Rapid Advances in Mobile Mass Spectrometry Enhance Tracer Hydrology and Water Management

Dissolved gases, including noble gases, are versatile environmental tracers. Historically, the application of dissolved (noble) gases as tracers in hydrology used to be limited because their measurement required expensive, laboratory-based instrumentation operated by highly trained personnel. Here, we highlight recent advances in mobile mass spectrometry (MS) methods for noble and other dissolved gases, which enable low cost, high-throughput, real-time measurements. We also present applications using mobile MS to quantify hydrological and biogeochemical processes in groundwater and surface waters and to assess hazards and risks to aquatic environments. Finally, we indicate potential future applications of these instruments to enhance hydrological research

ΔO2/N2′ as a New Tracer of Marine Net Community Production: Application and Evaluation in the Subarctic Northeast Pacific and Canadian Arctic Ocean

We compared field measurements of the biological O2 saturation anomalies, 1O2/Ar and 1O2/N2, from simultaneous oceanographic deployments of a membrane inlet mass spectrometer and optode/gas tension device (GTD). Data from the Subarctic Northeast Pacific and Canadian Arctic Ocean were used to evaluate 1O2/N2 as an alternative to 1O2/Ar for estimates of mixed layer net community production (NCP). We observed strong spatial coherence between 1O2/Ar and 1O2/N2, with small offsets resulting from differences in the solubility properties of Ar and N2 and their sensitivity to vertical mixing fluxes. Larger offsets between the two tracers were observed across hydrographic fronts and under elevated sea states, resulting from the differential time-response of the optode and GTD, and from bubble dissolution in the ship’s seawater lines. We used a simple numerical framework to correct for physical sources of divergence between N2 and Ar, deriving the tracer 1O2/N20. Over most of our survey regions, 1O2/N20 provided a better analog for 1O2/Ar, and thus more accurate NCP estimates than 1O2/N2. However, in coastal Arctic waters, 1O2/N2 and 1O2/N20 performed equally well as NCP tracers. On average, mixed layer NCP estimated from 1O2/Ar and 1O2/N20agreed to within ∼2 mmol O2 m−2 d−1, with offsets typically smaller than other errorsin NCP calculations. Our results demonstrate a significant potential to derive NCP from underway O2/N2 measurements across various oceanic regions. Optode/GTD systems could replace mass spectrometers for autonomous NCP derivation under many oceanographic conditions, thereby presenting opportunities to significantly expand global NCP coverage from various underway platforms

First estimation of the diffusive methane flux and concentrations from Lake Winnipeg, a large, shallow and eutrophic lake

Freshwater lakes are increasingly recognized as significant sources of atmospheric methane (CH4), potentially offsetting the terrestrial carbon sink. We present the first study of dissolved CH4 distributions and lake-air flux from Lake Winnipeg, based on two-years of observations collected during all seasons. Methane concentrations across two years had a median of value of 24.6 nmol L-1 (mean: 41.6 ± 68.2 nmol L-1) and ranged between 5.0 and 733.8 nmol L-1, with a 2018 annual median of 24.4 nmol L-1 (mean: 46.8 ± 99.3 nmol L-1) and 25.1 nmol L-1 (mean: 38.8 ± 45.2 nmol L-1) in 2019. The median lake-air flux was 1.1 µmol m−2 h−1 (range: 0.46–70.1 µmol m−2h−1, mean: 2.9 ± 10.2 µmol m−2 h−1) in 2018, and 5.5 µmol m−2h−1 (range: 0.0–78.4 µmol m−2 h−1, mean: 2.7 ± 8.5 µmol m−2 h−1) in 2019, for a total diffusive emission of 0.001 Tg of CH4-C yr−1. We found evidence of consistent spatial variability, with higher concentrations near river inflows. Significant seasonal trends in CH4 concentrations were not observed, though fluxes were highest during the fall season due to strong winds. Our findings suggest Lake Winnipeg is a CH4 source of similar mean magnitude to Lake Erie, with lower concentrations and fluxes per unit area than smaller mid- to high-latitude lakes. Additional work is needed to understand the factors underlying observed spatial variability in dissolved gas concentration, including estimations of production and consumption rates in the water column and sediments

Characterization of marine microbial communities around an Arctic seabed hydrocarbon seep at Scott Inlet, Baffin Bay

Seabed hydrocarbon seeps present natural laboratories for investigating responses of marine ecosystems to petroleum input. A hydrocarbon seep near Scott Inlet, Baffin Bay, was visited for in situ observations and sampling in the summer of 2018. Video evidence of an active hydrocarbon seep was confirmed by methane and hydrocarbon analysis of the overlying water column, which is 260 m at this site. Elevated methane concentrations in bottom water above and down current from the seep decreased to background seawater levels in the mid-water column >150 m above the seafloor. Seafloor microbial mats morphologically resembling sulfide-oxidizing bacteria surrounded areas of bubble ebullition. Calcareous tube worms, brittle stars, shrimp, sponges, sea stars, sea anemones, sea urchins, small fish and soft corals were observed near the seep, with soft corals showing evidence for hydrocarbon incorporation. Sediment microbial communities included putative methane-oxidizing Methyloprofundus, sulfate-reducing Desulfobulbaceae and sulfide-oxidizing Sulfurovum. A metabolic gene diagnostic for aerobic methanotrophs (pmoA) was detected in the sediment and bottom water above the seep epicentre and up to 5 km away. Both 16S rRNA gene and pmoA amplicon sequencing revealed that pelagic microbial communities oriented along the geologic basement rise associated with methane seepage (running SW to NE) differed from communities in off-axis water up to 5 km away. Relative abundances of aerobic methanotrophs and putative hydrocarbon-degrading bacteria were elevated in the bottom water down current from the seep. Detection of bacterial clades typically associated with hydrocarbon and methane oxidation highlights the importance of Arctic marine microbial communities in mitigating hydrocarbon emissions from natural geologic sources