Garry Codling

Polyfluoroalkyl compounds in the Canadian Arctic atmosphere

Environmental context Perfluoroalkyl compounds are of rising environmental concern because of their ubiquitous distribution in remote regions like the Arctic. The present study quantifies these contaminants in the gas and particle phases of the Canadian Arctic atmosphere. The results demonstrate the important role played by gas–particle partitioning in the transport and fate of perfluoroalkyl compounds in the atmosphere. Abstract Polyfluoroalkyl compounds (PFCs) were determined in high-volume air samples during a ship cruise onboard the Canadian Coast Guard Ship Amundsen crossing the Labrador Sea, Hudson Bay and the Beaufort Sea of the Canadian Arctic. Five PFC classes (i.e. perfluoroalkyl carboxylates (PFCAs), polyfluoroalkyl sulfonates (PFSAs), fluorotelomer alcohols (FTOHs), fluorinated sulfonamides (FOSAs), and sulfonamidoethanols (FOSEs)) were analysed separately in the gas phase collected on PUF/XAD-2 sandwiches and in the particle phase on glass-fibre filters (GFFs). The method performance of sampling, extraction and instrumental analysis were compared between two research groups. The FTOHs were the dominant PFCs in the gas phase (20–138 pg m–3), followed by the FOSEs (0.4–23 pg m–3) and FOSAs (0.5–4.7 pg m–3). The PFCAs could only be quantified in the particle phase with low levels (  FOSAs (~9 %) > FTOHs (~1 %). Significant positive correlation between ∑FOSA concentrations in the gas phase and ambient air temperature indicate that cold Arctic surfaces, such as the sea-ice snowpack and surface seawater could be influencing FOSAs in the atmosphere.

Organophosphorus insecticides in honey, pollen and bees (Apis mellifera L.) and their potential hazard to bee colonies in Egypt

There is no clear single factor to date that explains colony loss in bees, but one factor proposed is the wide-spread application of agrochemicals. Concentrations of 14 organophosphorous insecticides (OPs) in honey bees (Apis mellifera) and hive matrices (honey and pollen) were measured to assess their hazard to honey bees. Samples were collected during spring and summer of 2013, from 5 provinces in the middle delta of Egypt. LC/MS-MS was used to identify and quantify individual OPs by use of a modified Quick Easy Cheap Effective Rugged Safe (QuEChERS) method. Pesticides were detected more frequently in samples collected during summer. Pollen contained the greatest concentrations of OPs. Profenofos, chlorpyrifos, malation and diazinon were the most frequently detected OPs. In contrast, ethoprop, phorate, coumaphos and chlorpyrifos-oxon were not detected. A toxic units approach, with lethality as the endpoint was used in an additive model to assess the cumulative potential for adverse effects posed by OPs. Hazard quotients (HQs) in honey and pollen ranged from 0.01-0.05 during spring and from 0.02-0.08 during summer, respectively. HQs based on lethality due to direct exposure of adult worker bees to OPs during spring and summer ranged from 0.04 to 0.1 for best and worst case respectively. It is concluded that direct exposure and/or dietary exposure to OPs in honey and pollen pose little threat due to lethality of bees in Egypt.

Concentrations of neonicotinoid insecticides in honey, pollen and honey bees (Apis mellifera L.) in central Saskatchewan, Canada.

Neonicotinoid insecticides (NIs) and their transformation products were detected in honey, pollen and honey bees, (Apis mellifera) from hives located within 30 km of the City of Saskatoon, Saskatchewan, Canada. Clothianidin and thiamethoxam were the most frequently detected NIs, found in 68 and 75% of honey samples at mean concentrations of 8.2 and 17.2 ng g(-1) wet mass, (wm), respectively. Clothianidin was also found in >50% of samples of bees and pollen. Concentrations of clothianidin in bees exceed the LD50 in 2 of 28 samples, while for other NIs concentrations were typically 10-100-fold less than the oral LD50. Imidaclorpid was detected in ∼30% of samples of honey, but only 5% of pollen and concentrations were <LOD in bees. Transformation products of Imidaclorpid, imidaclorpid-Olefin and imidacloprid-5-Hydroxy were detected with greater frequency and at greater mean concentrations indicating a need for more focus on potential effects of these transformation products than the untransformed, active ingredient NIs. Results of an assessment of the potential dietary uptake of NIs from honey and pollen by bees over winter, during which worker bees live longer than in summer, suggested that, in some hives, consumption of honey and pollen during over-wintering might have adverse effects on bees.

Occurrence and trends in concentrations of perfluoroalkyl substances (PFASs) in surface waters of eastern China

Spatial distributions of perfluoroalkyl substances (PFASs) were investigated in surface waters in Shanghai, Jiangsu and Zhejiang Provinces of eastern China during 2011. A total of 39 samples of surface waters, including 29 rivers, 6 lakes and 4 reservoirs were collected. High performance liquid chromatography/negative electrospray ionization-tandem mass spectrometry (HPLC/(-)ESI-MS/MS) was used to identify and quantify PFASs. Concentrations of PFAS were greater in Shanghai than that in Zhejiang Province. Concentrations of the sum of PFASs (∑PFASs) in Shanghai and Kunshan ranged from 39 to 212 ng L(-1), while in Zhejiang Province, concentrations of ∑PFASs ranged from 0.68 to 146 ng L(-1). Perfluorooctanoic acid (PFOA) was the prevalent PFAS in Shanghai. In contrast, PFOA and perfluorohexanoic acid (PFHxA) were the prevalent PFASs in Zhejiang Province. Concentrations of perfluorooctane sulfonate (PFOS) ranged from <0.07 to 9.7 ng L(-1). Annual mass of ∑PFASs transported by rivers that flow into the East China Sea were calculated to be more than 4000 kg PFASs. Correlation analyses between concentrations of individual PFASs showed the correlation between PFHxA and PFOA was positive, while the correlation between PFHxA and perfluorooctane sulfonamide (FOSA) was negative in Shanghai, which indicated that PFHxA and PFOA have common sources. Principal component analysis (PCA) was employed to identify important components or factors that explain different compounds, and results showed that PFHxA and FOSA dominated factor loadings.

Accumulation of Perfluoroalkyl Compounds in Tibetan Mountain Snow: Temporal Patterns from 1980 to 2010

The use of snow and ice cores as recorders of environmental contamination is particularly relevant for per- and polyfluoroalky substances (PFASs) given their production history, differing source regions and varied mechanisms driving their global distribution. In a unique study perfluoroalkyl acids (PFAAs) were analyzed in dated snow-cores obtained from high mountain glaciers on the Tibetan Plateau (TP). One snow core was obtained from the Mt Muztagata glacier (accumulation period of 1980-1999), located in western Tibet and a second core from Mt. Zuoqiupo (accumulation period: 1996-2007) located in southeastern Tibet, with fresh surface snow collected near Lake Namco in 2010 (southern Tibet). The higher concentrations of ∑PFAAs were observed in the older Mt Muztagata core and dominated by perfluorooctanesulfonic acid (PFOS) (61.4-346 pg/L) and perfluorooctanoic acid (PFOA) (40.8-243 pg/L), whereas in the Mt Zuoqiupu core the concentrations were lower (e.g., PFOA: 37.8-183 pg/L) with PFOS below detection limits. These differences in PFAA concentrations and composition profile likely reflect the upwind sources affecting the respective sites (e.g., European/central Asian sources for Mt Muztagata and India sources for Mt Zuoqiupu). Perfluorobutanoic acid (PFBA) dominated the recent surface snowpack of Lake Namco which is mainly associated with India sources where the shorter chain volatile PFASs precursors predominate. The use of snow cores in different parts of Tibet provides useful recorders to examine the influence of different PFASs source regions and reflect changing PFAS production/use in the Northern Hemisphere.

Historical trends of inorganic and organic fluorine in sediments of Lake Michigan

Total fluorine (TF), extractable organic fluorine (EOF) and poly- and per-fluorinated compounds (PFCs) were measured in eight dated cores of sediment taken along with 27 surface sediments from Lake Michigan in 2010. Based on rates of sedimentation, total concentrations of PFCs (∑PFCs) reached a maximum in the later 1990s and early 2000s. This result is consistent with rapid changes in production and subsequent sedimentation. Perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) are still the predominant PFCs in the cores, but in surface sediments, concentrations of perfluorobutane sulfonate (PFBS) and perfluorobutanoic acid (PFBA) are now occurring at concentrations comparable to those of PFOS and PFOA. This observation is consistent with shifts in patterns of production and use in the US and Canada. Concentrations of TF in sediments were greater than those of EOF. This result is consistent with a larger proportion of un-extractable fluorinated material in both surface sediments and in cores.

Bioaccumulation characteristics of perfluoroalkyl acids (PFAAs) in coastal organisms from the west coast of South Korea

Year-round monitoring for perfluoroalkyl acids (PFAAs) along the west coast of South Korea targeting long-term changes in water and coastal organisms has been conducted since 2008. In this study, we present the most recent 5-years of accumulated data and scrutinize the relationship between concentrations in water and biota highlighting bioaccumulation characteristics. Twelve individual PFAAs in samples of water (n=43) and biota (n=59) were quantified by use of HPLC-MS/MS after solid phase extraction. In recent years, concentrations of PFAAs in water have been generally decreasing, but profiles of relative concentrations of individual PFAAs vary among location and year. Bioaccumulation of PFAAs in various organisms including fishes, bivalves, crabs, gastropods, shrimps, starfish, and polychaetes varied among species. However, overall bioaccumulation of PFAAs was dependent on corresponding concentrations of PFAAs in water within an area. In organ-specific distributions of PFAAs, greater concentrations of PFAAs were found in intestine of fish (green eel goby). This result suggests that PFAAs are mainly accumulated via dietary exposure, while greater concentrations were found in gill and intestine of bivalve (oyster) which suggests both waterborne and dietary exposures to these organisms. Concentrations of PFAAs in biota did not decrease over time (2008-2010), indicating that continuing bioaccumulation followed by slow degradation or excretion of PFAAs accumulated in biota. Overall, spatio-temporal distributions of PFAAs in water and bioaccumulation characteristics seemed to be associated with recent restrictions of PFOS-based products and uses of PFBS-based substitutes.

Untargeted Identification of Organo-Bromine Compounds in Lake Sediments by Ultrahigh-Resolution Mass Spectrometry with the Data-Independent Precursor Isolation and Characteristic Fragment Method

While previous studies have found that unknown natural and synthetic organo-bromine compounds (NSOBCs) contributed more than 99% of the total organic bromine (Br) in the environment, there was no efficient method for untargeted screening to identify NSOBCs in environmental matrixes. A novel untargeted method for identifying NSOBCs, based on ultrahigh-resolution mass spectrometry (UHRMS) with the Q Exactive instrument was developed. This method included a data-independent precursor isolation and characteristic fragment (DIPIC-Frag) procedure to identify NSOBCs. A total of 180 successive 5-m/z-wide windows were used to isolate precursor ions. This resulted in a sufficient dynamic range and specificity to identify peaks of Br fragment ions for analysis. A total of 2520 peaks of NSOBC compounds containing Br were observed in sediments from Lake Michigan, United States. A new chemometric strategy which combined chromatographic profiles, isotopic peaks, precursor isolation window information, and intensities was used to identify precursor ions and chemical formulas for detecting NSOBCs. Precursor ions for 2163 of the 2520 NSOBCs peaks (86%) were identified, and chemical formulas for 2071 NSOBCs peaks (82%) were determined. After exclusion of isotopic peaks, 1593 unique NSOBCs were identified and chemical formulas derived for each. Most of the compounds identified had not been reported previously and had intensities which were 100- to 1000-fold greater than the congeners of polybrominated diphenyl ethers (PBDEs). In extracts of sediments, these compounds exhibited variations in intensities (<10(3) to ∼10(8)), m/z values (170.9438-997.5217), retention times on a C18 column (1.0-29.3 min), and the number of Br atoms (1-8). Generally, compounds with greater m/z values had longer retention times and greater numbers of Br atoms. Three compounds were used in a proof-of-concept experiment to demonstrate that structures of some of the screened NSOBCs could be further predicted by combining searching of database libraries and high-resolution MS(2) spectra.

Untargeted Screening and Distribution of Organo-Bromine Compounds in Sediments of Lake Michigan

Previously unreported natural and synthetic organo-bromine compounds (NSOBCs) have been found to contribute more than 99% of total organic bromine (TOB) in environmental matrices. We recently developed a novel untargeted method (data-independent precursor isolation and characteristic fragment, DIPIC-Frag) and identified ∼2000 NSOBCs in two sediments from Lake Michigan. In this study, this method was used to investigate the distributions of these NSOBCs in 23 surficial samples and 24 segments of a sediment core from Lake Michigan. NSOBCs were detected in all 23 surficial samples and exhibited 10- to 100-fold variations in peak abundance among locations. The pattern of distributions of NSOBCs was correlated with depth of the water column (r(2) = 0.61, p < 0.001). Hierarchical cluster analysis showed that sediments in close proximity exhibited similar profiles of NSOBCs. Distributions of NSOBCs in 24 segments of a sediment core dated from 1766 to 2008 were investigated, and samples from similar depths exhibited similar profiles of NSOBCs. NSOBCs were grouped into four clusters (soft-cluster analysis) with different temporal trends of abundances. 515 and 768 of the NSOBCs were grouped into cluster 1 and cluster 3 with increasing temporal trends, especially since 1950, indicating that abundances of these compounds might have been affected by human activities.

Detection, Identification, and Quantification of Hydroxylated Bis(2-ethylhexyl)-Tetrabromophthalate Isomers in House Dust

Ultra-High Resolution LC/mass spectrometry (LC-UHRMS; Thermo Fisher Q-Exactive) was used to identify two novel isomers of hydroxylated bis(2-ethylhexyl)-tetrabromophthalate (OH-TBPH) which were unexpectedly observed in a commercial standard of TBPH. By combining ultra-high resolution (UHR) mass spectra (MS(1)), mass errors to theoretical [TBPH-Br+O](-) were 2.1 and 1.0 ppm for the two isomers, UHR-MS(2) spectra and NMR analysis; the structures of the two compounds were identified as hydroxylated TBPH with a hydroxyl group on the aromatic ring. Relatively great proportions of the two isomers of OH-TBPH were detected in two technical products, Firemaster 550 (FM-550; 0.1% and 6.2%, respectively) and Firemaster BZ 54 (BZ-54; 0.1% and 7.9%), compared to a commercial standard (0.4% and 0.9%). To simultaneously analyze OH-TBPH isomers and TBPH in samples of dust, a method based on LC-UHRMS was developed to quantify the two compounds, using negative and positive ion modes, respectively. The instrumental limit of detection for TBPH was 0.01 μg/L, which was 200-300 times better than traditional methods (2.5 μg/L) based on gas chromatography-mass spectrometry. The analytical method combined with a Florisil cleanup was successfully applied to analyze TBPH and OH-TBPH in 23 indoor dust samples from Saskatoon, Saskatchewan, Canada. Two OH-TBPH isomers, OH-TBPH1 and OH-TBPH2, were detected in 52% and 91% of dust samples, respectively. Concentrations of OH-TBPH2 (0.35 ± 1.0 ng/g) were 10-fold greater than those of OH-TBPH1 (0.04 ± 0.88 ng/g) in dust, which was similar to profiles in FM-550 and BZ-54. TBPH was also detected in 100% of dust samples with a mean concentration of 733 ± 0.87 ng/g. A significant (p < 0.001) log-linear relationship was observed between TBPH and OH-TBPH isomers, further supporting the hypothesis of a common source of emission. Relatively small proportions of OH-TBPH isomers were detected in dust (0.01% ± 0.67 OH-TBPH1 and 0.1% ± 0.60 OH-TBPH2), which were significantly less than those in technical products (p < 0.001). This result indicated different environmental behaviors of OH-TBPH and TBPH. Detection of isomers of OH-TBPH is important, since compounds with phenolic groups have often shown relatively greater toxicities than nonhydroxylated analogues. Further study is warranted to clarify the environmental behaviors and potential toxicities of OH-TBPH isomers.