Enhancement of perfluorooctanoate and perfluorooctanesulfonate activity at acoustic cavitation bubble interfaces

Acoustic cavitation driven by ultrasonic irradiation decomposes and mineralizes the recalcitrant perfluorinated surfactants perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA). Pyrolytic cleavage of the ionic headgroup is the rate-determining step. In this study, we examine the sonochemical adsorption of PFOX, where X = S for PFOS and A for PFOA, by determining kinetic order and absolute rates over an initial PFOX concentration range of 20 nM to 200 μM. Sonochemical PFOX kinetics transition from pseudo-first-order at low initial concentrations, [PFOX]_i 40 μM, as the bubble interface sites are saturated. At PFOX concentrations below 100 μM, concentration-dependent rates were modeled with Langmuir−Hinshelwood (LH) kinetics. Empirically determined rate maximums, V_(Max)^(−PFOA) = 2230 ± 560 nM min^−1 and V_(Max)^(−PFOS) = 230 ± 60 nM min^−1, were used in the LH model, and sonochemical surface activities were estimated to be K_(Sono)^(PFOS) = 120000 M^−1 and K_(Sono)^(PFOA) = 28500 M^−1, 60 and 80 times greater than equilibrium surface activities, K_(Eq)^(PFOS) and K_(Eq)^(PFOA). These results suggest enhanced sonochemical degradation rates for PFOX when the bubble interface is undersaturated. The present results are compared to previously reported sonochemical kinetics of nonvolatile surfactants

What general practitioners need to know about patent foramen ovale

A patent foramen ovale (PFO) consists of a hole between the right and left atriums of the heart that did not close the way it should after birth. Twenty five percent of the population have a PFO, but this usually does not cause problems, because the opening is functionally closed by the difference in pressure between the heart and the chest. This study is a literature review about the clinical significance of PFO and its management in three clinical situations: cryptogenic strokes, migraine with aura and scuba divers who sustained a decompression sickness. PFOs had been linked with various medical conditions such as strokes, migraine, and with certain types of decompression sickness (DCS). In general, this association is not very well established. Young patients who sustain a cardiovascular event without a known cause (cryptogenic stroke) have resulted in the tendency to screen these patents becoming the norm and more PFOs are being closed using standard methods and devices. The association of PFOs and migraine attacks is less clear. In the case of scuba divers the risk of suffering from a decompression accident is increased if one has a PFO. The management of these patients remains difficult.peer-reviewe

Perfluorooctane Sulfonate (PFOS) and Related Perfluorinated Compounds in Human Maternal and Cord Blood Samples: Assessment of PFOS Exposure in a Susceptible Population during Pregnancy

Fluorinated organic compounds (FOCs), such as perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), and perfluorooctane sulfonylamide (PFOSA), are widely used in the manufacture of plastic, electronics, textile, and construction material in the apparel, leather, and upholstery industries. FOCs have been detected in human blood samples. Studies have indicated that FOCs may be detrimental to rodent development possibly by affecting thyroid hormone levels. In the present study, we determined the concentrations of FOCs in maternal and cord blood samples. Pregnant women 17–37 years of age were enrolled as subjects. FOCs in 15 pairs of maternal and cord blood samples were analyzed by liquid chromatography–electrospray mass spectrometry coupled with online extraction. The limits of quantification of PFOS, PFOA, and PFOSA in human plasma or serum were 0.5, 0.5, and 1.0 ng/mL, respectively. The method enables the precise determination of FOCs and can be applied to the detection of FOCs in human blood samples for monitoring human exposure. PFOS concentrations in maternal samples ranged from 4.9 to 17.6 ng/mL, whereas those in fetal samples ranged from 1.6 to 5.3 ng/mL. In contrast, PFOSA was not detected in fetal or maternal samples, whereas PFOA was detected only in maternal samples (range, < 0.5 to 2.3 ng/mL, 4 of 15). Our results revealed a high correlation between PFOS concentrations in maternal and cord blood (r(2) = 0.876). However, we did not find any significant correlations between PFOS concentration in maternal and cord blood samples and age bracket, birth weight, or levels of thyroid-stimulating hormone or free thyroxine. Our study revealed that human fetuses in Japan may be exposed to relatively high levels of FOCs. Further investigation is required to determine the postnatal effects of fetal exposure to FOCs

Sonochemical Degradation of Perfluorooctane Sulfonate (PFOS) and Perfluorooctanoate (PFOA) in Landfill Groundwater: Environmental Matrix Effects

Perfluorinated chemicals such as perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) are environmentally persistent and recalcitrant to most conventional chemical and microbial treatment technologies. In this paper, we show that sonolysis is able to decompose PFOS and PFOA present in groundwater beneath a landfill. However, the pseudo first-order rate constant for the sonochemical degradation in the landfill groundwater is reduced by 61 and 56% relative to MilliQ water for PFOS and PFOA, respectively, primarily due to the presence of other organic constituents. In this study, we evaluate the effect of various organic compounds on the sonochemical decomposition rates of PFOS and PFOA. Organic components in environmental matrices may reduce the sonochemical degradation rates of PFOS and PFOA by competitive adsorption onto the bubble−water interface or by lowering the average interfacial temperatures during transient bubble collapse events. The effect of individual organic compounds depends on the Langmuir adsorption constant, the Henry’s law constant, the specific heat capacity, and the overall endothermic heat of dissociation. Volatile organic compounds (VOCs) are identified as the primary cause of the sonochemical rate reduction for PFOS and PFOA in landfill groundwater, whereas the effect of dissolved natural organic matter (DOM) is not significant. Finally, a combined process of ozonation and sonolysis is shown to substantially recover the rate loss for PFOS and PFOA in landfill groundwater

Exposure to perfluoroalkyl acids and markers of kidney function among children and adolescents living near a chemical plant.

BACKGROUND: Serum levels of perfluorooctanoic acid (PFOA) have been associated with decreased renal function in cross-sectional analyses, but the direction of the association is unclear. OBJECTIVES: We examined the association of measured and model-predicted serum PFOA concentrations with estimated glomerular filtration rate (eGFR), a marker of kidney function, in a highly exposed population (median serum PFOA, 28.3 ng/mL). METHODS: We measured serum creatinine, PFOA, perfluorooctane sulfonate (PFOS), perfluorononanoic acid (PFNA), and perfluorohexane sulfonate (PFHxS) and calculated eGFR in 9,660 children 1 to < 18 years of age at study enrollment. We predicted concurrent and historical serum PFOA concentrations using a validated environmental, exposure, and pharmacokinetic model based on individual residential histories, and used linear regression to estimate the association between eGFR and measured and predicted serum PFOA concentrations. We hypothesized that predicted serum PFOA levels would be less susceptible to reverse causation than measured levels. RESULTS: An interquartile range increase in measured serum PFOA concentrations [IQR ln(PFOA) = 1.63] was associated with a decrease in eGFR of 0.75 mL/min/1.73 m(2) (95% CI: -1.41, -0.10; p = 0.02). Measured serum levels of PFOS, PFNA, and PFHxS were also cross-sectionally associated with decreased eGFR. In contrast, predicted serum PFOA concentrations at the time of enrollment were not associated with eGFR (-0.10; 95% CI: -0.80, 0.60; p = 0.78). Additionally, predicted serum PFOA levels at birth and during the first ten years of life were not related to eGFR. CONCLUSIONS: Our findings suggest that the cross-sectional association between eGFR and serum PFOA observed in this and prior studies may be a consequence of, rather than a cause of, decreased kidney function

Reducing exposure to high levels of perfluorinated compounds in drinking water improves reproductive outcomes: evidence from an intervention in Minnesota.

BackgroundPer- and polyfluoroalkyl substances (PFASs) have been detected in drinking water supplies around the world and are the subject of intense regulatory debate. While they have been associated with several illnesses, their effects on reproductive outcomes remains uncertain.MethodsWe analyzed birth outcomes in the east Minneapolis-St. Paul metropolitan area from 2002 to 2011, where a portion of the population faced elevated exposure to PFASs due to long-term contamination of drinking water supplies from industrial waste disposal. Installation of a water filtration facility in the highly contaminated city of Oakdale, MN at the end of 2006 resulted in a sharp decrease in exposure to PFASs, creating a "natural experiment". Using a difference-in-differences approach, we compare the changes in birth outcomes before and after water filtration in Oakdale to the changes over the same period in neighboring communities where the treatment of municipal water remained constant.ResultsAverage birth weight and average gestational age were statistically significantly lower in the highly exposed population than in the control area prior to filtration of municipal water supply. The highly exposed population faced increased odds of low birth weight (adjusted odds ratio 1.36, 95% CI 1.25-1.48) and pre-term birth (adjusted odds ratio 1.14, 95% CI 1.09-1.19) relative to the control before filtration, and these differences moderated after filtration. The general fertility rate was also significantly lower in the exposed population (incidence rate ratio 0.73, 95% CI 0.69-0.77) prior to filtration and appeared to be rebounding post-2006.ConclusionsOur findings provide evidence of a causal relationship between filtration of drinking water containing high levels of exposure to PFASs and improved reproductive outcomes

Exposure to Endocrine Disruptors and Nuclear Receptors Gene Expression in Infertile and Fertile Men from Italian Areas with Different Environmental Features

Internal levels of selected endocrine disruptors (EDs) (i.e., perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), di-2-ethylhexyl-phthalate (DEHP), mono-(2-ethylhexyl)-phthalate (MEHP), and bisphenol A (BPA)) were analyzed in blood/serum of infertile and fertile men from metropolitan, urban and rural Italian areas. PFOS and PFOA levels were also evaluated in seminal plasma. In peripheral blood mononuclear cells (PBMCs) of same subjects, gene expression levels of a panel of nuclear receptors (NRs), namely estrogen receptor α (ERα) estrogen receptor β (ERβ), androgen receptor (AR), aryl hydrocarbon receptor (AhR), peroxisome proliferator-activated receptor γ (PPARγ) and pregnane X receptor (PXR) were also assessed. Infertile men from the metropolitan area had significantly higher levels of BPA and gene expression of all NRs, except PPARγ, compared to subjects from other areas. Subjects from urban areas had significantly higher levels of MEHP, whereas subjects from rural area had higher levels of PFOA in both blood and seminal plasma. Interestingly, ERα, ERβ, AR, PXR and AhR expression is directly correlated with BPA and inversely correlated with PFOA serum levels. Our study indicates the relevance of the living environment when investigating the exposure to specific EDs. Moreover, the NRs panel in PBMCs demonstrated to be a potential biomarker of effect to assess the EDs impact on reproductive health

Omnipresent Chemicals: TSCA Preemption in the Wake of PFAS Contamination

Over the past few decades, studies addressing the harms of PFAS have gradually progressed, and now scientists believe increased exposure could lead to reproductive defects and a higher risk of cancer. Given the amplified concern surrounding these pervasive chemicals, states are proactively filing lawsuits on behalf of their citizens and enacting legislation to combat this nation-wide contamination epidemic. However, given the 2016 Amendment to the Toxic Substances Control Act of 1976, states looking to regulate the manufacturing or looking to ratify a state- wide ban on the manufacturing of such chemicals may face preemption under actions taken by the United States Environmental Protection Agency. This Note focuses on the possible loss of state autonomy with regards to PFAS regulation. It addresses the issues states might face given the restrictive nature of the newly enacted preemption provisions of the Toxic Substances Control Act, while also examining the Act’s possible deficiencies. Ultimately, recognizing a need for creative solutions outside the scope of manufacturing regulations may provide the best solutions for states to combat these ubiquitous chemicals

Photochemical transformation of perfluoroalkyl acid precursors in water using engineered nanomaterials

The production of perfluoroalkyl acids (PFAAs) has been phased out over recent decades; however, no significant decline in their environmental concentrations has been observed. This is partly due to the photochemical decomposition of PFAAs precursors (PrePFAAs) which remain in extensive use. The decomposition of PrePFAAs may be accelerated by the light-activated engineered nanomaterials (ENMs) in water. In light of this hypothesis, we investigated the photochemical transformation of three PrePFAAs, which are 8:2 fluorotelomer sulfonic acid (8:2 FTSA), 8:2 fluorotelomer alcohol (8:2 FTOH), and 2-(N-ethylperfluorooctane-1-sulfonamido ethyl] phosphate (SAmPAP), in the presence of six ENMs under simulated sunlight irradiation. The transformation rates of 8:2 FTSA and 8:2 FTOH were increased by 2–6 times when in the presence of six ENMs. However, most of ENMs appeared to inhibit the decomposition of SAmPAP. The transformation rates of PrePFAAs were found to depend on the yield of reactive oxygen species generated by ENMs, but the rates were also related to compound photo-stability, adsorption to surfaces, and photo-shielding effects. The PrePFAAs are transformed to perfluorooctanoic acid (PFOA) or/and perfluorooctane sulfonate (PFOS) with higher toxicity and longer half-life, PFOA or PFOS and a few PFAAs having shorter carbon chain lengths. Higher concentrations of the PFAAs photodegradation products were observed in the presence of most of the ENMs