Closing the Organofluorine Mass Balance in Marine Mammals Using Suspect Screening and Machine Learning-Based Quantification.

High-resolution mass spectrometry (HRMS)-based suspect and nontarget screening has identified a growing number of novel per- and polyfluoroalkyl substances (PFASs) in the environment. However, without analytical standards, the fraction of overall PFAS exposure accounted for by these suspects remains ambiguous. Fortunately, recent developments in ionization efficiency (IE) prediction using machine learning offer the possibility to quantify suspects lacking analytical standards. In the present work, a gradient boosted tree-based model for predicting log IE in negative mode was trained and then validated using 33 PFAS standards. The root-mean-square errors were 0.79 (for the entire test set) and 0.29 (for the 7 PFASs in the test set) log IE units. Thereafter, the model was applied to samples of liver from pilot whales (n = 5; East Greenland) and white beaked dolphins (n = 5, West Greenland; n = 3, Sweden) which contained a significant fraction (up to 70%) of unidentified organofluorine and 35 unquantified suspect PFASs (confidence level 2-4). IE-based quantification reduced the fraction of unidentified extractable organofluorine to 0-27%, demonstrating the utility of the method for closing the fluorine mass balance in the absence of analytical standards.

Retinal vessel diameters and risk of impaired fasting glucose or diabetes: the Rotterdam study.

The association between a smaller retinal arteriolar-to-venular ratio (AVR) and incident diabetes may be due to arteriolar narrowing, venular dilatation, or both. We investigated associations between baseline vessel diameters and incident impaired fasting glucose or diabetes in a population-based cohort (aged > or =55 years). Baseline retinal vessel diameters (1990-1993) were measured on digitized images of 2,309 subjects with a normal glucose tolerance test (postload glucose <7.8 mmol/l). At follow-up (1997-1999), impaired fasting glucose was defined as 6.1-7.0 mmol/l and diabetes as > or =7.0 mmol/l and/or antidiabetic medication use. Odds ratios (ORs) per SD increase in venular diameters were 1.13 (95% CI 1.00-1.29) for impaired fasting glucose and 1.09 (0.90-1.33) for diabetes. ORs per SD decrease in arteriolar diameters were 1.12 (0.98-1.27) and 1.08 (0.89-1.31) and per SD decrease in AVR were 1.29 (1.13-1.46) and 1.19 (0.98-1.45). After adjustment for cardiovascular risk factors, the associations were unaltered for venules and disappeared for arterioles. After stratification on age, associations between venular dilatation and impaired fasting glucose (1.23 [1.02-1.47]) or diabetes (1.18 [0.89-1.56]) were mainly present in participants aged <70 years. In conclusion, in our study, the risk of impaired fasting glucose and diabetes with AVR was explained by venular dilatation rather than arteriolar narrowing, warranting more focus on the causes of this dilatation.

High prevalence of proposed Müllerian duct remnant cysts on the spermatic duct in wild Eurasian otters (Lutra lutra) from Sweden.

The spermatic ducts (vasa deferentia) of 235 otters (Lutra lutra) found dead between 1999 and 2012 in Sweden were examined for presence of paraductular cysts. Single or multiple elongated uni- or bilateral cysts parallel to the spermatic duct were noted in 72% of the examined males. The cysts were adjacent to, but did not communicate with the lumen of the spermatic duct, and were usually located within a few centimeters of the testis and epididymis. The cysts are proposed to be congenital Müllerian duct remnants. Other morphologic abnormalities in the reproductive organs were not noted within this study. Possible causes of the incomplete regression of the embryonic female gonadal duct are exposure to environmental contaminants such as elevated concentrations of estrogen-like compounds (endocrine disrupting chemicals), inbreeding, or a naturally occurring anatomic defect. No obvious geographical pattern was observed for otters with or without cysts. This is the first study and description of cysts on the spermatic duct in otters.

Improved reproductive success in otters (Lutra lutra), grey seals (Halichoerus grypus) and sea eagles (Haliaeetus albicilla) from Sweden in relation to concentrations of organochlorine contaminants.

We studied indices of reproductive outcome in three aquatic species in relation to organochlorine concentrations during four decades. In female otters, the frequency of signs of reproduction increased after 1990. In grey seals, pregnancy rate increased 1990-2010 and uterine obstructions ceased after 1993. The frequency of uterine tumours was highest 1980-2000. The number of sea eagle nestlings per checked nest increased 1985-2000, while the frequency of desiccated eggs decreased. Organochlorine concentrations decreased at annual rates between 3.5 and 10.2%. The estimated mean concentration (mg/kg lw) for total-PCB decreased from 70 to 8 (otters), from 110 to 15 (seals) and from 955 to 275 (eagles). The corresponding concentrations for ΣDDT decreased from 3.4 to 0.2 (otters), from 192 to 2.8 (seals) and from 865 to 65 (eagles). This study adds evidence to support the hypothesis that PCBs and DDTs have had strong negative effects on the reproduction and population levels of these species.