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- New priority substances of the European Water Framework Directive: Biocides, pesticides and brominated flame retardants in the aquatic environment of Denmark. [JOURNAL ARTICLE]
- Sci Total Environ 2013 Oct 20.:459-468.
The biocides cybutryn (Irgarol) and terbutryn, the herbicides aclonifen and bifenox, the insecticides cypermethrin and heptachlor/heptachlor epoxide and the brominated flame retardant hexabromocyclododecane (HBCD) are new priority substances of the Water Framework Directive of the European Union. In order to gain knowledge about their presence in the aquatic environment in an off-season situation with regard to pesticide and biocide applications, these substances were analysed in freshwater, seawater and fish samples from Denmark. Aclonifen, bifenox, cypermethrin and heptachlor were below the limits of detection (LODs) in all samples. However, the LODs for cypermethrin and heptachlor exceeded the annual average environmental quality standards (AA-EQSs). Cybutryn, terbutryn, heptachlor epoxide and HBCD were detected in the majority of samples, with detection frequencies of 100% for heptachlor epoxide and HBCD in water and 90% in fish. No concentration was above maximum allowable concentration (MAC)-EQS values, but AA-EQS values were exceeded for all four compounds by several samples, including 100% of the water samples with regard to heptachlor epoxide. Methodological issues remain for cypermethrin, and to a certain extent for heptachlor/heptachlor epoxide, for which water LODs were above AA-EQSs although a water volume of 12L was combined with very sensitive high resolution mass spectrometry.
- Levels and trends of toxaphene and chlordane-related pesticides in peregrine falcon eggs from South Greenland. [Journal Article]
- Sci Total Environ 2014 Jan 15.:614-21.
Peregrine falcon eggs were collected in South Greenland between 1986 and 2003 and analysed for 6 congeners of toxaphene and 5 chlordane-related pesticides (cis-chlordane, trans-chlordane, cis-nonachlor, trans-nonachlor and oxychlordane). Oxychlordane had the highest median concentration of 1448ng/g lipid weight (lw) or 79ng/g wet weight (ww) of all compounds. Of the toxaphene congeners, CHB-50 was the predominant congener, with a median concentration of 215ng/g lw (15.5ng/g ww). Chlordane-related concentrations were comparable with results from the USA, but lower than those from Canada and Norway. Toxaphene was considerably higher than in eggs of Norwegian peregrine falcon eggs, possibly reflecting different toxaphene usage in the areas of peregrine falcon migration. Toxaphene information in birds of prey is limited and comparisons with other species indicate differences in concentrations and organochlorine pattern. Temporal trends showed significant log-linear decreases for cis-chlordane and trans-chlordane, but no significant trends for other chlordanes or the toxaphene congeners, probably affected by the large variation between eggs, also of the same bird. Correlations between chlordanes and toxaphene in the Greenland peregrine falcon eggs might suggest similar sources of exposure.
- Species-specific time trends and enantiomer fractions of hexabromocyclododecane (HBCD) in biota from East Greenland. [Journal Article, Research Support, Non-U.S. Gov't]
- Environ Sci Technol 2012 Oct 2; 46(19):10549-55.
Time trends of hexabromocyclododecane (HBCD) isomers were studied for glaucous gull and ringed seal from East Greenland. The ringed seal results extended a previous time trend (1986-2008) to 2010. α-HBCD was the only isomer consistently above quantification limits. For glaucous gull liver, annual median values of α-HBCD (1994-2010) ranged from 22 to 120 ng/g lipid weight (lw) with no significant trend, while HBCD in ringed seal blubber from the same area showed a significant increase from 3.9 to 11 ng/g lw (1986-2010). Reasons for this difference are unknown, but might include different feeding habits and species-specific metabolisation processes. Concentrations of several organochlorine (OC) compounds were determined for glaucous gull and ringed seal samples collected from the same area in 2004. HBCD concentrations in glaucous gull liver appeared relatively low when compared to OC concentrations in the same tissue and to both HBCD and OCs in ringed seal blubber from the same area. Enantiomer fractions (EF) deviated significantly from racemic for all annual mean EFs in glaucous gull suggesting metabolisation processes toward an enrichment of (-)α-HBCD. For ringed seal, this enrichment was less pronounced and only significant for two of the ten years. For neither species, significant changes in EF were found over time.
- Characteristics and Comorbid Symptoms of Older Adults Reporting Death Ideation. [JOURNAL ARTICLE]
- Am J Geriatr Psychiatry 2012 Jun 13.
OBJECTIVE::To determine whether death ideation in late life is associated with markers of elevated risk for suicide, or reflects normal psychological processes in later life. DESIGN/
SETTING:: Population-based cross-sectional study in Gothenburg, Sweden.
PARTICIPANTS:: The sample consists of 345 men and women of age 85 years (born 1901-1902) and living in Gothenburg, Sweden.
MAIN OUTCOME MEASURES:: The Paykel Scale measured the most severe level of suicidality over an individual's lifetime. Other key measures were severity of depression and anxiety and frequency of death/suicidal ideation over the previous month.
RESULTS::Latent class analysis revealed distinct groups of older adults who reported recent death ideation. Recent death ideation did not occur apart from other risk factors for suicide; instead individuals reporting recent death ideation also reported either 1) recent high levels of depression and anxiety, or 2) more distant histories of serious suicidal ideation (indicative of worst point severity of suicidal ideation)-both of which elevate risk for eventual suicide.
CONCLUSIONS::Our results indicate a heterogeneous presentation of older adults who report death ideation, with some presenting with acute distress and suicidal thoughts, and others presenting with low distress but histories of serious suicidal ideation. The presence of death ideation is associated with markers of increased risk for suicide, including "worst point" active suicidal ideation.
- Polychlorinated biphenyls, organochlorine pesticides and polycyclic aromatic hydrocarbons in a one-off global survey of bivalves. [Journal Article, Research Support, Non-U.S. Gov't]
- J Environ Monit 2010 May; 12(5):1141-52.
During the Danish Galathea 3 expedition, bivalve samples were collected at the Faroe Islands, Greenland, Ghana, South Africa, Australia, Solomon Islands, New Zealand, Chile, US Virgin Islands, Boston, Newfoundland and Shetland Islands and analysed for organochlorines and PAHs. Concentration differences of up to three orders of magnitude were observed, with the highest concentrations at Boston harbour (SPCB 338 ng g(-1) dw, ΣSPAH 5966 ng g(-1) dw) and the Sydney estuary (ΣSPCB 282 ng g(-1) dw, SPAH 1453 ng g(-1) dw). Local impacts were also found for the Greenland capital Nuuk in terms of PCB and PAH levels, while other Greenland samples came closest to representing PAH background levels. Several locations had undetectable organochlorine levels, including Hobart and Chile, which had the lowest SPAH concentrations (<200 ng g(-1) dw). It was possible to group the stations according to their pyrogenic/petrogenic influence using Principal Component Analyses, and indications of petroleum sources were found at Nuuk.
- Explorations of new second-order nonlinear optical materials in the potassium vanadyl iodate system. [Journal Article]
- J Am Chem Soc 2011 Apr 13; 133(14):5561-72.
Four new potassium vanadyl iodates based on lone-pair-containing IO(3) and second-order Jahn-Teller distorted VO(5) or VO(6) asymmetric units, namely, α-KVO(2)(IO(3))(2)(H(2)O) (Pbca), β-KVO(2)(IO(3))(2)(H(2)O) (P2(1)2(1)2(1)), K(4)[(VO)(IO(3))(5)](2)(HIO(3))(H(2)O)(2)·H(2)O (P1), and K(VO)(2)O(2)(IO(3))(3) (Ima2) have been successfully synthesized by hydrothermal reactions. α-KVO(2)(IO(3))(2)(H(2)O) and β-KVO(2)(IO(3))(2)(H(2)O) exhibit two different types of 1D [VO(2)(IO(3))(2)](-) anionic chains. Neighboring VO(6) octahedra in the α-phase are corner-sharing into a 1D chain with the IO(3) groups attached on both sides of the chain in a uni- or bidentate bridging fashion, whereas those of VO(5) polyhedra in the β-phase are bridged by IO(3) groups into a right-handed helical chain with remaining IO(3) groups being grafted unidentately on both sides of the helical chain. The structure of K(4)[(VO)(IO(3))(5)](2)(HIO(3))(H(2)O)(2)·H(2)O contains novel isolated [(VO)(IO(3))(5)](2-) units composed of one VO(6) octahedron linked to five IO(3) groups and one terminal O(2-) anion. The structure of K(VO)(2)O(2)(IO(3))(3) exhibits a 1D [(VO)(2)O(2)(IO(3))(3)](-) chain in which neighboring VO(6) octahedra are interconnected by both oxo and bridging iodate anions. Most interestingly, three of four compounds are noncentrosymmetric (NCS), and K(VO)(2)O(2)(IO(3))(3) displays a very strong second-harmonic generation response of about 3.6 × KTP, which is phase matchable. It also has high thermal stability, a wide transparent region and moderate hardness as well as an excellent growth habit. Thermal analyses and optical and ferroelectric properties as well as theoretical calculations have also been performed.
- Temporal trends of hexabromocyclododecane, polybrominated diphenyl ethers and polychlorinated biphenyls in ringed seals from East greenland. [Journal Article, Research Support, Non-U.S. Gov't]
- Environ Sci Technol 2011 Feb 15; 45(4):1243-9.
Concentrations of hexabromocyclododecane (HBCD) were determined in a combination of archived and fresh blubber samples of juvenile ringed seals from East Greenland collected between 1986 and 2008. α-HBCD was the only diastereoisomer consistently above levels of quantification and showed a significant log-linear (exponential) increase from 2.0 to 8.7 ng/g lipid weight (median concentrations) with an annual rate of +6.1%. The concentrations were up to several orders of magnitude lower than those reported for marine mammals from industrialized areas. Previously presented time trends on polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) have been extended with new data for 2006 and 2008. ΣPBDE in juvenile seals was the only parameter with a slight upward trend, however, dependent on the low 1986 concentration. Removing this data point resulted in a downward trend, which also was found for adult seals with a time trend starting in 1994. ΣPCB decreased significantly in juvenile seals, again due to the 1986 value, while no trend was found for the adult animals. This indicates stagnating PCB concentrations at a relatively high level, in some cases possibly exceeding tolerable daily intake rates for seal blubber as traditional Arctic food items.
- Polybrominated diphenyl ethers (PBDEs) in the indoor environment and associations with prenatal exposure. [Journal Article, Research Support, Non-U.S. Gov't]
- Environ Int 2011 Jan; 37(1):1-10.
As part of a larger exposure study, samples of dust and indoor air were collected in the homes of 43 pregnant women living in the Copenhagen area (Denmark) and analysed for 12 polybrominated diphenyl ethers using GC-MS. A second dust sample collected after delivery was analysed for BDE-183 and BDE-209, which were highly correlated with the pre-delivery samples, but did not reproduce the actual values. Concentrations as high as 80 μg/g were measured for the dominant BDE congener BDE-209, with median concentrations of 332 and 432 ng/g, respectively, in pre- and post-delivery dust samples. In 12% of the dust samples, the concentration of BDE-209 was lower than that of the summed concentration of PentaBDE congeners. The median concentrations of BDE-47 and BDE-99 in dust were 16.9 and 13.6 ng/g, respectively. The dust concentrations were in line with other European studies and confirmed previously established geographical differences between continental Europe and North America. Additional octa- and nonaBDE congeners (BDE-197, BDE-203, BDE-206, BDE-207, and BDE-208) were analysed in dust and analytical issues were discussed as these congeners also can be a product of thermal degradation of BDE-209 in gas chromatographic analysis. BDE-206 was the dominating nonaBDE, with median and maximum concentrations of 12.8 and 2217 ng/g, respectively, but the ratio of nonaBDEs to the sum of nona- and decaBDEs was relatively constant, despite a large range in absolute dust concentrations. While the congeners of the PentaBDE mixture were highly inter-correlated for both dust and air, no correlation was found with BDE-209 in either matrix. Air concentrations were relatively high in an international context, with median concentrations of 134, 63.7 and 119 pg/m³ for BDE-47, BDE-99 and BDE-209, respectively, and not correlated with dust concentrations. Additional placenta data were available for the study group and found to correlate significantly with dust concentrations for some PentaBDE congeners, but not BDE-209, indicating that dust may be an important exposure pathway for PentaBDE congeners. While BDE-209 also was present in placenta, it did not exceed the other congeners by the same factors as in dust. This might be caused by a combination of the compound's physical-chemical properties affecting bioavailability, uptake, partitioning and metabolisation, and other sources of exposure, but was not investigated further in this study. For all matrices, the PBDE profile resembled that of the technical product Bromkal 70-5DE, but air contained higher percentages of the lower brominated congeners and placenta tissue was dominated by BDE-153. The predominance of BDE-153 has been described in other studies on human samples and related to the highest retention in the body, but further research into toxicokinetics will be required to clarify mechanisms.
- Persistent organochlorine compounds in peregrine falcon (Falco peregrinus) eggs from South Greenland: levels and temporal changes between 1986 and 2003. [Journal Article, Research Support, Non-U.S. Gov't]
- Environ Int 2009 Feb; 35(2):336-41.
Thirty-seven addled peregrine falcon eggs collected in South Greenland between 1986 and 2003 were analysed for their content of the organochlorine compounds polychlorinated biphenyls (PCBs), dichlorodiphenyl tricloroethane (DDT) and its degradation products, hexachlorocyclohexane (HCH) isomers and hexachlorobenzene (HCB). PCBs and DDT (including metabolites) were by far the most abundant OC groups, with median concentrations of 55 and 40 microg/g lw, respectively. The concentrations were high in an Arctic context, but similar to previously reported levels from Alaska and Norway and slightly lower than concentrations measured in eggs from industrialised regions. Geographical differences may be of importance, considering the migration of peregrine falcons and their prey. SigmaHCH and HCB had median concentrations of 0.39 and 0.17 microg/g lw, respectively. On average, DDE accounted for 97% of SigmaDDT, but was below critical levels for eggshell thinning. All compound groups showed a weak decreasing trend over the study period, which was statistically significant for HCB and close to being significant for SigmaHCH. The weak decrease of SigmaPCB and SigmaDDT is different from other time trend studies from Greenland, usually showing a more pronounced decrease in the beginning of the study period, followed by a certain stabilisation in recent years.
- Insulin mimetic peroxo complexes of vanadium containing uracil or Cytosine as ligand. [Journal Article]
- Met Based Drugs 2000; 7(3):157-64.
Mixed ligand oxo peroxo complexes of vanadium (V), M[VO(O(2))L(2)].nH(2)O where M = K or NH(4), HL = uracil or cytosine and n = 1 or 2, have been isolated from aqueous methanolic medium. The complexes were characterised by elemental analysis, conductance, TGA, UV-Visible, IR and NMR spectral studies. Both the peroxide and the other ligands acts as chelates coordinating through their oxygen at C (2) and nitrogen at N (3) and the presence of monomeric oxoperoxovanadium (V) species, have been established by IR, (1)H and (51)V NMR studies. The complexes appeared to possess pentagonal bipyramidal geometry. The terminal oxo ligand and the oxygen of the uracil or cytosine at C (2) occupy the axial position while the peroxide and the other donor ligands are in the equatorial position. The UV spectral studies confirm the presence of Vanadium in its +5 oxidation state. The administration of the potassium salts of the complexes reduces the blood glucose level in Swiss Albino mice compared to that of KVO(3). The complexes also readily oxidise cysteine to Cystine in aqueous solution. The possible mechanism for the insulin-mimic activity of the complexes is discussed.