The TALKS study to improve communication, logistical, and financial barriers to live donor kidney transplantation in African Americans: protocol of a randomized clinical trial.

BACKGROUND: Live donor kidney transplantation (LDKT), an optimal therapy for many patients with end-stage kidney disease, is underutilized, particularly by African Americans. Potential recipient difficulties initiating and sustaining conversations about LDKT, identifying willing and medically eligible donors, and potential donors' logistical and financial hurdles have been cited as potential contributors to race disparities in LDKT. Few interventions specifically targeting these factors have been tested. METHODS/DESIGN: We report the protocol of the Talking about Living Kidney Donation Support (TALKS) study, a study designed to evaluate the effectiveness of behavioral, educational and financial assistance interventions to improve access to LDKT among African Americans on the deceased donor kidney transplant recipient waiting list. We adapted a previously tested educational and social worker intervention shown to improve consideration and pursuit of LDKT among patients and their family members for its use among patients on the kidney transplant waiting list. We also developed a financial assistance intervention to help potential donors overcome logistical and financial challenges they might face during the pursuit of live kidney donation. We will evaluate the effectiveness of these interventions by conducting a randomized controlled trial in which patients on the deceased donor waiting list receive 1) usual care while on the transplant waiting list, 2) the educational and social worker intervention, or 3) the educational and social worker intervention plus the option of participating in the financial assistance program. The primary outcome of the randomized controlled trial will measure potential recipients' live kidney donor activation (a composite rate of live donor inquiries, completed new live donor evaluations, or live kidney donation) at 1 year. DISCUSSION: The TALKS study will rigorously assess the effectiveness of promising interventions to reduce race disparities in LDKT. TRIAL REGISTRATION: NCT02369354.

Recent developments in trace analysis of poly- and perfluoroalkyl substances.

Recent developments, improvements, and trends in the ultra-trace determination of per- and polyfluoroalkyl substances (PFASs) in environmental and human samples are highlighted and the remaining challenges and uncertainties are outlined and discussed. Understanding the analytical implications of such things as adsorption of PFASs to surfaces, effects of differing matrices, varying PFAS isomer response factors, potential bias effects of sampling, sample preparation, and analysis is critical to measuring highly fluorinated compounds at trace levels. These intricate analytical issues and the potential consequences of ignoring to deal with them correctly are discussed and documented with examples. Isomer-specific analysis and the development of robust multi-chemical methods are identified as topical trends in method development for an ever-increasing number of PFASs of environmental and human interest. Ultimately, the state-of-the-art of current analytical method accuracy is discussed on the basis of results from interlaboratory comparison studies.

Understanding potential exposure sources of perfluorinated carboxylic acids in the workplace.

This paper integrates perspectives from analytical chemistry, environmental engineering, and industrial hygiene to better understand how workers may be exposed to perfluorinated carboxylic acids when handling them in the workplace in order to identify appropriate exposure controls. Due to the dramatic difference in physical properties of the protonated acid form and the anionic form, this family of chemicals provides unique industrial hygiene challenges. Workplace monitoring, experimental data, and modeling results were used to ascertain the most probable workplace exposure sources and transport mechanisms for perfluorooctanoic acid (PFOA) and its ammonium salt (APFO). PFOA is biopersistent and its measurement in the blood has been used to assess human exposure since it integrates exposure from all routes of entry. Monitoring suggests that inhalation of airborne material may be an important exposure route. Transport studies indicated that, under low pH conditions, PFOA, the undissociated (acid) species, actively partitions from water into air. In addition, solid-phase PFOA and APFO may also sublime into the air. Modeling studies determined that contributions from surface sublimation and loss from low pH aqueous solutions can be significant potential sources of workplace exposure. These findings suggest that keeping surfaces clean, preventing accumulation of material in unventilated areas, removing solids from waste trenches and sumps, and maintaining neutral pH in sumps can lower workplace exposures.

A nutritional model of late embryonic vitamin A deficiency produces defects in organogenesis at a high penetrance and reveals new roles for the vitamin in skeletal development.

Vitamin A plays an essential role in vertebrate embryogenesis. In the present study, pregnant vitamin A-deficient (VAD) rats were maintained during early pregnancy on the short half-life vitamin A metabolite, all-trans retinoic acid (atRA), in an amount sufficient to support normal development to E10.5, with a higher level of atRA (250 microg atRA/g diet) provided from embryonic day (E) 8.5-10.5 to prevent mid-gestational resorption. When limiting amounts of atRA (1.5 or 12 microg/g diet) were provided after E10.5, a highly reproducible and penetrant state of late fetal vitamin A deficiency (late VAD) was induced in the organs of developing fetuses. In addition, late VAD fetuses displayed both anteriorization of cervical regions and novel posteriorization events at the thoracic and sacral levels of the skeleton, and showed sternal and pelvic malformations not previously observed in early VAD or genetic models. The expression of several Hox genes (Hoxd3 and Hoxb4) was altered in late VAD embryos, with a reduction in Hoxd3 noted as early as 1 day after instituting deficiency. All late VAD-induced malformations were prevented by the addition of retinol starting at E10.5, whereas provision of a high level of atRA throughout pregnancy improved but could not completely rescue the development of all organ systems. This work defines a nutritional model in which vitamin A deficiency can be induced during fetal development, and reveals new functions for the vitamin in the development of the axial and appendicular skeleton.

Development and validation of a wipe test method using liquid chromatography with tandem mass spectrometry for the determination of Perfluorooctanoate (PFO) on various surfaces.

Perfluorooctanoate (PFO) is the anion of perfluorooctanoic acid. As the ammonium salt, PFO has been used for 50 years as a processing aid in the commercial production of perfluorinated and highly fluorinated polymers. To assess the effectiveness of industrial hygiene controls in processes involving PFO products and intermediates, a wipe test was developed and validated to determine quantitatively the PFO concentration on six surfaces: stainless steel, polycarbonate, Formica, butyl acid suit material, laminated disposable suit material, and a painted surface. Acceptable recovery and precision results were obtained for nonporous surfaces, such as stainless steel, polycarbonate, Formica, acid suit material, and painted surfaces on a 10-cm x 10-cm surface. The analytical method was evaluated over a range of 1 to 23 ng/cm2, or 100 to 2300 ng/100 cm2. The reporting limit for the method was 100 ng/wipe.

A method for the low-level (ng/g) determination of perfluorooctanoate in carpet by LC-MS-MS using matrix extracted standards.

Fluorotelomer-based acrylic polymers are applied to the surface of carpet to impart oil, stain, and water repellence properties. Concerns that fluorotelomer-based polymers are a possible source of "low level" exposure to humans, coupled with their widespread use have prompted the need to develop a method to detect and measure perfluorooctanoate (PFO) in carpet. A liquid chromatography tandem mass spectrometry method for the determination of PFO in carpet using a dual labeled 13C-perfluoroctanoic acid (13C-PFOA) internal standard is successfully developed and validated. Levels of PFO are determined using a gradient, reversed-phase high-performance liquid chromatography (HPLC) method with acetic acid acidified water-methanol, separated on a 50 mm Phenomenex Synergi Polar RP column. Ions monitored are 413 (parent) and 369 (daughter) for PFO and 415 (parent) and 370 (daughter) for dual labeled 13C-PFOA internal standard. Accuracy and precision over three days for 5 to 900 ng/g PFO in carpet ranged from 2.4% to 7.6% and 3.7% to 14.1%, respectively. Overall extraction efficiency for samples (n=30) fortified with 13C-PFOA at 20 ng/g and perfluorooctanoic acid (PFOA) at 5, 50, and 500 ng/g is 98.9%+/-8.1%. Specificity of the method was evaluated with two different carpet samples.

Transport of ammonium perfluorooctanoate in environmental media near a fluoropolymer manufacturing facility.

In order to understand better the pathways for transport of ammonium perfluorooctanoate (APFO) from a point source, a focused investigation of environmental media (water and soil) near a fluoropolymer manufacturing facility (Site) was undertaken. Methods were developed and validated at 2 microg kg(-1) [the limit of quantitation (LOQ)] in soil, and at 50 ng l(-1) in water. Environmental media were sampled from a public water supply well field located north of the Site, across a river. The data suggest that APFO air emissions from the Site are transported to the well field, deposited onto the soil, and then migrate downward with precipitation into the underlying aquifer.

Vapor pressure determinations of 8-2 fluorortelomer alcohol and 1-H perfluorooctane by capillary gas chromatography Relative retention time versus headspace methods.

Two distinctly different capillary gas chromatographic methods were used to determine the vapor pressure of 8-2 fluorotelomer alcohol (8-2 FTOH) and 1-H perfluoroheptane at several temperatures. For measurements employing the relative retention-time method, a short polymethylsiloxane column was used from 25 to 65 degrees C. For the 8-2 FTOH, hydrocarbon alcohols and perfluoroalcohols were used as reference standards. For 1-H perfluoroheptane, hydrocarbons were used as reference standards. Vapor pressure estimates could differ by as much as an order of magnitude compared to published results determined by other (nonchromatographic) methods. This variance may be a function of solvent-solute interactions within the gas chromatographic column and the infinite dilution assumption, both used in the relative retention method. For comparison, data were also gathered using headspace gas chromatography (GC) with atomic emission detection (AED). The results from this novel GC/AED method were consistent with prior nonchromatographic results. A discussion of why headspace is the preferred technique for the determination of vapor pressure for fluorinated compounds is presented.

A method for the low-level (ng g(-1)) determination of perfluorooctanoate in paper and textile by liquid chromatography with tandem mass spectrometry.

The determination of perfluorooctanoate (PFO) in articles of commerce has become increasingly important to understand if treated products are a possible source of PFO. An LC-MS/MS method for the determination of PFO in paper and textile using a dual labeled 13C-PFOA internal standard was successfully developed and validated. Residues of PFO were determined using an isocratic, reversed-phase high-performance liquid chromatography (HPLC) method with an ammonium acetate/methanol buffer. Ions monitored were 413 (parent) and 369 (daughter) for PFO and 415 (parent) and 370 (daughter) for dual labeled 13C-PFOA internal standard. As a precaution against ubiquitous PFO that occasionally occurs in mobile phase or instrument components, two Hypercarb cartridges (4 mm) were placed before the HPLC injector. Any PFO that was captured by the cartridges was removed before each injection by flushing the system with 100% methanol prior to equilibration with the isocratic mobile phase. Overall recovery and standard deviation over a 3 day validation regimen for samples (n=54-55) fortified with PFOA at 5, 50, and 200 ng g(-1) were 114+/-4.9% for textile and 110+/-7.6% for paper. The results also established a limit of detection (LOD) of 1 ng g(-1) in textile and 2 ng g(-1) in paper based upon S/N of the 5.0 ng g(-1) fortification versus the untreated paper and textile.

Characterizing perfluorooctanoate in ambient air near the fence line of a manufacturing facility: comparing modeled and monitored values.

In order to improve our understanding of the nature, measurement and prediction of salts of perfluorooctanoic acid (PFOA) in air, two studies were performed along the fence line of a fluoropolymer manufacturing facility. First, a six-event, 24-hr monitoring series was performed around the fence line using the OSHA versatile sampler (OVS) system. Perfluorooctanoate concentrations were determined as perfluorooctanoic acid (PFOA) via liquid chromatography and mass spectrometry. Those data indicated that the majority of the PFOA was present as a particulate. No vapor-phase PFOA was detected above a detection limit of approximately 0.07 microg/m3. A follow-up study using a high-volume cascade impactor verified the range of concentrations observed in the OVS data. Both studies aligned with the major transport direction and range of concentrations predicted by an air dispersion model, demonstrating that model predictions agreed with monitoring results. Results from both monitoring methods and predictions from air dispersion modeling showed the primary direction of transport for PFOA was in the prevailing wind direction. The PFOA concentration measured at the site fence over the 10-week sampling period ranged from 0.12 to 0.9 microg/m3. Modeled predictions for the same time period ranged from 0.12 to 3.84 microg/m3. Less than 6% of the particles were larger than 4 microm in size, while almost 60% of the particles were below 0.3 microm. These studies are believed to be the first published ambient air data for PFOA in the environment surrounding a manufacturing facility.

Thermal degradation of fluorotelomer treated articles and related materials.

This study reports the first known studies to investigate the thermal degradation of a polyester/cellulose fabric substrate ("article") treated with a fluorotelomer-based acrylic polymer under laboratory conditions conservatively representing typical combustion conditions of time, temperature, and excess air level in a municipal incinerator, with an average temperature of 1000 degrees C or greater over approximately 2s residence time. The results demonstrate that the polyester/cellulose fabric treated with a fluorotelomer-based acrylic polymer is destroyed and no detectable amount of perfluorooctanoic acid (PFOA) is formed under typical municipal incineration conditions. Therefore, textiles and paper treated with such a fluorotelomer-based acrylic polymer disposed of in municipal waste and incinerated are expected to be destroyed and not be a significant source of PFOA in the environment.

Visual cues for manual control of headway.

The ability to maintain appropriate gaps to objects in one's environment is important when navigating through a three-dimensional world. Previous research has shown that the visual angle subtended by a lead/approaching object and its rate of change are important variables for timing interceptions, collision avoidance, continuous regulation of braking, and manual control of headway. However, investigations of headway maintenance have required participants to maintain a fixed distance headway and have not investigated how information about own-speed is taken into account. In the following experiment, we asked participants to use a joystick to follow computer-simulated lead objects. The results showed that ground texture, following speed, and the size of the lead object had significant effects on both mean following distances and following distance variance. Furthermore, models of the participants' joystick responses provided better fits when it was assumed that the desired visual extent of the lead object would vary over time. Taken together, the results indicate that while information about own-speed is used by controllers to set the desired headway to a lead object, the continuous regulation of headway is influenced primarily by the visual angle of the lead object and its rate of change. The reliance on visual angle, its rate of change, and/or own-speed information also varied depending on the control dynamics of the system. Such findings are consistent with an optimal control criterion that reflects a differential weighting on different sources of information depending on the plant dynamics. As in other judgements of motion in depth, the information used for controlling headway to other objects in the environment varies depending on the constraints of the task and different strategies of control.

Partitioning and removal of perfluorooctanoate during rain events: the importance of physical-chemical properties.

The potential for airborne emissions to undergo long-range transport or to be removed from the atmosphere is influenced by their physical-chemical properties. When perfluorooctanate (PFO) enters the environment, its physical-chemical properties can vary significantly, depending on whether it exists as an acid, a salt, or a dissociated ion. A summary of the physical-chemical properties of the three most likely environmental states: ammonium perfluorooctanoate (APFO), perfluorooctanoic acid (PFOA) and the dissociated perfluorooctanoate anion (PFO(-)) is presented to illustrate the distinct environmental properties of each. The most volatile species, PFOA, is shown to have a pH-dependent air-water partitioning coefficient (K(aw)). The variability of K(aw) with pH influences the potential for vapor formation from aqueous environments, including rain events. Using the pH-dependent K(aw) and measured rain and air concentrations, it is shown that vapor-phase PFOA is not likely to be present above measurable levels of 0.2 ng m(-3) (12 parts per quadrillion v/v) during a rain event. Because rain concentrations determined in this work are comparable to measurements in other parts of North America, it is unlikely that rain events are a significant source of vapor-phase PFOA for the general North American region. It is shown that PFOA exists primarily in the particle phase in ambient air near direct sources of emissions and is efficiently scavenged by rain droplets, making wet deposition an important removal mechanism for emissions originating as either PFOA or APFO. Washout ratios of particle-associated PFO were determined to range between 1 x 10(5) and 5 x 10(5), in the same range as other semi-volatile compounds for which wet deposition is an important mechanism for atmospheric removal and deposition onto soils and water bodies.

Efficient "total" extraction of perfluorooctanoate from polytetrafluoroethylene fluoropolymer.

To determine the optimum conditions for the complete extraction of perfluorooctanoate (PFO) from polytetrafluoroethylene fluoropolymers, sample preparation and pressurized solvent extraction (PSE) conditions were investigated. Solvent extraction temperature, solvent residence time, relaxation time between extractions, and the effects of heating before PSE showed that methanol at 150 degrees C extraction temperature and a 12 min solvent residence time were the most efficient conditions. Preheating the polymer before extraction at 150 degrees C for 24 h significantly enhanced the quantity of PFO removed. Heating above 150 degrees C resulted in loss of PFO. PFO was determined by liquid chromatography with tandem mass spectrometry.

Determination of perfluorooctanoic acid (PFOA) extractable from the surface of commercial cookware under simulated cooking conditions by LC/MS/MS.

Salts of pentadecafluorooctanoic acid (PFOA) are polymerization aids used in the manufacture of fluoropolymers; one of the applications of fluoropolymers is the coating of metal cookware products. A method was developed to determine if PFOA might be present in and extracted from the surface of commercial frying pans coated with a DuPont fluoropolymer under simulated cooking conditions. Commercial grade cookware was obtained, then extracted with water and ethanol/water mixtures at 100 and 125 degrees C, and the resulting extracts were analyzed by liquid chromatography tandem mass spectrometry (LC/MS/MS). Detection and quantification limits as low as 100 pg cm(-2) were demonstrated. None of the fluoropolymer treated cookware samples analyzed showed detectable levels of PFOA when extracted under simulated cooking conditions.

Comparison of pressurized solvent and reflux extraction methods for the determination of perfluorooctanoic acid in polytetrafluoroethylene polymers using LC-MS-MS.

Both pressurized solvent extraction (PSE) and reflux extraction in various solvents were used to select the most efficient system for the determination of the quantity of perfluorooctanoic acid (PFOA) present in polytetrafluoroethylene polymers. After evaporating the solvent, PFOA was determined using liquid chromatography tandem mass spectrometry. Ethanol, water and methanol gave comparable results and were shown to be good solvents for this extraction. Acetonitrile was a reasonable solvent using the reflux extraction method, but not with PSE. Chloroform resulted in poor recovery for both extraction methods. PSE proved to be the more efficient extraction method.

Method for the determination of perfluorooctanoic acid in air samples using liquid chromatography with mass spectrometry.

Perfluorooctanoic acid is a completely fluorinated carboxylic acid that is usually used in the ammonium salt form as a processing aid in the production of many fluoropolymers and fluoroelastomers. Ammonium perfluorooctanoate readily dissociates in water to give the ammonium and perfluorooctanoate ions. Perfluorooctanoate has been reported to be present in low levels in human serum in the United States and Europe. This study reports on the development and validation of a method for the determination of perfluorooctanoic acid in air samples. This method uses the Occupational Safety and Health Administration (OSHA) Versatile Sampler (OVS) with a nominal 0.3 micro m filter and polystyrene resin sorbent (XAD-2 or XAD-4) followed by determination of the perfluorooctanoate anion by liquid chromatography mass spectrometry. The method was validated in the range of 0.474 to 47.4 microg/m3 for a 480-L sample. Breakthrough studies showed samples could be collected at 1 L/min for 24 hours or at 15 L/min up to 8 hours without breakthrough. Extract storage stability tests showed that sample extracts in methanol remain stable in glass autosampler vials for up to 13 days following initial injection. Perfluorooctanoic acid stability on OVS tubes was unaffected at both refrigerated and ambient temperatures. The overall average retention efficiency was 92.1% with a pooled RSD95 of 5.8% at five concentration levels (0.474 microg/m3 to 47.4 microg/m3).

Vapor pressure and intramolecular hydrogen bonding in fluorotelomer alcohols.

Vapor pressure and aqueous solubility are important parameters used to estimate the potential for transport of chemical substances in the atmosphere. For fluorotelomer alcohols (FTOHs), currently under scrutiny by environmental scientists as potential precursors of persistent perfluorocarboxylates (PFCAs), vapor pressure is the more significant property since these compounds are only very sparingly soluble in water. We have measured the vapor pressures of a homologous series of fluorotelomer alcohols, F(CF2CF2)nCH2CH2OH (n = 2-5), in the temperature range 21-250 degrees C by three independent methods: (a) a method suitable for very low vapor pressures at ambient temperatures (gas-saturation method), (b) an improved boiling point method at controlled pressures (Scott method), and (c) a novel method, requiring milligram quantities of substance, based on gas-phase NMR, a technique largely unfamiliar to chemists and holding promise for studies of relevance to environmental chemistry. The concordant values obtained indicate that recently published vapor pressure data overestimate the vapor pressure at ambient temperature, and therefore the volatility, of this series of fluorinated compounds. It was suggested that substantial intramolecular -O-H...F- hydrogen bonding between the hydroxylic proton and the two fluorines next to the ethanol moiety was responsible for their putative high volatility. Therefore, we have used gas-phase NMR, gas-phase FTIR, 2D NMR heteronuclear Overhauser effect measurements, and high-level ab initio computations to investigate the intramolecular hydrogen bonding in fluorotelomer alcohols. Our studies unequivocally show that hydrogen bonding of this type is not significant and cannot contribute to and cause unusual volatility. The substantially lower vapor pressure at ambient temperatures than previously reported resulting from our work is important in developing a valid understanding of the environmental transport behavior of this class of compounds.

Perceived orientation in physical and virtual environments: changes in perceived orientation as a function of idiothetic information available.

Two experiments examined perceived spatial orientation in a small environment as a function of experiencing that environment under three conditions: real-world, desktop-display (DD), and head-mounted display (HMD). Across the three conditions, participants acquired two targets located on a perimeter surrounding them, and attempted to remember the relative locations of the targets. Subsequently, participants were tested on how accurately and consistently they could point in the remembered direction of a previously seen target. Results showed that participants were significantly more consistent in the real-world and HMD conditions than in the DD condition. Further, it is shown that the advantages observed in the HMD and real-world conditions were not simply due to nonspatial response strategies. These results suggest that the additional idiothetic information afforded in the real-world and HMD conditions is useful for orientation purposes in our presented task domain. Our results are relevant to interface design issues concerning tasks that require spatial search, navigation, and visualization.

Vitamin A deficiency in the late gastrula stage rat embryo results in a one to two vertebral anteriorization that extends throughout the axial skeleton.

Vitamin A and its metabolites are known to be involved in patterning the vertebrate embryo. Study of the effect of vitamin A on axial skeletal patterning has been hindered by the fact that deficient embryos do not survive past midgestation. In this study, pregnant vitamin A-deficient rats were maintained on a purified diet containing limiting amounts of all-trans retinoic acid (12 microg atRA/g diet) and given a daily oral bolus dose of retinol starting at embryonic day 0.5, 8.25, 8.5, 8.75, 9.25, 9.5, 9.75, or 10.5. Embryos were recovered at E21.5 for analysis of the skeleton and at earlier times for analysis of select mRNAs. Normal axial skeletal development and patterning were observed in embryos from pregnant animals receiving retinol starting on or before E8.75. Delay of retinol supplementation to E9.5 or later resulted in a marked increase in both occurrence and severity of skeletal malformations, extending from the craniocervical to sacral regions. Embryos from the groups receiving retinol starting at E9.5 and E9.75 had one-vertebral anterior transformations of the cervical, thoracic, lumbar, and sacral vertebrae. Few embryos survived in the E10.5 group, but these embryos yielded the most severe and extensive anteriorization events. The skeletal alterations seen in vitamin A deficiency are associated with posterior shifts in the mesodermal expression of Hoxa-4, Hoxb-3, Hoxd-3, Hoxd-4, and Hoxa-9 mRNAs, whereas the anterior domains of Hoxb-4 and Cdx2 expression are unaltered. This work defines a critical window of development in the late gastrula-stage embryo when vitamin A is essential for normal axial skeletal patterning and shows that vitamin A deficiency causes anterior homeotic transformations extending from the cervical to lumbosacral regions.