Reactive iron and organic carbon are intimately associated in soils and sediments. However, to date, the organic compounds involved are uncharacterized on the molecular level. At redox interfaces in ...peatlands, where the biogeochemical cycles of iron and dissolved organic matter (DOM) are coupled, this issue can readily be studied. We found that precipitation of iron hydroxides at the oxic surface layer of two rewetted fens removed a large fraction of DOM via coagulation. On aeration of anoxic fen pore waters, >90% of dissolved iron and 27 ± 7% (mean ± SD) of dissolved organic carbon were rapidly (within 24 h) removed. Using ultra-high-resolution MS, we show that vascular plant-derived aromatic and pyrogenic compounds were preferentially retained, whereas the majority of carboxyl-rich aliphatic acids remained in solution. We propose that redox interfaces, which are ubiquitous in marine and terrestrial settings, are selective yet intermediate barriers that limit the flux of land-derived DOM to oceanic waters.
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The role of algae for sequestration of atmospheric mercury in the ocean is largely unknown owing to a lack of marine sediment data. We used high-resolution cores from marine Antarctica to estimate ...Holocene global mercury accumulation in biogenic siliceous sediments (diatom ooze). Diatom ooze exhibits the highest mercury accumulation rates ever reported for the marine environment and provides a large sink of anthropogenic mercury, surpassing existing model estimates by as much as a factor of 7. Anthropogenic pollution of the Southern Ocean began ~150 years ago, and up to 20% of anthropogenic mercury emitted to the atmosphere may have been stored in diatom ooze. These findings reveal the crucial role of diatoms as a fast vector for mercury sequestration and diatom ooze as a large marine mercury sink.
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Peatlands of the Northern Hemisphere and Central European coniferous forests experience significant environmental change. The resultant browning of surface waters, that is, elevated concentrations of ...dissolved organic matter (DOM) and metals, is of interest in the context of the global C cycle, peatland and forest management, and water treatment. In an attempt to identify the causes of this process in the Harz Mountains (Central Germany), we studied the spatiotemporal variations in DOM molecular composition (thermally assisted hydrolysis and methylation combined with GC–MS) and metal concentrations in headwater stream samples. We found strong relationships between DOM and metals and seasonal variations in the DOM quality and tentatively DOM–metal binding mode: during summer base flow, DOM and metal concentrations are low, and all elements other than the alkali and alkaline earth metals (Ca, Mg, Sr, K, and Na) are positively correlated to DOM, whereas during spring and autumn (high discharge), only metals with strong affinity for DOM (Fe, As, Cu, Cr, Pb, and Ti), but not weakly binding ones (Al, Cd, La, Mn, Ni, Zn, and Zr), are correlated to DOM, indicative of selectivity in DOM–metal interactions. The products of polyphenols are the key ingredients of the DOM–metal complexes. We argue the importance of spruce lignin-derived vanillic acid moieties, which are involved in weak (all seasons) and strong, multidentate and/or colloidal, binding (spring and autumn) of metals. Considering the ongoing spruce forest dieback and climate change acceleration, it is tempting to conclude that spruce necromass and forest soils may release vast amounts of lignin-derived DOM and associated metals to headwater streams. This would have significant implications for forest soil C stocks and the management of connected drinking water reservoirs.
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Peatlands and peaty riparian zones are major sources of dissolved organic matter (DOM), but are poorly understood in terms of export dynamics and controls thereof. Thereby quality of DOM affects ...function and behavior of DOM in aquatic ecosystems, but DOM quality can also help to track DOM sources and their export dynamics under specific hydrologic preconditions. The objective of this study was to elucidate controls on temporal variability in DOM concentration and quality in stream water draining a bog and a forested peaty riparian zone, particularly considering drought and storm flow events. DOM quality was monitored using spectrofluorometric indices for aromaticity (SUVA254), apparent molecular size (SR) and precursor organic material (FI), as well as PARAFAC modeling of excitation emission matrices (EEMs). Indices for DOM quality exhibited major changes due to different hydrologic conditions, but patterns were also dependent on season. Stream water at the forested site with mineral, peaty soils generally exhibited higher variability in DOM concentrations and quality compared to the outflow of an ombrotrophic bog, where DOM was less susceptible to changes in hydrologic conditions. During snowmelt and spring events, near-surface protein-like DOM pools were exported. A microbial DOM fraction originating from groundwater and deep peat layers was increasing during drought, while a strongly microbially altered DOM fraction was also exported by discharge events with dry preconditions at the forested site. This might be due to accelerated microbial activity in the peaty riparian zone of the forested site under these preconditions. Our study demonstrated that DOM export dynamics are not only a passive mixing of different hydrological sources, but monitoring studies have to consider that DOM quality depends on hydrologic preconditions and season. Moreover, the forested peaty riparian zone generated the most variability in headwater DOM quantity and quality, as could be tracked by the used spectrofluorometric indices.
There is an ongoing debate on the fate of mercury (Hg) in areas affected by artisanal and small-scale gold mining (ASGM). Over the last 30 years, ASGM has released 69 tons of Hg into the southeastern ...Peruvian Amazon. To investigate the role of suspended matter and hydrological factors on the fate of ASGM-Hg, we analysed riverbank sediments and suspended matter along the partially ASGM-affected Malinowski-Tambopata river system and examined Hg accumulation in fish. In addition, local impacts of atmospheric Hg emissions on aquatic systems were assessed by analysing a sediment core from an oxbow lake. Hg concentrations in riverbank sediments are lower (20–53 ng g−1) than in suspended matter (∼400–4000 ng g−1) due to differences in particle size. Elevated Hg concentrations in suspended matter from ASGM-affected river sections (∼1400 vs. ∼30–120 ng L−1 in unaffected sections) are mainly driven by the increased amount of suspended matter rather than increased Hg concentrations in the suspended matter. The oxbow lake sediment record shows low Hg concentrations (64–86 ng g−1) without evidence of any ASGM-related increase in atmospheric Hg input. Hg flux variations are mostly an effect of variations in sediment accumulation rates. Moreover, only 5% of the analysed fish (only piscivores) exceed WHO recommendations for human consumption (500 ng g−1). Our findings show that ASGM-affected river sections in the Malinowski-Tambopata system do not exhibit increased Hg accumulation, indicating that the released Hg is either retained at the spill site or transported to areas farther away from the ASGM areas. We suspect that the fate of ASGM-Hg in such tropical rivers is mainly linked to transport associated with the suspended matter, especially during high water situations. We assume that our findings are typical for ASGM-affected areas in tropical regions and could explain why aquatic systems in such ASGM regions often show comparatively modest enrichment in Hg levels.
•Hg concentrations in river sediments cannot be linked to the location of ASGM.•Suspended matter loads and hydrological variations determine water-borne Hg levels.•Hydrology should be considered while tracking the final sink of ASGM-Hg.•Lake sediments show no evidence of atmospheric Hg deposition in the last 100 years.•Hg levels in fish cannot be linked to ASGM-Hg but are linked to fish trophic level.
Low mercury concentrations in river-borne suspended matter, riverbanks, and lake sediments from a gold mining area in southeastern Peru suggest that mercury dispersion is largely controlled by hydrology and that mercury pollution is transported to distant aquatic sinks.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
Understanding marine mercury (Hg) biogeochemistry is crucial, as the consumption of Hg-enriched ocean fish is the most important pathway of Hg uptake in humans. Although ocean sediments are seen as ...the ultimate Hg sink, marine sediment studies on Hg accumulation are still rare. In this context, studying Hg behavior in the marine environment, especially in upwelling environments, is of particular interest due to its importance in these great upwelling regions for the global fishery. There are contradictory statements about the fate of Hg in upwelling regions. Some studies have suggested high biotic reduction of oxidized Hg and gaseous elemental mercury evasion to the atmosphere. More recent work has suggested that in upwelling regions, where productivity is high, evasion of gaseous elemental mercury is diminished due to scavenging and sedimentation of Hg by organic particles. In this study, we compared Hg concentrations and accumulation rates in the past ∼4,300 and 19,400 years derived from sediment cores collected in the Peruvian upwelling region (Peru Margin) and compared them with those of two other cores collected from the sediment fan of the Amazon and a core from the Congo Basin, which is influenced by both seasonal coastal upwelling and discharge from the river. Median Hg concentrations were higher at the Peru Margin (90.7 μg kg
–1
) and in the Congo Basin (93.4 μg kg
–1
) than in the Amazon Fan (35.8 μg kg
–1
). The average Hg accumulation rates in sediments from the Peru Margin (178 μg m
–2
yr
–1
) were factors of ∼4 and ∼39 times higher than those from the Congo Basin (46.7 μg m
–2
yr
–1
) and Amazon Fan (4.52 μg m
–2
yr
–1
), respectively. Principal component analysis (PCA) of the geochemical data set reveals that Amazon Fan sediments are strongly influenced by the deposition of terrestrial material, which is of less importance in the Congo Basin and of minor importance in Peru Margin sediments. Accordingly, Hg export to sediments in upwelling areas largely surpasses that in fans of large rivers that drain large terrestrial catchments. The high Hg accumulation rates in the sediments from the upwelling area and the minor influence of terrestrial Hg fluxes there suggest that atmospheric-derived Hg in upwelling areas is effectively exported to the sediments through scavenging by organic particles.
•Neither pH adjustment nor chloride introduction facilitated Hg removal from soil.•No correlation was found between Hg and total/dissolved soil organic matter.•Hg was firmly bound to soil making ...washing insufficient for soil clean-up.
Feasibility of soil washing to remediate Hg contaminated soil was studied. Dry sieving was performed to evaluate Hg distribution in soil particle size fractions. The influence of dissolved organic matter and chlorides on Hg dissolution was assessed by batch leaching tests. Mercury mobilization in the pH range of 3–11 was studied by pH-static titration. Results showed infeasibility of physical separation via dry sieving, as the least contaminated fraction exceeded the Swedish generic guideline value for Hg in soils. Soluble Hg did not correlate with dissolved organic carbon in the water leachate. The highest Hg dissolution was achieved at pH 5 and 11, reaching up to 0.3% of the total Hg. The pH adjustment was therefore not sufficient for the Hg removal to acceptable levels. Chlorides did not facilitate Hg mobilization under acidic pH either. Mercury was firmly bound in the studied soil thus soil washing might be insufficient method to treat the studied soil.
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Despite numerous existing publications, the fate of mercury (Hg) in ASGM-affected tropical aquatic systems remains uncertain. This is driven by an incomplete understanding of the factors controlling ...Hg distribution and transport in tropical ecosystems. The review of existing Hg research into ASGM indicated that hydrology exerts major control on the final sink of Hg in tropical rivers. Total Hg concentrations in river water increase during high discharge events due to increased erosion and Hg export from soils. Geochemical composition and grain-size distribution strongly control Hg concentrations and distribution in sediment and soils. This review highlights the absence of standardized protocols for investigating ASGM-related Hg pollution, and that the applied research methodologies are often unsuitable for adequately assessing the processes involved. We underline the need to consider an extensive suite of biogeochemical, physical and hydrological information when investigating the final sink and risks of ASGM-related Hg. Standardized and accurate research methodologies, applicable to the challenges presented by these tropical environments, would greatly ease not only data comparability and synthesis between studies, but also help to differentiate between anthropogenic and natural Hg. Establishing background values in tropical regions is also imperative for accurate quantifications of Hg enrichment levels in ASGM-affected sites.
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We present unambiguous records of preindustrial atmospheric mercury (Hg) pollution, derived from lake-sediment cores collected near Huancavelica, Peru, the largest Hg deposit in the New World. ...Intensive Hg mining first began ca. 1400 BC, predating the emergence of complex Andean societies, and signifying that the region served as a locus for early Hg extraction. The earliest mining targeted cinnabar (HgS) for the production of vermillion. Pre-Colonial Hg burdens peak ca. 500 BC and ca. 1450 AD, corresponding to the heights of the Chavín and Inca states, respectively. During the Inca, Colonial, and industrial intervals, Hg pollution became regional, as evidenced by a third lake record almost equal to225 km distant from Huancavelica. Measurements of sediment-Hg speciation reveal that cinnabar dust was initially the dominant Hg species deposited, and significant increases in deposition were limited to the local environment. After conquest by the Inca (ca. 1450 AD), smelting was adopted at the mine and Hg pollution became more widely circulated, with the deposition of matrix-bound phases of Hg predominating over cinnabar dust. Our results demonstrate the existence of a major Hg mining industry at Huancavelica spanning the past 3,500 years, and place recent Hg enrichment in the Andes in a broader historical context.
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