Experimental assessment of elemental analyzer isotope ratio mass spectrometry normalization methodologies for environmental stable isotopes.

RATIONALE: In stable isotope mass spectrometry, isotope delta values are normalized to internationally recognized reference scales using a combination of certified and in-house isotope reference materials. Numerous techniques exist for performing this normalization, but these methodologies need to be experimentally assessed to compare their effect on reproducibility of isotope results. METHODS: We tested normalization methods by the number of reference materials used, their matrix, their isotope range, and whether normalization required extrapolating beyond the isotope range. We analyzed eight commercially available isotope reference materials on a ThermoFinnigan Delta-V isotope ratio mass spectrometer (IRMS) and an Elementar VisION IRMS for nitrogen and carbon isotope composition via solid combustion with an elemental analyzer and computed every possible isotope normalization (n = 612). Additionally, we assessed how sample matrix affected linearity effects on both instruments using five in-house reference materials. RESULTS: Normalizations exhibited the best performance when the reference materials spanning an isotope range of at least 20‰ were matrix matched with the samples and did not require extrapolation beyond the calibration curve. When these conditions were not met, the number of reference materials used had a significant effect on accuracy, with normalizations composed of two reference materials exhibiting particularly inconsistent performance at isotope ranges below 20‰. Linearity effects were found to exceed instrument precision by two orders of magnitude irrespective of matrix type and were not predicted by working gas diagnostics. CONCLUSIONS: Interlaboratory comparability of isotope results is improved when operators of elemental analyzer isotope ratio mass spectrometry (EAIRMS) systems select reference materials spanning an isotope range of at least 20‰. Additionally, using three or more isotopic reference materials, avoiding extrapolation beyond the range of the normalization curve, and matching the matrix of the reference materials to the samples improve normalizations.

Ammonium loss microbiologically mediated by Fe(III) and Mn(IV) reduction along a coastal lagoon system.

Anaerobic ammonium oxidation, associated with both iron (Feammox) and manganese (Mnammox) reduction, is a microbial nitrogen (N) removal mechanism recently identified in natural ecosystems. Nevertheless, the spatial distributions of these non-canonical Anammox (NC-Anammox) pathways and their environmental drivers in subtidal coastal sediments are still unknown. Here, we determined the potential NC-Anammox rates and abundance of dissimilatory metal-reducing bacteria (Acidomicrobiaceae A6 and Geobacteraceae) at different horizons (0-20 cm at 5 cm intervals) of subtidal coastal sediments using the 15N isotope-tracing technique and molecular analyses. Sediments were collected across three sectors (inlet, transition, and inner) in a coastal lagoon system (Bahia de San Quintin, Mexico) dominated by seagrass meadows. The positive relationship between 30N2 production rates and dissimilatory Fe and Mn reduction provided evidence for Feammox's and Mnammox's co-occurrence. N loss through NC-Anammox was detected in subtidal sediments, with potential rates of 0.07-0.62 µg N g-1 day-1. NC-Anammox process in vegetated sediments tended to be higher than those in adjacent unvegetated ones. NC-Anammox rates showed a subsurface peak (between 5 and 15 cm) in the vegetated sediments but decreased consistently with depth in the adjacent bare bottoms. Thus, the presence/absence of seagrasses and sediment characteristics, particularly the availability of organic carbon and microbiologically reducible Fe(III) and Mn(IV), affected the abundance of dissimilatory metal-reducing bacteria, which mediated NC-Anammox activity and the associated N removal. An annual loss of 32.31 ± 3.57 t N was estimated to be associated with Feammox and Mnammox within the investigated area, accounting for 2.8-4.7% of the gross total import of reactive N from the ocean into the Bahia de San Quintin. Taken as a whole, this study reveals the distribution patterns and controlling factors of the NC-Anammox pathways along a coastal lagoon system. It improves our understanding of the coupling between N and trace metal cycles in coastal environments.

Ecological characteristics impact PFAS concentrations in a U.S. North Atlantic food web.

This is the first comprehensive study of per- and polyfluoroalkyl substances (PFAS) in a coastal food web of the U.S. North Atlantic, in which we characterize the presence and concentrations of 24 targeted PFAS across 18 marine species from Narragansett Bay, Rhode Island, and surrounding waters. These species reflect the diversity of a typical North Atlantic Ocean food web with organisms from a variety of taxa, habitat types, and feeding guilds. Many of these organisms have no previously reported information on PFAS tissue concentrations. We found significant relationships of PFAS concentrations with respect to various ecological characteristics including species, body size, habitat, feeding guild, and location of collection. Based upon the 19 PFAS detected in the study (5 were not detected in samples), benthic omnivores (American lobsters = 10.5 ng/g ww, winter skates = 5.77 ng/g ww, Cancer crabs = 4.59 ng/g ww) and pelagic piscivores (striped bass = 8.50 ng/g ww, bluefish = 4.30 ng/g ww) demonstrated the greatest average ∑PFAS concentrations across all species sampled. Further, American lobsters had the highest concentrations detected in individuals (∑PFAS up to 21.1 ng/g ww, which consisted primarily of long-chain PFCAs). The calculation of field-based trophic magnification factors (TMFs) for the top 8 detected PFAS determined that perfluorodecanoic acid (PFDA), perfluorooctane sulfonic acid (PFOS), and perfluorooctane sulfonamide (FOSA) associated with the pelagic habitat biomagnified, whereas perfluorotetradecanoic acid (PFTeDA) associated with the benthic habitat demonstrated trophic dilution in this food web (calculated trophic levels ranged from 1.65 to 4.97). While PFAS exposure to these organisms may have adverse implications for ecological impacts via toxicological effects, many of these species are also key recreational and commercial fisheries resulting in potential for human exposure via dietary consumption.