Comparison of perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA) and perfluorobutane sulfonate (PFBS) removal in a combined adsorption and electrochemical oxidation process.

This study focused on three of the most studied PFAS molecules, namely perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA) and perfluorobutane sulfonate (PFBS). They were compared in terms of their adsorption capacity onto graphite intercalated compound (GIC), a low surface area, highly conductive and cheap adsorbent. The adsorption on GIC followed a pseudo second order kinetics and the maximum adsorption capacity using Langmuir was 53.9 µg/g for PFOS, 22.3 µg/g for PFOA and 0.985 µg/g for PFBS due to electrostatic attraction and hydrophobic interactions. GIC was added into an electrochemical oxidation reactor and >100 µg/L PFOS was found to be fully degraded (<10 ng/L) leaving degradation by-products such as PFHpS, PFHxS, PFPeS, PFBS, PFOA, PFHxA and PFBA below 100 ng/L after 5 cycles of adsorption onto GIC for 20 min followed by regeneration at 28 mA/cm2 for 10 min. PFBS was completely removed due to degradation by aqueous electrons on GIC flakes. Up to 98 % PFOA was removed by the process after 3 cycles of adsorption onto GIC for 20 min followed by regeneration at 25 mA/cm2 for 10 min. When PFBS was spiked individually, only 17 % was removed due to poor adsorption on GIC. There was a drop of 3-40 % by treating PFOS, PFOA and smaller sulfonates in a real water matrix under the same electrochemical conditions (20 mA/cm2), but PFOS and PFOA removal percentage were 95 and 68 % after 20 min at 20 mA/cm2.

Role of ABCB1 and ABCB4 in renal and biliary excretion of perfluorooctanoic acid in mice.

BACKGROUND: Perfluorooctanoic acid (PFOA) is one of the major per- and polyfluoroalkyl substances. The role of ATP-binding cassette (ABC) transporters in PFOA toxicokinetics is unknown. METHODS: In this study, two ABC transporters, ABCB1 and ABCB4, were examined in mice with single intravenous PFOA administration (3.13 µmol/kg). To identify candidate renal PFOA transporters, we used a microarray approach to evaluate changes in gene expression of various kidney transporters in Abcb4 null mice. RESULTS: Biliary PFOA concentrations were lower in Abcb4 null mice (mean ± standard deviation: 0.25 ± 0.12 µg/mL) than in wild-type mice (0.87 ± 0.02 µg/mL). Immunohistochemically, ABCB4 expression was confirmed at the apical region of hepatocytes. However, renal clearance of PFOA was higher in Abcb4 null mice than in wild-type mice. Among 642 solute carrier and ABC transporters, 5 transporters showed significant differences in expression between wild-type and Abcb4 null mice. These candidates included two major xenobiotic transporters, multidrug resistance 1 (Abcb1) and organic anion transporter 3 (Slc22a8). Abcb1 mRNA levels were higher in Abcb4 null mice than in wild-type mice in kidney. In Abcb4 null mice, Abcb1b expression was enhanced in proximal tubules immunohistochemically, while that of Slc22a8 was not. Finally, in Abcb1a/b null mice, there was a significant decrease in the renal clearance of PFOA (0.69 ± 0.21 vs 1.1 mL ± 0.37/72 h in wild-type mice). A homology search of ABCB1 showed that several amino acids are mutated in humans compared with those in rodents and monkeys. CONCLUSIONS: These findings suggest that, in the mouse, Abcb4 and Abcb1 are excretory transporters of PFOA into bile and urine, respectively.

Association between lignan polyphenol bioavailability and enterotypes of isoflavone metabolism: A cross-sectional analysis.

Lignan polyphenols derived from plants are metabolized by bacteria in the gut to mammalian lignans, such as enterolactone (ENL) and enterodiol (END). Mammalian lignan intake has been reported to be associated with obesity and low blood glucose levels. However, the factors that are responsible for individual differences in the metabolic capacity for ENL and END are not well understood. In the present study, the effects of enterotypes of isoflavone metabolism, equol producers (EQP) and O-desmethylangolensin producers (O-DMAP), on lignan metabolism were examined. EQP was defined by urinary daidzein (DAI) and equol concentrations as log(equol/DAI) ≥ -1.42. O-DMAP was defined by urinary DAI and O-DMA concentrations as O-DMA/DAI > 0.018. Isoflavone and lignan concentrations in urine samples from 440 Japanese women were measured by gas chromatography-mass spectrometry. Metabolic enterotypes were determined from the urinary equol and O-DMA concentrations. Urinary END and ENL concentrations were compared in four groups, combinations of EQP (+/-) and O-DMAP (+/-). The urinary lignan concentration was significantly higher in the O-DMAP/EQP group (ENL: P<0.001, END: P<0.001), and this association remained significant after adjusting for several background variables (END: ß = 0.138, P = 0.00607 for EQP and ß = 0.147, P = 0.00328 for O-DMAP; ENL: ß = 0.312, P<0.001 for EQP and ß = 0.210, P<0.001 for O-DMAP). The ENL/END ratio was also highest in the O-DMAP/EQP group, indicating that equol and O-DMA metabolizing gut bacteria may be involved in lignan metabolism. In conclusion, urinary lignan concentrations were significantly higher in groups containing either EQP or O-DMAP than in the non-EQP/non-O-DMAP group. The variables and participants in this study were limited, which the possibility of confounding by other variables cannot be ruled out. However, there are no established determinants of lignan metabolism to date. Further research is needed to determine what factors should be considered, and to examine in different settings to confirm the external validity.

Association between urinary zinc excretion and isoflavone-metabolizing enterotypes among Japanese females: a cross-sectional study.

BACKGROUND: Zinc absorption and competition among gut bacteria have been reported in animal studies. Thus, gut bacteria may modify zinc availability in humans. Metabolism of intestinal bacteria is known to be necessary for the activation of several phytoconstituents in the body. For example, equol, a typical substance of soybean isoflavone, is produced by intestinal bacteria metabolizing daidzein and the enterotype is one of distinct ones among Japanese population. The difference in the intestinal microflora can modify the bioavailability of zinc. In this study, we examined urinary zinc concentrations in adult female equol producers (EQPs). METHODS: Urine samples from women participating in health examinations in Miyagi, Okinawa, Kyoto, Kochi, and Hokkaido prefectures were used; from total 17,484 samples, approximately 25 samples were randomly selected for each age group from 30 to 60 years per region (subsample: n = 520), and 520 samples with available urinary zinc concentration (determined by flame atomic absorption analysis) and enterobacterial type were analyzed. EQP was defined as log(equol/daidzein) ≥ -1.42, and urinary concentrations were corrected for creatinine concentration. Urinary zinc concentrations were compared by Student's t-test and multiple regression analyses. RESULTS: The geometric mean urinary zinc concentration (µg/g-Cr) was lower in EQP than in non-EQP (p = 0.0136 by t-test after logarithm transformation). On the other hand, there was no correlation between urinary zinc concentration with daidzein (r = -0.0495, P = 0.436) and equol concentrations (r = -0.0721, P = 0.256). There was a significant negative association between urinary zinc concentration and EQP (ß = -0.392, P = 0.0311) after adjusting with other potential confounding variables, such as daidzein intake. CONCLUSIONS: The results suggest that gut bacteria that produce equol are involved in the metabolism of zinc. Based on previous studies, the bacteria that affect the metabolism of both substances are thought to be Enterococcus. Future studies are expected to identify specific intestinal bacteria for zinc availability and understand individual differences in the effects of micronutrients.

History of Changes in the Protocol of Clinical Trial of Zinc Supplementation in Treatment of COVID-19 by Hydroxychloroquine.

An article published in this journal used a randomized controlled trial to evaluate the efficacy of combining chloroquine/hydroxychloroquine (CQ/HCQ) and zinc in the treatment of COVID-19 patients. Findings from this study indicate that zinc supplements did not enhance the clinical efficacy of hydroxychloroquine in improving COVID-19 treatment. Although this finding is consistent with many previous studies, several concerns regarding study protocol and trial registration, including interventions and primary outcomes, have been raised in which the protocol has been changed after the completion of the recruitment.

Plasma eicosapentaenoic acid, a biomarker of fish consumption, is associated with perfluoroalkyl carboxylic acid exposure in residents of Kyoto, Japan: a cross-sectional study.

BACKGROUND: Per- and polyfluoroalkyl substances (PFASs) are highly fluorinated organic compounds that have been widely used in industry during the past few decades. The main exposure routes for PFASs are thought to be the diet, drinking water, and dust. In this study, we aimed to evaluate the relationship between perfluoroalkyl carboxylic acids (PFCAs, members of the PFAS family) and the plasma eicosapentaenoic acid-to-arachidonic acid ratio (EPA/AA), a biological indicator of seafood intake, to determine whether seafood intake may represent a means of exposure to PFASs in the Japanese population. METHODS: We performed a cross-sectional study using 131 plasma samples collected from residents of Kyoto, Japan in 2013 and held in the Kyoto University biological sample bank. The concentrations of perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluoroundecanoic acid (PFDA), perfluoroundecanoic acid (PFUnDA), perfluorododecanoic acid (PFDoDA), perfluorotridecanoic acid (PFTrDA), EPA, and AA were quantified by gas chromatography-mass spectrometry, and multiple linear regression was used to analyze the results. RESULTS: In multiple linear regression analyses with age and eGFR, PFOA showed a significant positive linear association with age (p = 0.0005); PFHpA showed a significant negative linear association with estimated glomerular filtration rate (eGFR; p = 0.0338); and PFHpA, PFOA, PFNA, PFUnDA, and PFDoDA exhibited significant positive linear associations with EPA/AA (p = 0.0358, 0.0056, 0.0242, <0.0001, and <0.0001, respectively). Because only PFHpA and PFOA were associated with smoking, their concentrations were examined again with smoking variable included and neither showed an association with smoking habit. PFOA showed a significant linear association with EPA/AA ratio (p = 0.0072), but PFHpA did not (p = 0.051). CONCLUSIONS: The plasma concentrations of PFOA, PFNA, PFUnDA and PFDoDA significantly associated with the EPA/AA ratio in residents of Kyoto.

Chlorinated persistent organic pollutants in human breast milk in the Miyagi Prefecture disaster-affected area 1 year after the Great East Japan Earthquake of 2011.

BACKGROUND: In the Great East Japan Earthquake of 11 March 2011, an earthquake and accompanying tsunami struck the Tohoku region of northeastern Japan. Buildings collapsed and the tsunami spread waste, including hazardous materials. This study aimed to determine the concentrations of persistent organic pollutants (POPs) in the breast milk of mothers living in the disaster-affected area of Sendai 1 year after the earthquake. Temporal trends in the POPs concentrations were evaluated by comparison with previous studies. METHODS: One hundred breast milk samples were obtained from lactating mothers at a hospital in Sendai in 2012. The results were compared with those from other years to examine whether there were changes in the POPs concentrations after the earthquake. We measured polychlorinated biphenyls (PCBs) and organochlorine pesticides, such as chlordanes, using gas chromatography-mass spectrometer (GC-MS) with negative chemical ionization, and dichlorodiphenyl trichloroethane (DDT) and its metabolites using GC-MS with electron impact ionization. RESULTS: The mean total PCBs (11 congeners), total chlordane, and total DDT concentrations were 76.2 ng/g lipid, 39.8 ng/g lipid, and 73.5 ng/g lipid, respectively. For the samples collected in 2012, the concentrations of POPs in breast milk showed minimal changes compared with results from previous years for samples collected at the same hospital in Sendai. CONCLUSIONS: Our study demonstrates that 1 year after the earthquake and tsunami, the concentrations of chlorinated POPs in breast milk had not changed substantially.

Formation and Degradability of Per- and Polyfluoroalkyl Substances in River Soils around a Fluoropolymer-Manufacturing Plant in Osaka, Japan.

Our previous studies reported that perfluorooctanoic acid (PFOA) contamination decreased in well, tap, and surface water around a fluoropolymer plant in Osaka, Japan, between 2003 and 2016. In this study, we evaluated the degradability of PFOA and perfluorohexanoic acid in river soils to identify the influence of the degradation on the perfluorocarboxylic acids (PFCAs) in the Yodo River Basin. We also investigated the influence of abiotic oxidation on the formation of PFCAs in soils and measured the fluorotelomer alcohols (FTOHs) as precursors of PFCAs in the soil and air samples collected at Osaka and Kyoto. No major degradations were observed in soils contaminated with PFCA during the 24-week experimental period, while the PFOA levels increased only in the control group. The PFCA levels significantly increased after oxidation in this group. The dominant FTOH in soils was 10:2 FTOH, whereas 6:2 FTOH was dominant in the air samples. These findings suggest that PFOA was rapidly removed from water system but persist in soils. Moreover, the results indicate the need to evaluate not only the PFCAs, but also the FTOHs and other precursors for the accurate prediction of PFCA accumulation and fates in the environment.

Efficacy of personal protective equipment to prevent environmental infection of COVID-19 among healthcare workers: a systematic review.

BACKGROUND: Healthcare workers (HCWs) employed personal protective equipment (PPE) during the COVID-19 pandemic, crucial to protecting themselves from infection. To highlight the efficacy of PPE in preventing environmental infection among HCWs, a systematic review was conducted in line with PRISMA guidance. METHODS: A search of the PubMed and Web of Science databases was conducted from January 2019 to April 2021 using pre-defined search terms. Articles were screened by three researchers. The approved papers were read in full and included in this review if relevance was mutually agreed upon. Data were extracted by study design and types of PPEs. RESULTS: 47 of 108 identified studies met the inclusion criteria, with seven reviews and meta-analyses, seven cohort, nine case-control, fifteen cross-sectional studies, four before and after, four case series, and one modeling studies. Wearing PPE offered COVID-19 protection in HCWs but required adequate training. Wearing surgical masks provided improved protection over cloth masks, while the benefit of powered air-purifying respirators is less clear, as are individual gowns, gloves, and/or face shields. CONCLUSIONS: Wearing PPE, especially facial masks, is necessary among HCWs, while training in proper use of PPE is also important to prevent COVID-19 infection.

Temporal trends in bisphenol exposures and associated health risk among Japanese women living in the Kyoto area from 1993 to 2016.

BACKGROUND: Bisphenols, and especially bisphenol A, are widely used as components of epoxy resins and polycarbonate. Widespread detection and potential health risks have led to bisphenol A being replaced by other alternatives, including structurally similar bisphenol analogs. Several bisphenol analogs are suspected to have similar adverse health consequences. This study examined the temporal trends in bisphenol exposure among a group of Japanese women from 1993 to 2016, and assessed the associated health risks. METHODS: We used archived single spot urine samples of healthy Japanese women living in the Kyoto area (n = 133) collected in 1993, 2000, 2003, 2009, 2011, and 2016. We measured the concentrations of 10 bisphenols in these samples. RESULTS: A sharp increase in the detection rates of bisphenol F was observed after 2000. There was a distinct downward trend in urinary bisphenol A concentrations and an upward trend in bisphenol E concentrations after 2009. While the hazard index for all measured bisphenols was below 1 in all subjects, bisphenol F was determined as the most important risk driver after 2000, rather than bisphenol A. DISCUSSION: Trends of decreasing bisphenol A and increasing bisphenol E exposure especially after 2011, along with no significant change in the sum of all bisphenol analogs in urine, provide clear evidence that bisphenol A has been replaced by other bisphenols in the study population. We found no significant change in the total exposure to bisphenols during the study period. Bisphenol F might become the most important bisphenol in terms of risk, while cumulative risks due to all bisphenol exposure were deemed insignificant. Considering the accumulating evidence indicating adverse effects at lower exposure levels, further studies are warranted to assess exposure and risk from bisphenol A analogs.