Microscale Investigation of Arsenic Distribution and Species in Cement Product from Cement Kiln Coprocessing Wastes

To improve the understanding of the immobilization mechanism and the leaching risk of Arsenic (As) in the cement product from coprocessing wastes using cement kiln, distribution and species of As in cement product were determined by microscale investigation methods, including electron probe microanalysis (EPMA) and X-ray absorption spectroscopy. In this study, sodium arsenate crystals (Na3AsO412H2O) were mixed with cement production raw materials and calcined to produce cement clinker. Then, clinker was mixed water to prepare cement paste. EPMA results showed that As was generally distributed throughout the cement paste. As content in calcium silicate hydrates gel (C-S-H) was in low level, but higher than that in other cement mineral phases. This means that most of As is expected to form some compounds that disperse on the surfaces of cement mineral phases. Linear combination fitting (LCF) of the X-ray absorption near edge structure spectra revealed that As in the cement paste was predominantly As(V) and mainly existed as Mg3(AsO4)2, Ca3(AsO4)2, and Na2HAsO4

BERBERINE INDUCES AUTOPHAGY, APOPTOSIS AND MODULATES MIR-155 IN HEAD AND NECK SQUAMOUS CARCINOMA CELLS.

Berberine (BBR) an active natural plant alkaloid extracted from Coptidis rhizoma, displays potent anticancer activity over a variety of cancer cell lines. The cytotoxic activity of BBR in cancer cells is attributed to persuade, programmed cell death characterized by the release of cytochrome c, accompanied by activation of caspase-3 and caspase-9. In the present study, we evaluated BBR significantly reduces the cell viability and clonogenic property of head and neck squamous carcinoma (HNSC) cells. Our results revealed that BBR simultaneously induces apoptosis and autophagy in HNSC cells. Mechanistically, BBR induces autophagy in HNSC cells which were confirmed by acridine orange (AO) staining by visualization of prominent orange red color acidic autophagosomes in the cytoplasm. However, immunoblotting shows the steady conversion of MAP-LC-3I to LC-3II with concomitant degradation of autophagy substrate protein SQSTM1/p62. Annexin V FITC staining analysis by flow cytometry revealed a significant induction of apoptosis at higher doses of BBR. Furthermore, the immunoblotting analysis revealed a prominent cleavage of proapoptotic proteins procaspase-3 and PARP1 at higher doses of BBR. Additionally, we found significant upregulation and downregulation of tumor suppressor microRNA-155 (miR-155) and oncogenic miR-21 respectively, when HNSC cells were exposed to higher doses of BBR. In conclusion, these results demonstrate that BBR exhibits a significant anti-proliferative effect with the simultaneous induction of autophagy and apoptosis and modulates miRNA expression in HNSC cells

Novel Finding of Widespread Occurrence and Accumulation of Bisphenol A Diglycidyl Ethers (BADGEs) and Novolac Glycidyl Ethers (NOGEs) in Marine Mammals from the United States Coastal Waters

Bisphenol A diglycidyl ether (BADGE)- and bisphenol F diglycidyl ether (BFDGE)-based epoxy resins have a broad range of applications, including serving as inner coatings of food and beverage cans and as protective coatings in marine construction. Prior to this study, no studies had examined the occurrence and bioaccumulation of BADGEs or BFDGEs in aquatic organisms. In this study, BADGE, BFDGE, and nine of their derivatives were determined in 121 tissue (liver, kidney, blubber, and brain) samples from eight species of marine mammals collected from the U.S. coastal waters of Florida, California, Washington, and Alaska. BADGE·2HCl was the predominant compound found in the majority (78.5%) of the marine mammal tissues analyzed, at concentrations of up to 2950 ng/g (wet weight (wt)) found in the liver of a sea otter from Kachemak Bay, Alaska. The measured concentrations of BADGE·2HCl in marine mammals were on the order of hundreds of nanograms per gram tissue, which are some of the highest concentrations ever reported for this compound in biota. Males contained greater concentrations of BADGE·2HCl than did females. BADGE·2HCl also was found in the brain tissues of sea otters. Trace levels of BADGE·2HCl were found in the livers of polar bears from Alaska, which suggested that BADGEs are widely distributed in the oceanic environment

Bisphenols, Benzophenones, and Bisphenol A Diglycidyl Ethers in Textiles and Infant Clothing

Little is known with regard to the occurrence of potentially toxic chemicals in textiles and clothes. In this study, 77 textiles and infant clothing pieces were analyzed for the determination of bisphenols including bisphenol A (BPA) and bisphenol S (BPS), benzophenones, bisphenol A diglycidyl ethers (BADGEs), and novolac glycidyl ethers (NOGEs). BPA and BPS occurred in 82% and 53% of the textile samples, respectively, and at mean concentrations of 366 and 15 ng/g, respectively. Benzophenone-3 (BP3) occurred in 70% of the samples at a mean concentration of 11.3 ng/g. Among 11 BADGEs and NOGEs analyzed, BFDGE was the predominant compound, with a mean concentration of 13.6 ng/g. Concentrations of target chemicals were assessed by fabric type, color, and uses. Socks contained the highest concentrations of BPA (mean: 1810 ng/g) with concentrations as high as 13 300 ng/g in a 97% polyester fabric marketed for infants. Calculated dermal exposure dose to BPA by infants via textiles was as high as 7280 pg/kg BW/d. This is the first study to report the occurrence of, and exposure to, BPA, BPS, BADGEs, and NOGEs in textiles and clothing

Widespread Occurrence and Accumulation of Bisphenol A Diglycidyl Ether (BADGE), Bisphenol F Diglycidyl Ether (BFDGE) and Their Derivatives in Human Blood and Adipose Fat

Despite the widespread use of bisphenol A diglycidyl ether (BADGE) and bisphenol F diglycidyl ether (BFDGE) in various consumer products, studies on human exposure to these compounds are scarce. In this study, BADGE, BFDGE, and seven of their derivatives were determined in human adipose fat and blood plasma samples collected from New York City, NY. Bisphenol A bis (2,3-dihydroxypropyl) ether [BADGE·2H₂O] was the major BADGE derivative found in 60% of the adipose samples and 70% of the plasma samples analyzed. High concentrations and detection frequencies of BFDGE were found in both adipose and plasma samples. BFDGE concentrations in adipose fat ranged from 19.1 to 4500 ng/g wet weight. A significant correlation between BADGE or BFDGE and their derivatives in adipose and plasma samples suggested hydration of these reactive compounds in humans. A significant positive correlation existed between BADGEs (i.e., the sum of BADGE and its five derivatives) and BFDGEs in adipose samples, which suggested similar exposure sources and pathways for these compounds in humans. Bisphenol A (BPA) also was analyzed in adipose fat and plasma, and its concentrations were positively correlated with those of BADGEs, which confirmed coexposure of BADGEs and BPA in humans

Trophic Magnification of Parabens and Their Metabolites in a Subtropical Marine Food Web

Despite the widespread use of parabens in a range of consumer products, little is known about bioaccumulation of these chemicals in aquatic environments. In this study, six parabens and four of their common metabolites were measured in abiotic (water, sediment) and biotic (fish including sharks, invertebrates, plants) samples collected from a subtropical marine food web in coastal Florida. Methyl paraben (MeP) was found in all abiotic (100%) and a majority of biotic (87%) samples. 4-Hydroxy benzoic acid (4-HB) was the most abundant metabolite, found in 97% of biotic and all abiotic samples analyzed. The food chain accumulation of MeP and 4-HB was investigated for this food web. The trophic magnification factor (TMF) of MeP was estimated to be 1.83, which suggests considerable bioaccumulation and biomagnification of this compound in the marine food web. In contrast, a low TMF value was found for 4-HB (0.30), indicating that this compound is metabolized and excreted along the food web. This is the first study to document the widespread occurrence of parabens and their metabolites in fish, invertebrates, seagrasses, marine macroalgae, mangroves, seawater, and ocean sediments and to elucidate biomagnification potential of MeP in a marine food web

Single Quadrupole Multiple Reaction Monitoring Q-MRM enables Quantitative Mass Spectrometry

A single quadrupole combined with enhanced in-source fragmentation/annotation (EISA) was used to perform multiple reaction monitoring (Q-MRM) for quantitative mass spectrometry analysis. EISA amplifies fragmentation of traditional soft electrospray ionization to produce fragment ions that have been found to be identical to those generated in tandem mass spectrometry. We have combined EISA fragmentation data with criteria established by the European Union Commission Directive 2002/657/EC for electron ionization single quadrupole quantitative analysis to perform quantitative Q-MRM experiments. These experiments were performed on multiple types of complex samples that included a mixture of 50 standards, as well as cell and plasma extracts. The dynamic range for Q-MRM quantitative analysis was comparable to triple quadrupole multiple reaction monitoring (QqQ-MRM) analyses at up to 5 orders of magnitude with the cell and plasma extracts showing similar matrix effects across both platforms. Amino acid and fatty acid measurements performed from certified NIST 1950 plasma with isotopically labelled standards demonstrated Q-MRM accuracy in the range of 91-110% for the amino acids, 76-129% for the fatty acids, and good precision (coefficient of variation < 10%). In order to enhance specificity, a newly developed Correlated Ion Monitoring (CIM) algorithm was designed to facilitate these analyses. CIM autonomously processes, aligns, filters, and compiles multiple ions within one chromatogram enabling both precursor and in-source fragment ions to be correlated within a single chromatogram, also enabling the detection of co-eluting species based on precursor and fragment ion ratios. Q-MRM and CIM with single quadrupole instrumentation has been designed as an alternative to QqQ-MRM technology by correlating precursor and fragment ions to facilitate high sensitivity Q-MRM quantitative analysis on existing instrumentation that are generally inexpensive, easy to operate, and technically less complex. @font-face {font-family:"Cambria Math"; panose-1:2 4 5 3 5 4 6 3 2 4; mso-font-charset:0; mso-generic-font-family:roman; mso-font-pitch:variable; mso-font-signature:3 0 0 0 1 0;}p.MsoNormal, li.MsoNormal, div.MsoNormal {mso-style-unhide:no; mso-style-qformat:yes; mso-style-parent:""; margin:0in; mso-pagination:widow-orphan; font-size:12.0pt; font-family:"Times New Roman",serif; mso-fareast-font-family:"Times New Roman";}.MsoChpDefault {mso-style-type:export-only; mso-default-props:yes; font-size:11.0pt; mso-ansi-font-size:11.0pt; mso-bidi-font-size:11.0pt; font-family:"Calibri",sans-serif; mso-ascii-font-family:Calibri; mso-ascii-theme-font:minor-latin; mso-fareast-font-family:DengXian; mso-fareast-theme-font:minor-fareast; mso-hansi-font-family:Calibri; mso-hansi-theme-font:minor-latin; mso-bidi-font-family:"Times New Roman"; mso-bidi-theme-font:minor-bidi; mso-fareast-language:ZH-CN;}.MsoPapDefault {mso-style-type:export-only; margin-bottom:8.0pt; line-height:107%;}div.WordSection1 {page:WordSection1;}</p

The occurrence of bisphenol plasticizers in paired dust and urine samples and its association with oxidative stress

Bisphenol A diglycidy ether (BADGE) and its derivatives are epoxy resins and widely used as emerging plasticizers in food packages and material coating. Though known as endocrine disruptors, little information is available on their occurrence, exposure routes and toxicity. Besides, the analysis of BADGE and its derivatives has always been a challenge due to their reactive chemical properties and the background contamination. Therefore, we firstly developed a novel water-free method to analyze BADGE and its derivatives in dust samples together with other two typical plasticizers bisphenol A (BPA) and bisphenol S (BPS). In order to investigate the levels in paired dust and urine samples, 33 paired samples were collected from Singapore. In both dust and urine samples, the predominant compounds were BPA, BADGE-2H2O and BPS. A significantly positive correlation of BPA levels in paired dust and urine samples was observed in this small-scale study. To tentatively explore the human health effect from exposure to these bisphenol plasticizers, we assessed the correlation between the urinary concentrations of these compounds and oxo-2’-deoxyguanosine (8-OHdG), an oxidative stress biomarker. The result showed that 8-OHdG levels in urine samples was positively correlated with urinary BPA level and body mass index (BMI), suggesting that elevated oxidative stress might be associated with BPA exposure and obesity. In the future, a larger scale study is warranted due to the limited sample size in this study.Building and Construction Authority (BCA)Ministry of Education (MOE)Nanyang Technological UniversityNational Environmental Agency (NEA)We appreciate the contributions of all volunteers in this study. This work was funded by Singapore Ministry of Education Academic Research Fund Tier 1 (M4011732.030), Start-Up Grant of Nanyang Technological University (M4081915, M060030008), Singapore National Environment Agency (M4061617) and Singapore Building and Construction Authority (M4062065)

Placental transfer of bisphenol diglycidyl ethers (BDGEs) and its association with maternal health in a population in South of China

Despite high production and usage, little is known about exposure to bisphenol diglycidyl ethers (BDGEs) and their derivatives in pregnant women and fetuses. In this study, we determined nine BDGEs in 106 paired maternal and cord serum samples collected from e-waste dismantling sites in South of China. Bisphenol A bis (2,3-dihydroxypropyl) glycidyl ether (BADGE·2H2O), bisphenol A (3-chloro-2-hydroxypropyl) (2,3-dihydroxypropyl) glycidyl ether (BADGE·HCl·H2O), and bisphenol F diglycidyl ether (BFDGE) were the major BDGEs, with median concentrations of 0.57, 4.07, and 1.60 ng/mL, respectively, in maternal serum, and of 3.58, 5.61, and 0.61 ng/mL, respectively, in cord serum. The transplacental transfer efficiencies (TTEs) were estimated for BDGEs found in samples, and median values were in the range of 0.98 (BFDGE) to 5.91 (BADGE·2H2O). Our results suggested that passive diffusion plays a role in the placental transfer of BADGE·HCl·H2O and BFDGE, whereas several mechanisms contribute to the high accumulation of BADGE·2H2O in cord serum. Multiple linear regression analysis indicated significant associations between maternal serum concentrations of BDGEs and blood clinical biomarkers, especially those related to liver injuries, such as alanine aminotransferase (ALT), aspartate aminotransferase (AST), alkaline phosphatase (ALP), and adenosine deaminase (ADA) (P < 0.05). To our knowledge, this is the first study to report the occurrence of BDGEs in paired maternal–fetal serum samples and provide new insights into prenatal and fetal exposures. The newly discovered TTEs in maternal–fetal pairs contribute to a fuller inventory of the transmission activity of pollutants in the human body, ultimately adding to a more significant comprehensive risk evaluation

Elevated Accumulation of Parabens and their Metabolites in Marine Mammals from the United States Coastal Waters

The widespread exposure of humans to parabens present in personal care products is well-known. Nevertheless, little is known about the accumulation of parabens in marine organisms. In this study, six parabens and four common metabolites of parabens were measured in 121 tissue samples from eight species of marine mammals collected along the coastal waters of Florida, California, Washington, and Alaska. Methyl paraben (MeP) was the predominant compound found in the majority of the marine mammal tissues analyzed, and the highest concentration found was 865 ng/g (wet weight [wet wt]) in the livers of bottlenose dolphins from Sarasota Bay, FL. 4-Hydroxybenzoic acid (4-HB) was the predominant paraben metabolite found in all tissue samples. The measured concentrations of 4-HB were on the order of hundreds to thousands of ng/g tissue, and these values are some of the highest ever reported in the literature. MeP and 4-HB concentrations showed a significant positive correlation (<i>p</i> < 0.05), which suggested a common source of exposure to these compounds in marine mammals. Trace concentrations of MeP and 4-HB were found in the livers of polar bears from the Chuckchi Sea and Beaufort Sea, which suggested widespread distribution of MeP and 4-HB in the oceanic environment