Phosphorus (P) binding groups were identified in phytoplankton, settling particles, and sediment profiles by 31 P NMR spectroscopy from the Swedish mesotrophic Lake Erken. The 31 P NMR analysis revealed that polyphosphates and pyrophosphates were abundant in the water column, but rapidly mineralized in the sediment. Orthophosphate monoesters and teichoic acids degraded more slowly than DNA-P, polyphosphates, and P lipids. Humic acids and organic acids from phytoplankton were precipitated from the NaOH extract by acidification and identified by 31 P NMR spectroscopy. The precipitated P was significantly more recalcitrant than the P compound groups remaining in solution, but does not constitute a major sink of P as it did not reach a stable concentration with depth, which indicates that it may eventually be degraded. Since P also precipitated from phytoplankton, the origin of humic-P can not be related solely to allochthonous P.

In the sediment of the shallow, hypertrophic Lake Sønderby, Denmark, potentially mobile phosphorus (Pmobile) was determined by a sequential extraction technique as the sum of porewater P, iron-bound P, and nonreactive P (i.e., polyphosphates and organic P). A good agreement was observed between loss rates of Pmobile in the top 10 cm of the sediment from winter to summer, P release rates measured in undisturbed sediment cores, and rates of P accumulation in the lake water from winter to summer (22, 32, and 30 mg of P m(-2) day(-1), respectively). This suggests that the operationally defined Pmobile was the sediment P fraction responsible for the internal loading in the lake. In autumn 2001, 11 mg of aluminum (Al) L(-1), equivalent to 31 g of Al m(-2), was added to the lake water. This dosage represented a 4:1 molar ratio between Al and Pmobile. The Al treatment significantly decreased lake water P, and P precipitated from the lake water was recovered as Al-bound P in the sediment after the treatment. Internal P loading was reduced by 93% in the two posttreatment years, relative to 2001. Accordingly, average summer concentrations of total P in lake water declined from 1.28 (SE = 0.17) and 1.3 (SE = 0.14) mg L(-1) in the two pretreatment years to 0.09 (SE = 0.01) and 0.13 (SE = 0.01) mg L(-1) in the posttreatment years. pH levels remained unchanged relative to pretreatment levels, while the total alkalinity was reduced from 3.2 (SE = 0.04) to 2.7 (SE = 0.03) mequiv L(-1).

The NERC and CEH trademarks and logos ('the Trademarks') are registered trademarks of NERC in the UK and other countries, and may not be used without the prior written consent of the Trademark owner.© 2015 Elsevier Ltd. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/ This version available http://nora.nerc.ac.uk/512349/ NERC has developed NORA to enable users to access research outputs wholly or partially funded by NERC. Copyright and other rights for material on this site are retained by the rights owners. Users should read the terms and conditions of use of this material at http://nora.nerc.ac.uk/policies.html#access NOTICE: this is the author's version of a work that was accepted for publication in Water Research. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. This paper reviews the scientific knowledge on the use of a lanthanum modified bentonite (LMB) to 25 manage eutrophication in surface water. The LMB has been applied in around 200 environments 26 worldwide and it has undergone extensive testing at laboratory, mesocosm, and whole lake scales. 27The available data underline a high efficiency for phosphorus binding. This efficiency can be 28 limited by the presence of humic substances and competing oxyanions. Lanthanum concentrations 29 detected during a LMB application are generally below acute toxicological threshold of different 30 organisms, except in low alkalinity waters. To date there are no indications for long-term negative 31 effects on LMB treated ecosystems, but issues related to La accumulation, increase of suspended 32 solids and drastic resources depletion still need to be explored, in particular for sediment dwelling 33 organisms. Application of LMB in saline waters need a careful risk evaluation due to potential 34 lanthanum release. 35 36

The NERC and CEH trademarks and logos ('the Trademarks') are registered trademarks of NERC in the UK and other countries, and may not be used without the prior written consent of the Trademark owner.© 2016 Elsevier Ltd. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/ This version available http://nora.nerc.ac.uk/513724/ NERC has developed NORA to enable users to access research outputs wholly or partially funded by NERC. Copyright and other rights for material on this site are retained by the rights owners. Users should read the terms and conditions of use of this material at http://nora.nerc.ac.uk/policies.html#access NOTICE: this is the author's version of a work that was accepted for publication in Water Research. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. load reduction. This is due to internal cycling of phosphorus (P). Geo-engineering, which we 30 can here define as activities intervening with biogeochemical cycles to control eutrophication 31 in inland waters, represents a promising approach, under appropriate conditions, to reduce P 32 release from bed sediments and cyanobacteria accumulation in surface waters, thereby 33 speeding up recovery. In this overview, we draw on evidence from this special issue 34Geoengineering in Lakes, and on supporting literature to provide a critical perspective on the 35 approach. We demonstrate that many of the strong P sorbents in the literature will not be 36 applicable in the field because of costs and other constraints. Aluminium and lanthanum 37 modified compounds are among the most effective compounds for targeting P. Flocculants 38 and ballast compounds can be used to sink cyanobacteria, in the short term. We emphasize 39 that the first step in managing eutrophication is a system analysis that will reveal the main 40 water and P flows and the biological structure of the waterbody. These site specific traits can 41 be significant confounding factors dictating successful eutrophication management. Geo-42 engineering techniques, considered collectively, as part of a tool kit, may ensure successful 43 management of eutrophication through a range of target effects. In addition, novel 44 developments in modified zeolites offer simultaneous P and nitrogen control. To facilitate 45 research and reduce the delay from concept to market a multi-national centre of excellence is 46 required. 47 48

No abstract

Phosphate (Pi) sequestration by a lanthanum (La) exchanged clay mineral (La-Bentonite), which is extensively used in chemical lake restoration, was investigated on the molecular level using a combination of (31)P and (139)La solid state NMR spectroscopy (SSNMR), extended X-ray absorption spectroscopy (EXAFS), powder X-ray diffraction (PXRD) and sorption studies. (31)P SSNMR show that all Pi was immobilized as rhabdophane (LaPO4·n H2O, n ≤ 3), which was further supported by (139)La SSNMR and EXAFS. However, PXRD results were ambiguous with respect to rhabdophane and monazite (LaPO4). Adsorption studies showed that at dissolved organic carbon (DOC) concentration above ca. 250 μM the binding capacity was only 50% of the theoretical value or even less. No other La or Pi phases were detected by SSNMR and EXAFS indicating the effect of DOC is kinetic. Moreover, (31)P SSNMR showed that rhabdophane formed upon Pi sequestration is in close proximity to the clay matrix.

The composition and abundance of phosphorus extracted by NaOH-ethylenediaminetetraacetic acid from anoxic Northwest Baltic Sea sediment was characterized and quantified using solution 31 P nuclear magnetic resonance. Extracts from sediment depths down to 55 cm, representing 85 yr of deposition, contained 18.5 g m 22 orthophosphate. Orthophosphate monoesters, teichoic acid P, microbial P lipids, DNA P, and pyrophosphate corresponded to 6.7, 0.3, 1.1, 3.0, and 0.03 g P m 22 , respectively. The degradability of these compound groups was estimated by their decline in concentration with sediment depth. Pyrophosphate had the shortest half-life (3 yr), followed by microbial P lipids with a half-life of 5 yr, DNA P (8 yr), and orthophosphate monoesters (16 yr). No decline in concentration with sediment depth was observed for orthophosphate or teichoic acid P.

114 lakes treated with aluminum (Al) salts to reduce internal phosphorus (P) loading were analyzed to identify factors driving longevity of post-treatment water quality improvements. Lakes varied greatly in morphology, applied Al dose, and other factors that may have affected overall treatment effectiveness. Treatment longevity based on declines in epilimnetic total P (TP) concentration averaged 11 years for all lakes (range of 0-45 years). When longevity estimates were used for lakes with improved conditions through the end of measurements, average longevity increased to 15 years. Significant differences in treatment longevity between deeper, stratified lakes (mean 21 years) and shallow, polymictic lakes (mean 5.7 years) were detected, indicating factors related to lake morphology are important for treatment success. A decision tree developed using a partition model suggested Al dose, Osgood index (OI, a morphological index), and watershed to lake area ratio (related to hydraulic residence time, WA:LA) were the most important variables determining treatment longevity. Multiple linear regression showed that Al dose, WA:LA, and OI explained 47, 32 and 3% respectively of the variation in treatment longevity. Other variables (too data limited to include in the analysis) also appeared to be of importance, including sediment P content to Al dose ratios and the presence of benthic feeding fish in shallow, polymictic lakes.