Abundant stocks and mobilization of elements in boreal acid sulfate soils
- Authors: Yli-Halla, Markku , Virtanen, Seija , Mäkelä, Minna , Simojoki, Asko , Hirvi, Mirva , Innanen, Saila , Mäkelä, Jaakko , Sullivan, Leigh
- Date: 2017
- Type: Text , Journal article
- Relation: Geoderma Vol. 308, no. (2017), p. 333-340
- Full Text: false
- Reviewed:
- Description: Large amounts of sulfate and divalent iron (Fe) are released into the pore water of acid sulfate (AS) soils upon oxidation of sulfidic materials. The simultaneously produced acidity dissolves metals from the soil matrix. Reduced horizons of AS soils commonly have a large mineral nitrogen (N) stock in the form of NH4 +-N, which is a potential source of N leaching and gaseous emissions. This study was carried out at three AS soil sites in Finland. Cation composition of pore water was monitored in a monolithic lysimeter experiment. Timothy samples grown in an AS soil were analysed for mineral elements and the soil was investigated for zinc (Zn) distribution in different chemical species at four depths down to 85 cm. The composition of pipestems formed in previous root channels was investigated by SEM, X-ray EDX and XRD. Emissions of CO2 and N2O were measured in an AS field which had a peaty topsoil. Monitoring by closed chambers was carried out at three sites differing in the depth of peat layer (15, 30 and 60 cm). In the sulfuric horizon, large amounts of calcium and magnesium were mobilized. Reflooding stopped the mobilization of those elements but resulted in abundant dissolution of Fe, which became the dominant cation in the pore water. Timothy growing in an AS soil showed only small deviations from the average composition measured in Finland with the exception of Zn that was at the deficiency level. As Zn in the root zone had been dissolved and subsequently leached, it was recovered in easily soluble forms in the subsoil. Pipestem composition indicated accumulation of Fe and formation of a new solid phase probably mostly in the form of schwertmannite even though jarosite was also detected. The annual CO2 emissions from the peaty AS soil were about 6000 kg C ha− 1 but the N2O emissions were relatively small, with a magnitude more typical of mineral rather than organic soils. Thus, large N stock of an AS soil do not necessarily contribute to abundant gaseous N emissions. © 2017 Elsevier B.V.
Schwertmannite in soil materials : Limits of detection of acidified ammonium oxalate method and differential X-ray diffraction
- Authors: Vithana, Chamindra , Sullivan, Leigh , Bush, Richard , Burton, Edward
- Date: 2015
- Type: Text , Journal article
- Relation: Geoderma Vol. 249-250, no. (2015), p. 51-60
- Full Text: false
- Reviewed:
- Description: Schwertmannite is a secondary iron mineral, found in acid mine drainage (AMD) and acid sulfate soils (ASS), that generates acidity when it transforms to stable mineral phases. Acidity liberated during schwertmannite transformation can seriously diminish water quality and soil health. Acidified ammonium oxalate (AAO) extraction in the dark coupled with differential X-ray diffraction (DXRD) analysis is routinely used to identify and to quantify poorly crystalline iron oxide phases such as schwertmannite in AMD environments. However, management of ASS environments is largely impacted due to lack of reliable methods to identify/quantify schwertmannite in soil materials. Our study aimed to evaluate the 15. min AAO extraction method to identify/quantify schwertmannite in soil materials. We extracted soil samples spiked with synthetic and natural schwertmannite (termed as natural organic rich schwertmannitic material) with acidified ammonium oxalate (AAO) for 15. min. We also examined soil samples spiked with schwertmannite through the DXRD analysis under ideal conditions assuming that only schwertmannite would dissolve during the extraction. Our data show that synthetic schwertmannite dissolved partially during the 15. min AAO extraction and as a result the recovered Fe content from schwertmannite-spiked soils was underestimated by ~. 20%. The data also show that soil materials could also influence the recovery of schwertmannite. Fe/S molar ratios of schwertmannite spiked at higher rates (2% and 5%) were closer to the expected ratios. In addition to schwertmannite, goethite and other unidentified minerals in natural organic rich schwertmannitic material also dissolved during the 15. min extraction time. The DXRD analysis data show that schwertmannite in soil materials at contents >. 5% may be identifiable through this approach. Our findings highlight that both the 15. min AAO extraction procedure and the DXRD analysis have limited applicability towards detecting schwertmannite accurately in soil materials. © 2015 Elsevier B.V.
A sequential extraction procedure for acid sulfate soils : Partitioning of iron
- Authors: Claff, Salirian , Sullivan, Leigh , Burton, Edward , Bush, Richard
- Date: 2010
- Type: Text , Journal article
- Relation: Geoderma Vol. 155, no. 3-4 (2010), p. 224-230
- Full Text: false
- Reviewed:
- Description: A new sequential extraction scheme for acid sulfate soil materials has been evaluated for iron partitioning in a range of synthetic iron-bearing minerals and natural acid sulfate soil materials. This sequential extraction procedure employs six steps to quantify (1) exchangeable (magnesium chloride extractable), (2) acid (hydrochloric acid) soluble, (3) reactive organic-bound (pyrophosphate extractable), (4) crystalline oxide (citrate buffered dithionite (CBD)) extractable, (5) pyrite-bound (nitric acid extractable) and (6) residual (acid/peroxide digestible) forms of iron. Given its intended use for acid sulfate soil materials that frequently contain pyrite, a primary aim of this new sequential extraction procedure was to differentiate iron bound in pyrite from iron contained in other minerals. The results demonstrated that dissolution of pyrite was effectively isolated in the pyrite-bound extraction step, with dissolution of other iron mineral phases (i.e. akaganeite, ferrihydrite, goethite, hematite, jarosite, magnetite, and schwertmannite) occurring within the other five extraction steps. Following a systematic examination of these synthetic iron mineral phases, the sequential extraction scheme was applied to an acid sulfate soil profile, with detailed data presented for two soil layers: one representative of the sulfidic (unoxidised) conditions, and the other sulfuric (oxidised) conditions. Partitioning data for pyrite-bound iron in the acid sulfate soil profile showed good agreement with that calculated via the independently measured pyrite-bound reduced sulfur. This study indicates that the new sequential extraction procedure is suitable for the assessment of iron partitioning in acid sulfate soil materials. © 2009 Elsevier B.V. All rights reserved.
Pore water sampling in acid sulfate soils : A new peeper method
- Authors: Johnston, Scott , Burton, Edward , Keene, Annabelle , Bush, Richard , Sullivan, Leigh , Isaacson, Lloyd
- Date: 2009
- Type: Text , Journal article
- Relation: Journal of Environmental Quality Vol. 38, no. 6 (2009), p. 2474-2477
- Full Text: false
- Reviewed:
- Description: This study describes the design, deployment, and application of a modified equilibration dialysis device (peeper) optimized for sampling pore waters in acid sulfate soils (ASS). The modified design overcomes the limitations of traditional-style peepers, when sampling firm ASS materials over relatively large depth intervals. The new peeper device uses removable, individual cells of 25 mL volume housed in a 1.5 m long rigid, high-density polyethylene rod. The rigid housing structure allows the device to be inserted directly into relatively firm soils without requiring a supporting frame. The use of removable cells eliminates the need for a large glove-box after peeper retrieval, thus simplifying physical handling. Removable cells are easily maintained in an inert atmosphere during sample processing and the 25-mL sample volume is sufficient for undertaking multiple analyses. A field evaluation of equilibration times indicates that 32 to 38 d of deployment was necessary. Overall, the modified method is simple and effective and well suited to acquisition and processing of redox-sensitive pore water profiles > 1 m deep in acid sulfate soil or any other firm wetland soils. Copyright © 2009 by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America. All rights reserved.