The methylation of mercury is known to depend on the chemical forms of mercury (Hg) present in the environment and the methylating bacterial activity. In sulfidic sediments, under conditions of supersaturation with respect to metacinnabar, recent research has shown that mercury precipitates as β-HgS(s) nanoparticles (β-HgS(s) nano ). Few studies have examined the precipitation of β-HgS(s) nano in the presence of marine dissolved organic matter (DOM). In this work, we used dynamic light scattering (DLS) coupled with UV-Vis spectroscopy and transmission electron microscopy (TEM) to investigate the formation and fate of β-HgS(s) nano formed in association with marine DOM extracted from the east and west of Long Island Sound, and at the shelf break of the North Atlantic Ocean, as well as with low molecular weight thiols. We found that while the β-HgS(s) nano formed in the presence of oceanic DOM doubled in size after 5 weeks, those forming in solutions with coastal DOM did not grow over time. In addition, when the Hg II : DOM ratio was varied, β-HgS(s) nano only rapidly aggregated at high ratios (>41 μmol Hg II per mg C) where the concentration of thiol groups was determined to be substantially low relative to Hg II . This suggests that functional groups other than thiols could be involved in the stabilization of β-HgS(s) nano . Furthermore, we showed that β-HgS(s) nano forming under anoxic conditions remained stable and could therefore persist in the environment sufficiently to impact the methylation potential. Exposure of β-HgS(s) nano to sunlit and oxic environments, however, caused rapid aggregation and sedimentation of the nanoparticles, suggesting that photo-induced changes or oxidation of organic matter adsorbed on the surface of β-HgS(s) nano affected their stability in surface waters.
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Influence of dissolved organic matter on carbonyl sulfide and carbon disulfide formation from cysteine during sunlight photolysis
Carbonyl sulfide (COS) and carbon disulfide (CS 2 ) are important atmospheric gases that are formed from organic sulfur precursors present in natural waters when exposed to sunlight. However, it remains unclear how specific water constituents, such as dissolved organic matter (DOM), affect COS and CS 2 formation. To better understand the role of DOM, irradiation experiments were conducted in O 2 -free synthetic waters containing four different DOM isolates, acquired from freshwater to open ocean sources, and the sulfur-based amino acid, cysteine (CYS). CYS is a known natural precursor of COS and CS 2 . Results indicated that COS formation did not vary strongly with DOM type, although small impacts were observed on the kinetic patterns. COS formation also increased with increasing CYS concentration but decreased with increasing DOM concentration. Quenching experiments indicated that ˙OH was not involved in the rate-limiting step of COS formation, whereas excited triplet states of DOM ( 3 CDOM*) were plausibly involved, although the quenching agents used to remove 3 CDOM* may have reacted with the CYS-derived intermediates as well. CS 2 was not formed under any of the experimental conditions. Overall, DOM-containing synthetic waters had a limited to no effect towards forming COS and CS 2 , especially when compared to the higher concentrations formed in sunlit natural waters, as examined previously. The reasons behind this limited effect need to be explored further but may be due to the additional water quality constituents present in these natural waters. The findings of this study imply that multiple variables beyond DOM govern COS and CS 2 photoproduction when moving from freshwaters to open ocean waters.
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- Award ID(s):
- 1653726
- NSF-PAR ID:
- 10250418
- Date Published:
- Journal Name:
- Environmental Science: Processes & Impacts
- Volume:
- 22
- Issue:
- 9
- ISSN:
- 2050-7887
- Page Range / eLocation ID:
- 1852 to 1864
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Climate change is dramatically altering Arctic ecosystems, leading to shifts in the sources, composition, and eventual fate of riverine dissolved organic matter (DOM) in the Arctic Ocean. Here we examine a 6‐year DOM compositional record from the six major Arctic rivers using Fourier‐transform ion cyclotron resonance mass spectrometry paired with dissolved organic carbon isotope data (Δ14C, δ13C) to investigate how seasonality and permafrost influence DOM, and how DOM export may change with warming. Across the pan‐Arctic, DOM molecular composition demonstrates synchrony and stability. Spring freshet brings recently leached terrestrial DOM with a latent high‐energy and potentially bioavailable subsidy, reconciling the historical paradox between freshet DOM's terrestrial bulk signatures and high biolability. Winter features undiluted baseflow DOM sourced from old, microbially degraded groundwater DOM. A stable core Arctic riverine fingerprint (CARF) is present in all samples and may contribute to the potential carbon sink of persistent, aged DOM in the global ocean. Future warming may lead to shifting sources of DOM and export through: (1) flattening Arctic hydrographs and earlier melt modifying the timing and role of the spring high‐energy subsidy; (2) increasing groundwater discharge resulting in a greater fraction of DOM export to the ocean occurring as stable and aged molecules; and (3) increasing contribution of nitrogen/sulfur‐containing DOM from microbial degradation caused by increased connectivity between groundwater and surface waters due to permafrost thaw. Our findings suggest the ubiquitous CARF (which may contribute to oceanic carbon sequestration) underlies predictable variations in riverine DOM composition caused by seasonality and permafrost extent.
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Abstract Northern high‐latitude lakes are undergoing climate‐induced changes including shifts in their hydrologic connectivity with terrestrial ecosystems. How this will impact dissolved organic matter (DOM) biogeochemistry remains uncertain. We examined the drivers of DOM composition for lakes in the Yukon Flats Basin in Alaska, an arid region of low relief that is characteristic of over one‐quarter of circumpolar lake area. Utilizing the vascular plant biomarker lignin, chromophoric dissolved organic matter (CDOM), and ultrahigh‐resolution mass spectrometry, we interpreted DOM compositional changes using lake‐water stable isotope (δ18O‐H2O) composition as a proxy for lake hydrologic connectivity with the landscape. We observed a relative decrease in CDOM in more hydrologically isolated lakes (enriched δ18O‐H2O) without a corresponding decrease in dissolved organic carbon (DOC) concentration. Although DOC and CDOM were weakly correlated, a significant positive relationship between lignin and CDOM (
r 2= 0.67) demonstrates that optical parameters are useful for estimating lignin concentration and thus vascular plant contribution to lake DOM. Indicators of allochthonous DOM, including lignin carbon normalized yields, CDOM aromaticity proxies, and relative abundances of polyphenolic and condensed aromatic compound classes, were negatively correlated with δ18O‐H2O (r 2 > 0.45), suggesting there is little allochthonous DOM supplied to many of these hydrologically isolated lakes. We conclude that decreased lake hydrologic connectivity, driven by ongoing climate change (i.e., decreased precipitation, warming temperatures), will reduce allochthonous DOM contributions and shift lakes toward lower CDOM systems with ecosystem‐scale ramifications for heat transfer, photochemical reactions, productivity, and ultimately their biogeochemical function. -
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Abstract The dynamics of water and solutes were investigated in two northern bog ponds using sensor networks and discrete water samples. Embedded sensors monitored water level (S), precipitation (P), evaporation (E), water temperature (T) and specific conductivity (SC) in the peatlands and encircled ponds at 30 min time intervals from 2009 to 2015. Pond water chemistry was monitored seasonally from 2000 to 2020. Daily hydrographs and water budgets indicated that both bogs are ombrotrophic systems, perched above the local water table. Although the predominant flowpath for liquid water was precipitation → pond → peatland → underlying glacial deposits, evaporation accounted for 70% to 90% of water losses. High dissolved organic matter (DOM) in the ponds resulted from transient reversals of flowpath and from molecular diffusion across the peatland/pond interface (a tea bag effect). DOM of peatland origin dominated pond water chemistry, regulating the concentration of important metals, major nutrients and the acid–base status of both bog ponds. Elevated concentrations of Fe, Hg and MeHg in the ponds reflected ligand binding by DOM. The formation of DOM‐Fe‐PO4complexes likely accounted for >3‐fold higher P concentration relative to nearby clearwater lakes. Linear regression of dissolved organic carbon (DOC) against the anion deficit indicated that DOM contributed up to 6.6 mEq of strong acid per gramme carbon in pond waters. Winter maxima in the seasonal cycles of DOC, Ca, Mg, N, P, Hg and MeHg in both bog ponds were attributable, in large part, to salting out during ice formation. We conclude that multiple methods are needed to understand the dynamics of water and solutes in bog ecosystems.
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In sunlit waters, photodegradation of dissolved organic matter (DOM) yields completely oxidized carbon ( i.e. , CO 2 ) as well as a suite of partially oxidized compounds formed from oxygen incorporation ( i.e. , partial photo-oxidation). Of these two groups of DOM photo-products, more studies focus on CO 2 (a greenhouse gas) than on partially oxidized DOM, which is likely a diverse group of compounds with poorly constrained roles in aquatic carbon cycling or biogeochemistry. The objective of this study is to address knowledge gaps on the prevalence, products, and pathways of DOM partial photo-oxidation. Here we traced the photochemical incorporation of isotopically labelled 18 O 2 into DOM isolated from Alaskan Arctic surface waters using high-resolution mass spectrometry. Complete and partial photo-oxidation of DOM was also quantified as CO 2 production and O 2 consumption. The majority of 18 O-containing partial oxidation photo-products were classified as carboxylic rich alicyclic molecules (CRAM) and overlapped in composition with previously reported photo-products known to result from the oxidation of DOM by singlet oxygen. These results support a previously proposed hypothesis that photo-oxidation by singlet oxygen may contribute to the formation of CRAM, a compound class of DOM ubiquitously observed in surface waters. The novel application of an isotopic tracer for oxygen incorporation with a mass balance approach to quantify complete and partial photo-oxidation of DOM revealed that less than one mol of O 2 is required to produce one mol of CO 2 . A sensitivity analysis based on this new knowledge demonstrated that the magnitude of DOM partial photo-oxidation may be underestimated by up to four-fold. Consequently, partial photo-oxidation likely plays a more prominent role in shaping DOM composition in sunlit waters of the Arctic than previously understood. Therefore, partial photo-oxidation should be increasingly incorporated into the experimental framework of studies focused on DOM composition in surface waters.more » « less
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D0EM00219D
