Peter Österholm

Spatial trends and losses of major and trace elements in agricultural acid sulphate soils distributed in the artificially drained Rintala area, W. Finland

Acid sulphate soils, common in the coastal areas of Finland, contribute strongly to high acid, S and metal loadings on adjacent surface waters. This, in turn, is causing significant harm to the aquatic ecology. There is, however, limited knowledge on the total amounts of acidity and chemical elements leached from these soils. The overall objective of this study was to determine geochemical patterns in acid sulphate soils and their parent sediments and, based on the identified patterns assess the extent, mechanisms and present state of leaching of major and trace elements from these soils. The distribution of pH, aqua regia extractable concentrations of P and metals (Al, Ba, Ca, Co, Cr, Cu, Fe, K, La, Mg, Mn, Na, Ni, Sr, Th, Ti, V, Zn) and total concentrations of S and C were determined in 30 vertical profiles collected in the 23 km2 large Rintala agricultural area (mid-western Finland) underlain largely with S-rich sediments. It was found that approximately 70% of the area consists of acid sulphate soils with a minimum pH 4%. Four different methods were used to estimate the losses of chemical elements from the acid sulphate soils: (1) the concentrations in the soil were compared with those in the parent sediments, (2) due to indicated heterogeneities in several profiles, the vertical changes of the immobile Ti was used to re-calculate element losses, (3) element depletions in the acid sulphate soils (as compared to those in the parent sediments) were compared to the corresponding depletions in the non acid sulphate soils, (4) element concentrations in drainage waters were compared with those in the parent sediments. Based on these calculations, it was assessed that the percentual leaching of the aqua regia extractable fraction (total for S) has been as follows: S (40–50%), Na (30–50%), Mn (25–35%), Sr (15–20%), Ca–Ni–Co (approximately 10%), Mg–K–Zn (5–10%), Th–La–Cu–Al–P–Ti–Fe (<5%), and Ba–Cr–V (<1%). While it was possible to quite accurately estimate the percentages and thus the amounts of elements lost, it was not possible to estimate the rate of leaching as there is no available detailed information on dates when ditching activities and thus oxidation-acidification processes started. Other calculations indicated that the mobile S reservoir is still some 15 ton/hectare, which is huge but still smaller than the losses that have occurred since the area was drained (23–28 ton/hectare).

Estuarine behaviour of metal loads leached from coastal lowland acid sulphate soils

The estuarine behaviour of the metal load leaching from acid sulphate (AS) soils was studied in a selected river system (the Vörå River), in western Finland. Large amounts of metals were transported with the river and deposited within the estuary, causing highly elevated metal concentrations in both the sediment traps and in the underlying bottom sediments. Among the metals, there was a diverging deposition pattern where Al, Cu, La and U demonstrated a strong association with organic matter and were deposited within approximately 4 km from the river mouth. In contrast, the deposition of Co, Mn, Ni and Zn occurred when pH reached circumneutral conditions further out in the estuary. Yet other metals were not abundantly leached from the AS soils and thus not elevated in the river and estuary (Fe, Ti, Cr, V). Five separate chemical extractions indicated the geochemical speciation of the metals.

Quantification of current and future leaching of sulfur and metals from Boreal acid sulfate soils, western Finland

The leaching of sulfur (S) and metals (Al, Ca, Cd, Co, Cu, Fe, K, Mg, Mn, Ni, Zn) from an acid sulfate soil (ASS) area in western Finland was determined on the basis of hydrochemical analyses (ICP-MS) of water samples collected monthly for 3 years from the stream draining that area. The average annual amount of leaching was as follows (kg/ha.year): S (633), Ca (281), Mg (199), Al (54), K (54), Mn (35), Fe (5.6), Zn (1.7), Ni (0.84), Co (0.79), Cu (0.070), Cd (0.0068). These high values are due to extensive oxidation of metal sulfides and weathering of minerals in the ASS profile. Calculations showed that other S inputs such as deposition and fertiliser use, and S outputs such as degassing and plant removal, are insignificant in comparison with current leaching losses. Before the area was artificially drained, the leaching losses of S from the study area must have been very small; otherwise, the S residual in the soil would have been depleted a long time ago. With current drainage practices, the leachable soil S residual will be halved in roughly 30 years, after which the S and metal loads of the drainage will have decreased. However, more time is needed before the concentrations will have decreased to an environmentally acceptable level, unless environmentally friendly measures are found and implemented.

Microbial community potentially responsible for acid and metal release from an Ostrobothnian acid sulfate soil.

Soils containing an approximately equal mixture of metastable iron sulfides and pyrite occur in the boreal Ostrobothnian coastal region of Finland, termed ‘potential acid sulfate soil materials’. If the iron sulfides are exposed to air, oxidation reactions result in acid and metal release to the environment that can cause severe damage. Despite that acidophilic microorganisms catalyze acid and metal release from sulfide minerals, the microbiology of acid sulfate soil (ASS) materials has been neglected. The molecular phylogeny of a depth profile through the plough and oxidized ASS layers identified several known acidophilic microorganisms and environmental clones previously identified from acid- and metal-contaminated environments. In addition, several of the 16S rRNA gene sequences were more similar to sequences previously identified from cold environments. Leaching of the metastable iron sulfides and pyrite with an ASS microbial enrichment culture incubated at low pH accelerated metal release, suggesting microorganisms capable of catalyzing metal sulfide oxidation were present. The 16S rRNA gene analysis showed the presence of species similar to Acidocella sp. and other clones identified from acid mine environments. These data support that acid and metal release from ASSs was catalyzed by indigenous microorganisms adapted to low pH.

Assessment of aquatic pollution, remedial measures and juridical obligations of an acid sulphate soil area in western Finland

Assessment of aquatic pollution, remedial measures and juridical obligations of an acid sulphate soil area in western Finland

Arsenic removal from contaminated brackish sea water by sorption onto Al hydroxides and Fe phases mobilized by land-use.

This study examines the spatial and temporal distribution patterns of arsenic (As) in solid and aqueous materials along the mixing zone of an estuary, located in the south-eastern part of the Bothnian Bay and fed by a creek running through an acid sulfate (AS) soil landscape. The concentrations of As in solution form (<1 kDa) increase steadily from the creek mouth to the outer estuary, suggesting that inflowing seawater, rather than AS soil, is the major As source in the estuary. In sediments at the outer estuary, As was accumulated and diagenetically cycled in the surficial layers, as throughout much of the Bothnian Bay. In contrast, in sediments in the inner estuary, As concentrations and accumulation rates showed systematical peaks at greater depths. These peaks were overall consistent with the temporal trend of past As discharges from the Rönnskär smelter and the accompanied As concentrations in past sea-water of the Bothnian Bay, pointing to a connection between the historical smelter activities and the sediment-bound As in the inner estuary. However, the concentrations and accumulation rates of As peaked at depths where the smelter activities had already declined, but a large increase in the deposition of Al hydroxides and Fe phases occurred in response to intensified land-use in the mid 1960s and early 1970s. This correspondence suggests that, apart from the inflowing As-contaminated seawater, capture by Al hydroxides, Fe hydroxides and Fe-organic complexes is another important factor for As deposition in the inner estuary. After accumulating in the sediment, the solid-phase As was partly remobilized, as reflected by increased pore-water As concentrations, a process favored by As(V) reduction and high concentrations of dissolved organic matter.

Groundwater management of acid sulfate soils using controlled drainage, by-pass flow prevention, and subsurface irrigation on a boreal farmland

Sulfide-bearing anoxic sediments are found in coastal regions around the world including Australia and the Baltic. Upon lowering of the groundwater by drainage, they are oxidized and form acid sulfate soils (pH < 4) that mobilize plenty of potentially toxic metals into watercourses with serious environmental consequences. Being highly valued for their excellent crop yields, there is an urgent need to find management solutions that minimize the oxidation. In this study, possibilities to manage the groundwater with controlled subsurface drainage (CD) and subsurface irrigation (CDI), which included a vertical plastic sheet to prevent by-pass flow into the main drain, was examined on a Boreal farmland in Western Finland. During a 3-year study, the groundwater in the reference field (Ref) with conventional subsurface drainage pipes at 1.1–1.4 m depth typically dropped down to almost 2 m in the end of summers (September) due to evapotranspiration exceeding precipitation. CD delayed the groundwater drop, shortening the time of oxidation. In CDI system, the groundwater could be kept at c. 1 m or shallower throughout the summers, thereby preventing oxidation of critical sulfide horizons in the lower subsoil. Differences in total discharge and soil geochemistry features were small during the course of the study period. Salt accumulation seemed to be a small risk for crop growth but the capillary rise of acidity to the surface horizon may be increased in CDI, possibly increasing the need for surface liming. A “floating groundwater antenna,” indicating groundwater fluctuations, proved to be an easy and reliable tool to farmers for proper management of controlled drainage.

Metal concentrations in oats (Avena sativa L.) grown on acid sulphate soils

The aim of the study was to investigate the impact of soil chemistry on the concentrations of Co, Ni, Zn, Mn, Cu and Fe in oats (Avena sativa L. cv. Fiia) grown on Finnish acid sulphate (AS) soils with varying geochemical characteristics. Twenty two soil profiles, which were sampled to a depth of 1 m (five 20 cm section splits), and 26 composite oat grain samples were collected on a total of five fields. The concentrations of Co, Ni, Zn and Mn in the grains were correlated with the NH4Ac-EDTA-extractable concentrations in the soils. However, as these four chalcophilic metals are in general easily lost to drains and not retained as a large pool in the soil in easily-extractable form, also the concentrations in the oats were not in general elevated as compared with average values on other soils. On one of the fields, however, the Co and Ni concentrations in the soil, and thus also in the oats, were clearly elevated. Copper and Fe displayed no correlation between the soil and oat concentrations, indicating that the plant-uptake mechanisms are much more important than variations in geochemistry. It was suggested that the NH4Ac-EDTA solution was not efficient in extracting Fe and Cu, which shows that these metals are bound in relatively immobile oxyhydroxides.;

Impact of mitigation strategies on acid sulfate soil chemistry and microbial community

Potential acid sulfate soils contain reduced iron sulfides that if oxidized, can cause significant environmental damage by releasing large amounts of acid and metals. This study examines metal and acid release as well as the microbial community capable of catalyzing metal sulfide oxidation after treating acid sulfate soil with calcium carbonate (CaCO3) or calcium hydroxide (Ca(OH)2). Leaching tests of acid sulfate soil samples were carried out in the laboratory. The pH of the leachate during the initial flushing with water lay between 3.8 and 4.4 suggesting that the jarosite/schwertmannite equilibrium controls the solution chemistry. However, the pH increased to circa 6 after treatment with CaCO3 suspension and circa 12 after introducing Ca(OH)2 solution. 16S rRNA gene sequences amplified from community DNA extracted from the untreated and both CaCO3 and Ca(OH)2 treated acid sulfate soils were most similar to bacteria (69.1% to 85.7%) and archaea (95.4% to 100%) previously identified from acid and metal contaminated environments. These species included a Thiomonas cuprina-like and an Acidocella-like bacteria as well as a Ferroplasma acidiphilum-like archeon. Although the CaCO3 and Ca(OH)2 treatments did not decrease the proportion of microorganisms capable of accelerating acid and metal release, the chemical effects of the treatments suggested their reduced activity.

Chemical and microbiological evaluation of novel chemical treatment methods for acid sulfate soils

Naturally occurring sulfide rich deposits are common along the northern Baltic Sea coast that when exposed to air, release large amounts of acid and metals into receiving water bodies. This causes severe environmental implications for agriculture, forestry, and building of infrastructure. In this study, we investigated the efficiency of ultrafine-grained calcium carbonate and peat (both separately and in combination) to mitigate acid and metal release. The experiments were carried out aerobically that mimicked summer conditions when the groundwater level is low and acid sulfate soils are exposed to oxygen, and anaerobically that is similar to autumn to spring conditions. The ultrafine-grained calcium carbonate dissipated well in the soil and its effect alone and when mixed with peat raised the pH and reduced pyrite dissolution while peat alone was similar to the controls and did not halt metal and acid release. High throughput 16S rRNA gene sequencing identified populations most similar to characterized acidophiles in the control and peat treated incubations while the acidophilic like populations were altered in the calcium carbonate alone and calcium carbonate plus peat treated acid sulfate soils. Coupled with the geochemistry data, it was suggested that the acidophiles were inactivated by the high pH in the presence of calcium carbonate but catalyzed pyrite dissolution in the controls and peat incubations. In conclusion, the anaerobic conditions during winter would likely be sufficient to mitigate acid production and metal release from acid sulfate soils and in the summer, treatment with calcium carbonate was the best mitigation method.