Mercury Isotope Fractionation during Dark Abiotic Reduction of Hg(II) by Dissolved, Surface-Bound, and Structural Fe(II).

Stable mercury (Hg) isotope ratios are an emerging tracer for biogeochemical transformations in environmental systems, but their application requires knowledge of isotopic enrichment factors for individual processes. We investigated Hg isotope fractionation during dark, abiotic reduction of Hg(II) by dissolved iron(Fe)(II), magnetite, and Fe(II) sorbed to boehmite or goethite by analyzing both the reactants and products of laboratory experiments. For homogeneous reduction of Hg(II) by dissolved Fe(II) in continuously purged reactors, the results followed a Rayleigh distillation model with enrichment factors of -2.20 ± 0.16‰ (ε202Hg) and 0.21 ± 0.02‰ (E199Hg). In closed system experiments, allowing reequilibration, the initial kinetic fractionation was overprinted by isotope exchange and followed a linear equilibrium model with -2.44 ± 0.17‰ (ε202Hg) and 0.34 ± 0.02‰ (E199Hg). Heterogeneous Hg(II) reduction by magnetite caused a smaller isotopic fractionation (-1.38 ± 0.07 and 0.13 ± 0.01‰), whereas the extent of isotopic fractionation of the sorbed Fe(II) experiments was similar to the kinetic homogeneous case. Small mass-independent fractionation of even-mass Hg isotopes with 0.02 ± 0.003‰ (E200Hg) and ≈ -0.02 ± 0.01‰ (E204Hg) was consistent with theoretical predictions for the nuclear volume effect. This study contributes significantly to the database of Hg isotope enrichment factors for specific processes. Our findings show that Hg(II) reduction by dissolved Fe(II) in open systems results in a kinetic MDF with a larger ε compared to other abiotic reduction pathways, and combining MDF with the observed MIF allows the distinction from photochemical or microbial Hg(II) reduction pathways.

Isotopic Characterization of Atmospheric Gaseous Elemental Mercury by Passive Air Sampling.

Tracing emission sources and transformations of atmospheric mercury with Hg stable isotopes depends on the ability to collect amounts sufficient for reliable quantification. Commonly employed active sampling methods require power and long pumping times, which limits the ability to deploy in remote locations and at high spatial resolution and can lead to compromised traps. In order to overcome these limitations, we conducted field and laboratory experiments to assess the preservation of isotopic composition during sampling of gaseous elemental mercury (GEM) with a passive air sampler (PAS) that uses a sulfur-impregnated carbon sorbent and a diffusive barrier. Whereas no mass independent fractionation (MIF) was observed during sampling, the mass dependent fractionation (MDF, δ202Hg) of GEM taken up by the PAS was lower than that of actively pumped samples by 1.14 ± 0.24‰ (2SD). Because the MDF offset was consistent across field studies and laboratory experiments conducted at 5, 20, and 30 °C, the PAS can be used for reliable isotopic characterization of GEM (±0.3‰ for MDF, ±0.05‰ for MIF, 2SD). The MDF offset occurred more during the sorption of GEM rather than during diffusion. PAS field deployments confirm the ability to record differences in the isotopic composition of GEM (i) with distance from point sources and (ii) sampled at different background locations globally.

Concurrently Measured Concentrations of Atmospheric Mercury in Indoor (household) and Outdoor Air of Basel, Switzerland.

Indoor air pollution can be a major health risk because urban populations spend up to 90% of their time in closed rooms. Gaseous elemental mercury (GEM) has not been measured as routinely as other indoor air pollutants due to the high costs and limited mobility of active Hg analyzers. However, household GEM concentrations may exceed Hg air quality guidelines as a result of potential indoor GEM sources like broken Hg thermometers. Here we deploy novel low-cost mercury passive air samplers (MerPAS) in 27 households (7 days) and at 14 outdoor locations (29-31 days) in Basel, Switzerland. Average Hg concentrations ranged from 2.0 to 10.8 ng m-3 indoors and from 1.8 to 2.5 ng m-3 outdoors. These results reveal that households are a net source of Hg to the urban atmosphere and exceed outdoor Hg levels by a factor of 2 on average. We estimated an average weekly intake rate of 0.01 µg of Hg/kg of body weight for adult residents in Basel, which is usually lower than Hg exposure of people with dental amalgam fillings. Our campaign demonstrates that air monitoring programs can easily be complemented by straightforward Hg measurements using MerPAS.

Comparing winter-time herbicide behavior and exports in urban, rural, and mixed-use watersheds.

The presence of pesticides in streams in winter, five to six years following bans on their municipal use suggests that complicated transport behaviour, such as subsurface retention and/or accumulation of pesticides and its release during storms, could be important for understanding recovery time frames following bans or legislation that aim to reduce chemical inputs. We investigated late fall and winter dynamics of four herbicides in paired urban and rural watersheds in Toronto, Canada during rainfall and snowmelt. The range of average concentrations and loads of the sum of atrazine, metolachlor, 2,4-D and mecoprop overlapped in the two types of watersheds, with slightly higher average concentrations in the rural watershed. Relatively consistent herbicide concentration-discharge patterns (i.e. dilution) were observed in the urban sub-watersheds during rainfall, while concentration-discharge patterns were much more variable in the rural watershed. This suggests relatively uniform transport pathways across the urban sub-watersheds, compared to the rural watershed. Concentration-discharge patterns of the neutral herbicides atrazine and metolachlor were similar in both watersheds during snowmelt, though varying discharge patterns resulted in divergent timings of peak concentrations. In contrast, the acidic pesticides 2,4-D and mecoprop, which are primarily associated with urban uses, showed much more variable behavior across both watersheds and merit further investigation. Overall, this work highlights the need to consider pesticide dynamics throughout the year in order to more thoroughly assess the long-term efficacy of legislation governing their use.

Signals from the south; humpback whales carry messages of Antarctic sea-ice ecosystem variability.

Southern hemisphere humpback whales (Megaptera novaeangliae) rely on summer prey abundance of Antarctic krill (Euphausia superba) to fuel one of the longest-known mammalian migrations on the planet. It is hypothesized that this species, already adapted to endure metabolic extremes, will be one of the first Antarctic consumers to show measurable physiological change in response to fluctuating prey availability in a changing climate; and as such, a powerful sentinel candidate for the Antarctic sea-ice ecosystem. Here, we targeted the sentinel parameters of humpback whale adiposity and diet, using novel, as well as established, chemical and biochemical markers, and assembled a time trend spanning 8 years. We show the synchronous, inter-annual oscillation of two measures of humpback whale adiposity with Southern Ocean environmental variables and climate indices. Furthermore, bulk stable isotope signatures provide clear indication of dietary compensation strategies, or a lower trophic level isotopic change, following years indicated as leaner years for the whales. The observed synchronicity of humpback whale adiposity and dietary markers, with climate patterns in the Southern Ocean, lends strength to the role of humpback whales as powerful Antarctic sea-ice ecosystem sentinels. The work carries significant potential to reform current ecosystem surveillance in the Antarctic region.

The transport of polycyclic aromatic hydrocarbons during rainfall and snowmelt in contrasting landscapes.

Though it has been established that stream concentrations of polycyclic aromatic hydrocarbons (PAHs) in urban watersheds can be much greater than those in less developed watersheds, knowledge of transport mechanisms is lacking, particularly in temperate, Northern climates with seasonal snow packs. We combine high-resolution stream water sampling with air, suspended solid and stream flow monitoring to investigate the source to stream transport of PAHs during rainfall and snowmelt in paired watersheds with contrasting land use. Despite similar particle loads, contamination of particles that is 8-48 times higher in the urban watersheds leads to area-normalized loads of PAHs that are 6-82 times greater than in the agricultural watersheds. In the urban watershed, average volumetric storm flow concentrations increase with longer antecedent dry period that allows build-up of PAHs on watershed surfaces. Cluster analysis suggests road dust is a minor source of suspended solid-bound PAHs in more agricultural watersheds during rainfall. During snowmelt, earlier peaks in concentration in the urban watershed are likely due to melt from snow packs and snow banks travelling quickly to the stream network via impervious surfaces and sewer drains. While road-derived inputs also appear to be important during snowmelt in the agricultural watershed, relatively delayed peak concentrations result from delayed inputs from snow packs in more pervious areas of the watershed.

An Antarctic research station as a source of brominated and perfluorinated persistent organic pollutants to the local environment.

This study investigated the role of a permanently manned Australian Antarctic research station (Casey Station) as a source of contemporary persistent organic pollutants (POPs) to the local environment. Polybrominated diphenyl ethers (PBDEs) and poly- and perfluoroalkylated substances (PFASs) were found in indoor dust and treated wastewater effluent of the station. PBDE (e.g., BDE-209 26-820 ng g(-1) dry weight (dw)) and PFAS levels (e.g., PFOS 3.8-2400 ng g(-1) (dw)) in dust were consistent with those previously reported in homes and offices from Australia, reflecting consumer products and materials of the host nation. The levels of PBDEs and PFASs in wastewater (e.g., BDE-209 71-400 ng L(-1)) were in the upper range of concentrations reported for secondary treatment plants in other parts of the world. The chemical profiles of some PFAS samples were, however, different from domestic profiles. Dispersal of chemicals into the immediate marine and terrestrial environments was investigated by analysis of abiotic and biotic matrices. Analytes showed decreasing concentrations with increasing distance from the station. This study provides the first evidence of PFAS input to Polar regions via local research stations and demonstrates the introduction of POPs recently listed under the Stockholm Convention into the Antarctic environment through local human activities.