Iron‑sulfur geochemistry and acidity retention in hydrologically active macropores of boreal acid sulfate soils : Effects of mitigation suspensions of fine-grained calcite and peat

Acid sulfate soils discharge large amounts of sulfuric acid along with toxic metals, deteriorating water quality and ecosystem health of recipient waterbodies. There is thus an urgent need to develop cost-effective and sustainable measures to mitigate the negative effects of these soils. In this study, we flushed aseptically-prepared MQ water (reference) or mitigation suspensions containing calcite, peat or a combination of both through 15-cm-thick soil cores from an acid sulfate soil field in western Finland, and investigated the geochemistry of Fe and S on the surfaces of macropores and in the solid columnar blocks (interiors) of the soil columns. The macropore surfaces of all soil columns were strongly enriched in total and HCl-extractable Fe and S relative to the interiors, owing to the existence of abundant Fe oxyhydroxysulfates (schwertmannite and partly jarosite) as yellow-to-brownish surface-coatings. The dissolution/hydrolysis of Fe oxyhydroxysulfates (predominantly jarosite) on the macropore surfaces of the reference columns, although being constantly flushed, effectively buffered the permeates at pH close to 4. These results suggest that Fe oxyhydroxysulfates accumulated on the macropore surfaces of boreal acid sulfate soils can act as long-lasting acidification sources. The treatments with mitigation suspensions led to a (near-)complete conversion of jarosite to Fe hydroxides, causing a substantial loss of S. In contrast, we did not observe any recognizable evidence indicating transformation of schwertmannite. However, sulfate sorbed by this mineral might be partially lost through anion-exchange processes during the treatments with calcite. No Fe sulfides were found in the peat-treated columns. Since Fe sulfides can support renewed acidification events, the moderate mineralogical changes induced by peat are desirable. In addition, peat materials can act as toxic-metal scavengers. Thus, the peat materials used here, which is relatively cheap in the boreal zone, is ideal for remediating boreal acid sulfate soils and other similar jarosite-bearing soils

Dredging and deposition of metal sulfide rich river sediments results in rapid conversion to acid sulfate soil materials

Sediments along the Baltic Sea coast can contain considerable amounts of metal sulfides that if dredged and the spoils deposited such that they are exposed to air, can release high concentrations of acid and toxic metals into recipient water bodies. Two river estuaries in western Finland were dredged from 2013 to 2018 and the dredge spoils were deposited on land previously covered with agricultural limestone to buffer the pH and mitigate acid and metal release. In this study, the geochemistry and 16S rRNA gene amplicon based bacterial communities were investigated over time to explore whether the application of lime prevented a conversion of the dredge spoils into acid producing and metal releasing soil. The pH of the dredge spoils decreased with time indicating metal sulfide oxidation and resulted in elevated sulfate concentrations along with a concomitant release of metals. However, calculations indicated only approximately 5% of the added lime had been dissolved. The bacterial communities decreased in diversity with the lowering of the pH as taxa most similar to extremely acidophilic sulfur, and in some cases iron, oxidizing Acidithiobacillus species became the dominant characterized genus in the deposited dredge spoils as the oxidation front moved deeper. In addition, other taxa characterized as involved in oxidation of iron or sulfur were identified including Gallionella, Sulfuricurvum, and Sulfurimonas. These data suggest there was a rapid conversion of the dredge spoils to severely acidic soil similar to actual acid sulfate soil and that the lime placed on the land prior to deposition of the spoils, and later ploughed into the dry dredge spoils, was insufficient to halt this process. Hence, future dredging and deposition of dredge spoils containing metal sulfides should not only take into account the amount of lime used for buffering but also its grain size and mixing into the soil

Comparison of boreal acid sulfate soil microbial communities in oxidative and reductive environments

Due to land uplift after the last ice age, previously stable Baltic Sea sulfidic sediments are becoming dry land. When these sediments are drained, the sulfide minerals are exposed to air and can release large amounts of metals and acid into the environment. This can cause severe ecological damage such as fish kills in rivers feeding the northern Baltic Sea. In this study, five sites were investigated for the occurrence of acid sulfate soils and their geochemistry and microbiology was identified. The pH and soil chemistry identified three of the areas as having classical acid sulfate soil characteristics and culture independent identification of 16S rRNA genes identified populations related to acidophilic bacteria capable of catalyzing sulfidic mineral dissolution, including species likely adapted to low temperature. These results were compared to an acid sulfate soil area that had been flooded for ten years and showed that the previously oxidized sulfidic materials had an increased pH compared to the unremediated oxidized layers. In addition, the microbiology of the flooded soil had changed such that alkalinity producing ferric and sulfate reducing reactions had likely occurred. This suggested that flooding of acid sulfate soils mitigates their environmental impact

Manganese cycling and transport in boreal estuaries impacted by acidic Mn-rich drainage

As critical transition zones between the land and the sea, estuaries are not only hotspots of hydrogeochemical and microbial processes/reactions, but also play a vital role in processing and transferring terrestrial fluxes of metals and nutrients to the sea. This study focused on three estuaries in the Gulf of Bothnia. All of them experience frequent inputs of acidic and Mn/metal-rich creek waters due to flushing of acid sulfate soils that are widespread in the creekś catchments. Analyzing existing long-term water chemistry data revealed a strong seasonal variation of Mn loads, with the highest values in spring (after snow melt) and autumn (after heavy rains). We sampled surface waters, suspended particulate matter (SPM), and sediments from the estuarine mixing zones and determined the loads and solid-phase speciation of Mn as well as the composition and metabolic potentials of microbial communities. The results showed that the removal, cycling, and lateral transport of Mn were governed by similar phases and processes in the three estuaries. Manganese X-ray absorption spectroscopy data of the SPM suggested that the removal of Mn was regulated by silicates (e.g., biotite), organically complexed Mn(II), and MnOx (dominated by groutite and phyllomanganates). While the fractional amounts of silicate-bound Mn(II) were overall low and constant throughout the estuaries, MnOx was strongly correlated with the Mn loadings of the SPM and thus the main vector for the removal of Mn in the central and outer parts of the estuaries, along with organically complexed Mn(II). Down estuary, both the fractional amounts and average Mn oxidation state of the MnOx phases increased with (i) the total Mn loads on the SPM samples and (ii) the relative abundances of several potential Mn-oxidizing bacteria (Flavobacterium, Caulobacter, Mycobacterium, and Pedobacter) in the surface waters. These features collectively suggested that the oxidation of Mn, probably mediated by the potential Mn-oxidizing microorganisms, became more extensive and complete towards the central and outer parts of the estuaries. At two sites in the central parts of one estuary, abundant phyllomanganates occurred in the surface sediments, but were converted to surface-sorbed Mn(II) phases at deeper layers (>3–4 cm). The occurrence of phyllomanganates may have suppressed the reduction of sulfate in the surface sediments, pushing down the methane sulfate transition zone that is typically shallow in estuarine sediments. At the outermost site in the estuary, deposited MnOx were reduced immediately at the water–sediment interface and converted most likely to Mn carbonate. The mobile Mn species produced by the Mn reduction processes (e.g., aqueous Mn(II) and ligand complexed Mn(III)) could partly diffuse into the overlying waters and, together with the estuarine Mn loads carried by the surface waters, transfer large amounts of reactive Mn into open coastal areas and subsequently contribute to Mn shuttling and inter-linked biogeochemical processes over the seafloor. Given the widespread occurrence of acid sulfate soils and other sulfidic geological materials on many coastal plains worldwide, the identified Mn attenuation and transport mechanisms are relevant for many estuaries globally.Mn geochemistry in boreal estuaries receiving acidic metal rich drainag

Multilocus Sequence Typing Identifies Epidemic Clones of Flavobacterium psychrophilum in Nordic Countries

Flavobacterium psychrophilum is the causative agent of bacterial cold water disease (BCWD), which affects a variety of freshwater-reared salmonid species. A large-scale study was performed to investigate the genetic diversity of F. psychrophilum in the four Nordic countries: Denmark, Finland, Norway, and Sweden. Multilocus sequence typing of 560 geographically and temporally disparate F. psychrophilum isolates collected from various sources between 1983 and 2012 revealed 81 different sequence types (STs) belonging to 12 clonal complexes (CCs) and 30 singleton STs. The largest CC, CC-ST10, which represented almost exclusively isolates from rainbow trout and included the most predominant genotype, ST2, comprised 65% of all isolates examined. In Norway, with a shorter history (<10 years) of BCWD in rainbow trout, ST2 was the only isolated CC-ST10 genotype, suggesting a recent introduction of an epidemic clone. The study identified five additional CCs shared between countries and five country-specific CCs, some with apparent host specificity. Almost 80% of the singleton STs were isolated from non-rainbow trout species or the environment. The present study reveals a simultaneous presence of genetically distinct CCs in the Nordic countries and points out specific F. psychrophilum STs posing a threat to the salmonid production. The study provides a significant contribution toward mapping the genetic diversity of F. psychrophilum globally and support for the existence of an epidemic population structure where recombination is a significant driver in F. psychrophilum evolution. Evidence indicating dissemination of a putatively virulent clonal complex (CC-ST10) with commercial movement of fish or fish products is strengthened