Amine-Functionalized A-Center Sphalerite for Selective and Efficient Destruction of Perfluorooctanoic Acid.

Perfluorochemicals (PFCs), especially perfluorooctanoic acid (PFOA), have contaminated the ground and surface waters throughout the world. Efficient removal of PFCs from contaminated waters has been a major challenge. This study developed a novel UV-based reaction system to achieve fast PFOA adsorption and decomposition without addition of sacrificial chemicals by using synthetic photocatalyst sphalerite (ZnS-[N]) with sufficient surface amination and defects. The obtained ZnS-[N] has the capability of both reduction and oxidation due to the suitable band gap and photo-generated hole-trapping properties created by surface defects. The cooperated organic amine functional groups on the surface of ZnS-[N] play a crucial role in the selective adsorption of PFOA, which guarantee the efficient destruction of PFOA subsequently, and 1 µg L-1 PFOA could be degraded to <70 ng L-1 after 3 h in the presence of 0.75 g L-1 ZnS-[N] under 500 W UV irradiation. In this process, the photogenerated electrons (reduction) and holes (oxidation) on the ZnS-[N] surface work in a synergistic manner to achieve complete defluorination of PFOA. This study not only provides promising green technology for PFC-pollution remediation but also highlights the significance of developing a target system capable of both reduction and oxidation for PFC degradation.

Per- and polyfluoroalkyl substances and sleep health in U.S. adults, NHANES 2005-2014.

BACKGROUND: Per- and polyfluoroalkyl substances (PFAS) are synthetic chemicals that induce oxidative inflammatory responses and disrupt the endocrine and central nervous systems, all of which can influence sleep. OBJECTIVE: To investigate the association between PFAS exposure and sleep health measures in U.S. adults. METHODS: We analyzed serum concentration data of four PFAS [perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), perfluorohexane sulfonic acid (PFHxS), and perfluorononanoic acid (PFNA)] reported for 8913 adults in NHANES 2005-2014. Sleep outcomes, including trouble sleeping, having a diagnosis of sleep disorder, and recent daily sleep duration classified as insufficient or excessive sleep (<6 or >9 h/day) were examined. Weighted logistic regression was used to estimate the association between the sleep outcomes and each PFAS modeled continuously (log2) or in exposure tertiles. We applied quantile g-computation to estimate the effect of the four PFAS as a mixture on the sleep outcomes. We conducted a quantitative bias analysis to assess the potential influence of self-selection and uncontrolled confounding. RESULTS: We observed some inverse associations between serum PFAS and trouble sleeping or sleep disorder, which were more consistent for PFOS (e.g., per log2-PFOS (ng/ml) and trouble sleeping OR = 0.93, 95%CI: 0.89, 0.98; sleep disorder OR = 0.89, 95%CI: 0.83, 0.95). Per quartile increase of the PFAS mixture was inversely associated with trouble sleeping and sleep disorder. No consistent associations were found for sleep duration across analyses. Our bias analysis suggests that the finding on sleep disorder could be explained by a moderate level of self-selection and negative confounding effects. CONCLUSIONS: We found no evidence to suggest exposure to four legacy PFAS worsened self-reported sleep health among U.S. adults. While some inverse associations between specific PFAS and sleep disorder were observed, self-selection and uncontrolled confounding biases may play a role in these findings.

Bioremediation of perfluorochemicals: current state and the way forward.

Perfluorochemicals are widely found in the environment due to their versatile uses and persistent nature. Perfluorochemicals have also been detected in human and animals due to direct or indirect exposures, giving rise to health concerns. This review aims to examine the bioremediation of perfluorochemicals with plants, bacteria and fungi, including their efficiency and limitations. It also aims to propose the future prospects of bioremediation of perfluorochemicals. This review retrieved peer-reviewed journal articles published between 2010 and 2021 from journal databases consisting of Web of Science, Scopus and ScienceDirect. This review shows that multiple Pseudomonas species could degrade perfluorochemicals particularly perfluoroalkyl acids under aerobic condition. Acidimicrobium sp. degraded perfluoroalkyl acids anaerobically in the presence of electron donors. A mixed Pseudomonas culture was more effective than pure cultures. Multiple plants were found to bioconcentrate perfluorochemicals and many demonstrated the ability to hyperaccumulate perfluoroalkyl acids, particularly Festuca rubra, Salix nigra and Betula nigra. Fungal species, particularly Pseudeurotium sp. and Geomyces sp., have the potential to degrade perfluorooctanoic acid or perfluorooctane sulphonic acid. Perfluorochemicals bioremediation could be advanced with identification of more candidate species for bioremediation, optimization of bioremediation conditions, mixed culturing, experiments with environmental media and studies on the biochemical pathways of biotransformation. This review provides comprehensive insight into the efficiency of different bacterial, plant and fungal species in perfluorochemicals bioremediation under different conditions, their limitations and improvement.

Research progress on the removal of hazardous perfluorochemicals: A review.

Perfluorinated substances are global and ubiquitous pollutants. The persistent organic pollution of perfluorochemicals (PFCs) have drawn attentions worldwide. In view of the current need for sustainable development, many researchers began to study the remediation techniques for PFCs. Due to its unique hydrophobic and oil-phobic characteristics, the requirements for the PFCs removal process are different, so that their remediation techniques are still under continuous exploration. Hence, this review summarized the removal behaviors of various PFCs on different materials which supply a good foundation for future investigations in this field. It is evident from previous literature that every remediation techniques for PFCs has its own advantages. Among various currently evaluated removal methods, adsorption seems to be one of the most commonly used and recognized techniques for PFCs pollution control. Other innovative and promising techniques, such as physical and/or chemical methods, have also been tested for their effectiveness in removing perfluorinated compounds.

Associations of perfluorinated chemical serum concentrations and biomarkers of liver function and uric acid in the US population (NHANES), 2007-2010.

BACKGROUND: Perfluorinated chemicals (PFCs) are a group of manmade compounds that are not broken down in the body. Four PFCs (PFHxS, PFOS, PFOA, and PFNA) have been found in the blood of more than 98% of the United States population. OBJECTIVES: Our goal was to assess associations between PFHxS, PFOS, PFOA, and PFNA and uric acid, alanine transferase (ALT), gamma-glutamyl transferase (GGT), asparate aminotransferase (AST), alkaline phosphate (ALP), and total bilirubin in 2007-2008 and 2009-2010 combined National Health and Nutrition Examination Survey (NHANES). METHODS: We used multivariate linear regression and logistic regression adjusted for age, gender, race/ethnicity and BMI group, poverty, smoking, and/or alcohol consumption to estimate associations. Trend analysis was performed. RESULTS: PFHxS was associated with ALT. Each quartile of PFOS was statistically associated with total bilirubin [(Q2: OR=1.44, 95% CI 1.12-1.84), (Q3: OR=1.65, 95% CI 1.25-2.18), and (Q4: OR=1.51, 95% CI 1.06-2.15)], with evidence of an increasing trend (p-value=0.028). PFOA was associated with uric acid, ALT, GGT, and total bilirubin. PFNA was linearly associated with ALT (p-value <0.001), and there was statistically significant increasing trend (p-value=0.042). CONCLUSIONS: Our analysis found evidence of associations of biomarkers of liver function and uric acid with PFHxS, PFOS, PFOA, and PFNA at levels found in the general U.S. population.

Efficient removal of per- and polyfluoroalkyl substances (PFASs) from stored rainwater by composite metal salt /polydimethyldiallylammonium chloride coagulants.

Stored rainwater, the primary source of drinking water in the villages and towns of the Loess Plateau in northwest China, has been found to contain per- and polyfluoroalkyl substances (PFASs) and lacks necessary treatment measures. Coagulation is a common water treatment process, and enhancing its efficacy in removing PFASs can significantly improve treatment efficiency, reduce costs, and minimize the environmental and health risks associated with perfluorinated compounds. This study investigated the removal efficiency of perfluorobutanoic acid (PFBA), perfluorobutanesulfonic acid (PFBS), perfluorooctanoic acid (PFOA), and perfluorooctanesulfonic acid (PFOS) using inorganic salt coagulants alone and in combination with polydimethyldiallylammonium chloride (PDMDAAC). The results indicated that the removal efficiencies of the four PFASs by polyferric chloride (PFCl) and polyaluminum chloride (PACl) increased with alkalinity. PDMDAAC significantly enhanced the coagulation removal efficiency of the four PFASs. The removal efficiency of the four PFASs was highest when the raw water pH was near 7. Within the molecular weight range of 0-500,000 for PDMDAAC, the removal efficiency of the four PFASs increased with increasing molecular weight. Charge neutralization is the primary coagulation mechanism for the removal of anionic PFASs. Therefore, this study provides guidance for selecting coagulants to remove PFASs from stored rainwater.

Per- and poly-fluoroalkyl substances in Tawny Owl (Strix aluco) feathers from Trøndelag, Norway.

Per- and polyfluoroalkyl substances (PFASs) are contaminants of global concern due to their ubiquitous occurrence in the environment, bioaccumulation and the adverse effects on organisms. Tawny Owls (Strix aluco) are documented to be exposed to increasing concentrations of perfluoroalkyl carboxylic acids (PFCAs), and have been suggested in literature as a key raptor monitoring species. Therefore, non-destructive biomonitoring efforts are of high interest. Thus far, the use of feathers for biomonitoring PFASs in Tawny Owls has not been investigated. In this study, 32 PFASs were analyzed in 49 Tawny Owl body feather samples collected from 2017 to 2020 in Trøndelag, Norway. There were 30 PFASs detected in at least one feather, with the sum concentrations ranging from 31 to 203 ng/g (w.w.). Perfluoroheptanoic acid (PFHpA) (median: 33 ng/g) and perfluorooctane sulfonamidoacetic acid (FOSAA) (median: 18 ng/g) were the two compounds with the highest concentrations. Perfluorooctane sulfonic acid (PFOS), which is banned for production and use in Norway since 2007, was found in all samples (median: 4.14 ng/g), indicating its high persistence. 8 PFASs were detected in at least 50 % of the samples: FOSAA (11-127 ng/g), PFHpA (<0.04-115 ng/g), perfluorobutanesulfonic acid (PFBS) (<0.28-21 ng/g), PFOS (0.23-13 ng/g), perfluorotridecanoic acid (PFTrDA) (0.24-5.15 ng/g), perfluorododecanoic acid (PFDoDA) (<0.28-4.45 ng/g), perfluoroundecanoic acid (PFUnDA) (<0.28-2.33 ng/g), and 1H,1H,2H,2H-perfluorooctanesulfonic acid (6:2 FTSA) (0.07-1.01 ng/g). No significant differences were found for the concentrations of PFASs between calendar years and locations, but a slight increase could be observed in the sum concentration of PFASs (Æ©32PFASs) over the sampling years. As Tawny Owls are residential owls that usually do not cover great distances, their feathers can be used as a potential alternative matrix for future biomonitoring studies. To our knowledge, this is the first study on the occurrence of 32 PFASs investigated in feathers of a Tawny Owl population.

Association between serum concentrations of perfluoroalkyl substances and global DNA methylation levels in peripheral blood leukocytes of Japanese women: A cross-sectional study.

Global DNA methylation levels in peripheral blood leukocytes can be a biomarker for cancer risk; however, levels can be changed by various factors such as environmental pollutants. We investigated the association between serum concentrations of perfluoroalkyl substances (PFASs) and global DNA methylation levels of leukocytes in a cross-sectional study using the control group of a Japanese breast cancer case-control study [397 women with a mean age of 54.1 (SD 10.1) years]. Importantly, our analysis distinguished branched PFAS isomers as different from linear isomers. The serum concentrations of 20 PFASs were measured by in-port arylation gas-chromatography negative chemical ionization mass spectrometry. Global DNA methylation levels in peripheral blood leukocytes were measured using a luminometric methylation assay. Associations between log10-transformed serum PFAS concentrations and global DNA methylation levels were evaluated by regression coefficients in multivariable robust linear regression analyses. Serum concentrations of 13 PFASs were significantly associated with increased global DNA methylation levels in leukocytes. Global DNA methylation was significantly increased by 1.45 %-3.96 % per log10-unit increase of serum PFAS concentration. Our results indicate that exposure to PFASs may increase global DNA methylation levels in peripheral blood leukocytes of Japanese women.

Double Filtration Plasmapheresis with Polyvinyl Alcohol-Based Membrane Lowers Serum Inflammation and Toxins in Patients with Hyperlipidemia.

Hyperlipidemia is increasing in prevalence and is highly correlated with cardiovascular disease (CVD). Lipid-lowering medications prevent CVD but may not be suitable when the side effects are intolerable or hypercholesterolemia is too severe. Double-filtration plasmapheresis (DF) has shown its therapeutic effect on hyperlipidemia, but its side effects are not yet known. We enrolled 45 adults with hyperlipidemia in our study. The sera before and two weeks after DF were evaluated, and we also analyzed perfluorochemicals to see if DF could remove these lipophilic toxins. After DF, all lipid profile components (total cholesterol, triglycerides, high-density lipoprotein [HDL], and low-density lipoprotein [LDL]) had significantly decreased. Leukocyte counts increased while platelet levels decreased, which may have been caused by the puncture wound from DF and consumption of platelets during the process. As for uremic toxins and inflammation, levels of C-reactive protein, uric acid, and alanine transaminase (ALT) all decreased, which may be related to the removal of serum perfluorooctane sulfonate (PFOS) and improvement of renal function. The total cholesterol/HDL ratio and triglycerides were significantly higher in the diabetes mellitus (DM) group at baseline but did not significantly differ after DF. In conclusion, DF showed potential for improving inflammation and removing serum lipids and PFOS in adults with hyperlipidemia.

Occurrence and tissue distribution of 33 legacy and novel per- and polyfluoroalkyl substances (PFASs) in Baikal seals (Phoca sibirica).

Per- and polyfluoroalkyl substances (PFASs) are bioaccumulative and associated with adverse effects in both wildlife and humans. The occurrence of 33 PFASs was assessed in the plasma, liver, blubber, and brain of 18 Baikal seals (Phoca sibirica) (16 pups and 2 adult females) from Lake Baikal, Russia (in 2011). Of the 33 congeners analysed for: perfluorooctanosulfonic acid (PFOS), 7 long chain perfluoroalkyl carboxylic acids (C8-C14 PFCAs) and 1 branched PFCA (perfluoro-3,7-dimethyloctanoic acid; P37DMOA) were most frequently detected. The PFASs in plasma and liver with the highest median concentrations were legacy congeners: perfluoroundecanoic acid (PFUnA; plasma: 11.2 ng/g w.w.; liver: 7.36 ng/g w.w.), PFOS (plasma: 8.67 ng/g w.w.; liver: 9.86 ng/g w.w.), perfluorodecanoic acid (PFDA; plasma: 5.13 ng/g w.w.; liver: 6.69 ng/g w.w.), perfluorononanoic acid (PFNA; plasma: 4.65 ng/g w.w.; liver: 5.83 ng/g w.w.) and perfluorotridecanoic acid (PFTriDA; plasma: 4.29 ng/g w.w.; liver: 2.55 ng/g w.w.). PFASs were detected in the brain of Baikal seals, indicating that PFASs cross through the blood-brain barrier. In blubber, the majority of PFASs were detected in low abundance and concentrations. In contrast to legacy PFASs, novel congeners (e.g., Gen X) were either detected infrequently or not found in Baikal seals. The worldwide occurrence of PFASs in pinnipeds was compared and lower median concentrations of PFOS were observed in Baikal seals relative to other pinnipeds. Conversely, similar concentrations of long chain PFCAs were found in Baikal seals compared to other pinnipeds. Furthermore, human exposure was assessed by estimating weekly intakes (EWI) of PFASs through Baikal seal consumption. Although PFASs concentrations were comparatively low relative to other pinnipeds, consumption of Baikal seal could exceed current regulatory guidelines.

Administration of Drugs/Gene Products to the Respiratory System: A Historical Perspective of the Use of Inert Liquids.

The present review is a historical perspective of methodology and applications using inert liquids for respiratory support and as a vehicle to deliver biological agents to the respiratory system. As such, the background of using oxygenated inert liquids (considered a drug when used in the lungs) opposed to an oxygen-nitrogen gas mixture for respiratory support is presented. The properties of these inert liquids and the mechanisms of gas exchange and lung function alterations using this technology are described. In addition, published preclinical and clinical trial results are discussed with respect to treatment modalities for respiratory diseases. Finally, this forward-looking review provides a comprehensive overview of potential methods for administration of drugs/gene products to the respiratory system and potential biomedical applications.

PYK-1105: Preclinical Evaluation of a Novel Biodegradable Vitreous Substitute for Retinal Tamponade.

Purpose: Current retinal tamponade strategies are limited by anatomic considerations (retinal break location), durability (short-term vs need for removal), and patient adherence (positioning, travel/altitude restrictions). Here we describe the preclinical safety and toxicology of a novel biodegradable hydrogel tamponade agent (PYK-1105) with the potential to improve both patient experience and outcomes after retina surgery. Methods: We studied in vitro performance to assess hydrogel gelation time, modulus, viscosity, degradation time, refractive index, and transmittance. In addition to studying in vitro and in vivo (mice and rabbits) biocompatibility, testing was performed to assess cytotoxicity, intraocular irritation, acute systemic toxicity, genotoxicity, and pyrogenicity. Furthermore, clinical safety was assessed using in vivo (rabbits and minipigs) response to vitrectomy with PYK-1105 insertion with the following measures: clinical examination, multimodal imaging, full-field electroretinography, and histopathology. Results: PYK-1105 met the predefined performance testing criteria for optimal tamponade and demonstrated excellent biocompatibility. Animal studies showed the PYK-1105 formulation to be well tolerated and nontoxic in mice, rabbits, and pigs. Conclusions: PYK-1105 holds promise as a new biodegradable tamponade agent that has the potential to improve both the patient experience and outcomes after retina surgery. Human pilot studies are warranted to further assess for safety and efficacy.

Prenatal Exposure to Endocrine-Disrupting Chemicals and Subsequent Brain Structure Changes Revealed by Voxel-Based Morphometry and Generalized Q-Sampling MRI.

Previous studies have indicated that prenatal exposure to endocrine-disrupting chemicals (EDCs) can cause adverse neuropsychiatric disorders in children and adolescents. This study aimed to determine the association between the concentrations of prenatal EDCs and brain structure changes in teenagers by using MRI. We recruited 49 mother-child pairs during the third trimester of pregnancy, and collected and examined the concentration of EDCs-including phthalate esters, perfluorochemicals (PFCs), and heavy metals (lead, arsenic, cadmium, and mercury)-in maternal urine and/or serum. MRI voxel-based morphometry (VBM) and generalized q-sampling imaging (GQI) mapping-including generalized fractional anisotropy (GFA), normalized quantitative anisotropy (NQA), and the isotropic value of the orientation distribution function (ISO)-were obtained in teenagers 13-16 years of age in order to find the association between maternal EDC concentrations and possible brain structure alterations in the teenagers' brains. We found that there are several specific vulnerable brain areas/structures associated with prenatal exposure to EDCs, including decreased focal brain volume, primarily in the frontal lobe; high frontoparietal lobe, temporooccipital lobe and cerebellum; and white matter structural alterations, which showed a negative association with GFA/NQA and a positive association with ISO, primarily in the corpus callosum, external and internal capsules, corona radiata, superior fronto-occipital fasciculus, and superior longitudinal fasciculus. Prenatal exposure to EDCs may be associated with specific brain structure alterations in teenagers.

Posterior Retinotomy vs Perfluorocarbon Liquid to Aid Drainage of Subretinal Fluid During Primary Rhegmatogenous Retinal Detachment Repair (PRO Study Report No. 10).

Purpose: This work compares posterior retinotomy vs perfluorocarbon liquid (PFCL) for subretinal fluid (SRF) drainage during pars plana vitrectomy for primary rhegmatogenous retinal detachment (RRD). Methods: In this large, multicenter, retrospective comparative study, 2620 patients underwent pars plana vitrectomy (with or without scleral buckle) for uncomplicated RRD. Patients for whom SRF was drained via the primary break without retinotomy or PFCL were excluded; those who required both retinotomy and PFCL were similarly excluded. Remaining patients were separated into "retinotomy" and "PFCL" cohorts. Subgroup analysis was conducted for macula-on and macula-off subgroups. Postoperative outcomes were analyzed and compared. Results: A total of 760 eyes (82.7%) had retinotomy and 159 eyes (17.3%) had PFCL for drainage of SRF, and baseline characteristics between the 2 groups were similar. Postoperative analysis showed similar outcomes between the retinotomy and PFCL cohorts, including final visual acuity (P = .19), redetachment rate (P = .30), anatomic success (P = .28), presence of postoperative epiretinal membrane (P = .75), and other macular pathologies (P > .99). Subgroup analysis yielded similar outcomes for macula-on and macula-off subgroups. Postoperative presence of retained PFCL was 2.4%, possibly a factor in the slightly higher number of subsequent surgical procedures (P = .03) in the PFCL cohort. Conclusions: Postoperative outcomes for retinotomy vs PFCL during RRD repair are comparable, aside from slightly greater number of subsequent surgical procedures needed in the PFCL cohort. Our analysis suggests both techniques are reasonable tools in the repair of macula-on or macula-off RRD.

Photochemical decomposition of perfluorochemicals in contaminated water.

Perfluorochemicals (PFCs) are a set of chemicals containing C-F bonds, which are concerned due to their bioaccumulation property, persistent and toxicological properties. Photocatalytic approaches have been widely studied for the effective removal of PFCs due to the mild operation conditions. This review aims to provide a comprehensive and up-to-date summary on the homogenous and heterogeneous photocatalytic processes for PFCs removal. Specifically, the homogenous photocatalytic methods for remediating PFCs are firstly discussed, including generation of hydrated electrons (eaq‒) and its performance and mechanisms for photo-reductive destruction of PFCs, the active species responsible for photo-oxidative degradation of PFCs and the corresponding mechanisms, and metal-ion-mediated (Fe(III) mainly used) processes for the remediation of PFCs. The influences of molecular structures of PFCs and water matrix, such as dissolved oxygen, humic acid, nitrate, chloride on the homogenous photocatalytic degradation of PFCs are also discussed. For heterogeneous photocatalytic processes, various semiconductor photocatalysts used for the decomposition of perfluorooctanoic acid (PFOA) are then discussed in terms of their specific properties benefiting photocatalytic performances. The preparation methods for optimizing the performance of photocatalysts are also overviewed. Moreover, the photo-oxidative and photo-reductive pathways are summarized for remediating PFOA in the presences of different semiconductor photocatalysts, including active species responsible for the degradation. We finally put forward several key perspectives for the photocatalytic removal of PFCs to promote its practical application in PFCs-containing wastewater treatment, including the treatment of PFCs degradation products such as fluoride ion, and the development of noble-metal free photocatalysts that could efficiently remove PFCs under solar light irradiation.

Perfluorochemical-facilitated plasminogen activator delivery to the airways: A novel treatment for inhalational smoke-induced acute lung injury.

BACKGROUND: Effective clinical management of airway clot and fibrinous cast formation of severe inhalational smoke-induced acute lung injury (ISALI) is lacking. Aerosolized delivery of tissue plasminogen activator (tPA) is confounded by airway bleeding; single-chain urokinase plasminogen activator (scuPA) moderated this adverse effect and supported transient improvement in gas exchange and lung mechanics. However, neither aerosolized plasminogen activator (PA) yielded durable improvements in physiologic responses or reduction in cast burden. Here, we hypothesized that perfluorochemical (PFC) liquids would facilitate PA distribution and sustain improvements in physiologic outcomes in ISALI. METHODS: Spontaneously breathing adult sheep (n = 36) received anesthesia and analgesia and were instrumented, exposed to cotton smoke inhalation, and supported by mechanical ventilation for 48 h. Groups (n = 6/group) were studied without supplemental treatment, or, starting 4 h post injury, they received intratracheal low volume (8 mL) PFC liquid alone or a dose range of tPA/PFC or scuPA/PFC suspensions (4 or 8 mg in 8 mL PFC) every 8 h. Outcomes were evaluated by sequential measurements of cardiopulmonary parameters, lung histomorphology, and biochemical analyses of bronchoalveolar lavage fluid. RESULTS: Dose-response and PA-type comparisons of outcomes demonstrated sustained superiority with low-volume PFC suspensions of scuPA over tPA or PFC alone, favoring the highest dose of scuPA/PFC suspension over lower doses, without airway bleeding. CONCLUSIONS: We propose that this improved profile over previously reported aerosolized delivery is likely related to improved dose distribution. Sustained salutary responses to scuPA/PFC suspension delivery in this translational model are encouraging and support the possibility that the observed outcomes could be of clinical importance.

[Progress on the sample techniques and analytical methods for typical perfluorinated organic acids].

Perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA) are typical perfluorinated organic acids with hepatotoxicity, embryonic toxicity, reproductive toxicity, and neurotoxicity. As the final degradation products of perfluorochemicals (PFCs) precursors, PFOS and PFOA are detected frequently. Presently, there are no unified standards for the detection of PFOS and PFOA. The analytical techniques used for PFCs in China are much less sophisticated than those in the developed countries. In this paper, the characteristics of PFOS and PFOA are introduced. Sample preparation technologies (liquid-liquid extraction, solid-phase extraction, solid-phase microextraction, ultrasonic extraction, and QuEChERS), and analytical methods (chromatography-mass spectrometry, spectrometry, ELISA, and electrochemical methods) are summarized and reviewed, so as to provide reference for monitoring and setting standards.

Theoretical studies of perfluorochemicals (PFCs) adsorption mechanism on the carbonaceous surface.

Understanding the mechanism by which perfluorochemicals (PFCs) adsorbed on carbonaceous surface is eventually important to the design and process optimization of effective PFCs removal technologies. In this study, the possible binding mechanism of six different PFCs onto carbonaceous surface was investigated by means of first principles quantum mechanical methods based on density functional theory (DFT) calculation and wave function analysis. The adsorption process fitted well with pseudo-second-order kinetic indicated that chemical bonding could not be underestimated. The results indicate that there were monolayer adsorption, electrostatic and hydrophobic interactions existed in PFCs adsorption process. DFT results suggested that the adsorption of PFCs on carbonaceous surface was one chemisorption process that accompanied by Van der Waals interactions. As there was different head functional groups in PFOS and PFOA, their adsorption capacity mainly controlled by the availability of active sites that was occupied by PFCs. The variation of chain length of PFBS and PFOS also take a certain responsible for different adsorption paths, due mainly to their hydrophobic effect. The obtained results from wave function and DFT analysis give in-depth understanding of PFCs adsorption on carbonaceous surface and help to their effectively removal.

Dialysis Membranes Influence Perfluorochemical Concentrations and Liver Function in Patients on Hemodialysis.

Introduction: Perfluoro-octanesulfonate (PFOS) and perfluoro-octanoic acid (PFOA) are two toxic perfluorochemicals (PFCs) commonly used as surfactants. PFCs are difficult to be eliminated from the body. We investigated the influence of different dialysis membranes on the concentrations of PFCs in patients under hemodialysis. Method: We enrolled 98 patients. Of these, 58 patients used hydrophobic polysulfone (PS) dialysis membranes, and the other 40 had hydrophilic membranes made by poly-methyl methacrylate (PMMA) or cellulose triacetate (CTA). Liquid chromatography tandem mass spectrometry coupled was used with isotope dilution to quantify PFOA and PFOS. Results: The predialysis concentrations of PFOA and PFOS in patients with hydrophobic PS dialysis membranes were 0.50 and 15.77 ng/mL, respectively, lower than the concentrations of 0.81 and 22.70 ng/mL, respectively, in those who used hydrophilic membranes (such as CTA or PMMA). Older patients have higher PFOS and poorer body function, with lower Karnofsky Performance Status Scale (KPSS) scores. The demographic data of the two groups were similar. However, patients with hydrophobic PS dialysis membranes had lower predialysis aspartate transaminase (AST) (p = 0.036), lower glucose levels (p = 0.017), and better body function (nonsignificantly higher KPSS scores, p = 0.091) compared with patients who used other membranes. These differences may be associated with the effects of different membranes, because PFOA positively correlated with AST, while PFOS negatively correlated with body function. Conclusions: This is the first study comparing PFC levels in uremic patients with different dialysis membrane. PS membrane may provide better clearance of PFCs and may, therefore, be beneficial for patients.

Study of endocrine disrupting compound release from different medical devices through an on-line SPE UHPLC-MS/MS method.

The paper deals with the development of an online UHPLC-MS/MS method for the identification and determination of 25 Endocrine Disrupting Chemicals (EDCs) belonging to different chemical classes (perfluorochemicals, bisphenols, alkylphenols, phthalates, and parabens). The study regards the possible EDC migration from different medical devices of diverse materials used in the routine hospitals for blood sampling or for the parenteral nutrition therapies. In order to evaluate the release of EDCs, the equipment used for blood sampling (syringes, butterfly, cannula-needle, microcapillary tube) was put in contact with a physiological solution at a prefixed time. As regards the migration tests carried out on the medical devices used in the parenteral nutrition therapy (infusion tubes, venous catheters), the catheters were undergone to internal contact with parenteral solution and external contact with physiological one, whereas the infusion tubes were subjected only to internal migration test with parenteral solution. The results demonstrated the released of some ECDs (such as parabens at the concentration of few pg mL-1, diethylphthalate and dibutylphthlate at ng mL-1, level), when using physiological solution as the leaching agent. In addition, the presence of a PFOS structural isomer was found at 29.0 ng mL-1: this compound was released in part from the infusion tubes and mostly from the venous catheters, particularly from silicone ones. Using a more lipophilic solution, such as parenteral preparations, a greater amount of EDCs was released, among which also the diethylhexylphthalate that was quantified in all the investigated devices (without highlighting particular trends or migration from PVC devices), but its concentration remained always lower than imposed maximum threshold limit on medical device of 0.1% w/w. The releases from the infusion tubes of the same materials (polyethylene) from different manufacturers are very comparable, whereas the catheter of silicone releases greater amount of EDCs than that of polyurethane.