-M), and its long-term behavior is determined by foulant-fouled-membrane interaction (F-F). Nevertheless, the transitional fouling behavior from F-M to F-F has not been fully understood. This study reports a novel collision attachment (CA)-Monte Carlo (MC) approach, with the stochastic colloid-membrane collision events modeled by MC and the probability of colloidal attachment to the membrane determined by the interplay of flux and the energy barrier arising from colloid-membrane interaction (Em for F-M and Ef for F-F). The long-term membrane flux remains stable for large Ef, whereas severe fouling occurs when both Em and Ef are small. Our study reveals the existence of a metastable flux behavior for the combination of large Em but small Ef. The time evolution of flux behavior and colloidal deposition patterns shows a nearly constant flux for an extended period, with the high energy barrier Em retarding initial colloidal deposition. However, accidental random deposition of a colloidal particle could reduce the local energy barrier (toward the smaller Ef), seeding for further colloidal deposition in its vicinity. This initiates an uneven patch-wise fouling and eventually leads to a complete transition to F-F-dominated behavior. The metastable period can be effectively extended by increasing the energy barrier (Em or Ef) or lowering flux, which provides important implications to membrane design and operation.

Modeling Dynamics of Colloidal Fouling of RO/NF Membranes with A Novel Collision-Attachment Approach.

We report a novel collision-attachment approach for modeling the dynamics of colloidal fouling. The model treats fouling as a two-step process: colloidal particles colliding with a membrane surface followed by their attachment onto the surface. An attachment coefficient is adopted to describe the probability of successful foulant attachment for any given collision event, the value of which can be determined by the classical Boltzmann distribution. Our model shows excellent agreement with experimental data in terms of both the kinetics of flux decline and foulant mass deposition. Modeling results reveal the critical roles of water flux and energy barrier in governing colloidal fouling. Greater water flux or lower energy barrier can lead to a collision-controlled condition, where severe fouling occurs and nearly all collision events lead to successful foulant attachment. On the contrary, fouling is increasingly controlled by the probability of successful attachment at lower water flux and/or greater energy barrier. Our model provides deep insights into the various mechanisms governing the dynamics of colloidal fouling (i.e., concentration polarization, collision, and attachment) and the self-limiting fouling behavior under constant-pressure mode.

A self-assembled superhydrophobic electrospun carbon-silica nanofiber sponge for selective removal and recovery of oils and organic solvents.

An oil spill needs timely cleanup before it spreads and poses serious environmental threat to the polluted area. This always requires the cleanup techniques to be efficient and cost-effective. In this work, a lightweight and compressible sponge made of carbon-silica nanofibers is derived from electrospinning nanotechnology that is low-cost, versatile, and readily scalable. The fabricated sponge has high porosity (>99 %) and displays ultra-hydrophobicity and superoleophilicity, thus making it a suitable material as an oil adsorbent. Owing to its high porosity and low density, the sponge is capable of adsorbing oil up to 140 times its own weight with its sorption rate showing solution viscosity dependence. Furthermore, sponge regeneration and oil recovery are feasible by using either cyclic distillation or mechanical squeezing.

Effect of humic acid on the sorption of perfluorooctane sulfonate (PFOS) and perfluorobutane sulfonate (PFBS) on boehmite.

The sorption of PFOS and PFBS on boehmite was significantly retarded by the competitive sorption of humic acid (HA), implying that PFOS and PFBS are likely more mobile in water and groundwater systems enriched with HA. The sorption behavior of PFOS and PFBS on the HA-modified boehmite surface were also found to differ due to their different chain lengths. For a partially HA-modified boehmite surface, the isotherm study showed that PFOS had a much higher maximum sorption capacity than PFBS and that PFOS might possess additional surface interactions besides electrostatic interaction. For a HA-saturated boehmite, a linear sorption isotherm was found for PFOS while nearly no PFBS sorption was observed. This indicates that sorption behavior between PFOS and the sorbed HA on boehmite was dominated by hydrophobic interactions, instead of electrostatic interaction. In addition, a conceptual model combining hydrophobic and electrostatic interaction was established to explain the sorption behavior of PFOS and PFBS on HA-modified boehmite. Finally, the results revealed that the sorption of PFOS and PFBS on HA-modified boehmite is pH-dependent. The neutralization of negative sites on HA-modified boehmite reduced the electrostatic repulsion and enhanced the partitioning of PFBS on the sorbed HA.

Highly efficient and flexible electrospun carbon-silica nanofibrous membrane for ultrafast gravity-driven oil-water separation.

A novel free-standing and flexible electrospun carbon-silica composite nanofibrous membrane is newly introduced. The characterization results suggest that the electrospun composite nanofibers are constructed by carbon chains interpenetrated through a linear network of 3-dimensional SiO2. Thermogravimetric analysis indicates that the presence of insulating silica further improve the thermal resistance of the membrane. Additionally, the mechanical strength test shows that the membrane's toughness and flexibility can be enhanced if the concentration of SiO2 is maintained below 2.7 wt %. Thermal and chemical stability test show that the membrane's wettability properties can be sustained at an elevated temperature up to 300 °C and no discernible change in wettability was observed under highly acidic and basic conditions. After surface-coating with silicone oil for 30 mins, the composite membrane exhibits ultra-hydrophobic and superoleophilic properties with water and oil contact angles being 144.2 ± 1.2° and 0°, respectively. The enhanced flexibility and selective wetting property enables the membrane to serve as an effective substrate for separating free oil from water. Lab-scale oil-water separation test indicates that the membrane possesses excellent oil-water separation efficiency. In addition, its inherent property of high porosity allows oil-water separation to be performed in a gravity-driven process with high-flux. We anticipate that this study will open up a new avenue for fabrication of free-standing carbonaceous composite membrane with tunable flexibility for energy efficient and high-throughput production of clean water.

Enterococcus spp on fomites and hands indicate increased risk of respiratory illness in child care centers.

BACKGROUND: Surface-mediated transmission is a potential route for respiratory disease in child care centers, but evidence of its importance relative to other routes (eg, airborne) is limited. METHODS: We tracked respiratory disease and monitored bacteria contamination on hands and fomites over 4 months during 64 visits at 2 child care centers. Staff monitored health daily by recording respiratory symptoms. We measured concentrations of Escherichia coli, Enterococcus spp, and fecal coliform in hand rinses and on select fomites. RESULTS: We demonstrated that symptomatic respiratory illness was positively associated with microbial contamination on hands and fomites, as measured using Enterococcus spp. Enterococcus spp were 0.28 (95% confidence interval: 0.08-0.48)-log10 (colony-forming units per 2 hands) higher when an individual had symptomatic respiratory illness. Susceptible individuals were 1.62 (95% confidence interval: 1.06-2.46) times more likely to develop respiratory illness within 4 days with every log10 increase of Enterococcus spp on hands. CONCLUSION: The findings imply that hand contamination as measured using Enterococcus spp is a risk factor for onset of respiratory illness and highlight the utility of fecal indicator bacteria as a metric for hand and fomite contamination.

Effects of inorganic anions on cadmium sorption behaviours on titanate nanotube surfaces.

This manuscript describes the characterization of as-synthesized titanate nanotube (TNT) and its sorption behaviours on cadmium with the interactions of inorganic anions. The X-ray diffraction and transmission electron microscopy found that the nanotube is in sodium titanate crystal phase (Na2Ti3O7) and the pores of TNT are bimodally distributed with nominal pore sizes of 3 and 15 nm. In the binary systems between TNT and anions, the binding affinity is fluoride > phosphate > sulphate with sulphate being the least preferred. The order is similar to that of their first acidity constants, pKa1. In the presence of cadmium ions, slight decreases in fluoride and sulphate uptakes were observed. Phosphate uptake was, however, synergistically improved when cadmium was introduced. In the same ternary systems, it was found that these anions decreased the cadmium uptakes by TNT with the effect of sulphate being the most prominent.

Effects of chlorine exposure conditions on physiochemical properties and performance of a polyamide membrane--mechanisms and implications.

Understanding the effects of chlorine exposure on polyamide (PA) based membranes is essential in membrane lifespan improvement. In this study, NF90 nanofiltration membrane was treated with sodium hypochlorite at different concentrations, pHs and durations. The changes in membrane elemental composition and bonding chemistry obtained from XPS and ATR-FTIR revealed the impacts of two competing mechanisms: N-chlorination and chlorination-promoted hydrolysis. More chlorine was incorporated into the PA matrix at pH <7, at which HOCl is dominant, while chlorine-promoted hydrolysis was more favorable at pH >7 with abundant hydroxyl groups. The membrane surface became more hydrophobic when chlorination was dominant, which in turn caused the water permeability of chlorinated membrane to decrease. Meanwhile, membrane became more hydrophilic and less cross-linked when hydrolysis effects were governing, which made the membrane more permeable for water. Rejection of charged solutes [NaCl, As(V)] improved in most chlorinating conditions due to increased charge density. However, when hydrolysis was severe (≥ 1000 ppm, pH 7 and 9), the enhanced charge repulsion effect could not compensate for the extensive amide bond cleavage, resulting in declined rejection. The lower rejection of neutral boric acid provided strong evidence of a less cross-linked separation layer.

Effects of hypochlorous acid exposure on the rejection of salt, polyethylene glycols, boron and arsenic(V) by nanofiltration and reverse osmosis membranes.

The separation layer of polyamide-based (PA) thin film composite (TFC) membranes can be modified by active chlorine species. The PA-TFC membranes, NF90, BW30 and NF270, were exposed to different concentrations of sodium hypochlorite (NaOCl) at pH 5 for 24 h. Elemental composition obtained from X-ray Photoelectron Spectroscopy (XPS) showed that the chlorine content in the PA layer increased with the chlorine concentrations. Treatment of membranes with 10 ppm Cl increased the membrane hydrophilicity. By contrast, when treated with 1000 ppm Cl or more, the membranes became less hydrophilic. Water permeability values for all 3 membrane types declined with increased chlorine concentrations. Filtration of polyethylene glycols (PEGs) with molecular weights of 200, 400 and 600 Daltons (Da) was performed to investigate the influence of chlorine treatment on membrane molecular weight cut off (MWCO) and rejection by size exclusion. Treatment with 10 and 100 ppm Cl lowered the MWCO while treatment with higher concentrations increased the MWCO. All chlorinated membranes experienced higher NaCl rejection compared to virgin ones. The performance of NF90 was tested with respect to the rejection of inorganic contaminants including boron (H(3)BO(3)) and arsenic (H(2)AsO(4)(-)). The boron rejection results paralleled PEG rejection whereas those for arsenic followed NaCl rejection patterns. The changes in membrane performance due to chlorine treatment were explained in terms of competing mechanisms: membrane tightening, bond cleavage by N-chlorination and chlorination promoted polyamide hydrolysis.

Relative pesticide and exposure route contribution to aggregate and cumulative dose in young farmworker children.

The Child-Specific Aggregate Cumulative Human Exposure and Dose (CACHED) framework integrates micro-level activity time series with mechanistic exposure equations, environmental concentration distributions, and physiologically-based pharmacokinetic components to estimate exposure for multiple routes and chemicals. CACHED was utilized to quantify cumulative and aggregate exposure and dose estimates for a population of young farmworker children and to evaluate the model for chlorpyrifos and diazinon. Micro-activities of farmworker children collected concurrently with residential measurements of pesticides were used in the CACHED framework to simulate 115,000 exposure scenarios and quantify cumulative and aggregate exposure and dose estimates. Modeled metabolite urine concentrations were not statistically different than concentrations measured in the urine of children, indicating that CACHED can provide realistic biomarker estimates. Analysis of the relative contribution of exposure route and pesticide indicates that in general, chlorpyrifos non-dietary ingestion exposure accounts for the largest dose, confirming the importance of the micro-activity approach. The risk metrics computed from the 115,000 simulations, indicate that greater than 95% of these scenarios might pose a risk to children's health from aggregate chlorpyrifos exposure. The variability observed in the route and pesticide contributions to urine biomarker levels demonstrate the importance of accounting for aggregate and cumulative exposure in establishing pesticide residue tolerances in food.

Degradation of polyamide nanofiltration and reverse osmosis membranes by hypochlorite.

The degradation of polyamide (PA) nanofiltration and reverse osmosis membranes by chlorine needs to be understood in order to develop chlorine-resistant membranes. Coated and uncoated fully aromatic (FA) and piperazine (PIP) semi-aromatic PA membranes were treated with hypochlorite solution and analyzed by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR). XPS results showed that in chlorine treated FA PA membranes the ratio of bound chlorine to surface nitrogen was 1:1 whereas it was only 1:6 in the case of PIP PA membranes. Surface oxygen of uncoated FA and PIP membranes increased with increasing hypochlorite concentration whereas it decreased for coated FA membranes. High resolution XPS data support that chlorination increased the number of carboxylic groups on the PA surface, which appear to form by hydrolysis of the amide bonds (C(O)-N). FTIR data indicated the disappearance of the amide II band (1541 cm(-1)) and aromatic amide peak (1609 cm(-1)) in both coated and uncoated chlorinated FA membranes, consistent with the N-chlorination suggested by the XPS results. Furthermore, the surface charge of chlorinated membranes at low pH (<6) became negative, consistent with amide-nitrogen chlorination. Chlorination appeared to both increase and decrease membrane hydrophobicity depending on chlorination exposure conditions, which implied that N-chlorination and hydrolysis may be competing processes. The effects of property changes on the membrane performance were also observed for NF90, BW30, and NF270 membranes.

Quantified outdoor micro-activity data for children aged 7-12-years old.

Estimation of aggregate exposure and risk requires detailed information regarding dermal contact and mouthing activity. We analyzed micro-level activity time series (MLATS) of children aged 7-12 years to quantify these contact behaviors and evaluate differences by age and gender. In all, 18 children, aged 7-12 years, were videotaped while playing outdoors. Video footage was transcribed via Virtual Timing Device (VTD) software. We calculated the hand and mouth contact frequency, hourly duration and median duration of contact with 16 object categories. Median mouthing frequencies were 12.6 events/h and 2.6 events/h for hands and non-dietary objects, respectively. Median hourly mouthing duration was 0.4 min/h and 0.1 min/h with hands and objects. Median mouthing contact duration was 1 s and 1.5 s with hands and objects, respectively. The median object contact frequency for both the hands combined was 537.3 events/h with an hourly contact duration of 81.8 min/h and a median contact duration of 3 s. There were no significant differences in the mouthing activity between genders or age groups. Female children had longer and more frequent hand contacts with several surface types. Age was negatively correlated with hand contacts of floor and wood surfaces. Contact frequencies in this study are higher than current regulatory recommendations for this age group.

Comparison of surface sampling methods for virus recovery from fomites.

The role of fomites in infectious disease transmission relative to other exposure routes is difficult to discern due, in part, to the lack of information on the level and distribution of virus contamination on surfaces. Comparisons of studies intending to fill this gap are difficult because multiple different sampling methods are employed and authors rarely report their method's lower limit of detection. In the present study, we compare a subset of sampling methods identified from a literature review to demonstrate that sampling method significantly influences study outcomes. We then compare a subset of methods identified from the review to determine the most efficient methods for recovering virus from surfaces in a laboratory trial using MS2 bacteriophage as a model virus. Recoveries of infective MS2 and MS2 RNA are determined using both a plaque assay and quantitative reverse transcription-PCR, respectively. We conclude that the method that most effectively recovers virus from nonporous fomites uses polyester-tipped swabs prewetted in either one-quarter-strength Ringer's solution or saline solution. This method recovers a median fraction for infective MS2 of 0.40 and for MS2 RNA of 0.07. Use of the proposed method for virus recovery in future fomite sampling studies would provide opportunities to compare findings across multiple studies.

Selective sorption of divalent cations using a high capacity sorbent.

This manuscript describes the application of a novel sorbent, sodium titanate nanotube (STN) on partitioning of various divalent cations. Seven divalent cations, from alkaline earth, transition and post-transition groups, were used to determine the capacity and selectivity of STN. At pH 3 ± 0.02 and 0.1M ionic strength, STN displayed high capacity for Pb and Cd (1.27 and 0.39 mmol/g, correspondingly). The affinity of divalent cations was in the order Pb ≫ Cd>Cu>Zn>Ca>Sr>Ni. For six of the tested cations, their sorption capacity can be linearly correlated to its hydrolysis constant and electronegativity. STN has unusually low affinity for Ni and correlations of sorption capacity of Ni falls outside the 95% confidence intervals. Furthermore, it exhibited sorption behavior similar to alkaline earth cations, significant uptakes occurred only when pH>point of zero charge. In competitive sorption tests, STN preferentially sorb Cd over other metals (Zn, Ni, Ca and Sr) which coexist in industrial wastewater. As such STN is a potential novel sorbent useful for partitioning Cd from other metals in industrial wastewater.

Sequestration of cadmium ions using titanate nanotube.

In this manuscript, titanate (Na(2)Ti(3)O(7)) nanotubes synthesized from alkali hydrothermal route, with high BET surface area (206 m(2)/g), were used as an effective sorbent to remove cadmium ions from water. Sorption capacity (q(m,Langmuir) = 1.1 mmol/g at pH 7) was higher than other sorbents. X-ray photoelectron spectroscopy (XPS) analyses performed on fresh and cadmium-sorbed samples reveal intensities of Na 1s peak decreased after sorption indicating ion-exchanging between cadmium and sodium ions occurred at interlayer of nanotubes. However kinetic study did not show a stoichiometrically equivalent amount of Na(+) being released suggesting Cd uptake was not due solely to ion-exchange mechanism. Batch tests also showed that cadmium uptake was not significantly affected by variation in ionic strength, signifying cadmium ions form an inner-sphere complexation with surface hydroxyl groups. Finally, surface complexation modeling was performed based on charge distribution multisite ion complexation (CDMUSIC) model. It was found that CDMUSIC was able to fit the experimental data best when inner-sphere complexation and ion-exchange were applied together.

Formation of copper aluminate spinel and cuprous aluminate delafossite to thermally stabilize simulated copper-laden sludge.

The study reported herein indicated the stabilization mechanisms at work when copper-laden sludge is thermally treated with gamma-alumina and kaolinite precursors, and evaluated the prolonged leachability of their product phases. Four copper-containing phases - copper oxide (CuO), cuprous oxide (Cu(2)O), copper aluminate spinel (CuAl(2)O(4)), and cuprous aluminate delafossite (CuAlO(2)) - were found in the thermal reactions of the investigated systems. These phases were independently synthesized for leaching by 0.1M HCl aqueous solution, and the relative leachabilities were found to be CuAl(2)O(4)

Effect of solution chemistry on the adsorption of perfluorooctane sulfonate onto mineral surfaces.

Perfluorooctane sulfonate (PFOS) is an emergent contaminant of substantial environmental concerns, yet very limited information has been available on PFOS adsorption onto mineral surfaces. PFOS adsorption onto goethite and silica was investigated by batch adsorption experiments under various solution compositions. Adsorption onto silica was only marginally affected by pH, ionic strength, and calcium concentration, likely due to the dominance of non-electrostatic interactions. In contrast, PFOS uptake by goethite increased significantly at high [H+] and [Ca2+], which was likely due to enhanced electrostatic attraction between the negatively charged PFOS molecules and positively charged goethite surface. The effect of pH was less significant at high ionic strength, likely due to electrical double layer compression. PFOS uptake was reduced at higher ionic strength for a strongly positively charged goethite surface (pH 3), while it increased for a weakly charged surface (pH 7 and 9), which could be attributed to the competition between PFOS-surface electrostatic attraction and PFOS-PFOS electrostatic repulsion. A conceptual model that captures PFOS-surface and PFOS-PFOS electrostatic interactions as well as non-electrostatic interaction was also formulated to understand the effect of solution chemistry on PFOS adsorption onto goethite and silica surfaces.

Farmworker children's residential non-dietary exposure estimates from micro-level activity time series.

Farmworkers' children may have increased pesticide exposure through dermal absorption and non-dietary ingestion, routes that are difficult to measure and model. The Cumulative Aggregate Simulation of Exposure (CASE) model, integrates the complexity of human behavior and variability of exposure processes by combining micro-level activity time series (MLATS) and mechanistic exposure equations. CASE was used to estimate residential non-dietary organophosphate pesticide exposure (i.e., inhalation, dermal, and non-dietary ingestion) to California farmworker children and evaluate the micro-activity approach. MLATS collected from children and distributions developed from pesticide measurements in farmworkers' residences served as inputs. While estimated diazinon exposure was greater for inhalation, chlorpyrifos exposure was greater for the other routes. Greater variability existed between children (sigma(B)(2)=0.22-0.39) than within each child's simulations (sigma(W)(2)=0.01-0.02) for dermal and non-dietary ingestion. Dermal exposure simulations were not significantly different than measured values from dosimeters worn by the children. Non-dietary ingestion exposure estimates were comparable to duplicate diet measurements, indicating this route may contribute substantially to aggregate exposure. The results suggest the importance of the micro-activity approach for estimating non-dietary exposure. Other methods may underestimate exposure via these routes. Model simulations can be used to identify at-risk children and target intervention strategies.