Occurrence of orthophosphate monoesters in lake sediments: significance of myo- and scyllo-inositol hexakisphosphate.

Orthophosphate monoesters often constitute a significant fraction of total phosphorus in lake sediments. The knowledge on the specific composition and recalcitrance of these compounds is however limited. The main aim was therefore to identify and quantify specific orthophosphate monoesters in sediment from 15 Danish lakes by solution (31)P NMR spectroscopy. The four most quantitatively important orthophosphate monoesters were myo-inositol hexakisphosphate (myo-IP(6)), scyllo-inositol hexakisphosphate (scyllo-IP(6)) α-glycerophosphate (α-GP) and ß-glycerophosphate (ß-GP). The compounds were identified in 9, 4, 8 and in all 15 lakes, respectively. In total these four components made up 46-100% of the orthophosphate monoester pool. The glycerophosphates (GPs) are most likely degradation products of phospholipids, created as an artifact by the alkaline extraction procedure used for (31)P NMR spectroscopy, while the inositol hexakisphosphates (IPs) are naturally occurring compounds. There was a significant positive correlation between myo-IP(6) and total aluminium in the sediment and a negative correlation between myo-IP(6) and lake water pH, suggesting that myo-IP(6) is stabilized in the sediment by adsorption at slightly acidic or neutral conditions. In three lakes, the depth distribution of the orthophosphate monoesters was investigated. The content of scyllo-IP(6) and myo-IP(6) was constant with sediment depth in two of the lakes while the content of myo-IP(6) decreased with depth in one of the lakes. In all cases the IPs seem to be preserved with sediment depth to a higher extent than the orthophosphate diesters and especially the GPs suggesting that IPs can be a sink for phosphorus in the lake ecosystem or at least delay P-recycling for years.

The Role of Groundwater for Lake-Water Quality and Quantification of N Seepage.

The heterogeneous nature of both groundwater discharge to a lake (inflow) and nitrate concentrations in groundwater can lead to significant errors in calculations of nutrient loading. Therefore, an integrated approach, combining groundwater flow and transport modelling with observed nitrate and ammonium groundwater concentrations, was used to estimate nitrate loading from a catchment via groundwater to an oligotrophic flow-through lake (Lake Hampen, Denmark). The transport model was calibrated against three vertical nitrate profiles from multi-level wells and 17 shallow wells bordering a crop field near the lake. Nitrate concentrations in groundwater discharging to the lake from the crop field were on average 70 times higher than in groundwater from forested areas. The crop field was responsible for 96% of the total nitrate loading (16.2 t NO3 /year) to the lake even though the field only covered 4.5% of the catchment area. Consequently, a small change in land use in the catchment will have a large effect on the lake nutrient balance and possible lake restoration. The study is the first known attempt to estimate the decrease of nitrate loading via groundwater to a seepage lake when an identified catchment source (a crop field) is removed.

Phosphate adsorption by lanthanum modified bentonite clay in fresh and brackish water.

Effects of pH, alkalinity and conductivity on the adsorption of soluble reactive phosphorus (SRP) onto lanthanum (La) modified bentonite clay (Phoslock(®)) were investigated in laboratory experiments using eight different types of filtered water representing freshwater with low and normal alkalinity and brackish water with high alkalinity. Different dose ratios (0-200; w/w) of Phoslock(®):P were applied to determine the maximum P binding capacity of Phoslock(®) at SRP concentrations typical of those of sediment pore water. The 100:1 Phoslock(®:)P dose ratio, recommended by the manufacturer, was tested with 12 days exposure time and generally found to be insufficient at binding whole target SRP pool. The ratio performed best in the soft water from Danish Lake Hampen and less good in the hard water from Danish Lake Langesø and in brackish water. The explanation may be an observed negative relationship between alkalinity and the SRP binding capacity of Phoslock(®). A comparative study of Lake Hampen and Lake Langesø suggested that the recorded differences in P adsorption between the two lakes could be attributed to a more pronounced dispersion of Phoslock(®) in the soft water of Lake Hampen, leading to higher fractions of dissolved (<0.2 µm) La and of La in fine particles. In the same two lakes, pH affected the SRP binding of Phoslock(®) negatively at a pH level above 8.1, the effect being reversible, however. The negative pH effect was most significant in hard water Lake Langesø, most likely because of higher [Formula: see text] concentrations.

Chemical lake restoration products: sediment stability and phosphorus dynamics.

Laboratory experiments with sediments from three shallow Danish lakes were conducted to evaluate the effects of chemical lake restoration products during resuspension. Phosphorus (P) removal, sediment stability, sediment consolidation and color reduction were studied over time. The investigated products were aluminum (Al), Phoslock (a commercial bentonite product coated with lanthanum) and a combination of Al covered with bentonite (Al/Ben). All treatments effectively reduced the P concentration in the water. However, the treatments containing Al reduced the P concentration immediately after resuspension, whereas Phoslock required several days after resuspension to reduce the P concentration. Especially Phoslock, but also Al/Ben, increased the sediment stability threshold by 265% and 101%, respectively, whereas Al had no stabilizing effect. The fresh Al floc was resuspended 5x easier than untreated sediment. The largest consolidation of the sediment occurred with addition of Phoslock, followed by Al/Ben, while Al alone had no effect. Enhanced consolidation may be of importance for macrophyte colonisation of organic sediment. Phoslock improved the light climate moderately by removing color, whereas Al was very effective in removing color. Ben/Al showed intermediate effects on color reduction. These findings are important when decisions are made on restoration method for a specific lake, which may be more or less wind exposed.

Identification of dissolved nonreactive phosphorus in freshwater by precipitation with aluminum and subsequent 31P NMR analysis.

Little information exists on nonreactive phosphorus (nrP) in the water column, because the concentration is much lower than that in the sediment. Here we present a novel method for up-concentration and identification of nrP in lake water: nrP is precipitated with poly aluminum chloride and the precipitate is subsequently recovered and dissolved by NaOH. Additional up-concentration by rotary evaporation increases P concentrations up to 5500 times. Furthermore, there is only a low up-concentration of paramagnetic metals. The method is sensitive and easy to use. Bottom water from five Danish lakes was sampled in autumn 2008 and in four of the five lakes orthophosphate monoesters constituted the largest fraction of nrP (50-86%), whereas DNA-P was the largest fraction in the fifth lake (67%). The pyro-P/poly-P concentration varied between 0 and 33% of nrP in the lakes. Thus, most of the P compounds usually found in lake sediments were also found in the bottom water of these lakes.

Phosphate adsorption by fresh and aged aluminum hydroxide. Consequences for lake restoration.

Lake restoration by in-lake precipitation of PO4(3-) with Al(OH)3 is commonly used but there is currently no good guidelines for calculating doses (amounts and application) that can ensure long lasting effects. We studied the effect of aging of Al(OH)3 on PO4(3-) adsorption and desorption properties with and without PO4(3-) in solution and found that Al(OH)3 aged without PO4(3-) lost 75% of the maximum adsorption capacity in 90 days after which no further changes occurred. Al(OH)3 aged in presence of PO4(3-) maintained the adsorption capacity through 6 months and even increased it for PO4(3-) concentrations < 150 microM. On this basis, we suggest that repeated dosing of smaller Al-aliquots may be more efficient than adding a single big dose. Also, Al should be added at the time when PO4(3-) availability in the lake is highest. At laboratory conditions we obtained molar P:Al binding ratios of 0.12-0.19 at PO4(3-) concentrations similar to those in eutrophic lake sediments, but when examining Al(OH)3 aged in situ in two lake sediments lower ratios (approximately 0.1) were found. We suggest that total Al-dosage should be calculated relative to the pool of potential mobile P in the lake with a molar ratio not less than 10 Al: 1 P.

Lake restoration by dosing aluminum relative to mobile phosphorus in the sediment.

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).

Colonisation and molecular diversity of arbuscular mycorrhizal fungi in the aquatic plants Littorella uniflora and Lobelia dortmanna in southern Sweden.

The colonisation intensity and composition of the mycorrhizal community in the aquatic plants Lobelia dortmanna and Littorella uniflora were studied. The mycorrhizal fungi were characterised by fungal specific nested PCR and sequencing using the 5'-end of the LSU rDNA as target. For this, primers for the clade of Acaulospora, the clade including Glomus mosseae and G. intraradices and the clade containing G. etunicatum and G. claroideum were used. The nested PCR products were screened for different sequence types using single stranded conformation polymorphism (SSCP) and representatives for each type were sequenced. A phylogenetic analysis of the sequences showed two phylotypes of Acaulospora, one phylotype within the clade of G. etunicatum/G. claroideum and five within the G. mosseae/ G. intraradices clade. The colonisation intensity was comparable to that seen in typical grassland vegetation. The neutral lipid fatty acid 16: 1omega5 was seen to be indicative of mycorrhizal colonisation with concentrations up to 35 nmol mg(-1) root DW, which indicates that the fungi are active.