Fluorotelomer acids are more toxic than perfluorinated acids

Saturated and unsaturated fluorotelomer carboxylic acids have been identified as intermediates in the degradation of fluorotelomer alcohols to perfluorinated carboxylic acids (PFCAs). Although surface waters are the likely environmental sink for telomer acids, no fate or toxicity data exist for this matrix. We assessed the acute toxicity of the 4:2, 6:2, 8:2, and 10:2 saturated (FTCA) and unsaturated (FTUCA) fluorotelomer carboxylic acids to Daphnia magna, Chironomus tentans, and Lemna gibba. In general, toxicity increased with increasing fluorocarbon (FC) chain length, particularly for telomer acids of > or =8 FCs. In addition, the FTCAs were generally more toxic than the corresponding FTUCAs. Acute EC50s ranged from 0.025 mg/L (0.04 micromol/L) for D. magna (10:2 FTCA, immobility) to 63 mg/L (167 micromol/L) for C. tentans (6:2 FTCA, growth). While chain-length trends observed in the current study agree with those previously reported for PFCAs, the toxicity thresholds generated here are up to 10,000 times smaller. Our data provide the first evidence that PFCA precursors are more toxic than the PFCAs themselves.     

Biomagnification of perfluoroalkyl compounds in the bottlenose dolphin (Tursiops truncatus) food web

The environmental distribution and the biomagnification of a suite of perfluoroalkyl compounds (PFCs), including perfluorooctane sulfonate (PFOS) and C8 to C14 perfluorinated carboxylates (PFCAs), was investigated in the food web of the bottlenose dolphin (Tursiops truncatus). Surficial seawater and sediment samples, as well as zooplankton, fish, and bottlenose dolphin tissue samples, were collected at two U.S. locations: Sarasota Bay, FL and Charleston Harbor, SC. Wastewater treatment plant (WWTP) effluents were also collected from the Charleston area (n = 4). A solid-phase extraction was used for seawater and effluent samples and an ion-pairing method was used for sediment and biotic samples. PFCs were detected in seawater (range <1-12 ng/L), sediment (range <0.01-0.4 ng/g wet weight (ww)), and zooplankton (range 0.06-0.3 ng/g ww). The highest PFC concentrations were detected in WWTP effluents, whole fish, and dolphin plasma and tissue samples in which PFOS, C8 and C10-PFCAs predominated in most matrices. Contamination profiles varied with location suggesting different sources of PFC emissions. Biomagnification factors (BMFs) ranged from <1 to 156 at Sarasota Bay and <1 to 30 at Charleston. Trophic magnification factors (TMFs) for PFOS and C8-C11 PFCAs indicated biomagnification in this marine food web. The results indicate that using plasma and liver PFC concentrations as surrogate to whole body burden in a top marine predator overestimates the BMFs and TMFs.     

Temporal trends of perfluoroalkyl contaminants in polar bears (Ursus maritimus) from two locations in the North American Arctic, 1972-2002

Perfluoroalkyl substances are globally distributed anthropogenic contaminants. Their production and use have increased dramatically from the early 1980s. While many recent publications have reported concentrations of perfluorooctane sulfonate (PFOS) and other perfluoroalkyl acids (PFAs) in biotic and abiotic samples, only limited work has addressed temporal trends. In this study we analyzed archived polar bear(Ursus maritimus) livertissue samples from two geographic locations in the North American Arctic, collected from 1972 to 2002. The eastern group, taken from the vicinity of northern Baffin Island, Canada, comprised 31 samples, and the western group, from the vicinity of Barrow, Alaska, comprised 27 samples. Samples were analyzed for perfluorocarboxylic acids (PFCAs) from carbon chain length C8 to C15, perfluorohexane sulfonate, PFOS, the neutral precursor perfluorooctane sulfonamide (PFOSA), as well as 8:2 and 10:2 fluorotelomer acids and their alpha,beta unsaturated acid counterparts. Concentrations of PFOS and PFCAs with carbon chain lengths from C9 to C11 showed an exponential increase between 1972 and 2002 at both locations. Doubling times ranged from 3.6 +/- 0.9 years for perfluorononanoic acid in the eastern group to 13.1 +/- 4.0 years for PFOS in the western group. PFOSA showed decreasing concentrations over time at both locations, while the remaining PFAs showed no significant trends or were not detected in any sample. The doubling time for PFOS was similar to the doubling time of production of perfluoroctylsulfonyl-fluoride-based products during the 1990s.     

Accumulation and depuration of polychlorinated biphenyls from field-collected sediment in three freshwater organisms

As laboratory-based bioaccumulation methods are standardized and expanded to include other test species, kinetic studies assessing the major classes of contaminants with these species are needed to adequately select the standard duration for bioaccumulation tests. In the present study we measured the uptake (28-d exposure) of polychlorinated biphenyls (PCBs; total and selected congeners) from field-contaminated sediment in the oligochaete Lumbriculus variegatus, mayfly nymph Hexagenia spp., and fathead minnow Pimephales promelas. Depuration (25 d) of PCBs was measured in organisms that had been transferred to clean sediment after the 28-d exposure. Uptake and elimination of PCBs was rapid in L. variegatus and Hexagenia spp. Tissue residues reached steady-state concentrations within 28 d; elimination rates and biota-sediment accumulation factors (BSAFs) of the PCB congeners were not correlated with K(OW). Uptake and elimination rates of PCBs were slower in P. promelas, and it is not clear whether steady-state was reached in fish tissues. Elimination rates of the PCB congeners significantly decreased with increasing K(OW) in fish. The appropriateness of a 28-d exposure for measuring steady-state concentrations in tissue of the invertebrates was confirmed, but further study is required for fish.     

SHAPE GENERALIZED ISOTHERMAL EFFECTIVENESS FACTOR FOR FIRST-ORDER KINETICS

A generalized effectiveness factor equation (Eq. (32)), in terms of modified Bessel functions, is derived for a catalyst pellet of arbitrary shape. The derivation is based on utilizing an appropriate one-dimensional approximation for the Laplacian in an arbitrary shaped body subjected to a uniform external concentration field. The comparison of the result with the available expressions for various geometries is highly satisfactory. It unifies the expressions for the three fundamental shapes, viz., infinite slab, infinite cylinder and sphere, and also compares very well with the exact solutions for finite shapes over the entire range of the Thiele modulus.     

Reactivity of functional groups in surface coating polymers. Part I. Hydroxyl groups in alkyd resins

The factors which can influence the availability of functional groups in polymers are considered. In particular, the importance of hydroxyl groups in the formation and Film-forming reactions of alkyd resins is discussed, and evidence is presented to suggest that the number of hydroxyl groups available for chemical reaction is not necessarily equivalent to the theoretical value. Factors which influence the availability of the hydroxyl groups are considered, and some of the properties of the alkyd are related to the available hydroxyl content.     

Radical bulk polymerization of N-vinylcaprolactam

Bulk radical polymerization of N-vinylcaprolactam was studied at temperatures between 60 and 120°C. with different initiators. Satisfactory results were obtained with azobisisobutyronitrile, tert-butyl perbenzoate, and tert-butyl peroxide as initiators. The polymerization reaction of N-vinylcaprolactam with these initiators is first order with respect to the monomer and 0.5 order with respect to the initiator. A linearity of the kinetic curves up to high conversions was observed. The cause of this behavior is a feeble gel effect, which also induces an increase of the molecular weight during polymerization.     

Synthesis,structural analysis and microwave dielectric properties of LnTiSb<Subscript>x</Subscript>Nb<Subscript>1−x</Subscript>O<Subscript>6</Subscript> (Ln = Ce,Pr) ceramics

LnTiSb_xNb_1−xO₆ (Ln = Ce, Pr) ceramics were prepared by the conventional solid state ceramic route for x = 0, 0.05, 0.1, 0.15, 0.2 and 0.25. The structure of the materials was analyzed using X-ray diffraction techniques. The cell parameters and the theoretical densities of the samples were calculated using least square methods. The samples are sintered to more than 90% of the theoretical density at 1,325–1,350 °C. The microwave dielectric properties were measured using the cavity resonator method. The surface morphology of the sintered sample was analyzed using Scanning Electron Microscopy. All the materials have good microwave dielectric properties and are suitable for dielectric resonator applications.     

A mild,protective and efficient procedure for grinding coal: cryocrushing

Conventional grinding methods are harsh and produce dramatic changes in coal. When coal, initially at room temperature, is ground in the presence of air, the high localized temperatures produced are known to cause both the production of gases and surface oxidation. These perturbations make meaningful measurements on the product very difficult. A technique that minimizes these effects is the pulverization of coal in liquid nitrogen. Compared with conventional methods, the process is rapid and appears to be less destructive chemically. Electron Spectroscopy for Chemical Analysis (ESCA) measurements support this conclusion. Surface oxidation is significantly reduced by this mild treatment. The method produces more particles below 38 μm than does conventional grinding and these fine particles are less prone to agglomeration.     

Evolution of fuel nitrogen in coal devolatilization

The distribution of fuel nitrogen in the devolatilization products of a lignite and 12 bituminous coals has been observed experimentally. For these coals under isothermal conditions (300 < T < 1000 °Cand 5 < t < 80 s) the behaviour of the nitrogen evolution was found to be similar. Nitrogen which is initially released is contained almost entirely in the tar. The chemical composition, ¹³C-n.m.r. spectra and infrared spectra of the tars and parent coals are strikingly similar and it is reasonable to suspect that the tar nitrogen occurs in the same structures as in the parent coal. Secondary release of nitrogen into nontar volatiles occurs only at high temperature. Results can be described with first-order kinetics using the same rate constant for all the coals studied. Initial nitrogen release is described by the tar release rate constant, k = 81 exp (−5800/T) (s⁻¹), which is similar to the rate constant for initial nitrogen release measured by Pohl and Sarofim. Secondary release of nitrogen is described with a rate constant which is similar to the results measured by Blair, Wendt and Bartok. This rate is smaller than that measured for the decomposition of nitrogen-ring compounds such as pyridines or pyrroles. The results suggest that coal nitrogen is contained almost entirely in tightly bound rings which are released without breakage in the tar during the initial stage of devolatilization; the remainder is released at higher temperatures when rings are ruptured.