EVALUATION OF TRACE ELEMENT CONCENTRATIONS IN THE SERUM AND VIBRISSAE OF PERUVIAN PINNIPEDS (ARCTOCEPHALUS AUSTRALIS AND OTARIA BYRONIA)

Concentrations of 15 trace elements (aluminum, arsenic, cadmium, chromium, cobalt, copper, iron, lead, manganese, mercury, nickel, selenium, tin, vanadium, and zinc) were determined in vibrissae (whiskers) and serum of two sympatric pinniped species, the Peruvian fur seal population (PFS; Arctocephalus australis Peruvian subpopulation) and South American sea lion (SASL; Otaria byronia) at Punta San Juan, Peru during 2011–19 sampling events. Element concentrations were 2–20 times higher in vibrissae than in serum. Vibrissae and serum concentrations of several elements, including aluminum, arsenic, and lead, suggest that environmental contaminants may affect the health of pinnipeds at Punta San Juan. Although toxicity thresholds are unknown in pinnipeds, high concentrations of some elements (especially aluminum, arsenic, and lead) may have adverse impacts on their health such as immunosuppression and impaired reproduction. Arsenic was the only element that increased in mean vibrissae concentration throughout the study period. Female SASL vibrissae contained a mean arsenic concentration three times higher than the male SASL vibrissae mean arsenic concentration, and twice as high as the arsenic mean for all PFS vibrissae. The mean male SASL vibrissae cadmium concentration was five times higher than the vibrissae cadmium mean for both PFS males and females and nearly three times higher than the vibrissae cadmium mean for SASL females. Serum concentrations of aluminum, arsenic, copper, and manganese were significantly higher during moderate to extreme El Niño years compared to La Niña years. With stronger and more frequent El Niño-Southern Oscillation events predicted in the future, it is vital to understand how these trace elements may affect pinniped population health

Elemental concentrations and persistent organic pollutants in the endangered Hawaiian monk seal and select prey species from the Northwest Hawaiian Islands

The endangered Hawaiian monk seal (HMS), endemic to the Northwest Hawaiian Islands (NWHI), is slowly becoming established within the Main Hawaiian Islands (MHI) (state of Hawai’i), which may place the seals in areas of higher anthropogenic (urban industrialization, agricultural practices, and military activity) and natural (volcanic activity) sources of trace elemental contaminants (heavy metals) and persistent organic pollutants (POP) compared to the NWHI. HMS bone, which represents up to 10 years of a seal’s life, was opportunistically collected from skeletons of naturally deceased seals from the NWHI as were whole dominant fish prey species from the southern NWHI. Preliminary data from 6 NWHI females from early 2000s show Zn (108 – 203 µg/g) yielded the highest concentrations followed by Cu (0.73 – 3.3 µg/g), Cr (0.97 – 6.3 µg/g), and Pb (0.75 – 4.8 µg/g), and no detectable Ni. Preliminary data from 8 fish species show Cr (67.8 – 462 µg/g) and Zn (150 – 501 µg/g) yielded the highest concentrations followed by Cu (23.1 – 144 µg/g) and Ni (13.6 – 28.8 µg/g), and no detectable Pb. Lead (Pb) is the only nonessential element tested in the preliminary study and the only element to show an order of magnitude higher concentration than potential prey. Five samples each of bone and homogenized prey were analyzed for polychlorinated biphenyls (PCB); it yielded total PCB concentration 4280 ng/g – 10400 ng/g in seal bone, similar to or slightly less than an order higher than previously reported values in HMS blubber and serum. Whole prey contained total PCBs of 5830 – 16500 ng/g. Further analyses of more trace elements as well as specific herbicides/insecticides (PCB), flame retardants (PBDE), and petroleum products (PAH) are ensuing. By studying the spatial distribution of the seals relative to crustal weathering and anthropogenic inputs, we may use the seals as biomonitors of these environmental contaminants

Cytokine Data for Cytokine Profile Assessment from Peruvian Pinniped (Arctocephalus australis and Otaria byronia) Plasma

Large colonies of two vulnerable, sympatric pinniped species, Peruvian fur seals (Arctocephalus australis Peruvian subpopulation; PFS) and South American sea lions (Otaria byronia; SASL), reside and reproduce in Punta San Juan, Peru (PSJ) where they are exposed to stressors such as contaminants and El Niño Southern Oscillation (ENSO) events. The use of cytokines as immune biomarkers can be indicative of an animal’s health and function by allowing for the assessment of an individual\u27s cytokine balance as type I helper T cells (Th1) or type II helper T cells (Th2) dominant. Utilizing archived pinniped plasma samples from 2009-2019 (n=148), 13 cytokines (GM-CSF, IFN-γ, KC-like, MCP-1, TNF-α, IL-2, IL-6, IL-7, IL-8, IL-10, IL-15, IL-18, and IP-10) were analyzed in PFS and SASL. All cytokines, except for IP-10, were detected in at least one individual of each species. Significant differences were found between sex in SASL for IFN-γ, IL-6, and KC-like, which suggested differences in immune system functioning and/or development between sexes. Significant differences between species were found as PFS females displayed higher concentrations of Th2 cytokines (IL-6 and IL-10) than SASL females, and SASL males displayed higher concentrations of KC-like than PFS males. Cytokine analysis of PFS dam/pup pairs revealed an upregulated Th2 response in pups compared to dams, consistent with the immature immune system characteristics of newborn mammals. While no statistically significant relationships between cytokines and ENSO events were observed, comparisons of Th1/Th2 ratios displayed trends toward upregulated Th2 responses during El Niño conditions. This study shows differing cytokine profiles between sexes, age class, and species in Peruvian pinnipeds, as well as potential Th1/Th2 differences related to ENSO conditions, which may impact their ability to combat extracellular pathogens during stressful El Niño periods

Intermediates in the Catalytic Dehydrogenative Coupling of Arylgermanes

The use of a new electron-withdrawing germane, H 2 Ge[3,5-(CF 3 ) 2 C6H 3 ] 2 ( 3 ), has facilitated the isolation and characterization of three new complexes implicated in the dehydrogenative coupling of bisarylgermanes by Pt 0 -phos-phane complexes. The intermediates include a digermyl species, trans -[(Et 3 P) 2 Pt{GeH(Ar) 2 } 2 ] ( 7 ), a bound digermane showing the first stage of Ge-Ge catenation, cis -[(Et 3 P) 2 Pt(H){Ge(Ar) 2 -GeH(Ar) 2 }] ( 8 ), and the Ge-H activated form of this product, [(Et 3 P) 2 HPtGe(Ar) 2 -Ge(Ar) 2 PtH(PEt 3 ) 2 ] ( 6 ). Complexes such as 6 and 8 have not previously been isolated as intermediates in dehydrogenative coupling reactions. An X-ray crystal structure was determined for complex 6 , confirming the cis geometry of the hydrogen and germanium ligands; this provides yet another example of the stability of germyl hydrides towards reductive elimination. A similar cis geometry was observed for complex 8 . Performing the dehydrogenative coupling reaction under a CO 2 atmosphere failed to yield any products containing trapped germylene species.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/38880/1/19970031110_ftp.pd