Investigation of the primary plasticisers present in polyvinyl chloride (PVC) products currently authorised as food contact materials

PVC is a common food contact material that is usually plasticised to increase its flexibility. Phthalates are one class of chemical compounds that are often used as plasticisers in PVC in a wide range of industries. They may be used in packaging materials for foods and can also be found in components of certain food processing equipment such as conveyor belts and tubing. Transfer of plasticisers from packaging to foods can occur. In recent years, there has been increased interest in understanding the health effects of phthalates, as well as the possible human exposure levels. However, there is limited information available about the routes of exposure to phthalates. In July 2014, the Chronic Hazard Advisory Panel (CHAP) produced a report for the U.S. Consumer Product Safety Commission detailing the potential health hazards of phthalates and phthalate alternatives. This report listed diet as one factor contributing greater than or equal to 10% of total phthalate exposure. As a result of this report, the U.S. Food and Drug Administration (FDA) is interested in determining the types of the primary plasticiser present in food packaging and processing materials as well as their concentrations. An investigation was conducted of 56 different samples of PVC food packaging and food processing materials available in the US market using a solvent extraction and GC-MS analysis. Nine different plasticisers including three phthalates, di(2-ethylhexyl) phthalate, diisononyl phthalate and diisodecyl phthalate, were identified in the products tested. The plasticiser concentrations ranged from 1 to 53% depending on the types of food contact materials and the type of plasticiser. Overall, it appears that manufacturers are switching away from phthalates as their primary plasticiser to alternate compounds such as ESBO, ATBC, DEHT, DINCH, DEHA and DINA.     

An optimized FAIRE procedure for low cell numbers in yeast

We report an optimized low‐input FAIRE‐seq (Formaldehyde‐Assisted Isolation of Regulatory Elements‐sequencing) procedure to assay chromatin accessibility from limited amounts of yeast cells. We demonstrate that the method performs well on as little as 4 mg of cells scraped directly from a few colonies. Sensitivity, specificity and reproducibility of the scaled‐down method are comparable with those of regular, higher input amounts, and allow the use of 100‐fold fewer cells than existing procedures. The method enables epigenetic analysis of chromatin structure without the need for cell multiplication of exponentially growing cells in liquid culture, thus opening the possibility of studying colony cell subpopulations, or those that can be isolated directly from environmental samples.     

Outdoor grazing of dairy cows on pasture versus indoor feeding on total mixed ration: Effects on gross composition and mineral content of milk during lactation

The influence of feeding system and lactation period on the gross composition, macroelements (Ca, P, Mg, and Na), and trace elements (Zn, Fe, Cu, Mo, Mn, Se, and Co) of bovine milk was investigated. The feeding systems included outdoor grazing on perennial ryegrass pasture (GRO), outdoor grazing on perennial ryegrass and white clover pasture (GRC), and indoors offered total mixed ration (TMR). Sixty spring-calving Holstein Friesian dairy cows were assigned to 3 herds, each consisting of 20 cows, and balanced with respect to parity, calving date, and pre-experimental milk yield and milk solids yield. The herds were allocated to 1 of the 3 feeding systems from February to November. Milk samples were collected on 10 occasions over the period June 17 to November 26, at 2 or 3 weekly intervals, when cows were on average 119 to 281 d in lactation (DIL). The total lactation period was arbitrarily sub-divided into 2 lactation periods based on DIL, namely mid lactation, June 17 to September 9 when cows were 119 to 203 DIL; and late lactation, September 22 to November 26 when cows were 216 to 281 DIL. With the exception of Mg, Na, Fe, Mo, and Co, all other variables were affected by feeding system. The GRO milk had the highest mean concentrations of total solids, total protein, casein, Ca, and P. The TMR milk had the highest concentrations of lactose, Cu, and Se, and lowest level of total protein. The GRC milk had levels of lactose, Zn, and Cu similar to those of GRO milk, and concentrations of TS, Ca, and P similar to those of TMR milk. Lactation period affected all variables, apart from the concentrations of Fe, Cu, Mn, and Se. On average, the proportion (%) of total Ca, P, Zn, Mn, or Se that sedimented with the casein on high-speed ultracentrifugation at 100,000 × g was ≥60%, whereas that of Na, Mg, or Mo was ≤45% total. The results demonstrate how the gross composition and elemental composition of milk can be affected by different feeding systems.     

Sources of mercury wet deposition in Eastern Ohio, USA

In the fall of 2002, an enhanced air monitoring site was established in Steubenville, Ohio as part of a multi-year comprehensive mercury monitoring and source apportionment study to investigate the impact of local and regional coal combustion sources on atmospheric mercury deposition in the Ohio River Valley. This study deployed advanced monitoring instrumentation, utilized innovative analytical techniques, and applied state-of-the-art statistical receptor models. This paper presents wet deposition data and source apportionment modeling results from daily event precipitation samples collected during the calendar years 2003-2004. The volume-weighted mean mercury concentrations for 2003 and 2004 were 14.0 and 13.5 ng L(-1), respectively, and total annual mercury wet deposition was 13.5 and 19.7 microg m(-2), respectively. Two new EPA-implemented multivariate statistical models, positive matrix factorization (PMF) and Unmix, were applied to the data set and six sources were identified. The dominant contributor to the mercury wet deposition was found by both models to be coal combustion (approximately 70%). Meteorological analysis also indicated that a majority of the mercury deposition found at the Steubenville site was due to local and regional sources.     

Uranium sorption on various forms of titanium dioxide--influence of surface area, surface charge, and impurities

Titanium dioxide (TiO(2)) has often served as a model substrate for experimental sorption studies of environmental contaminants. However, various forms of Ti-oxide have been used, and the different sorption properties of these materials have not been thoroughly studied. We investigated uranium sorption on some thoroughly characterized TiO(2) surfaces with particular attention to the influence of surface area, surface charge, and impurities. The sorption of U(VI) differed significantly between samples. Aggressive pretreatment of one material to remove impurities significantly altered the isoelectric point, determined by an electroacoustic method, but did not significantly impact U sorption. Differences in sorption properties between the various TiO(2) materials were related to the crystallographic form, morphology, surface area, and grain size, rather than to surface impurities or surface charge. In-situ attenuated total reflection Fourier-transform infrared (ATR FT-IR) spectroscopic studies showed that the spectra of the surface species of the TiO(2) samples are not significantly different, suggesting the formation of similar surface complexes. The data provide insights into the effect of different source materials and surface properties on radionuclide sorption.     

Tertiary-treated municipal wastewater is a significant point source of antibiotic resistance genes into Duluth-Superior Harbor

In this study, the impact of tertiary-treated municipal wastewater on the quantity of several antibiotic resistance determinants in Duluth-Superior Harbor was investigated by collecting surface water and sediment samples from 13 locations in Duluth-Superior Harbor, the St. Louis River, and Lake Superior. Quantitative PCR (qPCR) was used to target three different genes encoding resistance to tetracycline (tet(A), tet(X), and tet(W)), the gene encoding the integrase of class 1 integrons (intI1), and total bacterial abundance (16S rRNA genes) as well as total and human fecal contamination levels (16S rRNA genes specific to the genus Bacteroides ). The quantities of tet(A), tet(X), tet(W), intI1, total Bacteroides , and human-specific Bacteroides were typically 20-fold higher in the tertiary-treated wastewater than in nearby surface water samples. In contrast, the quantities of these genes in the St. Louis River and Lake Superior were typically below detection. Analysis of sequences of tet(W) gene fragments from four different samples collected throughout the study site supported the conclusion that tertiary-treated municipal wastewater is a point source of resistance genes into Duluth-Superior Harbor. This study demonstrates that the discharge of exceptionally treated municipal wastewater can have a statistically significant effect on the quantities of antibiotic resistance genes in otherwise pristine surface waters.     

Glucose prevents citrate metabolism by enterococci

Enterococcus faecalis FAIR E-239, growing on glucose plus citrate, metabolized citrate at pH 6.5 or 7.5, but only when glucose had been exhausted; it did not metabolize citrate at pH 5.5 or 8.5. When grown on citrate only, the strain metabolized citrate at all pH values, and two growth rates were apparent. Citrate was mainly metabolized during the second, much slower growth rate. Glucose also inhibited citrate metabolism by E. faecalis FAIR E-237 and FAIR E-259 and Enterococcus faecium FAIR E-338 and FAIR E-371. Glucose-grown resting cells were unable to metabolize citrate. Citrate-grown resting cells had a pH optimum of 4.7 for citrate metabolism but also metabolized significant amounts of citrate at pH 4.2 and 6.5. Resting stationary phase cells used citrate more rapidly than resting log phase cells. Citrate metabolism was faster at citrate levels <10 mM than above 10 mM. These results suggest that some form of catabolite repression is occurring.     

Role of soil freezing events in interannual patterns of stream chemistry at the Hubbard Brook Experimental Forest,New Hampshire

Soil freezing is a disturbance of the below ground environment, potentially resulting in increased losses of NO3- and surface water acidification. Here, we report the effects of soil freezing on interannual variation in stream chemistry at the Hubbard Brook Experimental Forest, New Hampshire. Data from 1970 to 1997 of soil frost depth, snow cover, precipitation, air temperature, and stream discharge and chemistry were used in a stepwise linear regression model to select the variables that best predicted deviations of annual stream concentrations from 4-year running averages. Variables quantifying soil freezing severity were selected as significant predictors of short-term fluctuations in stream K+, NO3-, Ca2+, and Mg2+ concentrations from 1970 to 1989, explaining 59 and 47% of the short-term variability in K+ and NO3-, respectively. Fine-root mortality and disturbance of root-soil-microbe interactions, with subsequent effects on decomposition and nutrient uptake, likely contributed to the mobilization of K+ and NO3- to streamwater following severe soil freezing events. The relationship between soil freezing and stream chemistry, however, weakened during the period 1990-1997. Because soil freezing has had inconsistent effects on stream chemistry during the period 1970-1997, it is unclear whether future changes in the frequency, duration, and depth of soil freezing events as the result of changes in the snow cover regime under a warmer climate will have significant impacts on the losses of NO3- and nutrient-base cations from temperate northern ecosystems.     

Demonstration of a method for the direct determination of polycyclic aromatic hydrocarbons in submerged sediments

We describe the development of a novel method for real-time in situ characterization of polycyclic aromatic hydrocarbons (PAHs) in submerged freshwater sediments. Laser-induced fluorescence (LIF) spectroscopy, a mature technique for PAH characterization in terrestrial sediments, was adapted for shipboard use. A cone penetrometer-type apparatus was designed for probe penetration at a constant rate (1 cm/s) to a depth of 3 m. A field-portable LIF system was used for in situ measurements in which the output of a pulsed excimer laser was transmitted by optical fiber to a sapphire window (6.4-mm o.d.) in the probe wall; fluorescent emission was collected by a separate optical fiber for transmission to the spectrometer on deck. Four wavelengths (340, 390, 440, 490 nm) were selected via optical delay lines, and multiple-wavelength waveforms were created. These multiple-wavelength waveforms contain information on the fluorescence frequency, intensity, and emission decay rate. Field testing was conducted at 10 sites in Milwaukee Harbor (total PAH concentrations ranged from approximately 10 to 650 microg/g); conventional sediment core samples were collected concurrently. The core samples were analyzed by EPA methods 3545 (pressurized fluid extraction, PFE) and 8270C (gas chromatography-mass spectrometry, GC-MS) for PAHs. A partial least-squares regression (PLSR) model wasthen created based on laboratory LIF measurements and PFE-GC-MS of the core samples. The PLSR model was applied to the in situ field test data, and 13 of the 16 EPA-regulated PAHs were quantified with a relative error of <30% overall (the remaining three PAHs were found at levels insufficient to quantify). We additionally describe preliminary source apportionment relationships that were revealed by the PLSR model for the in situ LIF measurements.