Fatty acid isotopic composition in Atlantic pollock is not influenced by environmentally relevant dietary fat concentrations.

The application of fatty acid (FA) isotopic analysis has great potential in elucidating food web structure, but it has not experienced the same wide-spread use as amino acid isotopic analyses. The failure to adopt FA isotopic methods is almost certainly linked to a lack of reliable information on trophic fractionation of FA, particularly in higher predators. In this work, we attempt to address this shortfall, through comparison of FA δ13C values in captive Atlantic pollock (Pollachius virens) liver and their known diets. Since catabolism is likely the main cause of fractionation and it may vary with dietary fat content, we investigated the impact of dietary fat concentration on isotopic discrimination in FA. We fed Atlantic pollock three formulated diets with similar FA isotopic compositions but different fat concentrations (5-9% of diet), representative of the range found in natural prey, for 20 weeks. At the conclusion of the study, δ13C values of liver FA were very similar to the FA within the corresponding diets, with most discrimination factors < 1. For all FA except 22:6n-3, dietary fat had no effect on discrimination factors. Only for 22:6n-3 did fish fed the highest fat diet have lower δ13C values than the diet consumed. Thus, these FA-specific discrimination factors can be applied to evaluate diets in marine fish consuming natural diets and will serve as additional and valuable biomarkers in fish feeding ecology.

Microbial inputs at the litter layer translate climate into altered organic matter properties.

Plant litter chemistry is altered during decomposition but it remains unknown if these alterations, and thus the composition of residual litter, will change in response to climate. Selective microbial mineralization of litter components and the accumulation of microbial necromass can drive litter compositional change, but the extent to which these mechanisms respond to climate remains poorly understood. We addressed this knowledge gap by studying needle litter decomposition along a boreal forest climate transect. Specifically, we investigated how the composition and/or metabolism of the decomposer community varies with climate, and if that variation is associated with distinct modifications of litter chemistry during decomposition. We analyzed the composition of microbial phospholipid fatty acids (PLFAs) in the litter layer and measured natural abundance δ13 CPLFA values as an integrated measure of microbial metabolisms. Changes in litter chemistry and δ13 C values were measured in litterbag experiments conducted at each transect site. A warmer climate was associated with higher litter nitrogen concentrations as well as altered microbial community structure (lower fungi:bacteria ratios) and microbial metabolism (higher δ13 CPLFA ). Litter in warmer transect regions accumulated less aliphatic-C (lipids, waxes) and retained more O-alkyl-C (carbohydrates), consistent with enhanced 13 C-enrichment in residual litter, than in colder regions. These results suggest that chemical changes during litter decomposition will change with climate, driven primarily by indirect climate effects (e.g., greater nitrogen availability and decreased fungi:bacteria ratios) rather than direct temperature effects. A positive correlation between microbial biomass δ13 C values and 13 C-enrichment during decomposition suggests that change in litter chemistry is driven more by distinct microbial necromass inputs than differences in the selective removal of litter components. Our study highlights the role that microbial inputs during early litter decomposition can play in shaping surface litter contribution to soil organic matter as it responds to climate warming effects such as greater nitrogen availability.

Temperature sensitivity of biomass-specific microbial exo-enzyme activities and CO2 efflux is resistant to change across short- and long-term timescales.

Accurate representation of temperature sensitivity (Q10 ) of soil microbial activity across time is critical for projecting soil CO2 efflux. As microorganisms mediate soil carbon (C) loss via exo-enzyme activity and respiration, we explore temperature sensitivities of microbial exo-enzyme activity and respiratory CO2 loss across time and assess mechanisms associated with these potential changes in microbial temperature responses. We collected soils along a latitudinal boreal forest transect with different temperature regimes (long-term timescale) and exposed these soils to laboratory temperature manipulations at 5, 15, and 25°C for 84 days (short-term timescale). We quantified temperature sensitivity of microbial activity per g soil and per g microbial biomass at days 9, 34, 55, and 84, and determined bacterial and fungal community structure before the incubation and at days 9 and 84. All biomass-specific rates exhibited temperature sensitivities resistant to change across short- and long-term timescales (mean Q10  = 2.77 ± 0.25, 2.63 ± 0.26, 1.78 ± 0.26, 2.27 ± 0.25, 3.28 ± 0.44, 2.89 ± 0.55 for ß-glucosidase, N-acetyl-ß-d-glucosaminidase, leucine amino peptidase, acid phosphatase, cellobiohydrolase, and CO2 efflux, respectively). In contrast, temperature sensitivity of soil mass-specific rates exhibited either resilience (the Q10 value changed and returned to the original value over time) or resistance to change. Regardless of the microbial flux responses, bacterial and fungal community structure was susceptible to change with temperature, significantly differing with short- and long-term exposure to different temperature regimes. Our results highlight that temperature responses of microbial resource allocation to exo-enzyme production and associated respiratory CO2 loss per unit biomass can remain invariant across time, and thus, that vulnerability of soil organic C stocks to rising temperatures may persist in the long term. Furthermore, resistant temperature sensitivities of biomass-specific rates in spite of different community structures imply decoupling of community constituents and the temperature responses of soil microbial activities.

The origin of soil organic matter controls its composition and bioreactivity across a mesic boreal forest latitudinal gradient.

Warmer climates have been associated with reduced bioreactivity of soil organic matter (SOM) typically attributed to increased diagenesis; the combined biological and physiochemical transformation of SOM. In addition, cross-site studies have indicated that ecosystem regime shifts, associated with long-term climate warming, can affect SOM properties through changes in vegetation and plant litter production thereby altering the composition of soil inputs. The relative importance of these two controls, diagenesis and inputs, on SOM properties as ecosystems experience climate warming, however, remains poorly understood. To address this issue we characterized the elemental, chemical (nuclear magnetic resonance spectroscopy and total hydrolysable amino acids analysis), and isotopic composition of plant litter and SOM across a well-constrained mesic boreal forest latitudinal transect in Atlantic Canada. Results across forest sites within each of three climate regions indicated that (1) climate history and diagenesis affect distinct parameters of SOM chemistry, (2) increases in SOM bioreactivity with latitude were associated with elevated proportions of carbohydrates relative to plant waxes and lignin, and (3) despite the common forest type across regions, differences in SOM chemistry by climate region were associated with chemically distinct litter inputs and not different degrees of diagenesis. The observed climate effects on vascular plant litter chemistry, however, explained only part of the regional differences in SOM chemistry, most notably the higher protein content of SOM from warmer regions. Greater proportions of lignin and aliphatic compounds and smaller proportions of carbohydrates in warmer sites' soils were explained by the higher proportion of vascular plant relative to moss litter in the warmer relative to cooler forests. These results indicate that climate change induced decreases in the proportion of moss inputs not only impacts SOM chemistry but also increases the resistance of SOM to decomposition, thus significantly altering SOM cycling in these boreal forest soils.

Assessing the utility of dissolved organic matter photoreactivity as a predictor of in situ methylmercury concentration.

Methylmercury (MeHg) bioaccumulation is a growing concern in ecosystems worldwide. The absorption of solar radiation by dissolved organic matter (DOM) and other photoreactive ligands can convert MeHg into less toxic forms of mercury through photodemethylation. In this study, spectral changes and photoreactivity of DOM were measured to assess the potential to control photoreactions and predict in situ MeHg concentration. Water samples collected from a series of lakes in southwestern Nova Scotia in June, August, and September were exposed to controlled ultraviolet-A (UV-A) radiation for up to 24hr. Dissolved organic matter photoreactivity, measured as the loss of absorbance at 350nm at constant UV-A irradiation, was positively dependent on the initial DOM concentration in lake waters (r2=0.94). This relationship was consistent over time with both DOM concentration and photoreactivity increasing from summer into fall across lakes. Lake in situ MeHg concentration was positively correlated with DOM concentration and likely catchment transport in June (r=0.77) but not the other sampling months. Despite a consistent seasonal variation in both DOM and Fe, and their respective correlations with MeHg, no discernable seasonal trend in MeHg was observed. However, a 3-year dataset from the 6 study lakes revealed a positive correlation between DOM concentration and both Fe (r=0.91) and MeHg concentrations (r=0.51) suggesting a more dominant landscape mobility control on MeHg. The DOM-MeHg relationships observed in these lakes highlights the need to examine DOM photoreactivity controls on MeHg transport and availability in natural waters particularly given future climate perturbations.

Photoreducible Mercury Loss from Arctic Snow Is Influenced by Temperature and Snow Age.

Mercury (Hg) is an important environmental contaminant, due to its neurotoxicity and ability to bioaccumulate. The Arctic is a mercury-sensitive region, where organisms can accumulate high Hg concentrations. Snowpack mercury photoredox reactions may control how much Hg is transported with melting Arctic snow. This work aimed to (1) determine the significance of temperature combined with UV irradiation intensity and snow age on Hg(0) flux from Arctic snow and (2) elucidate the effect of temperature on snowpack Hg photoreduction kinetics. Using a Teflon flux chamber, snow temperature, UV irradiation, and snow age were found to significantly influence Hg(0) flux from Arctic snow. Cross-correlation analysis results suggest that UV radiation has a direct effect on Hg(0)flux, while temperature may indirectly influence flux. Laboratory experiments determined that temperature influenced Hg photoreduction kinetics when snow approached the melting point (>-2 °C), where the pseudo-first-order reduction rate constant, k, decreased twofold, and the photoreduced Hg amount, Hg(II)red, increased 10-fold. This suggests that temperature influences Hg photoreduction kinetics indirectly, likely by altering the solid:liquid water ratio. These results imply that large mass transfers of Hg from snow to air may take place during the Arctic snowmelt period, altering photoreducible Hg retention and transport with snow meltwater.

Contrasting patterns of allochthony among three major groups of crustacean zooplankton in boreal and temperate lakes.

The importance of terrestrial-derived organic matter for lake zooplankton communities remains debated, partly because little is known about the basic pathways by which allochthonous carbon is transferred to zooplankton, and whether these vary among the major taxonomic and functional groups. We quantified allochthony of three zooplankton groups (Cladocera, Calanoida, and Cyclopoida) across 18 lakes in Quebec, spanning broad gradients of dissolved organic matter (DOM) and lake trophy, using a multi-isotope (delta2H + delta13C), multi-source (terrestrial, phytoplanktonic, benthic) approach. All three zooplankton groups had significant levels of allochthony, but differed greatly in their respective patterns across lakes. Allochthony in Calanoida and Cyclopoida was linked to detrital food chains based on particulate organic matter (POM) and on DOM, respectively, whereas in Cladocera it appeared related to both pathways; not surprisingly this latter group had the highest mean allochthony (0.31; compared to 0.18 in Cyclopoida and 0.16 in Calanoida). This study highlights the complexity of the pathways of delivery and transfer of terrestrial organic matter in freshwaters, and underscores the role that microbial food webs play in this transfer.

Integrating terrestrial and aquatic ecosystems to constrain estimates of land-atmosphere carbon exchange.

In this Perspective, we put forward an integrative framework to improve estimates of land-atmosphere carbon exchange based on the accumulation of carbon in the landscape as constrained by its lateral export through rivers. The framework uses the watershed as the fundamental spatial unit and integrates all terrestrial and aquatic ecosystems as well as their hydrologic carbon exchanges. Application of the framework should help bridge the existing gap between land and atmosphere-based approaches and offers a platform to increase communication and synergy among the terrestrial, aquatic, and atmospheric research communities that is paramount to advance landscape carbon budget assessments.

Methylmercury photodemethylation is inhibited in lakes with high dissolved organic matter.

Photodemethylation can be one of the primary processes for loss of neurotoxic methylmercury (MeHg) in freshwater lakes. Few studies have quantified seasonal variations in photodemethylation rate constants as a function of dissolved organic matter (DOM). We conducted 1-week irradiation experiments in two seasons to test for spatial and temporal differences in photodemethylation potential in temperate lake waters. Six study lakes in Kejimkujik National Park, Nova Scotia were sampled in summer and fall to include a range of naturally occurring DOM concentrations (4.4-13.4 and 3.9-16.4 mg C L-1, respectively). A negative linear relationship (R2 = 0.76, p = 0.01) was found between DOM concentration and photodemethylation rate constant across seasons, indicating that DOM is a strong predictor of MeHg photodemethylation independent of seasonal effects. The two highest carbon lakes (BDW and PEB) had significantly higher energy-normalized photodemethylation rate constants in summer compared to fall corresponding with lower DOM concentrations in summer relative to fall. Additionally, there were negative linear relationships between MeHg photodemethylation and DOM photomineralization (R2s = 0.58-0.72) and DOM photobleaching (R2s = 0.83-0.90). This key finding suggests that competition for photons within DOM structures may reduce the potential for MeHg photodemethylation in high carbon waters and that this relationship persists across seasons.

Quantifying the effects of photoreactive dissolved organic matter on methylmercury photodemethylation rates in freshwaters.

The present study examined potential effects of seasonal variations in photoreactive dissolved organic matter (DOM) on methylmercury (MeHg) photodemethylation rates in freshwaters. A series of controlled experiments was carried out using natural and photochemically preconditioned DOM in water collected from 1 lake in June, August, and October. Natural DOM concentrations doubled between June and August (10.2-21.2 mg C L-1 ) and then remained stable into October (19.4 mg C L-1 ). Correspondingly, MeHg concentrations peaked in August (0.42 ng L-1 ), along with absorbances at 350 nm and 254 nm. Up to 70% of MeHg was photodemethylated in the short 48-h irradiation experiments, with June having significantly higher rates than the other sampling months (p < 0.001). Photodemethylation rate constants were not affected by photoreactive DOM, nor were they affected by initial MeHg concentrations (p > 0.10). However, MeHg photodemethylation efficiencies (quantified in moles MeHg lost/moles photon absorbed) were higher in treatments with less photoreactive DOM. Congruently, MeHg photodemethylation efficiencies also decreased over summer by up to 10 times across treatments in association with increased photoreactive DOM, and were negatively correlated with DOM concentration. These results suggest that an important driver of MeHg photodemethylation is the interplay between MeHg and DOM, with greater potential for photodemethylation in freshwaters with more photobleached DOM and lower DOM content. Environ Toxicol Chem 2017;36:1493-1502. © 2016 SETAC.

Investigations of potential microbial methanogenic and carbon monoxide utilization pathways in ultra-basic reducing springs associated with present-day continental serpentinization: the Tablelands, NL, CAN.

Ultra-basic reducing springs at continental sites of serpentinization act as portals into the biogeochemistry of a subsurface environment with H2 and CH4 present. Very little, however, is known about the carbon substrate utilization, energy sources, and metabolic pathways of the microorganisms that live in this ultra-basic environment. The potential for microbial methanogenesis with bicarbonate, formate, acetate, and propionate precursors and carbon monoxide (CO) utilization pathways were tested in laboratory experiments by adding substrates to water and sediment from the Tablelands, NL, CAD, a site of present-day continental serpentinization. Microbial methanogenesis was not observed after bicarbonate, formate, acetate, or propionate addition. CO was consumed in the live experiments but not in the killed controls and the residual CO in the live experiments became enriched in (13)C. The average isotopic enrichment factor resulting from this microbial utilization of CO was estimated to be 11.2 ± 0.2‰. Phospholipid fatty acid concentrations and δ(13)C values suggest limited incorporation of carbon from CO into microbial lipids. This indicates that in our experiments, CO was used primarily as an energy source, but not for biomass growth. Environmental DNA sequencing of spring fluids collected at the same time as the addition experiments yielded a large proportion of Hydrogenophaga-related sequences, which is consistent with previous metagenomic data indicating the potential for these taxa to utilize CO.