Polycyclic aromatic hydrocarbons in surface sediments held in experimental mesocosms

Sediment was collected from three locations along a pollution gradient in Narragansett Bay and transplanted to controlled mesocosms. Total hydrocarbons and eleven individual polycyclic aromatic hydrocarbons (PAHs) were measured in these sediments over a period of 394 days. Total hydrocarbon concentrations increased in the “relatively uncontaminated”; (Rhode Island Sound) sediment that was held in the mesocosms, but did not change in the two other sediments. The concentrations of four PAHs: naphthalene, 2‐methyl naphthalene, 1‐methyl naphthalene and biphenyl, decreased in the “contaminated”; (Providence River) sediment during the experiment and the calculated half‐lives for these compounds were 287, 353, 321 and 333 days, respectively.     

Modeling China's semiconductor industry fluorinated compound emissions and drafting a roadmap for climate protection

Fluorinated compounds (FC) are high-global warming potential (GWP) greenhouse gases used and emitted during the manufacture of silicon semiconductor devices. Following the U.S. EPA's PFC Emissions Vintage Model (PEVM), uncontrolled FC emissions are modeled as proportional to total manufactured layer area (TMLA) of silicon. FC emissions of World Semiconductor Council (WSC) charter member countries (Europe, Japan, Korea, Taiwan and the United States), which voluntarily committed in 1999 to lower FC emissions by 2010 to 10% of baseline year emissions, are modeled for the period 1995–2020. For this same period, emissions from Chinese manufacturers under alternative emission reduction scenarios are modeled. If Chinese manufacturers were to adopt a baseline year of 2005 and a reduction target of 10% below baseline year emissions to be achieved by 2020, emissions would be 3.4 MMTCO₂eq, comparable to the similarly projected controlled emissions of an average WSC charter member country (=16.3/5 MMTCO₂eq) in 2020. The relative stringency of the alternative reduction scenarios considered for China vary between 50 and 95% reduction compared to business as usual (BAU). This is comparable to the stringency of the WSC charter members’ goals for which FC emission reduction technologies are currently available.     

Bioavailability and tissue distribution of Dechloranes in wild frogs (Rana limnocharis) from an e-waste recycling area in Southeast China

Dechlorane Plus(DP), a flame retardant used as an alternative to decabromodiphenylether, has been frequently detected in organisms, indicating its bioaccumulation and biomagnification potential in aquatic and terrestrial species. However, little data is available on the bioaccumulation of DP in amphibians. Dechlorane Plus and its analogs(DPs) were detected in the liver, muscle and brain tissues of wild frogs(Rana limnocharis), which were collected from an e-waste recycling site, Southeast China. DP, Mirex, Dec 602 and a dechlorinated compound of DP(anti-Cl11-DP) varied in the range of 2.01–291, 0.650–179, 0.260–12.4, and not detected(nd)–8.67 ng/g lipid weight, respectively. No difference of tissue distribution was found for syn-DP, Mirex and Dec 602 between the liver and muscle tissue(liver/muscle concentration ratio close to 1, p 0.05). However, higher retention was observed for anti-DP and anti-Cl11-DP in the frog muscle relative to the liver tissue(liver/muscle concentration ratio 1, p 0.05). Additionally, the blood-brain barrier was found to work efficiently to suppress these compounds entering brain tissues in this species(liver/brain concentration ratio 1, p 0.05), and the molecular weight was a key factor impacting the extent of the blood-brain barrier. Compared to levels in the muscle and brain tissue, a preferential enrichment of syn-DP was observed in the liver tissue, suggesting the occurrence of stereo-selective bioaccumulation in the wild frog.     

Perfluorinated phosphine oxide and sulfides as extractants for heavy metals and radionuclides

New highly fluorinated monodentate and bidentate phosphine oxide compounds of the type {CF(3)(CF(2))(n)CH(2)CH(2)}(3)PO (n = 5, 9) and [{CF(3)(CF(2))(5)CH(2)CH(2)}(2)P(O)CH(2)CH(2)P(O){CH(2)CH(2)(CF(2))(5)CF(3)}] have been prepared. Their ability to extract a number of metals and radionuclides from aqueous solutions into perfluorinated solvents has been established and the extractable species investigated. All extractants extract the metals As(V), Cd(II), Co(II), Cr(VI), Hg(II), Pb(II), and Sn(II) with >75% removal. In addition, the radioisotopes (90)Sr(II), (133)Ba(II), and U(VI) have been investigated, whilst (59)Fe(III) has been used to model the extraction of plutonium. (133)Ba(II) shows a high distribution ratio for monodentate phosphine oxides, whilst for UO(2)(2+) and (59)Fe(III) bidentate phosphine oxides are superior.     

Mass spectral studies of 6‐n‐propyl‐2‐thiouracil,its oxygen,selenium and fluorinated congeners∗

The electron ionization mass spectra of the clinically used antithyroid agent 6‐n‐propyl‐2‐thiouracil (la), its minor metabolite, 6‐n‐propyluracil (lb) and their synthetic selenium and fluorinated analogs (1c and d) have been examined. The fragmentation pattern of these thiouracil and selenouracil studied bear strong similarities with those previously derived from a study of uracil analogs. Thus, the first step in the fragmentation is a retro Diel‐Alder decomposition with the loss of HCNX (X=O, S or Se) and the production of an ion radical which undergoes further fragmentation pathways which are discussed. 6‐n‐Propyl‐2‐selenouracil (1c) did show more complicated spectra due to the six natural isotopic abundance exhibited by the selenium atom. While the fluorinated analogs (1d) did substantiate the fact that the fragmentation pattern of these derivatives proceed through fragmentation between C₂ and N₃ bond since this produces the more resonance stabilized ion.     

Voluntary GHG reduction of industrial sectors in Taiwan

The present paper describes the voluntary greenhouse gas (GHG) reduction agreements of six different industrial sectors in Taiwan, as well as the fluorinated gases (F-gas) reduction agreement of the semiconductor and Liquid Crystal Display (LCD) industries. The operating mechanisms, GHG reduction methods, capital investment, and investment effectiveness are also discussed. A total of 182 plants participated in the voluntary energy saving and GHG reduction in six industrial sectors (iron and steel, petrochemical, cement, paper, synthetic fiber, and textile printing and dyeing), with 5.35 Mt reduction from 2004 to 2008, or 33% higher than the target goal (4.02 Mt). The reduction accounts for 1.6% annual emission or 7.8% during the 5-yr span. The petrochemical industry accounts for 49% of the reduction, followed by the cement sector (21%) and the iron and steel industry (13%). The total investment amounted to approximately USD 716 million, in which, the majority of the investment went to the modification of the manufacturing process (89%). The benefit was valued at around USD 472 million with an average payback period of 1.5 yr. Moreover, related energy saving was achieved through different approaches, e.g., via electricity (iron and steel), steam and oil consumption (petrochemical) and coal usage (cement). The cost for unit CO₂ reduction varies per industry, with the steel and iron industrial sector having the highest cost (USD 346 t⁻¹ CO₂) compared with the average cost of the six industrial sectors (USD 134 t⁻¹ CO₂). For the semiconductor and Thin-Film Transistor LCD industries, F-gas emissions were reduced from approximately 4.1 to about 1.7 Mt CO₂-eq, and from 2.2 to about 1.1 Mt CO₂-eq, respectively. Incentive mechanisms for participation in GHG reduction are also further discussed.     

Connecting today's climates to future climate analogs to facilitate movement of species under climate change

Increasing connectivity is an important strategy for facilitating species range shifts and maintaining biodiversity in the face of climate change. To date, however, few researchers have included future climate projections in efforts to prioritize areas for increasing connectivity. We identified key areas likely to facilitate climate‐induced species’ movement across western North America. Using historical climate data sets and future climate projections, we mapped potential species’ movement routes that link current climate conditions to analogous climate conditions in the future (i.e., future climate analogs) with a novel moving‐window analysis based on electrical circuit theory. In addition to tracing shifting climates, the approach accounted for landscape permeability and empirically derived species’ dispersal capabilities. We compared connectivity maps generated with our climate‐change‐informed approach with maps of connectivity based solely on the degree of human modification of the landscape. Including future climate projections in connectivity models substantially shifted and constrained priority areas for movement to a smaller proportion of the landscape than when climate projections were not considered. Potential movement, measured as current flow, decreased in all ecoregions when climate projections were included, particularly when dispersal was limited, which made climate analogs inaccessible. Many areas emerged as important for connectivity only when climate change was modeled in 2 time steps rather than in a single time step. Our results illustrate that movement routes needed to track changing climatic conditions may differ from those that connect present‐day landscapes. Incorporating future climate projections into connectivity modeling is an important step toward facilitating successful species movement and population persistence in a changing climate.     

Preliminary investigation on cytotoxicity of fluorinated polymer nanoparticles

As well-known persistent organic pollutants(POPs), organofluorine pollutants such as perfluorooctane sulfonate(PFOS) have been proven to be bioaccumulated and harmful to health. However, toxicological assessment of organofluorinated nanoparticles, which have emerged as a novel tool for biomedical and industrial applications, is lacking, to the best of our knowledge. To assess the biological effects and health risk of fluorinated nanoparticles,trifluoroethyl aryl ether-based fluorinated poly(methyl methacrylate) nanoparticles(PTFEPMMA NPs) were synthesized with various fluorine contents(PTFE-PMMA-1 NPs 12.0 wt.%,PTFE-PMMA-2 NPs 6.1 wt.% and PTFE-PMMA-3 NPs 5.0 wt.%), and their cytotoxicity was investigated in this study. The in vitro experimental results indicated that the cytotoxicity of PTFE-PMMA NPs was mild, and was closely related to their fluorine(F) contents and Fcontaining side chains. Specifically, the cytotoxicity of PTFE-PMMA NPs decreased with increasing F content and F-containing side chains. After exposure to PTFE-PMMA NPs at a sublethal dose(50 μg/m L) for 24 hr, the phospholipid bilayer was damaged, accompanied by increasing permeability of the cell membrane. Meanwhile, the intracellular accumulation of reactive oxygen species(ROS) occurred, resulting in the increase of DNA damage, cell cycle arrest and cell death. Overall, the PTFE-PMMA NPs were found to be relatively safe compared with typical engineered nanomaterials(ENMs), such as silver nanoparticles and graphene oxide, for biomedical and industrial applications.     

Synthesis and pharmacological properties of certain analogs of pilocarpine

The synthesis of 4‐(4'‐pyrimidinylmethyl)oxacyclohexan‐2‐one (2a) and 4‐(4'‐pyrimidinylmethyl)oxacycloheptan‐2‐one (3a) were achieved through the Michael addition of the anion derived from 4‐methylpyrimidine with oxacyclyo‐3‐hexen‐2‐one and oxacyclo‐3‐hepten‐2‐one respectively. These compounds 2a and 3a and their quaternary methiodide salts lack cholinomimetic activity.     

Comparative acute freshwater hazard assessment and preliminary PNEC development for eight fluorinated acids

Short-term 48, 72 and 96-h aquatic toxicity tests were conducted to evaluate the acute toxicity of eight fluorinated acids to the cladoceran, Daphnia magna, the green alga, Pseudokirchneriella subcapitata, and the rainbow trout, Oncorhynchus mykiss or the fathead minnow, Pimephales promelas. The eight fluorinated acids studied were tridecafluorohexyl ethanoic acid (6:2 FTCA), heptadecafluorooctyl ethanoic acid (8:2 FTCA), 2H-dodecafluoro-2-octenoic acid (6:2 FTUCA), 2H-hexadecafluoro-2-decenoic acid (8:2 FTUCA), 2H,2H,3H,3H-undecafluoro octanoic acid (5:3 acid), 2H,2H,3H,3H-pentadecafluoro decanoic acid (7:3 acid), n-perfluoropentanoic acid (PFPeA) and n-perfluorodecanoic acid (PFDA). The results of the acute toxicity tests conducted during this study suggest that the polyfluorinated acids, 8:2 FTCA, 8:2 FTUCA, 6:2 FTCA, 6:2 FTUCA, 7:3 acid and 5:3 acid, and the perfluorinated acids PFPeA and PFDA, are generally of low to medium concern based on evaluation of their acute freshwater toxicity (EC/LC50s typically between 1 and >100 mg L⁻¹) using the USEPA TSCA aquatic toxicity evaluation paradigm. For the polyfluorinated acids, aquatic toxicity generally decreased as the number of fluorinated carbons decreased and as the overall carbon chain length decreased from 12 to 8. Acute aquatic toxicity of the 5 and 10 carbon perfluorocarboxylic acids (EC/LC50s between 10.6 and >100 mg L⁻¹) was greater or similar to that of the 6-9 carbon perfluorocarboxylic acids (EC/LC50s > 96.5 mg L⁻¹). This study also provides the first report of the acute aquatic toxicity of the 5:3 acid (EC/LC50s of 22.5 to >103 mg L⁻¹) which demonstrated less aquatic toxicity than the 7:3 acid (EC/LC50s of 0.4-32 mg L⁻¹). The cladoceran, D. magna and the green alga, P. subcapitata had generally similar EC50 values for a given substance while fish were typically equally or less sensitive with the exception that PFPeA was most toxic to fish. Predicted no-effect concentrations (PNECs) were estimated using approaches consistent with REACH guidance and when compared with available environmental concentrations, these PNECs suggest that the fluorinated acids tested pose little risk for aquatic organisms.