Spruce forest afforestation leading to increased Fe mobilization from soils

Increasing exports of Fe and DOC from soils, causing browning of freshwaters, have been reported in recent decades in many regions of the northern hemisphere. Afforestation, and in particular an increase of Norway spruce forest in certain regions, is suggested as a driver behind these trends in water chemistry. In this study, we tested the hypothesis that the gradual accumulation of organic soil layers in spruce forests, and subsequent increase in organic acid concentrations and acidity enhances mobilization of Fe. First generation Norway spruce stands of different ages (35, 61, 90 years) and adjacent arable control plots were selected to represent the effects of aging forest. Soil solutions were sampled from suction lysimeters at two depths (below organic soil layer and in mineral soil) during two years, and analyzed for Fe concentration, Fe speciation (XAS analysis), DOC, metals, major anions and cations. Solution Fe concentrations were significantly higher in shallow soils under older spruce stands (by 5- and 6-fold) than in control plots and the youngest forest. Variation in Fe concentration was best explained by variation in DOC concentration and pH. Moreover, Fe in all soil solutions was present as mononuclear Fe(III)-OM complexes, showing that this phase is dominating Fe translocation. Fe speciation in the soil was also analyzed, and found to be dominated by Fe oxides with minor differences between plots. These results confirmed that Fe mobilization, by Fe(III)-OM complexes, was higher from mature spruce stands, which supports that afforestation with spruce may contribute to rising concentrations of Fe in surface waters.

Comparing CLE-AdCSV applications using SA and TAC to determine the Fe-binding characteristics of model ligands in seawater

Competitive ligand exchange–adsorptive cathodic stripping voltammetry (CLE-AdCSV) is used to determine the conditional concentration ([L]) and the conditional binding strength (logKcond) of dissolved organic Fe-binding ligands, which together influence the solubility of Fe in seawater. Electrochemical applications of Fe speciation measurements vary predominantly in the choice of the added competing ligand. Although different applications show the same trends, [L] and logKcond differ between the applications. In this study, binding of two added ligands in three different common applications to three known types of natural binding ligands is compared. The applications are (1) salicylaldoxime (SA) at 25 µM (SA25) and short waiting time, (2) SA at 5 µM (SA5), and (3) 2-(2-thiazolylazo)-ρ-cresol (TAC) at 10 µM, the latter two with overnight equilibration. The three applications were calibrated under the same conditions, although having different pH values, resulting in the detection window centers (D) DTAC > DSA25 ≥ SA5 (as logD values with respect to Fe3+: 12.3 > 11.2 ≥ 11). For the model ligands, there is no common trend in the results of logKcond. The values have a considerable spread, which indicates that the error in logKcond is large. The ligand concentrations of the nonhumic model ligands are overestimated by SA25, which we attribute to the lack of equilibrium between Fe-SA species in the SA25 application. The application TAC more often underestimated the ligand concentrations and the application SA5 over- and underestimated the ligand concentration. The extent of overestimation and underestimation differed per model ligand, and the three applications showed the same trend between the nonhumic model ligands, especially for SA5 and SA25. The estimated ligand concentrations for the humic and fulvic acids differed approximately 2-fold between TAC and SA5 and another factor of 2 between SA5 and SA25. The use of SA above 5 µM suffers from the formation of the species Fe(SA)x (x>1) that is not electro-active as already suggested by Abualhaija and van den Berg (2014). Moreover, we found that the reaction between the electro-active and non-electro-active species is probably irreversible. This undermines the assumption of the CLE principle, causes overestimation of [L] and could result in a false distinction into more than one ligand group. For future electrochemical work it is recommended to take the above limitations of the applications into account. Overall, the uncertainties arising from the CLE-AdCSV approach mean we need to search for new ways to determine the organic complexation of Fe in seawater.

The impact of postdepositional alteration on iron- and molybdenum-based redox proxies

Ratios of (un)reactive iron species, authigenic molybdenum contents (Moauth), and molybdenum isotope compositions (δ98Moauth) in sedimentary rocks are geochemical proxies that are widely used to reconstruct past marine redox states, which have been calibrated in modern marine settings covering oxic to euxinic conditions. However, syn- and postdepositional processes can result in alterations and ambiguities of proxy-derived redox signals that can challenge the validity of paleoreconstructions. We present new data from modern organic-rich sediments of two oxygen minimum zone settings in the Gulf of California and the Peruvian margin. The results show that Mo is fully immobilized shortly after deposition by reaction with hydrogen sulfide (H2S) produced during organoclastic sulfate reduction. Thus, any H2S produced deeper in the sediment (e.g., by sulfate reduction coupled to anaerobic methane oxidation) leaves the initially deposited Mo concentrations and δ98Mo signatures unaltered, which supports the robustness of Mo-based redox proxies. In contrast, the Fe speciation data reveal continued pyritization due to constant exposure of Fe minerals to H2S. Importantly, both Fe bound to oxides and carbonates (highly reactive Fe) and also poorly reactive Fe (e.g., sheet silicates) undergo pyritization during early diagenesis. This process generates Fe-based proxy signatures that falsely imply ferruginous or euxinic conditions.

Comparing CLE-AdCSV applications using SA and TAC to determine the Fe binding characteristics of model ligands in seawater

Competitive ligand exchange–adsorptive cathodic stripping voltammetry (CLE-AdCSV) is used to determine the conditional concentration ([L]) and the conditional binding strength (logKcond) of dissolved organic Fe-binding ligands, which together influence the solubility of Fe in seawater. Electrochemical applications of Fe speciation measurements vary predominantly in the choice of the added competing ligand. Although different applications show the same trends, [L] and logKcond differ between the applications. In this study, binding of two added ligands in three different common applications to three known types of natural binding ligands are compared. The applications are: 1) Salicylaldoxime (SA) at 25µM (SA25) and short waiting time, 2) SA at 5µM (SA5) and 3)2-(2-thiazolylazo)-ρ-cresol (TAC) at 10 µM, the latter two with overnight equilibration. The three applications were calibrated under the same conditions, although having different pH values, resulting in the detection window centers (D) DTAC > DSA25 ≥ SA5 (as log D values with respect to Fe3+: 12.3 > 11.2 ≥ 11). For the model ligands, there is no common trend in the results of logKcond. The values have a considerable spread, which indicates that the error in logKcond is large. The ligand concentrations of the non humic model ligands are overestimated by SA25 which we attribute to the lack of equilibrium between Fe-SA species in the SA25 application. The application TAC more often underestimated the ligand concentrations and the application SA5 over and under estimated the ligand concentration. The extent of overestimation and underestimation differed per model ligand, and the three applications showed the same trend between the non humic model ligands especially for SA5 and SA25. The estimated ligand concentrations for the humic and fulvic acids differed approximately 2 fold between TAC and SA5 and another factor of 2 between SA5 and SA25. The use of SA above 5 µM suffers from the formation of the species Fe(SA)x (x > 1) that is not electro-active as already suggested by Abualhaija and Van den Berg (2014). Moreover, we found that the reaction between the electro-active and non-electro-active species is probably irreversible. This undermines the assumption of the CLE principle, causes overestimation of [L] and could result in a false distinction into more than one ligand group. For future electrochemical work it is recommended to take the above limitations of the applications into account. Overall, the uncertainties arising from the CLE-AdCSV approach mean we need to search for new ways to determine the organic complexation of Fe in seawater.

Holocene Spatiotemporal Redox Variations in the Southern Baltic Sea

Low oxygen conditions in the modern Baltic Sea are exacerbated by human activities; however, anoxic conditions also prevailed naturally over the Holocene. Few studies have characterized the specific paleoredox conditions (manganous, ferruginous, euxinic) and their frequency in southern Baltic sub-basins during these ancient events. Here, we apply a suite of isotope systems (Fe, Mo, S) and associated elemental proxies (e.g., Fe speciation, Mn) to specifically define water column redox regimes through the Baltic Holocene in a sill-proximal to sill-distal transect (Lille Belt, Bornholm Basin, Landsort Deep) using samples collected during the Integrated Ocean Drilling Program Expedition 347. At the sill-proximal Lille Belt, there is evidence for anoxic manganous/ferruginous conditions for most of the cored interval following the transition from the Ancylus Lake to Littorina Sea but with no clear excursion to more reducing or euxinic conditions associated with the Holocene Thermal Maximum (HTM) or Medieval Climate Anomaly (MCA) events. At the sill-distal southern sub-basin, Bornholm Basin, a combination of Fe speciation, pore water Fe, and solid phase Mo concentration and isotope data point to manganous/ferruginous conditions during the Ancylus Lake-to-Littorina Sea transition and HTM but with only brief excursions to intermittently or weakly euxinic conditions during this interval. At the western Baltic Proper sub-basin, Landsort Deep, new Fe and S isotope data bolster previous Mo isotope records and Fe speciation evidence for two distinct anoxic periods but also suggest that sulfide accumulation beyond transient levels was largely restricted to the sediment-water interface. Ultimately, the combined data from all three locations indicate that Fe enrichments typically indicative of euxinia may be best explained by Fe deposition as oxides following events likely analogous to the periodic incursions of oxygenated North Sea waters observed today, with subsequent pyrite formation in sulfidic pore waters. Additionally, the Mo isotope data from multiple Baltic Sea southern basins argue against restricted and widespread euxinic conditions, as has been demonstrated in the Baltic Proper and Bothnian Sea during the HTM or MCA. Instead, similar to today, each past Baltic anoxic event is characterized by redox conditions that become progressively more reducing with increasing distance from the sill.

Mo isotope records from Lower Cambrian black shales, northwestern Tarim Basin (China): Implications for the early Cambrian ocean

The widely developed black shales deposited during the early Cambrian recorded paleoenvironmental information about coeval seawater. Numerous studies have been conducted on these shales to reconstruct the paleomarine environment during this time period. However, most research has been conducted on stratigraphic sections in South China, and equivalent studies of sections from other cratons are relatively rare. Here, we report Mo isotopic compositions as well as redox-sensitive trace-element and iron (Fe) speciation data for black shales of the Lower Cambrian Yuertusi Formation from the Tarim block (i.e., a small craton). The Fe speciation data show high FeHR/FeT and Fepy/FeHR ratios, indicating roughly sustained euxinic bottom-water conditions during their deposition. Based on Mo isotopic compositions (δ98/95Mo), we further classified the euxinic black shales into two intervals: a lower interval (0−21.3 m) and an upper interval (21.3−32.3 m). The lower interval is characterized by variable Mo isotopic compositions (−2.12‰ to +0.57‰, mean = −0.52‰ ± 0.72‰), with an obvious negative excursion in its middle portion. The overlying upper interval has relatively heavy δ98/95Mo values up to +1.42‰ (mean = +0.62‰ ± 0.37‰). We ascribe δ98/95Mo differences in the lower and upper intervals to inadequate aqueous H2S concentrations for quantitative thiomolybdate formation under euxinic conditions. The most negative Mo isotope excursion may have been caused by upwelling hydrothermal inputs during a transgression, consistent with significantly elevated total organic carbon (TOC) contents, Mo and U enrichments, and Fe supply. Relatively positive δ98/95Mo values in the upper interval have roughly similar variations with other coeval sections, indicating such variations were common for early Cambrian euxinic deposits, and they were most likely caused by local differences in [H2S]aq. Compilation of Mo isotope data from the early Cambrian and earlier times further indicates relatively oxygenated seawater, especially the deep-marine areas during the early Cambrian before reaching a state like modern seawater.

How are mineral and organic phases regulating burning-induced soil water repellency? Unravelling the crucial dynamics occurring in the Alps even at moderate fire intensities.

<p>Wildfires play the role of ecosystem shapers in the majority of terrestrial biomes, altering canopy and litter cover and imposing strong modifications on soils. Organic matter (OM) content and composition, mineralogy, pH, aggregate stability and water repellency (WR) are among the main edaphic properties to be affected by heat. Various studies dealt with occurrence, extent and persistence of burning-induced soil WR, but the dynamics at the basis of its formation (and loss) are still widely unclear. In addition, the vast majority of research on this topic has been carried out in the Mediterranean, even if alpine environments are far from being untouched by fires. Our aims were therefore to provide insight into the key mechanisms regulating WR thermal alterations in a relatively understudied environment.</p><p>Our sampling design aimed at collecting soils representative of the Western Italian Alps. Charring was simulated in the lab, at increasing temperatures (up to 300° C), on a set of A soil horizons developed under pine and beech forest covers. Water drop penetration time (WDPT) was employed to test WR persistence. Soils were analyzed in terms of organic carbon (OC) and nitrogen contents, pH, texture and iron (Fe) oxides composition (Fe-DCB and Fe-pyrophosphate extracted). Fe-speciation and OM composition of some selected samples were further characterized using Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy and Fourier transform-infra red (FT-IR) spectroscopy, respectively.</p><p>WR was found to be extremely variable, event at room temperature. For samples exhibiting an increase in WR upon burning intensity, maximum repellency was observed at 200° C. OC abundance (%) and coarse texture were found to be the main drivers of hydrophobicity in soil. WR was drastically lost when samples were exposed to temperatures higher than 200°C. Above this threshold, pH systematically increased and OC (%) sharply decreased. The increasingly negative charge of mineral surfaces, mirrored by pH increase, seems to result in a significant C volatilization by OM desorption, eventually leading to a super-hydrophilic behavior in soil.</p><p>Fe EXAFS allowed to evaluate different thermal-dictated pathways of Fe-speciation. The formation of more crystalline Fe-forms (e.g. hematite, meghemite) was observed above 200° C. Even though a reduction in surface area should be expected when observing an increase in crystallization degree (potentially giving rise to greater WR), OM adhesion to mineral surfaces seems to be inhibited by the change induced in their charge. A reduction in the OM-bound Fe pool (pyrophosphate extracted) above 200° C could be appreciated, supporting the interpretation of oxy-hydroxides transformations and OC (%) loss.  </p><p>The current investigation has been carried out to capture an in-depth picture of wildfire impacts on alpine soils, targeting factors responsible for WR enhancement and shred. Identifying the mechanisms regulating wildfire-related WR is a key issue, as the formation of hydrophobic layers in soil highly favors its erosion. Addressing such matters is crucial to tackle the issue of ecosystems recovery, considering that climate-change-related alterations in wildfires regimes are already causing the occurrence of more frequent and disruptive fires.</p>