Differential scanning calorimetry (DSC): An important tool for polymer identification and characterization of plastic marine debris.

Differential scanning calorimetry (DSC), a routine thermoanalytical method in material science, is gaining utility in plastic pollution research to improve polymer identification. We optimized a DSC method, experimentally testing pan types, temperature ramps, number of melts, and minimum sample masses. Using the optimized method, we created an in-house thermogram library from 201 polymer reference standards. We determined peak melting temperature cutoffs for differentiating variants of PE and nylon. PE cutoffs remained stable after experimentally weathering standards outdoors or for severely weathered HDPE debris found on Hawaii's beaches. Marine debris samples, across a range of weathering severity and previously identified as either low-density or high-density polyethylene (LDPE or HDPE) based on the 1377 cm-1 peak indicating methyl groups by attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FTIR), were analyzed by DSC to confirm or challenge the ATR-FTIR PE differentiation. ATR-FTIR was correct for >80% of the HDPE samples, but <40% of those initially identified as LDPE by ATR-FTIR. Accuracy did not relate to weathering extent. Most samples mis-identified as LDPE were HDPE that had formed methyl groups likely from chain scission during photooxidation. ATR-FTIR alone is unreliable for differentiating weathered PE, DSC is required. We provide a multiple-method workflow for complete and accurate polymer identification, even for microplastics ≥0.03 mg. Applying these methods can better identify the polymer composition of marine debris, essential for sourcing and recycling efforts.

Microplastics absent from reef fish in the Marshall Islands: Multistage screening methods reduced false positives.

Island communities, like the Republic of the Marshall Islands (RMI), depend on marine resources for food and economics, so plastic ingestion by those resources is a concern. The gastrointestinal tracts of nine species of reef fish across five trophic groups (97 fish) were examined for plastics >1 mm. Over 2100 putative plastic particles from 72 fish were identified under light microscopy. Only 115 of these from 47 fish passed a plastic screening method using Fourier-transform infrared microspectroscopy (µFTIR) in reflectance mode. All of these were identified as natural materials in a final confirmatory analysis, attenuated total reflectance FTIR. The high false-positive rate of visual and µFTIR methods highlight the importance of using multiple polymer identification methods. Limited studies on ingested plastic in reef fish present challenging comparisons because of different methods used. No plastic >1 mm were found in the RMI reef fish, reassuring human consumers.

Large floating abandoned, lost or discarded fishing gear (ALDFG) is frequent marine pollution in the Hawaiian Islands and Palmyra Atoll.

Abandoned, lost, or discarded fishing gear (ALDFG) is a major source of marine debris with significant ecological and economic consequences. We documented the frequency, types, sizes, and impacts of ALDFG recovered from Hawai'i and Palmyra Atoll in the Central North Pacific Ocean (CNPO) from 2009 to 2021. A total of 253 events weighing 15 metric tons were recovered, including 120 drifting fish aggregating device (dFAD) components, 61 conglomerates, fewer distinct nets, lines, buoys, and unique gear. The Hawaiian Islands were dominated by conglomerates and Palmyra Atoll by dFADs. DFADs were connected to the Eastern Pacific tropical tuna purse seine fishery. Windward O'ahu experienced up to seven events or 1800 kg of ALDFG per month. Across Hawai', ALDFG was present on 55 % of survey days, including hotspots with 100 % occurrence. Coral reef damage, entangled wildlife, navigational and removal costs are reported. The data highlight the large magnitude of ALDFG and associated impacts in the CNPO.

Polymer identification of floating derelict fishing gear from O'ahu, Hawai'i.

Discarded fishing gear (DFG) comprises most of the plastic in the North Pacific Ocean and causes environmental and economic losses. Building evidence on the material construction of fishing gear types is critical to develop solutions to reduce DFG amounts and impacts. We forensically assessed the construction and chemical composition of eight different gear types removed as DFG around O'ahu, Hawai'i. A thorough dissection and novel analysis was conducted including the documentation of gear constructions, polymer identification using attenuated total reflection-Fourier transform infrared spectroscopy and differential scanning calorimetry, and elemental additive detection using X-ray fluorescence. Twenty-six different polymers were identified, and most gear consisted of polyethylene variants or blends. This inventory of physical and chemical characterization of DFG can help future polymer identification of particular gear types through visual techniques. Additionally, it can aid in identifying sources of these gear types and promote recycling options.

Using Plasma Vitellogenin in Loggerhead Sea Turtles to Assess Reproductive Maturation and Estrogen-Like Contaminant Exposure.

Vitellogenin (VTG), an egg yolk precursor, is abnormally produced by male and juvenile oviparous species after exposure to estrogens. Plasma VTG in loggerhead sea turtles (Caretta caretta) helped us understand their reproductive maturation and investigate it as a biomarker of contaminant exposure. The presence of VTG was screened in plasma from 404 loggerheads from the northwestern Atlantic Ocean using a freshwater turtle antibody in western blots. The concentrations of VTG were semiquantified using band intensities calibrated to results from a loggerhead antibody enzyme-linked immunoassay. The detection and concentrations of VTG were in (from highest to lowest): nesting females, in-water adult females, subadult females, smaller females, unknown sex, and males. Loggerheads from this region begin vitellogenesis at ≅77 cm straight carapace length. We classified VTG expression as abnormal in nine male or juvenile turtles. Organochlorine contaminant (OC) concentrations were measured in blood and/or fat biopsies of some turtles. One abnormal VTG female had the second highest fat polychlorinated biphenyl (PCB) and 4,4'-dichlorodiphenyldichloroethylene concentrations compared among 43 VTG-negative juveniles. The nine VTG-abnormal turtles had average blood PCB concentrations 8.5% higher, but not significantly different, than 46 VTG-negative juveniles (p = 0.453). In turtles less than 77 cm, blood PCB concentrations were significantly, but weakly, correlated with semiquantified VTG concentrations (tau = 0.1, p = 0.004). Greater blood OC concentrations were found in adult females than in males, which motivated the creation of a conceptual model of OC, VTG, and hormone concentrations across a reproductive cycle. A decision tree is also provided incorporating VTG as a sexing tool. Abnormal VTG expression cannot conclusively be linked to endocrine disruption caused by these OC concentrations. Studies should further investigate causes of abnormal VTG expression in wild sea turtles. Environ Toxicol Chem 2023;42:1309-1325. © 2023 SETAC. This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.