Early diagenetic vivianite [Fe-3(PO4)(2) center dot 8H(2)O] in a contaminated freshwater sediment and insights into zinc uptake: a mu-EXAFS, mu-XANES and Raman study

The sediments in the Salford Quays, a heavily-modified urban water body, contain high levels of organic matter, Fe, Zn and nutrients as a result of past contaminant inputs. Vivianite [Fe3(PO4)2 · 8H2O] has been observed to have precipitated within these sediments during early diagenesis as a result of the release of Fe and P to porewaters. These mineral grains are small (<100 μm) and micron-scale analysis techniques (SEM, electron microprobe, μ-EXAFS, μ-XANES and Raman) have been applied in this study to obtain information upon the structure of this vivianite and the nature of Zn uptake in the mineral. Petrographic observations, and elemental, X-ray diffraction and Raman spectroscopic analysis confirms the presence of vivianite. EXAFS model fitting of the FeK-edge spectra for individual vivianite grains produces Fe–O and Fe–P co-ordination numbers and bond lengths consistent with previous structural studies of vivianite (4O atoms at 1.99–2.05 Å; 2P atoms at 3.17–3.25 Å). One analysed grain displays evidence of a significant Fe3+ component, which is interpreted to have resulted from oxidation during sample handling and/or analysis. EXAFS modelling of the Zn K-edge data, together with linear combination XANES fitting of model compounds, indicates that Zn may be incorporated into the crystal structure of vivianite (4O atoms at 1.97 Å; 2P atoms at 3.17 Å). Low levels of Zn sulphate or Zn-sorbed goethite are also indicated from linear combination XANES fitting and to a limited extent, the EXAFS fitting, the origin of which may either be an oxidation artifact or the inclusion of Zn sulphate into the vivianite grains during precipitation. This study confirms that early diagenetic vivianite may act as a sink for Zn, and potentially other contaminants (e.g. As) during its formation and, therefore, forms an important component of metal cycling in contaminated sediments and waters. Furthermore, for the case of Zn, the EXAFS fits for Zn phosphate suggest this uptake is structural and not via surface adsorption

Phosphorus–iron interaction in sediments : can an electrode minimize phosphorus release from sediments?

All restoration strategies to mitigate eutrophication depend on the success of phosphorus (P) removal from the water body. Therefore, the inputs from the watershed and from the enriched sediments, that were the sink of most P that has been discharged in the water body, should be controlled. In sediments, iron (hydr)oxides minerals are potent repositories of P and the release of P into the water column may occur upon dissolution of the iron (hydr)oxides mediated by iron reducing bacteria. Several species of these bacteria are also known as electroactive microorganisms and have been recently identified in lake sediments. This capacity of bacteria to transfer electrons to electrodes, producing electricity from the oxidation of organic matter, might play a role on P release in sediments. In the present work it is discussed the relationship between phosphorus and iron cycling as well as the application of an electrode to work as external electron acceptor in sediments, in order to prevent metal bound P dissolution under anoxic conditions.The authors are grateful to two anonymous reviewers of a previous version of the manuscript for the constructive comments and suggestions. The authors also acknowledge the Grant SFRH/BPD/80528/2011 from the Foundation for Science and Technology, Portugal, awarded to Gilberto Martins

Speciation forms of phosphorus in bottom sediments of three selected anthropogenic reservoirs with different trophy degree

The study presents the results of the research into different phosphorus forms in the bottom sediments of anthropogenic limnic ecosystems i.e. The reservoirs of Pławniowice, Rybnik and Goczałkowice (SP). The bottom sediments of dam reservoirs were investigated by chemical extraction procedure for phosphorus forms. The lowest value of the mean AAP form percentage in the Pławniowice bottom sediments reflected the effect of reclamation with the hypolimnetic removal that had been conducted in the reservoir since 2003. The highest percentage of the RDP form (2%) was found in the Goczałkowice bottom sediments. The order of the specific speciation forms in the bottom sediments of the examined reservoirs was: Rybnik: AAP > EP > WDP > RDP; 4,630> 3,740 > 117 > 65 > 3.5 mgP/kg Pławniowice: AAP > EP > WDP > RDP; 916 > 783 > 107 > 15 > 1.4 mgP/kg Goczałkowice: AAP > WDP > EP > RDP; 686 > 628 > 51 > 7 > 0.14 mgP/kg The mutual correlations between the phosphorus speciation forms (AAP : EP : WDP : RDP) were as follows: Rybnik: 1,323 : 1,068 : 33 : 18 : 1; Pławniowice: 654 : 559 : 76 : 11 : 1; Goczałkowice: 4,900 : 4,485 : 364 : 50 : 1. The comparison of the mean concentration values for specific phosphorus forms in the bottom sediments of the three investigated reservoirs demonstrated that the Rybnik sediments had the highest contents of phosphorus. The contents in Pławniowice and Goczałkowice were 5-7 times lowe

Methane production increases with warming and carbon additions to incubated sediments from a semiarid reservoir

<p>Methane production (MP) in aquatic systems is positively related to temperature and trophic state. Global warming and eutrophication are predicted to potentiate MP in freshwater reservoirs. The simultaneous impact of rising temperature and carbon and nutrient additions on MP were examined in a tropical semiarid hydropower reservoir. Sediments cores from 3 locations (profundal, littoral, and intermediate) with differing water depth were sectioned and slurries incubated at 20, 30, and 40 °C with or without additions of carbon, nitrogen, or phosphorus, or all combined. Maximal MP (4.2 μmol g DW⁻¹ d⁻¹), occurred under carbon addition, and mean MP was about twice as high than in the control, independent of temperature. The effect of carbon additions manifested differently at the 3 locations, with enhancement of MP greater in upper sediment layers of the profundal location and in deeper layers (4–8 cm) of littoral and intermediate locations. Without carbon addition, MP was slower and positive effects of warming were more frequent, especially in littoral. These results suggest that the combined effect of warming and land use changes, principally on carbon loads, will increase the MP and methane emissions potential in this semiarid reservoir. Differences in effects are linked to location in the reservoir.</p

Restoration of a eutrophic hard-water lake by applying an optimised dosage of poly-aluminium chloride (PAC)

Feldberger Haussee (NE Germany) was polluted for almost a century. During the late 1970s, the nutrient input reached a maximum of approximately 1.9/11.5 g TP/TN m−2 yr−1. As a result, the lake became a hypertrophic ecosystem and had largely lost its recreational value. In 1980, the sewage discharge was stopped, decreasing the external loading by approximately 90%. Because of vast amounts of phosphorus stored in the sediment, the lake remained highly eutrophic until 1985 with a TP concentration of ca. 1 mg L−1. To accelerate recovery, biomanipulation was applied from 1985 to 2002 but was successful to only a minor extent. Eventually, due to sediment sequestration and discharge to downstream lakes the TP spring maximum (2006–2010) dropped to 0.112–0.078 mg L−1. However, given the trend, it was obvious that it would take another 10–15 years for the concentration to approach the desired mesotrophic level. Thus, it was suggested to inactivate the surplus phosphorus by treating the lake with poly-aluminium chloride (PAC) as precipitant. To ensure good water quality, the objective was to decrease concentrations below 0.035 mg TP L−1, while optimising the amount of PAC applied (as much as needed, but as little as possible). As a prerequisite, the status of the lake was carefully studied; external phosphorus loading and the amount of mobile phosphorus stored in the sediment being of specific interest. Laboratory experiments, modelling studies and field observations eventually resulted in an estimated dosage of 27 g Al m−2 (molar Al/P 12). Following the treatment in April 2011, prime water quality parameters showed two opposing trends: (1) TP concentration immediately dropped below the restoration target (≤0.025/0.035 mg L−1), primary production and phytoplankton biomass declined substantially. (2) However, water clarity did not improve for another four years. The likely reason for the delay was the structure of the phytoplankton community. It was dominated by cyanobacteria with the potential to trigger intensive calcite precipitation and thus impair transparency. In spring 2015, the cyanobacteria suddenly disappeared and transparency increased significantly. We speculate that these changes of the planktonic community shifted the ratio of assimilation and respiration in favour of the latter. This allowed an increase of free CO2* (dissolved CO2 &amp; dissociated carbonic acid) altering the carbonate buffering system and thus halting the formation of calcite crystals. Also, the phytoplankton, now represented by small readily ingestible taxa, promoted a flourishing Daphnia population inflicting heavy grazing losses, resulting in clear water stages (2015 June, 4.20 m; 2016, August 3.70 m; 2017 August, 4.5 m). We conclude that the drastic decrease of phosphorus availability in concert with structural and functional changes of the plankton community eventually improved the water quality of Haussee significantly. The lake is now in a mesotrophic status; well in accordance with the aim of the restoration project