The global distribution of linear and cyclic volatile methyl silxoanes (VMS) was investigated at 20 sites worldwide, including 5 locations in the Arctic, using sorbent-impregnated polyurethane foam (SIP) disk passive air samplers. Cyclic VMS are currently being considered for regulation because they are high production volume chemicals that are potentially persistent, bioaccumulative, and toxic. Linear and cyclic VMS (including L3, L4, L5, D3, D4, D5, and D6) were analyzed for in air at all urban, background, and Arctic sites. Concentrations of D3 and D4 are significantly correlated, as are D5 and D6, which suggests different sources for these two pairs of compounds. Elevated concentrations of D3 and D4 on the West coast of North America and at high elevation sites suggest these sites are influenced by trans-Pacific transport, while D5 and D6 have elevated concentrations in urban areas, which is most likely due to personal care product use. Measured concentrations of D5 were compared to modeled concentrations generated using both the Danish Eulerian Hemispheric Model (DEHM) and the Berkeley-Trent Global Contaminant Fate Model (BETR Global). The correlation coefficients (r) between the measured and modeled results were 0.73 and 0.58 for the DEHM and BETR models, respectively. Agreement between measurements and models indicate that the sources, transport pathways, and sinks of D5 in the global atmosphere are fairly well understood.

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Sorbent-impregnated polyurethane foam (SIP) disk passive air samplers were deployed alongside polyurethane foam (PUF) disk samplers at 20 sites during the 2009 spring sampling period of the Global Atmospheric Passive Sampling (GAPS) Network. The SIP disk samplers consisted of PUF disks impregnated with finely ground XAD-4 resin. The addition of XAD-4 greatly improves the sorptive capacity of the PUF disk samplers for more volatile and polar chemicals, and allows for linear-phase sampling over several weeks for these compounds. The SIP and PUF disks were analyzed for polychlorinated biphenyls (PCBs), neutral polyfluoroalkyl compounds (PFCs), and ionic PFCs. Correlations between sampler-derived air concentrations for PCBs in the PUF and SIP disks samplers were significant (p < 0.05). The SIP disks effectively captured 4-50% more of the low molecular weight PCBs than the PUF disks samplers, and the PUF disks also had limitations for time-weighted passive sampling of neutral PFCs in air. Theoretical uptake curves for PUF disks showed rapid equilibration occurring in just hours for 8:2 FTOH and in a few days for MeFOSE, while theoretical curves for SIP disks showed superior sampling profiles for the neutral PFCs. PFCs were measured on SIP disks at all sites with 8:2 FTOH being the dominant compound detected and urban centers (n = 3) having the highest total neutral PFC concentrations ranging from 51.7 to 248 pg/m(3). A positive correlation was found between the FTOHs and FOSAs/FOSEs (p < 0.001, Pearson correlation) indicating similar contamination sources. The SIP disk appears to be a promising passive air sampler for measuring both emerging and legacy POPs on a global scale. They can also be used as a complement to the PUF disk sampler for capturing broader classes of compounds, or as a replacement for PUF disks entirely, especially when longer than quarterly deployment periods are desired.

In 1974, Junge postulated a relationship between variability of concentrations of gases in air at remote locations and their atmospheric residence time, and this Junge relationship has subsequently been observed empirically for a range of trace gases. Here, we analyze two previously-published datasets of concentrations of cyclic volatile methyl siloxanes (cVMS) in air and find Junge relationships in both. The first dataset is a time series of concentrations of decamethylcyclopentasiloxane (D5) measured between January and June, 2009 at a rural site in southern Sweden that shows a Junge relationship in the temporal variability of the measurements. The second dataset consists of measurements of hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4) and D5 made simultaneously at 12 sites in the Global Atmospheric Passive Sampling (GAPS) network that shows a Junge relationship in the spatial variability of the three cVMS congeners. We use the Junge relationship for the GAPS dataset to estimate atmospheric lifetimes of dodecamethylcyclohexasiloxane (D6), 8:2-fluorotelomer alcohol and trichlorinated biphenyls that are within a factor of 3 of estimates based on degradation rate constants for reaction with hydroxyl radical determined in laboratory studies.

Sudan I, II, III and IV dyes are banned for use as food colorants in the United States and European Union because they are toxic and carcinogenic. These dyes have been illegally used as food additives in products such as chilli spices and palm oil to enhance their red colour. From 2003 to 2005, the European Union made a series of decisions requiring chilli spices and palm oil imported to the European Union to contain analytical reports declaring them free of Sudan I–IV. In order for the USFDA to investigate the adulteration of palm oil and chilli spices with unapproved colour additives in the United States, a method was developed for the extraction and analysis of Sudan dyes in palm oil, and previous methods were validated for Sudan dyes in chilli spices. Both LC-DAD and LC-MS/MS methods were examined for their limitations and effectiveness in identifying adulterated samples. Method validation was performed for both chilli spices and palm oil by spiking samples known to be free of Sudan dyes at concentrations close to the limit of detection. Reproducibility, matrix effects, and selectivity of the method were also investigated. Additionally, for the first time a survey of palm oil and chilli spices was performed in the United States, specifically in the Washington, DC, area. Illegal dyes, primarily Sudan IV, were detected in palm oil at concentrations from 150 to 24 000 ng ml−1. Low concentrations (< 21 μg kg−1) of Sudan dyes were found in 11 out of 57 spices and are most likely a result of cross-contamination during preparation and storage and not intentional adulteration.