Bioaccumulation, temporal trend, and geographical distribution of synthetic musks in the marine environment

Bioaccumulation of synthetic musks in a marine food chain was investigated by analyzing marine organisms at various trophic levels, including lugworm, clam, crustacean, fish, marine mammal, and bird samples collected from tidal flat and shallow water areas of the Ariake Sea, Japan. Two of the polycyclic musks, HHCB and AHTN, were the dominant compounds found in most of the samples analyzed, whereas nitro musks were not detected in any of the organisms, suggesting greater usage of polycyclic musks relative to the nitro musks in Japan. The highest concentrations of HHCB were detected in clams (258-2730 ng/g lipid wt.), whereas HHCB concentrations in mallard and black-headed gull were low, and comparable with concentrations in fish and crab. These results are in contrast to the bioaccumulation pattern of polychlorinated biphenyls; for which a positive correlation between the concentration and the trophic status of organisms was found. Such a difference in the bioaccumulation is probably due to the metabolism and elimination of HHCB in higher trophic organisms. Temporal trends in concentrations of synthetic musks were examined by analyzing tissues of marine mammals from Japanese coastal waters collected during 1977-2005. HHCB concentrations in marine mammals have shown significant increase since the early 1990s, suggesting a continuous input of this compound into the marine environment. Comparison of the time trend for HHCB with those for PCBs and PBDEs suggested that the rates of increase in HHCB concentrations were higher than the other classes of pollutants. To examine the geographical distribution of HHCB, we have analyzed tissues of fish, marine mammals, and birds collected from several locations. Synthetic musks were not detected in a sperm whale (pelagic species) from Japanese coastal water and in eggs of south polar skua from Antarctica. While the number of samples analyzed is limited, these results imply a lack of long-range transportation potential of synthetic musks in the environment.     

Perfluorinated surfactants in surface, subsurface water and microlayer from Dalian Coastal waters in China

Two predominant perfluorinated compounds (PFCs), Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA), in surface water (SW, 0-20 cm), subsurface water (SSW, > 30 cm depth), and sea surface microlayer (SML, 50 microm thickness) were measured from Dalian Coastal waters in China. The SML samples were collected using glass-plate dipping method. Analysis of the PFCs was conducted through solid-phase extraction, followed by LC/MS-SIM. The PFC's concentrations in SW samples were consistent with previously reported data in this region. Significantly higher concentrations of PFCs were found in SML samples than corresponding SSW samples. The enrichment factors (EF = C(SML)/C(SSW)) for PFOS were as high as 24-109 atthree near-shore sites. The concentration in SW was also generally higher than corresponding SSW samples, giving C(SW)/C(SSW) mean ratios of 1.5 and 1.4 for PFOS and PFOA, respectively. This apparent enrichment of PFCs in surface water, especially in the microlayer, has implications for designing measurement techniques, understanding their distributions, and sea spray-mediated transport in the environment.     

Determination of acrylamide in processed foods by LC/MS using column switching

An LC/MS method was developed for the determination of acrylamide (AA) in processed or cooked foods. AA was extracted with a mixture of water and acetone from homogenized food samples after the addition of 13C-labeled acrylamide (AA-1-(13)C) as an internal standard. The extract was concentrated, washed with dichloromethane for defatting, and cleaned up on Bond Elut C18, PSA and ACCUCAT cartridge-columns, and then AA was determined by LC/MS in the selected ion recording (SIR) mode. For the LC/MS analysis, four LC columns were connected in-line and the flow of the mobile phase was switched according to a time-program. Monitoring ions for AA were m/z 72 and 55, and those for AA-1-(13)C were m/z 73 and 56. AA and AA-1-(13)C were determined without interference from the matrices in all samples. The recoveries of AA from potato chips, corn snack, pretzel and roasted tea spiked at the level of 500 ng/g of AA were 99.5-101.0% with standard deviations (SD) in the range from 0.3 to 1.6%. The limits of detection and quantification of the developed method were 9 and 30 ng/g for AA in samples, respectively. The method was applied to the analysis of AA in various processed or cooked food samples purchased from retail markets. High levels of AA were found in potato chips and French-fried potato (467-3,544 ng/g). Fried and sugar-coated dough cakes (karinto) contained 374 and 1,895 ng/g. Corn snacks contained 117-535 ng/g of AA. Roasted foods (such as roasted sesame seed, roasted barley (mugi-cha), roasted tea (hoji-cha), coffee beans and curry powder) contained 116-567 ng/g of AA. Foods made from fish, egg and meat contained lower levels of AA than the plant-based foods. Foods containing much water showed a tendency to have low levels of AA compared with dry foods. The proposed method was applicable to the analysis of AA in variety of processed foods.     

Modification of cleanup methods for dioxin analysis in green leafy vegetables and comparison of packing methods for a multi-layer silica gel column

To determine polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and coplanar polychlorinated biphenyls (Co-PCBs) in green leafy vegetables, the cleanup method was modified, and packing methods for a multi-layer silica gel column were compared in food samples. First, the additional cleanup was examined for a mono-ortho PCBs fraction obtained by alumina column chromatography from spinach extract. Small solids such as rough crystals that remained after concentration of the mono-ortho PCBs fraction were identified as long-chain hydrocarbons from leaf epicuticular wax by GC/MS. Cleanup using an activated carbon silica gel column with n-hexane as the washing solvent was effective. Next, multi-layer silica gel columns packed by wet packing and dry packing were compared using komatsuna, salmon and butter as samples. The columns prepared by both methods gave similar values at each isomeric concentration level and showed similar efficiency with favorable recoveries.     

Determination of ethychlozate and its degradation product in fruits by HPLC and LC/MS

A method was developed for the analysis of ethychlozate (CIE) and its decomposition compound, 5-chloro-3(1H)-indazolylacetic acid (CIA) in fruits by HPLC and LC/MS. The sample was homogenized with 1 mol/L HC1, and CIE and CIA were extracted with 5 mol/L HCl and acetone. They were extracted from the acetone extract with diethylether-n-hexane (2:1). CIE was hydrolyzed to CIA with methanol-4 mol/L KOH (1:1). The solution was made acidic, and CIA was extracted with diethylether-n-hexane (2:1). The extract was cleaned up on a silica gel column. CIA was determined by HPLC-UV and LC/MS (Scan or SIR). Four fruits were spiked with CIE or CIA at 0.5 microgram/g and analyzed by the proposed method with HPLC. The average recoveries were 77.2-83.2% for CIE and 71.2-89.2% for CIA. The concentrations determined by LC/MS were 10-25% higher than the values by HPLC. The limit of detection (LOD) of CIA standard solution by HPLC corresponds to 0.015 microgram/g of CIE in the sample. In the same way, the LOD of CIA by LC/MS (SIR) corresponds to 0.009 microgram/g of CIE in the sample.     

Complex formation, thermal properties, and in-vitro digestibility of gelatinized potato starch-fatty acid mixtures

Effects of the type and amount of fatty acid (0-2.0 mmol/g-starch of lauric, myristic, palmitic, stearic, oleic, and linoleic acids) on the complex formation, thermal properties, and in-vitro digestibility of gelatinized potato starch-fatty acid mixtures were investigated. Complex index (CI) evaluated by the reduction in the iodine binding capacity of starch increased with an increase in the amount of fatty acids, and reached a plateau depending on the type of fatty acid. The maximum CI value was higher in the order of lauric (49.9%), linoleic (47.6%), myristic (42.4%), oleic (36.7%), stearic (35.3%), and palmitic acid (30.9%). From the calorimetric study, it was demonstrated that melting temperature of the complexes was higher in the order of stearic (96.7 °C) > lauric, myristic, palmitic, and oleic (89.6-92.1 °C) > linoleic acid (78.3 °C). Melting enthalpy for complexes was roughly related to the CI value (R² = 0.667). From the in-vitro digestibility measurement, it was found that a certain amount of fatty acid reduced the starch content hydrolyzed at a given condition. Among them, 0.50 mmol/g-starch lauric and oleic acid samples showed the largest reduction in the hydrolyzed starch content. This result was related to the extent of complex formation characterized by CI value and its helical order characterized by melting temperature. In addition, there was a possibility of the complex formation between amylose and unsaturated fatty acid during the hydrolysis of gelatinized starch.     

High temperature catalytic combustion of methane and propane over hexaaluminate catalysts: NOx emission characteristics

Several hexaaluminate-related materials were prepared via hydrolysis of alkoxide and powder mixing method for high temperature combustion of CH₄ and C₃H₈, in order to investigate the effect of the concentration of the fuels, O₂ and H₂O on NO_x emission and combustion characteristics. Among the hexaaluminate catalysts, Sr_0.8La_0.2MnAl₁₁O₁₉₋ prepared by the alkoxide method exhibited the highest activity for methane combustion and low NO_x emission capability. NO_x emission at 1500 °C was increased linearly with O₂ concentration, whereas water vapor addition decreased NO_x emission in CH₄ combustion over the Sr_0.8La_0.2MnAl₁₁O₁₉₋ catalyst. In the catalytic combustion of C₃H₈ over the Sr_0.8La_0.2MnAl₁₁O₁₉₋ catalyst, the amount of NO_x emitted was raised in the temperature range between 1000 and 1500 °C when the C₃H₈ concentration increased from 1 to 2 vol.%. It was found that NO_x emission in this temperature range was reduced effectively by adding water vapor.     

Rewired Cellular Metabolic Profiles in Response to Metformin under Different Oxygen and Nutrient Conditions

Metformin is a metabolic disruptor, and its efficacy and effects on metabolic profiles under different oxygen and nutrient conditions remain unclear. Therefore, the present study examined the effects of metformin on cell growth, the metabolic activities and consumption of glucose, glutamine, and pyruvate, and the intracellular ratio of nicotinamide adenine dinucleotide (NAD⁺) and reduced nicotinamide adenine dinucleotide (NADH) under normoxic (21% O₂) and hypoxic (1% O₂) conditions. The efficacy of metformin with nutrient removal from culture media was also investigated. The results obtained show that the efficacy of metformin was closely associated with cell types and environmental factors. Acute exposure to metformin had no effect on lactate production from glucose, glutamine, or pyruvate, whereas long-term exposure to metformin increased the consumption of glucose and pyruvate and the production of lactate in the culture media of HeLa and HaCaT cells as well as the metabolic activity of glucose. The NAD⁺/NADH ratio decreased during growth with metformin regardless of its efficacy. Furthermore, the inhibitory effects of metformin were enhanced in all cell lines following the removal of glucose or pyruvate from culture media. Collectively, the present results reveal that metformin efficacy may be regulated by oxygen conditions and nutrient availability, and indicate the potential of the metabolic switch induced by metformin as combinational therapy.     

Preparation of Ba(Mg1/3Ta2/3)O3 Using Oxine

A solution containing Mg²⁺ and Ta⁵⁺ was added to an aqueous ammonia solution of oxine, resulting in a precipitate. After the precipitate was thermally decomposed and fired, it was mixed with BaCO₃ powder and fired again at high temperatures to obtain Ba(Mg_1/3Ta_2/3)O₃ (BMT). This method resulted in BMT formation at temperatures lower than those used in the conventional mixed-oxide method, and single-phase BMT formed directly at 1300°C without intermediates.