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At least 289 records · Page 16

Hair mercury concentrations and associated factors in an electronic waste recycling area, Guiyu, China

Objective: Toxic heavy metals are released to the environment constantly from unregulated electronic waste (e-waste) recycling in Guiyu, China, and thus may contribute to the elevation of mercury (Hg) and other heavy metals levels in human hair. We aimed to investigate concentrations of mercury in hair from Guiyu and potential risk factors and compared them with those from a control area where no e-waste processing occurs. Methods: A total of 285 human hair samples were collected from three villages (including Beilin, Xianma, and Huamei) of Guiyu (n=205) and the control area, Jinping district of Shantou city (n=80). All the volunteers were administered a questionnaire regarding socio-demographic characteristics and other possible factors contributed to hair mercury concentration. Hair mercury concentration was analyzed by hydride generation atomic fluorescence spectrometry (AFS). Results: Our results suggested that hair mercury concentrations in volunteers of Guiyu (median, 0.99; range, 0.18–3.98 μg/g) were significantly higher than those of Jinping (median, 0.59; range, 0.12–1.63 μg/g). We also observed a higher over-limit ratio (>1 μg/g according to USEPA) in Guiyu than in Jinping (48.29% vs. 11.25%, P<0.001). Logistic regression model showed that the variables of living house also served as an e-waste workshop, work related to e-waste, family income, time of residence in Guiyu, the distance between home and waste incineration, and fish intake were associated with hair mercury concentration. After multiple stepwise regression analysis, in the Guiyu samples, hair mercury concentration was found positively associated with the time residence in Guiyu (β=0.299, P<0.001), and frequency of shellfish intake (β=0.184, P=0.016); and negatively associated with the distance between home and waste incineration (β=−0.190, P=0.015) and whether house also served as e-waste workshop (β=−0.278, P=0.001). Conclusions: This study investigated human mercury exposure and suggested elevated hair mercury concentrations in an e-waste recycling area, Guiyu, China. Living in Guiyu for a long time and work related to e-waste may primarily contribute to the high hair mercury concentrations. -- Highlights: • Mercury levels in hair samples from Guiyu and risk factors were assessed. • The recruitments from Guiyu were exposed to high levels of mercury. • Primitive e-waste recycling resulted in high mercury exposure of local people.

54 ENVIRONMENTAL SCIENCES↗

Concentrations of Staphylococcus species in indoor air as associated with other bacteria, season, relative humidity, air change rate, and S. aureus-positive occupants

The aim of this study was to obtain knowledge about concentrations of Staphylococcus aureus, MRSA (methicillin-resistant S. aureus), and other Staphylococcus species in indoor air in Greater Copenhagen and about factors affecting the concentrations. The effects of season, temperature, relative humidity, air change rate (ACR), other bacterial genera, area per occupant, and presence of S. aureus-positive occupants were studied. In samples from 67 living rooms, S. hominis, S. warneri, S. epidermidis, and S. capitis were found in 13–25%; S. saprophyticus, S. cohnii, and S. pasteuri in 5–10%; and S. lugdunensis, S. haemolyticus, S. caprae, S. equorum, S. kloosii, S. pettenkoferi, S. simulans, and S. xylosus in less than 3%. Staphylococcus aureus were found in two of 67 living rooms: spa type t034 (an MRSA) was recovered from a farmhouse, while spa type t509 was found in an urban home. Two species, S. equorum and S. kloosii, were found only in the farmhouse. Staphylococcus was significantly associated with season with lowest concentration and richness in winter. Genera composition was associated with ACR with smaller fractions of Staphylococcus at higher ACR, while richness was significantly and negatively associated with area per occupant. Concentration of Staphylococcus correlated positively with the total concentration of bacteria, but negatively with the total concentration of other bacteria. The concentration of Staphylococcus was not significantly associated with concentrations of the other abundant genera Bacillus, Kocuria, and Micrococcus. In offices with S. aureus-positive occupants, airborne S. aureus was not found. In conclusion, Staphylococcus species constitute a considerable proportion of the airborne bacteria in the studied homes and offices. However, both S. aureus and MRSA had very low prevalence during all seasons. Thus, transmission of S. aureus and MRSA through the air in living rooms in Copenhagen is expected to be limited. The negative associations between ACR and the fraction Staphylococcus constituted out of total bacteria, and between area per occupant and Staphylococcus richness indicate that it might be possible to affect the presence of airborne Staphylococcus in homes.

54 ENVIRONMENTAL SCIENCES↗

Effect of molecular weight and concentration of hyaluronan on cell proliferation and osteogenic differentiation in vitro

Hyaluronan (HA), the simplest glycosaminoglycan and a major component of the extracellular matrix, exists in various tissues. It is involved in some critical biological procedures, including cellular signaling, cell adhesion and proliferation, and cell differentiation. The effect of molecular weight (MW) and concentration of HA on cell proliferation and differentiation was controversial. In this study, we investigated the effect of MW and concentration of HA on the proliferation and osteogenic differentiation of rabbit bone marrow-derived stem cells in vitro. Results showed that high MW HA decreased the cell adhesion rate in a concentration-dependant manner. The cell adhesion rate was decreased by increasing MW of HA. Cell proliferation was significantly enhanced by low MW HA (P < 0.05). The factorial analysis indicated that MW and concentration had an interactive effect on the cell adhesion rate and cell proliferation (P < 0.05). High MW HA increased the mRNA expressions of ALP, RUNX-2 and OCN. The higher the MW was, the higher the mRNA expressions were. The factorial analysis indicated that MW and concentration had an interactive effect on ALP mRNA expression (P < 0.05). HA of higher MW and higher concentration promoted bone formation. These findings provide some useful information in understanding the mechanism underlying the effect of MW and concentration of HA on cell proliferation and differentiation. - Highlights: • Effect of hyaluronan on cell proliferation and differentiation is evaluated in vitro. • Hyaluronan of low molecular weight increases cell proliferation. • Hyaluronan of high molecular weight promotes cell osteogenic differentiation. • Molecular weight and concentration of hyaluronan show interactive effect.

60 APPLIED LIFE SCIENCES↗

The Cr-substitution concentration dependence of the structural, electric and magnetic behaviors for Aurivillius Bi{sub 5}Ti{sub 3}FeO{sub 15} multiferroic ceramics

Aurivillius Bi{sub 5}Ti{sub 3}FeO{sub 15} (BTFO) multiferroic ceramics with different Cr-doped concentrations have been synthesized by the conventional solid state reaction method. The influences of Cr-doping concentrations on the structural, magnetic, dielectric, and ferroelectric properties of BTFO ceramics are investigated in detail. All these sintered Cr-substituted BTFO ceramics are determined to be layered perovskite Aurivillius structure by X-ray diffraction, as well as the lattice parameters a, b, and c are in good accordance with Vegard's law along with the Cr-doping concentration. The lattice distortion a/b for Aurivillius family decreases with increasing Cr-doping concentration. Moreover, Cr-doping can promote greatly the grain growth of BTFO samples confirmed from field emission scanning electron microscopy characterization. However, no obvious signs of the improvement in ferroelectric properties are found in Cr-doped BTFO ceramics, and abnormal ferroelectric polarization versus electric field (P-E) loops are observed as Cr-doping content is beyond 0.1. Similar ε (tanδ) versus frequency plots to those of the BTFO sample are exhibited when Cr-doping concentration is less than 0.1. Nevertheless, obvious dielectric dispersion phenomena are shown as the Cr-doping concentration is beyond 0.1, and this dispersion behavior becomes strong with further increasing Cr-doping concentration, which are clearly indicated by the appearance of dielectric loss relaxation peaks in the measurement frequency from 10{sup 2} Hz to 10{sup 6} Hz. In addition, the corresponding frequency to relaxation peak shifts towards high frequencies with the Cr-doping concentration. Finally, the same magnetic orderings for all these Cr-doped BTFO ceramics as those of the BTFO one, i.e., superparamagnetic state dominated with antiferromagnetic interaction, are unambiguously found, signifying that the predicted Fe{sup 3+}-O-Cr{sup 3+} 180° ferromagnetic superexchange interaction based on the Goodenough-Kanamori (G-K) rule might not be achieved in BTFO ceramics through Cr substitution by the conventional solid state reaction.

36 MATERIALS SCIENCE↗

ON THE DISCREPANCY BETWEEN THEORETICAL AND X-RAY CONCENTRATION-MASS RELATIONS FOR GALAXY CLUSTERS

In the past 15 years, the concentration-mass relation has been investigated diffusely in theoretical studies. On the other hand, only recently has this relation been derived from X-ray observations. When that happened, the results caused a certain level of concern: the X-ray normalizations and slopes were found significantly dissimilar from those predicted by theory. We analyzed 52 galaxy clusters and groups, simulated with different descriptions of the physical processes that affect the baryonic component, with the purpose of determining whether these discrepancies are real or induced by biases in the computation of the concentration parameter or in the determination of the selection function of the cluster sample for which the analysis is carried out. In particular, we investigate how the simulated concentration-mass relation depends (1) on the radial range used to derive the concentration; (2) on the presence of baryons in the simulations, and on the effect of star formation and feedback from supernovae and active galactic nuclei (AGNs). Finally, we evaluate (3) how the results differ when adopting an X-ray approach for the analysis and (4) how the selection function based on X-ray luminosity can impact the results. All effects studied go in the direction of alleviating the discrepancy between observations and simulations, although with different significance: while the choice of the radial range to fit the profiles and the inclusion of the baryonic component play only a minor role, the X-ray approach to reconstruct the mass profiles and the selection of the cluster sample have a strong impact on the resulting concentration-mass relation. Extending the fit to the most central regions or reducing the fitting radius from the virial boundary to the typical X-ray external radius causes an increase of the normalization in radiative simulations by 5%-10%. In the second case, we measure a slope that is up to twice steeper than that derived by using the typical theoretical radial range. Radiative simulations including only supernova feedback produce 30% higher concentrations than the dark matter case. Such a difference is largely reduced when including the effect of AGN feedback. The concentration-mass relation derived from the X-ray synthetic catalog is significantly steeper due to the combination of several different effects, such as environment, dynamical state and dynamical history of the clusters, bias in mass and temperature measurements, and their dependence on the radius and on the mass of the system. Finally, selecting clusters according to their X-ray luminosity produces a net increase in both normalization and slope of the relation, since at fixed mass, the most luminous clusters are also the most concentrated.

79 ASTRONOMY AND ASTROPHYSICS↗

MO-FG-BRA-09: Quantification of Nanoparticle Heating and Concentration for MR-Guided Laser Interstitial Thermal Therapy

Purpose: Nanoparticle Mediated Laser Interstitial Thermal Therapy (npLITT) is a technique that utilizes tumor localized optically activated nanoparticles to increase the conformality of laser ablation procedures. Temperatures in these procedures are dependent on the particle concentration which generally cannot be measured noninvasively prior to therapy. In this work we attempt to quantify particle concentration in vivo by estimating the increase in R2* relaxation induced by bifunctional magnetic resonance (MR)-visible gold-based nanoparticles (SPIO@Au) and relate it to the temperature increase observed during real time MR temperature imaging (MRTI) of laser ablation. Methods: SPIO@Au nanoparticles (90nm) were synthesized containing a silica-iron core (for MR visibility via R2*) and gold shell (for near-infrared absorption). High resolution R2* maps were acquired before and after injecting four different particle concentrations (saline,1e10, 5e10, and 10e10 particles/mL) into HN5 flank xenografts. Tumors were monitored using MRTI during treatment with an interstitial fiber. (1 watt, 808 nm, 3 minutes) Results: The maximum temperature within the tumors increased linearly with concentration of injected particles, reaching 34.0, 37.6, 45.8, and 55.4 {sup 0}C for saline, 1e10, 5e10 and 10e10 particles/mL injections, respectively (R2=.994). The highest temperatures occur at the injection site rather than the fiber, confirming that SPIO@Au nanoparticles are the primary absorber. The differences between the median R2* measured at the injection site and the rest of the tumor were −6, 134, 111, 156 s-1 for the saline,1e10,5e10 and 10e10 particles/mL injections, respectively. This R2* change is consistent with the measured relaxivity for the 1e10 particles/mL injection but does not maintain linearity at higher concentrations. Conclusion: Bifunctional SPIO@Au nanoparticles are a promising technology for providing noninvasive estimates of particle concentration via MRI and temperature increase in npLITT procedures. Future experiments will focus on lower, physiologically relevant particle concentrations and spin echo R2 mapping to better quantify the particle concentration. This research was supported by the National Institutes of Health and National Cancer Institute under Award Numbers TL1TR000369 and P30CA016672 and was conducted at the MD Anderson Center for Advanced Biomedical Imaging in-part with equipment support from General Electric Healthcare.

60 APPLIED LIFE SCIENCES↗

Krypton Concentration using HZ-PAN

Idaho National Laboratory (INL) has developed and tested engineered sorbents to separate and capture volatile fission products such iodine, xenon (Xe), and krypton (Kr) from off-gas streams. As noble gases, Xe and Kr can be difficult to capture and separate. Historically, cryogenic distillation has been used to execute the separation. However, performing this separation from bulk air streams is expensive and can pose significant hazards. INL has successfully developed two different sorbents for Xe and Kr capture, silver mordenite polyacrylonitrile and hydrogen mordenite polyacrylonitrile (HZ-PAN). Adsorption studies to date successfully separated and captured Kr from carrier gas streams, but those studies focused primarily on initial separation and capture. Successful utilization in a used nuclear fuel (UNF) reprocessing facility, however, requires further concentration of the Kr to minimize long term storage volumes. This study focuses on the concentration of Kr utilizing HZ PAN as the concentrating media. Concentrating Kr during desorption is ideal for two reasons: one, to produce Kr that can be used for commercial and research applications, or two, to minimize the volume of the radioactive gaseous waste stream for disposal. This report investigates the Kr concentrating potential of HZ-PAN by running multiple Kr adsorption-desorption cycles, collecting the desorbed effluent from a saturated HZ-PAN column, and loading it onto a fresh column. This study demonstrates that four adsorption-desorption cycles can transform a 150 ppmv Kr stream into a 37.5% Kr stream, an overall concentration factor of 2497. Each concentration step results in successively smaller volumes desorbed, reducing volume by a factor of approximately 40,000. Depending on the operational goals, during desorption one could collect smaller volume fractions of high concentration Kr (~ 67%). This demonstration should be considered proof-of-concept. Further refinement is necessary to develop optimum operating schemes to integrate into UNF off-gas treatment.

12 - MGMT OF RADIOACTIVE AND NON-RADIOACTIVE WASTE↗

Recent Greenhouse Gas Concentrations

Gases typically measured in parts per million (ppm), parts per billion (ppb) or parts per trillion (ppt) are presented separately to facilitate comparison of numbers. Global Warming Potentials (GWPs) and atmospheric lifetimes are from the Intergovernmental Panel on Climate Change (IPCC, 2013, Table 8.A.1), except for the atmospheric lifetime of carbon dioxide (CO2) which is explained in footnote 4. Additional material on greenhouse gases can be found in CDIAC's Reference Tools. To find out how CFCs, HFCs, HCFCs, and halons are named, see Name that compound: The numbers game for CFCs, HFCs, HCFCs, and Halons. Concentrations given apply to the lower 75-80 percent of the atmosphere, known as the troposphere. Sources of the current and preindustrial concentrations of the atmospheric gases listed in the table below are given in the footnotes. Investigators at the National Oceanic and Atmospheric Administration have provided the recent concentrations. Much of the data provided results from the work of various investigators at institutions other than CDIAC, and represent considerable effort on their part. We ask as a basic professional courtesy that you acknowledge the primary sources, indicated in the footnotes below, or in the links given in the footnotes. Concentrations of ozone and water vapor are spatially and temporally variable due to their short atmospheric lifetimes. A vertically and horizontally averaged water vapor concentration is about 5,000 ppm. Globally averaged water vapor concentration is difficult to measure precisely because it varies from one place to another and from one season to the next. This precludes a precise determination of changes in water vapor since pre-industrial time. However, a warmer atmosphere will likely contain more water vapor than at present. For a more detailed statement on water vapor from the National Oceanic and Atmospheric Administration, see the "water vapor" page at http://lwf.ncdc.noaa.gov/oa/climate/gases.html

54 ENVIRONMENTAL SCIENCES↗

High‐Concentration Antibody Formulation via Solvent‐Based Dehydration

Abstract Although subcutaneous (SC) delivery is the preferred administration route for immunotherapies and other biologics for improved patient compliance and lower healthcare costs, it necessitates high‐concentration antibody formulations. However, high‐concentration antibody solutions face significant instabilities and prohibitively high viscosities. Other approaches for high‐concentration formulations have been developed, including non‐aqueous solutions, which can be irritating or painful, and antibody‐laden hydrogel microparticles, which require centrifugation and are limited to concentrations <300 mg mL −1 . This work presents a new formulation process wherein the antibody is concentrated and encapsulated into hydrogel microparticles via solvent‐based dehydration. The final dosage form is an aqueous particle suspension with a formulation concentration of 360 mg mL −1 . In this process, microparticles are synthesized continuously, and antibody precipitation is realized simultaneously to dehydration, which allows for higher antibody concentrations. Antibody phase behavior and precipitation–dehydration kinetics are analyzed. The antibody is structurally and functionally stable in the microparticle post‐processing and after 4 months. Injectability of the suspension meets clinical standards with glide force <20 N. For the first time, an aqueous antibody formulation at high concentrations comparable to non‐aqueous formulations is presented, ideal for subcutaneous administration. The process is envisioned to be generalizable as a platform for SC delivery in multiple clinical applications.

Zheng, Talia [Department of Chemical Engineering M↗

Comparing Transcriptomic Points of Departure to Apical Effect Concentrations For Larval Fathead Minnow Exposed to Chemicals with Four Different Modes Of Action

It is postulated that below a transcriptomic-based point of departure, adverse effects are unlikely to occur, thereby providing a chemical concentration to use in screening level hazard assessment. The present study extends previous work describing a high-throughput fathead minnow assay that can provide full transcriptomic data after exposure to a test chemical. One-day post-hatch fathead minnows were exposed to ten concentrations of three representatives of four chemical modes of action: organophosphates, ecdysone receptor agonists, plant photosystem II inhibitors, and estrogen receptor agonists for 24 h. Concentration response modeling was performed on whole body gene expression data from each exposure, using measured chemical concentrations when available. Transcriptomic points of departure in larval fathead minnow were lower than apical effect concentrations across fish species but not always lower than toxic effect concentrations in other aquatic taxa like crustaceans and insects. The point of departure was highly dependent on measured chemical concentration which were often lower than the nominal concentration. Differentially expressed genes between chemicals within modes of action were compared and often showed statistically significant overlap. In addition, reproducibility between identical exposures using a positive control chemical (CuSO 4 ) and variability associated with the transcriptomic point of departure using in silico sampling were considered. Results extend a transcriptomic-compatible fathead minnow high-throughput assay for possible use in ecological hazard screening.

59 BASIC BIOLOGICAL SCIENCES↗

Influence of sizing concentration on strength, stiffness, and porosity in textile grade carbon fiber (TCF)-Epoxy composites: Revealing inverse trends

The effect of fiber sizing (i.e., surface treatment) concentration (0 %, 1.36 %, 1.52 %, 1.94 %, and 2.13 %) on the mechanical properties (tensile, flexural, interlaminar shear strength (ILSS), and low velocity impact) of textile grade carbon fiber (TCF)-epoxy composite is examined. An inverse relationship between the strength and stiffness of the composite is observed with increased sizing concentration. The root mean square (RMS) roughness of the fiber surface increased from 17.8 nm (unsized) to 22.7 nm with 2.13 % sizing concentration. It was found that the tensile strength increased by 131 % from 221.4 ± 18.5 MPa (unsized) to 510.8 ± 28.05 MPa (for 1.36 % sizing) and further by 155 %–563.7 ± 14.95 MPa at 2.13 % sizing. On the contrary, the stiffness is initially increased by 126 % from 33.52 ± 7.80 GPa (unsized) to 75.9 ± 3.21 GPa (for 1.36 % sizing) but reduced with further increase in the sizing concentration. A single fiber pull-out test is simulated using the finite element method to validate the reverse trend in strength and stiffness. The varying sizing concentration is simulated by introducing an interface of varying thickness between fibers and matrix. Simulation results confirm that a thicker interface, corresponding to a higher sizing concentration, decreases interfacial shear stress, enhancing material strength while decreasing stiffness. The reverse trend in strength and stiffness with the sizing concentration aligns with experimental observations. In conclusion, the present study emphasizes the importance of sizing concentration for mechanical properties and provide a design criterion for customized high-strength and high-stiffness applications.

Porosity↗

Self-rated health and chronic conditions are associated with blood concentrations of persistent organic pollutants in the general population of Catalonia, Spain

Background: Self-rated health (SRH) is a powerful predictor of mortality, morbidity, and need for health services. SRH generally increases with educational level, and decreases with age, number of chronic conditions, and body mass index (BMI). Because human concentrations of most persistent organic pollutants (POPs) also vary by age, education, and BMI, and because of the physiological and clinical effects of POPs, we hypothesized that body concentrations of POPs are inversely associated with SRH. Objectives: To analyze the relation between serum concentrations of POPs and SRH in the general population of Catalonia, Spain, taking into account sociodemographic factors and BMI, as well as chronic health conditions and mental disorders, measured by the General Health Questionnaire-12 (GHQ-12). Methods: POP serum concentrations were measured by gas chromatography with electron-capture detection in 919 participants of the Catalan Health Interview Survey. Results: Individuals with higher concentrations of POPs had significantly poorer SRH; e.g., the median concentration of HCB in subjects with poor SRH was twice as high as in subjects with excellent SRH (366 ng/g vs. 169 ng/g, respectively; p-value<0.001). In crude models and in models adjusted for sex and BMI, the POPs-SRH association was often dose-dependent, and the likelihood of poor or regular SRH was 2 to 4-times higher in subjects with POP concentrations in the top quartile. In models adjusted for age or for chronic conditions virtually all ORs were near unity. No associations were found between POP levels and GHQ-12. Conclusions: Individuals with higher concentrations of POPs had significantly poorer SRH, an association likely due to age and chronic conditions, but not to sex, education, social class, BMI, or mental disorders. - Highlights: • The relation between POPs and self-rated and mental health has seldom been studied. • Subjects with higher POP levels had poorer self-rated health (SRH) (dose-dependent). • The number of chronic conditions was positively related to POP levels. • The POPs-SRH association was likely due to age (or birth cohort), and to chronic conditions. • Causal or not, the fact is that people with poorer SRH often have higher levels of POPs.

54 ENVIRONMENTAL SCIENCES↗

Best practices for predictions of radionuclide activity concentrations and total absorbed dose rates to freshwater organisms exposed to uranium mining/milling

Predictions of radionuclide dose rates to freshwater organisms can be used to evaluate the radiological environmental impacts of releases from uranium mining and milling projects. These predictions help inform decisions on the implementation of mitigation measures. The objective of this study was to identify how dose rate modelling could be improved to reduce uncertainty in predictions to non-human biota. For this purpose, we modelled the activity concentrations of 210 Pb, 210 Po, 226 Ra, 230 Th, and 238 U downstream of uranium mines and mills in northern Saskatchewan, Canada, together with associated weighted absorbed dose rates for a freshwater food chain using measured activity concentrations in water and sediments. Differences in predictions of radionuclide activity concentrations occurred mainly from the different default partition coefficient and concentration ratio values from one model to another and including all or only some 238 U decay daughters in the dose rate assessments. Consequently, we recommend a standardized best-practice approach to calculate weighted absorbed dose rates to freshwater biota whether a facility is at the planning, operating or decommissioned stage. At the initial planning stage, the best-practice approach recommend using conservative site-specific baseline activity concentrations in water, sediments and organisms and predict conservative incremental activity concentrations in these media by selecting concentration ratios based on species similarity and similar water quality conditions to reduce the uncertainty in dose rate calculations. At the operating and decommissioned stages, the best-practice approach recommends relying on measured activity concentrations in water, sediment, fish tissue and wholebody of small organisms to further reduce uncertainty in dose rate estimates. This approach would allow for more realistic but still conservative dose assessments when evaluating impacts from uranium mining projects and making decision on adequate controls of releases.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗

Selective concentration of multivalent cations via electrodialysis through tandem membranes

Selective electrodialysis is attractive for recovering and recycling valuable ions. However, most studies in this field focus on membranes that are selective for monovalent ions. Multivalent cations preferentially partition into cation-exchange membranes, but low mobilities and concentration polarization limit electrodialysis selectivities for these cations. This work employs electrodialysis through an “in-series” combination of a Nafion membrane and a multilayer polyelectrolyte film (MPF)-coated Nafion membrane to concentrate and isolate La 3+ or Mg 2+ from monovalent ions. The bare Nafion membrane gives a La 3+ /Na + selectivity up to 4 (depending on conditions), which enables concentration of La 3+ with a high current efficiency. The MPF-coated membrane allows selective passage of Na + while rejecting La 3+ to increase the purity of the concentrated multivalent cation. For example, the concentration of La 3+ in the accumulation solution can reach 9 times its original concentration in the feed solution with a purity of 93 mol% (99 wt%) when starting with equimolar mixtures of NaNO 3 and La(NO 3 ) 3 . This study examines how the separation varies with the type of polyelectrolyte, the applied voltage, and the composition of feed, accumulation, and cathode solutions. Here, a high nitric acid concentration (0.5 M) in the cathode compartment allows monovalent anions to pass through the MPF-coated Nafion membrane to maintain the electroneutrality of the accumulation solution. With a low acid concentration (0.04 M) in the cathode chamber, water splitting occurs at the MPF-coated membrane and La(OH) 3 precipitates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Large seasonal fluctuations of groundwater radioiodine speciation and concentrations in a riparian wetland in South Carolina

Recent studies evaluating multiple years of groundwater radioiodine ( 129 I) concentration in a riparian wetland located in South Carolina, USA identified strong seasonal concentration fluctuations, such that summer concentrations were much greater than winter concentrations. These fluctuations were observed only in the wetlands but not in the upland portion of the plume and only with 129 I, and not with other contaminants of anthropogenic origin: nitrate/nitrite, strontium-90, technecium-99, tritium, or uranium. This unexplained observation was hypothesized to be the result of strongly coupled processes involving hydrology, water temperature, microbiology, and chemistry. To test this hypothesis, an extensive historical groundwater database was evaluated, and additional measurements of total iodine and iodine speciation were made from recently collected samples. During the summer, the water table decreased by as much as 0.7 m, surface water temperature increased by as much as 15 °C, and total iodine concentrations were consistently greater (up to 680%) than the following winter months. Most of the additional iodine observed in the summer could be attributed to proportional gains in organo-iodine, and not iodide or iodate. Furthermore, 129 I concentrations were observed to be two-orders-of-magnitude greater at the bottom of the upland aquifer than at the top. A coupled hydrological and biogeochemical conceptual model is proposed to tie these observations together. First, as the surface water temperature increased during the summer, microbial activity was enhanced, which in turn stimulated the formation of mobile organo-I. Hydrological processes were also likely involved in the observed iodine seasonal changes: (1) as the water table decreased in summer, the remaining upland water entering the wetland was comprised of a greater proportion of water containing elevated iodine concentrations from the low depths, and (2) water flow paths in summer changed such that the wells intercepted more of the contaminant plume and less of the diluting rainwater (due to evapotranspiration) and streamwater (as the lower levels promote a predominantly recharging system). Furthermore, these results underscore the importance of coupled processes influencing contaminant concentrations, and the need to assess seasonal contaminant variations to optimize long-term monitoring programs of wetlands.

54 ENVIRONMENTAL SCIENCES↗

High affinity capture and concentration of quinacrine in polymorphonuclear neutrophils via vacuolar ATPase-mediated ion trapping: Comparison with other peripheral blood leukocytes and implications for the distribution of cationic drugs

Many cationic drugs are concentrated in acidic cell compartments due to low retro-diffusion of the protonated molecule (ion trapping), with an ensuing vacuolar and autophagic cytopathology. In solid tissues, there is evidence that phagocytic cells, e.g., histiocytes, preferentially concentrate cationic drugs. We hypothesized that peripheral blood leukocytes could differentially take up a fluorescent model cation, quinacrine, depending on their phagocytic competence. Quinacrine transport parameters were determined in purified or total leukocyte suspensions at 37 °C. Purified polymorphonuclear leukocytes (PMNLs, essentially neutrophils) exhibited a quinacrine uptake velocity inferior to that of lymphocytes, but a consistently higher affinity (apparent K{sub M} 1.1 vs. 6.3 μM, respectively). However, the vacuolar (V)-ATPase inhibitor bafilomycin A1 prevented quinacrine transport or initiated its release in either cell type. PMNLs capture most of the quinacrine added at low concentrations to fresh peripheral blood leukocytes compared with lymphocytes and monocytes (cytofluorometry). Accumulation of the autophagy marker LC3-II occurred rapidly and at low drug concentrations in quinacrine-treated PMNLs (significant at ≥ 2.5 μM, ≥ 2 h). Lymphocytes contained more LAMP1 than PMNLs, suggesting that the mass of lysosomes and late endosomes is a determinant of quinacrine uptake V{sub max}. PMNLs, however, exhibited the highest capacity for pinocytosis (uptake of fluorescent dextran into endosomes). The selectivity of quinacrine distribution in peripheral blood leukocytes may be determined by the collaboration of a non-concentrating plasma membrane transport mechanism, tentatively identified as pinocytosis in PMNLs, with V-ATPase-mediated concentration. Intracellular reservoirs of cationic drugs are a potential source of toxicity (e.g., loss of lysosomal function in phagocytes). - Highlights: • Quinacrine is concentrated in acidic organelles via V-ATPase-mediated ion trapping. • Human peripheral blood leukocytes capture and concentrate quinacrine. • Polymorphonuclear leukocytes do so with higher apparent affinity. • Polymorphonuclear are also more competent than lymphocytes for pinocytosis.

60 APPLIED LIFE SCIENCES↗

Transport and Retention of Concentrated Oil-in-Water Emulsions in Porous Media

Oil-in-water emulsions are routinely used in subsurface remediation. In these applications, high oil loadings present a challenge to remedial design as mechanistic insights into transport and retention of concentrated emulsions is limited. In this paper, column experiments were designed to examine emulsion transport and retention over a range of input concentrations (1.3–23% wt). Droplet breakthrough and retention data from low concentration experiments were successfully described by existing particle transport models. These models, however, failed to capture droplet transport in more concentrated systems. At high oil fraction, breakthrough curves exhibited an early fall at the end of the emulsion pulse and extending tailing. Irrespective of input concentration, all retention profiles displayed hyper-exponential behavior. Here, we extended existing model formulations to include the additional mixing processes occurring when at high oil concentrations—with focus on the influence of deposited mass and viscous instabilities. The resulting model was parametrized with low concentration data and can successfully predict concentrated emulsion transport and retention. Finally, the role of retained mass and viscous instabilities on mixing conditions can also be applied more broadly to systems with temporal or spatially variant water saturation or when viscosity contrasts exist between fluids.

54 ENVIRONMENTAL SCIENCES↗

Understanding Inlet Concentration Effects on the Electrocatalytic Conversion of CO 2 to Formic Acid in Gas-Fed Electrolyzers

The electrochemical CO 2 reduction reaction (CO2RR) to produce value-added products remains a developing technology for utilizing waste CO 2 streams. Most device-level CO2RR studies use pure CO 2 gas feeds; however, the effect of dilute CO 2 on the electrolyzer performance is an important consideration for large-scale electrolyzer operation, single-pass conversion, and real-world CO 2 source utilization. This work investigates the effect that the CO 2 concentration has on the performance of formic acid (HCOOH) producing tin oxide (SnO 2 ) and bismuth oxide (Bi 2 O 3 ) catalysts in an electrolyzer device setting. Surprisingly, SnO2 demonstrated an approximately 20% increase in HCOOH selectivity (Faradaic efficiency) when the CO 2 concentration decreased from 100 to 20%. In contrast, Bi 2 O 3 consistently demonstrated high selectivity toward HCOOH across the same CO 2 concentration range. The effects of the CO 2 concentration on selectivity were further investigated with half-cell experiments and in situ Raman spectroscopy, which revealed dynamic changes in the cathodic overpotential and chemical state of the catalyst that depended on the CO 2 concentration. Density functional theory calculations showed how changes in the surface oxidation state of Sn, varying from fully oxidized SnO 2 to metallic Sn(0), affect the thermodynamic barriers of the three main observed products: HCOOH, CO, and H 2 . Our results indicate that dilute CO 2 concentrations required larger cathodic overpotentials to sustain a fixed current density, which, in turn, pushed the Sn-based catalyst toward a more reduced surface that was favorable to HCOOH formation. On the other hand, the Bi-based catalyst remained in a metallic state at CO2RR-relevant potentials and demonstrated a consistent product selectivity regardless of CO 2 concentration. These findings highlight how varying the CO 2 inlet gas concentrations affects the chemical state of catalysts and the resulting performance metrics.

42 ENGINEERING↗