Impact of forest fire on the mercury stable isotope composition in litter and soil in the Amazon.

Mercury (Hg) emissions from forest fires, especially tropical forests such as the Amazonian forest, were shown to contribute significantly to the atmospheric mercury budget, but new methods are still necessary to improve the traceability and to reduce the great uncertainties related to this emission source. Recent studies have shown that the combustion process can result in Hg stable isotope fractionation that allows tracking coal combustion Hg emissions, as influenced by different factors such as combustion temperature. The main goal of the present study was, therefore, to investigate for the first time the potential of Hg stable isotopes to trace forest fire Hg emissions and pathways. More specifically, small-scale and a large scale prescribed forest fire experiments were conducted in the Brazilian Amazonian forest to study the impact of fire severity on Hg isotopic composition of litter, soil, and ash samples and associated Hg isotope fractionation pathways. In the small-scale experiment, no difference was found in the mercury isotopic composition of the samples collected before and after burning. In contrast, the larger-scale experiment resulted in significant mass dependent fractionation (MDF δ202Hg) in soils and ash suggesting that higher combustion temperature influence Hg isotopic fractionation with the emission of lighter Hg isotopes to the atmosphere and enrichment with heavier Hg in ashes. As for coal combustion, mass independent fractionation was not observed. To our knowledge, these results are the first to highlight the potential of forest fires to cause Hg isotopic fractionation, depending on the fire severity. The results also allowed to establish an isotopic fingerprint for tropical forest fire Hg emissions that corresponds to a mixture of litter and soil Hg isotopic composition (resulting atmospheric δ202Hg, Δ200Hg and Δ199Hg were -1.79 ± 0.24‰, -0.05 ± 0.04‰ and -0.45 ± 0.12‰, respectively).

Elevated Mercury Concentrations and Isotope Signatures (N, C, Hg) in Yellowfin Tuna (Thunnus albacares) from the Galápagos Marine Reserve and Waters off Ecuador.

We examined how dietary factors recorded by C and N influence Hg uptake in 347 individuals of yellowfin tuna (Thunnus albacares), an important subsistence resource from the Galápagos Marine Reserve (Ecuador) and the Ecuadorian mainland coast in 2015-2016. We found no differences in total Hg (THg) measured in red muscle between the two regions and no seasonal differences, likely due to the age of the fish and slow elimination rates of Hg. Our THg concentrations are comparable to those of other studies in the Pacific (0.20-9.60 mg/kg wet wt), but a subset of individuals exhibited the highest Hg concentrations yet reported in yellowfin tuna. Mercury isotope values differed between Δ199 Hg and δ202Hg in both regions (Δ199 Hg = 2.86 ± 0.04‰ vs. Δ199 Hg = 2.33 ± 0.07‰), likely related to shifting food webs and differing photochemical processing of Hg prior to entry into the food web. There were significantly lower values of both δ15 N and δ13 C in tuna from Galápagos Marine Reserve (δ15 N: 8.5-14.2‰, δ13 C: -18.5 to -16.1‰) compared with those from the Ecuadorian mainland coast (δ15 N: 8.3-14.4‰, δ13 C: -19.4 to -11.9‰), of which δ13 C values suggest spatially constrained movements of tuna. Results from the pooled analysis, without considering region, indicated that variations in δ13 C and δ15 N values tracked changes of Hg stable isotopes. Our data indicate that the individual tuna we used were resident fish of each region and were heavily influenced by upwellings related to the eastern Pacific oxygen minimum zone and the Humboldt Current System. The isotopes C, N, and Hg reflect foraging behavior mainly on epipelagic prey in shallow waters and that food web shifts drive Hg variations between these populations of tuna. Environ Toxicol Chem 2022;41:2732-2744. © 2022 SETAC.

In Situ Photochemical Transformation of Hg Species and Associated Isotopic Fractionation in the Water Column of High-Altitude Lakes from the Bolivian Altiplano.

Photochemical reactions are major pathways for the removal of Hg species from aquatic ecosystems, lowering the concentration of monomethylmercury (MMHg) and its bioaccumulation in foodwebs. Here, we investigated the rates and environmental drivers of MMHg photodegradation and inorganic Hg (IHg) photoreduction in waters of two high-altitude lakes from the Bolivian Altiplano representing meso- to eutrophic conditions. We incubated three contrasting waters in situ at two depths after adding Hg-enriched isotopic species to derive rate constants. We found that transformations mostly occurred in subsurface waters exposed to UV radiation and were mainly modulated by the dissolved organic matter (DOM) level. In parallel, we incubated the same waters after the addition of low concentrations of natural MMHg and followed the stable isotope composition of the remaining Hg species by compound-specific isotope analysis allowing the determination of enrichment factors and mass-independent fractionation (MIF) slopes (Δ199Hg/Δ201Hg) during in situ MMHg photodegradation in natural waters. We found that MIF enrichment factors potentially range from -11 to -19‰ and average -14.3 ± 0.6‰ (1 SE). The MIF slope diverged depending on the DOM level, ranging from 1.24 ± 0.03 to 1.34 ± 0.02 for the low and high DOM waters, respectively, and matched the MMHg MIF slope recorded in fish from the same lake. Our in situ results thus reveal (i) a relatively similar extent of Hg isotopic fractionation during MMHg photodegradation among contrasted natural waters and compared to previous laboratory experiments and (ii) that the MMHg MIF recorded in fish is characteristic for the MMHg bonding environment. They will enable a better assessment of the extent and conditions conducive to MMHg photodegradation in aquatic ecosystems.

Mercury bioaccumulation in tilefish from the northeastern Gulf of Mexico 2 years after the Deepwater Horizon oil spill: Insights from Hg, C, N and S stable isotopes.

Mercury (Hg) concentration in fish of the Gulf of the Mexico (GoM) is a major concern due to the importance of the GoM for U.S. fisheries. The Deepwater Horizon (DWH) oil spill in April 2010 in the northern GoM resulted in large amounts of oil and dispersant released to the water column, which potentially modified Hg bioaccumulation patterns in affected areas. We measured Hg species (methylmercury (MMHg) and inorganic Hg (IHg)) concentrations, and light (C, N and S) and Hg stable isotopes in muscle and liver tissues from tilefish (Lopholatilus chamaleonticeps) sampled in 2012 and 2013 along the shelf break of the northeastern GoM. Fish located close to the mouth of the Mississippi River (MR) and northwest of the DWH well-head (47 km) showed significantly lower Hg levels in muscle and liver than fish located further northeast of the DWH (>109 km), where 98% of tilefish had Hg levels in the muscle above US consumption advisory thresholds (50% for tilefish close to the DWH). Differences in light and Hg stable isotopes signatures were observed between these two areas, showing higher δ15N, and lower δ202Hg, Δ199Hg and δ34S in fish close to the DWH/MR. This suggests that suspended particles from the MR reduces Hg bioavailability at the base of the GoM food chains. This phenomenon can be locally enhanced by the DWH that resulted in increased particles in the water column as evidenced by the marine snow layer in the sediments. On the other hand, freshly deposited Hg associated with organic matter in more oligotrophic marine waters enhanced Hg bioaccumulation in local food webs. Comparing Hg isotopic composition in liver and muscle of fish indicates specific metabolic response in fish having accumulated high levels of MMHg.

An investigation of mercury sources in the Puyango-Tumbes River: Using stable Hg isotopes to characterize transboundary Hg pollution.

Mercury (Hg) concentrations and stable isotopes along with other trace metals were examined in environmental samples from Ecuador and Peru's shared Puyango-Tumbes River in order to determine the extent to which artisanal- and small-scale gold mining (ASGM) in Portovelo-Zaruma, Ecuador contributes to Hg pollution in the downstream aquatic ecosystem. Prior studies investigated the relationship between ASGM activities and downstream Hg pollution relying primarily on Hg concentration data. In this study, Hg isotopes revealed an isotopically heavy Hg signature with negligible mass independent fractionation (MIF) in downstream sediments, which was consistent with the signature observed in the ASGM source endmember. This signature was traced as far as ∼120 km downstream of Portovelo-Zaruma, demonstrating that Hg stable isotopes can be used as a tool to fingerprint and trace sources of Hg over vast distances in freshwater environments. The success of Hg isotopes as a source tracer in fresh waters is largely due to the particle-reactive nature of Hg. Furthermore, the magnitude and extent of downstream Hg, lead, copper and zinc contamination coupled with the Hg isotopes suggest that it is unlikely that the smaller artisanal-scale activities, which do not use cyanidation, are responsible for the pollution. More likely it is the scale of ores processed and the cyanide leaching, which can release other metals and enhance Hg transport, used during small-scale gold mining that is responsible. Thus, although artisanal- and small-scale gold mining occur in tandem in Portovelo-Zaruma, a distinction should be made between these two activities.

Concentrations and isotope ratios of mercury in sediments from shelf and continental slope at Campos Basin near Rio de Janeiro, Brazil.

Mercury (Hg) may originate from both anthropogenic and natural sources. The measurement of spatial and temporal variations of Hg isotope ratios in sediments may enable source identification and tracking of environmental processes. In this study we establish the distribution of mercury concentrations and mercury isotope ratios in surface sediments of three transects along the continental shelf and slope in Campos Basin-RJ-Brazil. The shelf showed on average lower total Hg concentrations (9.2 ± 5.3 ng g-1) than the slope (24.6 ± 8.8 ng g-1). MMHg average concentrations of shelf 0.15 ± 0.12 ng g-1 and slope 0.13 ± 0.06 ng g-1 were not significantly different. Distinct differences in Hg isotope ratio signatures were observed, suggesting that the two regions were impacted by different sources of Hg. The shelf showed more negative δ202Hg and Δ199Hg values ranging from -0.59 to -2.19‰ and from -0.76 to 0.08‰, respectively. In contrast, the slope exhibited δ202Hg values from -0.29 to -1.82‰ and Δ199Hg values from -0.23 to 0.09‰. Mercury found on the shelf, especially along the "D" and "I" transects, is depleted in heavy isotopes resulting in more negative δ202Hg compared to the slope. Isotope ratios observed in the "D" and "I" shelf region are similar to Hg ratios commonly associated with plants and vegetation and very comparable to those detected in the estuary and adjoining mangrove forest, which suggests that Hg exported from rivers may be the dominating source of Hg in near coastal regions along the northern part of the shelf.

Isotopic profile and mercury concentration in fish of the lower portion of the rio Paraíba do Sul watershed, southeastern Brazil

The aim of this study was to evaluate the isotopic profile and mercury (Hg) concentrations in fish (carnivores, omnivores and detritivores) in the lower portion of the rio Paraíba do Sul watershed, southeastern Brazil. Carbon (δ13C) isotopic analyses revealed that pelagic and benthonic sources are part of the feeding of the fish from the different guilds (-14.0 to -24.8 ‰). The benthic sources are usually enriched in δ13C (-16.9‰, from watershed runoff) compared to pelagic sources because the phytoplankton, important primary producer that supports several pelagic chains, has δ13C signature lighter (-23.9‰). The nitrogen (δ15N) isotopic signatures indicated that most guilds were at the same trophic position (10.0 to 15.5 ‰), except for pelagic omnivorous fish, which had a lower trophic position. Niche overlap was observed among pelagic and demersal carnivorous fish, demersal omnivorous fish, and demersal detritivorous fish. The lower isotopic niche breadth of pelagic carnivorous fish reveals the specialized resource use by this guild. Hg concentrations (ng g-1 dry weight) differed significantly between demersal carnivorous fish (185.3 dry weight; 27.8 wet weight) and demersal omnivorous fish (277.9 dry weight; 41.7 wet weight) and between pelagic omnivorous fish (197.2 dry weight; 29.6 wet weight) and demersal omnivorous fish due to (1) differences in food sources: guilds that fed on bottom resources were more affected by contamination because the sediment is an important Hg accumulator in the study area, and (2) because of its trophic positions. Considering that the fish consumed prey of similar trophic positions, the guilds did not show a well-defined food hierarchy. Therefore, in this study, there was no clear relationship between Hg and δ15N.

O objetivo deste estudo foi avaliar o perfil isotópico e as concentrações de mercúrio (Hg) em peixes (carnívoros, onívoros e detritívoros) na bacia inferior do rio Paraíba do Sul, sudeste do Brasil. As análises isotópicas de carbono (δ13C) revelaram participação de fontes pelágica e bentônica na alimentação dos peixes das diferentes guildas (-14,0 a -24,8 ‰). As fontes bentônicas são usualmente mais enriquecidas em δ13C (-16,9‰, derivado do escoamento superficial da bacia de drenagem) comparadas às fontes pelágicas pois, o fitoplâncton, importante produtor primário que suporta inúmeras cadeias pelágicas, tem assinatura de δ13C mais leve (-23,9‰). As assinaturas isotópicas de nitrogênio (δ15N) indicaram que a maioria das guildas estava no mesmo nível trófico (10,0 a 15,5 ‰), exceto os peixes onívoros pelágicos cuja posição trófica foi inferior. Observou-se sobreposição de nicho entre peixes carnívoros pelágicos e demersais, onívoros demersais, e detritívoros demersais. A menor amplitude de nicho isotópico dos peixes carnívoros pelágicos revela o uso de recursos especializados por esta guilda. A concentração de Hg (ng g-1 peso seco) diferiu significativamente entre peixes carnívoros demersais (185,3 peso seco; 27,8 peso úmido) e onívoros demersais (277,9 peso seco; 41,7 peso úmido), e entre peixes onívoros pelágicos (197,2 peso seco; 29,6 peso úmido) e onívoros demersais devido a (1) diferenças nas fontes alimentares: guildas que utilizaram recursos de fundo foram mais afetadas pela contaminação pois o sedimento é um importante acumulador de Hg na área de estudo, e (2) por causa das suas posições tróficas. Tendo em vista que os peixes consumiram presas com níveis tróficos semelhantes, as guildas não apresentaram uma hierarquia alimentar definida. Desse modo, no presente estudo não se verificou uma relação clara entre Hg e δ15N.

Isotopic profile and mercury concentration in fish of the lower portion of the rio Paraíba do Sul watershed, southeastern Brazil

The aim of this study was to evaluate the isotopic profile and mercury (Hg) concentrations in fish (carnivores, omnivores and detritivores) in the lower portion of the rio Paraíba do Sul watershed, southeastern Brazil. Carbon (δ13C) isotopic analyses revealed that pelagic and benthonic sources are part of the feeding of the fish from the different guilds (-14.0 to -24.8 ‰). The benthic sources are usually enriched in δ13C (-16.9‰, from watershed runoff) compared to pelagic sources because the phytoplankton, important primary producer that supports several pelagic chains, has δ13C signature lighter (-23.9‰). The nitrogen (δ15N) isotopic signatures indicated that most guilds were at the same trophic position (10.0 to 15.5 ‰), except for pelagic omnivorous fish, which had a lower trophic position. Niche overlap was observed among pelagic and demersal carnivorous fish, demersal omnivorous fish, and demersal detritivorous fish. The lower isotopic niche breadth of pelagic carnivorous fish reveals the specialized resource use by this guild. Hg concentrations (ng g-1 dry weight) differed significantly between demersal carnivorous fish (185.3 dry weight; 27.8 wet weight) and demersal omnivorous fish (277.9 dry weight; 41.7 wet weight) and between pelagic omnivorous fish (197.2 dry weight; 29.6 wet weight) and demersal omnivorous fish due to (1) differences in food sources: guilds that fed on bottom resources were more affected by contamination because the sediment is an important Hg accumulator in the study area, and (2) because of its trophic positions. Considering that the fish consumed prey of similar trophic positions, the guilds did not show a well-defined food hierarchy. Therefore, in this study, there was no clear relationship between Hg and δ15N.(AU)

O objetivo deste estudo foi avaliar o perfil isotópico e as concentrações de mercúrio (Hg) em peixes (carnívoros, onívoros e detritívoros) na bacia inferior do rio Paraíba do Sul, sudeste do Brasil. As análises isotópicas de carbono (δ13C) revelaram participação de fontes pelágica e bentônica na alimentação dos peixes das diferentes guildas (-14,0 a -24,8 ‰). As fontes bentônicas são usualmente mais enriquecidas em δ13C (-16,9‰, derivado do escoamento superficial da bacia de drenagem) comparadas às fontes pelágicas pois, o fitoplâncton, importante produtor primário que suporta inúmeras cadeias pelágicas, tem assinatura de δ13C mais leve (-23,9‰). As assinaturas isotópicas de nitrogênio (δ15N) indicaram que a maioria das guildas estava no mesmo nível trófico (10,0 a 15,5 ‰), exceto os peixes onívoros pelágicos cuja posição trófica foi inferior. Observou-se sobreposição de nicho entre peixes carnívoros pelágicos e demersais, onívoros demersais, e detritívoros demersais. A menor amplitude de nicho isotópico dos peixes carnívoros pelágicos revela o uso de recursos especializados por esta guilda. A concentração de Hg (ng g-1 peso seco) diferiu significativamente entre peixes carnívoros demersais (185,3 peso seco; 27,8 peso úmido) e onívoros demersais (277,9 peso seco; 41,7 peso úmido), e entre peixes onívoros pelágicos (197,2 peso seco; 29,6 peso úmido) e onívoros demersais devido a (1) diferenças nas fontes alimentares: guildas que utilizaram recursos de fundo foram mais afetadas pela contaminação pois o sedimento é um importante acumulador de Hg na área de estudo, e (2) por causa das suas posições tróficas. Tendo em vista que os peixes consumiram presas com níveis tróficos semelhantes, as guildas não apresentaram uma hierarquia alimentar definida. Desse modo, no presente estudo não se verificou uma relação clara entre Hg e δ15N.(AU)

Stable isotope (N, C, Hg) study of methylmercury sources and trophic transfer in the northern gulf of Mexico.

We combined N, C, and Hg stable isotope measurements to identify the most important factors that influence MeHg accumulation in fish from the northern Gulf of Mexico (nGOM), and to determine if coastal species residing in the Mississippi River (MR) plume and migratory oceanic species derive their MeHg from the same, or different, sources. In six coastal species and two oceanic species (blackfin and yellowfin tuna), trophic position as measured by delta(15)N explained most of the variance in log[MeHg] (r(2) approximately 0.8), but coastal species and tuna fell along distinct, nearly parallel lines with significantly different intercepts. The tuna also had significantly higher delta(202)Hg (0.2-0.5 per thousand) and Delta(201)Hg ( approximately 1.5 per thousand) than the coastal fish (delta(202)Hg = 0 to -1.0 per thousand; Delta(201)Hg approximately 0.4 per thousand). The observations can be best explained by largely disconnected food webs rooted in different baseline delta(15)N signatures (MR-plume vs oceanic) and isotopically distinct MeHg sources, with oceanic MeHg having undergone substantial photodegradation ( approximately 50%) before entering the base of the food web. Given the MR's large, productive footprint in the nGOM and the potential for exporting prey and MeHg to the adjacent oligotrophic GOM, the disconnected food webs and different MeHg sources are consistent with recent evidence in other systems of important oceanic MeHg sources.