The impact of climate change and eutrophication on phosphorus forms in sediment: Results from a long-term lake mesocosm experiment.

Characteristics of bottom sediments in lake mesocosms 11 years after starting the experiment were studied in order to determine the effects of nutrient loading, temperature increase and vegetation type on concentration and vertical distribution of phosphorus (P) forms. The experimental setup consisted of 24 outdoor flow-through mesocosms with two nutrient treatments - low (L) and high (H) and 3 temperature levels - ambient (T0), heated by 2-4 °C (T1) and 3-6 °C (T2) in four replicates. Thickness of the organic sediment was measured and the sediment analysed for dry weight, organic matter, and P fractions (according to a sequential extraction scheme) and organic P compounds (by 31P nuclear magnetic resonance spectroscopy). Higher nutrient loading led to increased sediment accumulation and higher concentration of total P and most P fractions, except P bound to aluminium and humic matter. The dominant vegetation type covaried with nutrient levels. Vertical gradients in Ca bound P and mobile P in low nutrient mesocosms was perhaps a result of P coprecipitation with calcite on macrophytes and P uptake by roots indicating that in macrophyte-rich lakes, plants can be important modifiers of early P diagenesis. Temperature alone did not significantly affect sediment accumulation rate but the interaction effect between nutrient and temperature treatments was significant. At high nutrient loading, sediment thickness decreased with increasing temperature, but at low nutrient loading, it increased with warming. The effect of warming on sediment composition became obvious only in nutrient enriched mesocosms showing that eutrophication makes shallow lake ecosystems more susceptible to climate change.

The combined effects of macrophytes (Vallisneria denseserrulata) and a lanthanum-modified bentonite on water quality of shallow eutrophic lakes: A mesocosm study.

Establishment of submerged macrophyte beds and application of chemical phosphorus inactivation are common lake restoration methods for reducing internal phosphorus loading. The two methods operate via different mechanisms and may potentially supplement each other, especially when internal phosphorous loading is continuously high. However, their combined effects have so far not been elucidated. Here, we investigated the combined impact of the submerged macrophyte Vallisneria denseserrulata and a lanthanum-modified bentonite (Phoslock®) on water quality in a 12-week mesocosm experiment. The combined treatment led to stronger improvement of water quality and a more pronounced reduction of porewater soluble reactive phosphorus than each of the two measures. In the combined treatment, total porewater soluble reactive phosphorus in the top 10 cm sediment layers decreased by 78% compared with the control group without Phoslock® and submerged macrophytes. Besides, in the upper 0-1 cm sediment layer, mobile phosphorus was transformed into recalcitrant forms (e.g. the proportion of HCl-P increased to 64%), while in the deeper layers, (hydr)oxides-bound phosphorus species increased 17-28%. Phoslock®, however, reduced the clonal growth of V. denseserrulata by 35% of biomass (dry weight) and 27% of plant density. Our study indicated that Phoslock® and submerged macrophytes may complement each other in the early stage of lake restoration following external nutrient loading reduction in eutrophic lakes, potentially accelerating the restoration process, especially in those lakes where the internal phosphorus loading is high.

An Assessment of the Multifunctionality of Integrated Buffer Zones in Northwestern Europe.

Integrated buffer zones (IBZs) have recently been introduced in the Northwestern Europe temperate zone to improve delivery of ecosystem services compared with the services associated with long-established vegetated buffer zones. A common feature of all the studied IBZ sites is that tile drainage, which previously discharged directly into the streams, is now intercepted within the IBZ. Specifically, the design of IBZs combines a pond, where soil particles present in drain water or surface runoff can be deposited, and a planted subsurface flow infiltration zone. Together, these two components should provide an optimum environment for microbial processes and plant uptake of nutrients. Nutrient reduction capacities, biodiversity enhancement, and biomass production functions were assessed with different emphasis across 11 IBZ sites located in Denmark, Great Britain, and Sweden. Despite the small size of the buffer zones (250-800 m) and thus the small proportion of the drained catchment (mostly <1%), these studies cumulatively suggest that IBZs are effective enhancements to traditional buffer zones, as they (i) reduce total N and P loads to small streams and rivers, (ii) act as valuable improved habitats for aquatic and amphibian species, and (iii) offer economic benefits by producing fast-growing wetland plant biomass. Based on our assessment of the pilot sites, guidance is provided on the implementation and management of IBZs within agricultural landscapes.

Evaluation of dried amorphous ferric hydroxide CFH-12® as agent for binding bioavailable phosphorus in lake sediments.

Metal hydroxides formed from aluminum (Al) and iron (Fe) salts can be used as phosphorus (P) adsorbents in lake restoration, but the application entails problems in low-alkaline lakes due to acid producing hydrolysis and potential formation of toxic metal ions. Therefore, we tested the potential of applying CFH-12® (Kemira) - a dried, amorphous Fe-oxide with no pH effect - in lake restoration. Since Fe3+ may become reduced in lake sediments and release both Fe2+ and any associated P we also evaluated the redox sensitivity of CFH-12® in comparison with freshly formed Fe(OH)3. CFH-12® was added to undisturbed sediment cores from three Danish lakes relative to the size of their mobile P pool (molar Fe:PMobile dose ratio of ~10:1), and P and Fe fluxes across the sediment-water interface were compared with those from untreated cores and cores treated with freshly formed Fe(OH)3. Under anoxic conditions, we found that CFH-12® significantly reduced the P efflux from the sediments (by 43% in Lake Sønderby, 70% in Lake Hampen and 60% in Lake Hostrup) while the Fe2+ efflux remained unchanged relative to the untreated cores. Cores treated with freshly formed Fe(OH)3 retained more P, but released significantly more Fe2+, indicating continued Fe3+ reduction. Finally, experiments with pure phases showed that CFH-12® adsorbed less P than freshly formed Fe(OH)3 in the short term, but was capable of adsorbing up to 70% of P adsorbed by Fe(OH)3 over 3months. With product costs only 30% higher than Al salts we find that CFH-12® has potential for use in restoration of low-alkaline lakes.

Nitrogen and Phosphorus Removal from Agricultural Runoff in Integrated Buffer Zones.

Integrated buffer zones (IBZs) represent a novel form of edge-of-field technology in Northwest Europe. Contrary to the common riparian buffer strips, IBZs collect tile drainage water from agricultural fields by combining a ditch-like pond (POND), where soil particles can settle, and a flow-through filter bed (FILTERBED) planted with Alnus glutinosa (L.), a European alder (black alder). The first experimental IBZ facility was constructed and thoroughly tested in Denmark for its capability to retain various nitrogen (N) and phosphorus (P) species within the first three years after construction. We calculated the water and nutrient budget for the total IBZ and for the two compartments, POND and FILTERBED, separately. Furthermore, a tracer experiment using sodium bromide was conducted in order to trace the water flow and estimate the hydraulic residence time in the FILTERBEDs. The monthly average removal efficiency amounted to 10-67% for total N and 31-69% for total P, with performance being highest during the warm season. Accordingly, we suggest that IBZs may be a valuable modification of dry buffer strips in order to mitigate the adverse impacts of high nutrient loading from agricultural fields on the aquatic environment.

The influence of lake water alkalinity and humic substances on particle dispersion and lanthanum desorption from a lanthanum modified bentonite.

A 12 days laboratory study on potential desorption of Lanthanum (La) from a commercial La modified clay (Phoslock) was conducted using lake water from 17 Danish lakes with alkalinities between 0.02 and 3.7 meq L-1 and varying concentrations of DOC and humic acids (HA's). A similar study was conducted in artificial lake water with alkalinities from 0 to 2.5 meq L-1in order to exclude interference from dissolved HA's. To test if La in solution (FLa) was associated with fine particles, the water samples were filtered sequentially through three filter sizes (1.2 µm, 0.45 µm and 0.2 µm), and finally, ultracentrifugation was used in an attempt to separate colloidal La from dissolved La. The study showed that higher FLa (up to 2.5 mg L-1 or 14% of the total La in the Phoslock) concentrations were found in soft water lakes compared to hard water lakes, probably due to dispersion of the clay at low alkalinities. In addition, this study showed that HA's seem to increase the FLa concentrations in soft water lakes, most likely through complexation of La retained in the Phoslock matrix. In summary, we conclude that elevated La concentrations in lake water after a Phoslock treatment should only be expected in soft water lakes rich in DOC and HA's.

The importance of catchment vegetation for alkalinity, phosphorus burial and macrophytes as revealed by a recent paleolimnological study in a soft water lake.

The land use within a catchment may markedly affect the environmental conditions in a lake and the storage capability of its sediments. This study investigated how changes in the dominant catchment vegetation (from local stands of deciduous trees over extensive heathland with some agriculture to mainly coniferous forest) occurring during the last ca. 200years were reflected in the sediments of a soft water lake and how these changes influenced the lake ecosystem. Pollen, macrofossils, metals, different phosphorus (P) forms, organic matter, carbon and nitrogen contents were determined in short sediment cores. This novel combination of proxies revealed that 1) the reduction of deciduous trees in the watershed seemingly reduced the calcium (Ca) supply to the lake and thereby its buffering capacity. This development was accompanied by decreased abundances of Ca-dependent species and subsequent increases in acidophilic species. 2) The sedimentary contents of organic matter, non-reactive P and humic-bound P were evidently higher in sediments deposited during the time when deciduous trees were abundant, which is probably linked to a stabilising effect by Ca. 3) An erosion event clearly reduced the amounts of macrofossils of isoetid species and characeans, indicating a reduction in their maximum distribution depth because of lower water transparency. Overall, the results of our paleolimnological study are of importance within lake management by convincingly showing how land use changes may (irreversibly) affect environmental conditions and species composition in soft water lakes and the storage of organic matter and P in their sediments.

Phosphate adsorption to iron sludge from waterworks, ochre precipitation basins and commercial ferrihydrite at ambient freshwater phosphate concentrations.

Measures such as storm water ponds, constructed wetlands and buffer strips along streams are used to reduce diffuse phosphorus (P) loading to surface waters. These systems often retain particulate P well, whereas the retention of dissolved P is less efficient and might require addition of P adsorbents. In this study, we screened waterwork ochre sludge (WWS) originating from groundwater treatment and ochre sludge from ochre precipitation basins along streams for their applicability as P adsorbents at ambient P concentrations. We compared with a commercial ferric hydroxide (CFH 12™) for which adsorption properties is well described. The adsorption capacity of 9 products was measured over 24 h at different P concentrations (5-2000 µg L-1), a range that covers Danish drainage water and stormwater. WWS desorbed phosphate at concentrations below 50-200 µg P L-1 and should only be considered for use in systems with a constantly high load of dissolved P. High affinity combined with little or no desorption characterized the commercial product and the ochre sludge from the precipitation basins, rendering these useful for treating drainage water and storm water. The study underlines that waste products may act as potentially effective P adsorbers at environmentally relevant P levels.

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.

pH dependent dissolution of sediment aluminum in six Danish lakes treated with aluminum.

The possible pH dependent dissolution of aluminum hydroxides (Al(OH)(3)) from lake sediments was studied in six lakes previously treated with Al to bind excess phosphorus (P). Surface sediment was suspended for 2 h in lake water of pH 7.5, 8.5, or 9.5 with resulting stepwise increments in dissolved Al observed in all lakes. The amount of dissolved Al increased proportional to the sediment content of Al(OH)(3) as quantified by a sequential extraction technique. Up to 24% of the sediment Al(OH)(3) could dissolve within 2 h at pH 9.5 and a portion of sediment P was dissolved concomitantly. Lowering pH to 7 caused 30-100% of the dissolved Al to precipitate again after 24 h. Re-precipitation of mobilized P varied from 50% to more than 100%. A test with untreated sediment showed the same proportionality which means that also indigenous Al(OH)(3) can dissolve frequently in lakes with high pH water. Release rates of dissolved Al from intact sediment cores at the same three pH values was measured in three of the lakes, and showed increased Al release rates at pH 8.5 in one of the lakes and 9.5 in two of the lakes. Our study demonstrates a risk of dissolution of sediment Al(OH)(3) to form aluminate in shallow lakes, where resuspension and high pH in the water occurs frequently. In the worst case dissolved Al may reach toxic levels in lakes treated by Al but also the concomitant release of P and the possible loss of dissolved Al to downstream ecosystems are negative effects that may occur already at more modest dissolution of Al(OH)(3) and Al-bound P.

Vivianite precipitation and phosphate sorption following iron reduction in anoxic soils.

Phosphorus retention in lowland soils depends on redox conditions. The aim of this study was to evaluate how the Fe(III) reduction degree affects phosphate adsorption and precipitation. Two similarly P-saturated, ferric Fe-rich lowland soils, a sandy and a peat soil, were incubated under anaerobic conditions. Mössbauer spectroscopy demonstrated that Fe(III) in the sandy soil was present as goethite and phyllosilicates, whereas Fe(III) in the peat soil was mainly present as polynuclear, Fe-humic complexes. Following anoxic incubation, extensive formation of Fe(II) in the solids occurred. After 100 d, the Fe(II) production reached its maximum and 34% of the citrate-bicarbonate-dithionite extractable Fe (Fe(CBD)) was reduced to Fe(II) in the sandy soil. The peat soil showed a much faster reduction of Fe(III) and the maximum reduction of 89% of Fe(CBD) was reached after 200 d. Neoformation of a metavivianite/vivianite phase under anoxic conditions was identified by X-ray diffraction in the peat. The sandy soil exhibited small changes in the point of zero net sorption (EPC0) and P(i) desorption with increasing Fe(III) reduction, whereas in the peat soil P desorption increased from 80 to 3100 µmol kg⁻¹ and EPC0 increased from 1.7 to 83 µM, after 322 d of anoxic incubation. The fast Fe(III) reduction made the peat soils particularly vulnerable to changes in redox conditions. However, the precipitation of vivianite/metavivianite minerals may control soluble P(i) concentrations to between 2 and 3 µM in the long term if the soil is not disturbed.

Phosphorus load to surface water from bank erosion in a Danish lowland river basin.

Phosphorus loss from bank erosion was studied in the catchment of River Odense, a lowland Danish river basin, with the aim of testing the hypothesis of whether stream banks act as major diffuse phosphorus (P) sources at catchment scale. Furthermore, the study aimed at analyzing the impact of different factors influencing bank erosion and P loss such as stream order, anthropogenic disturbances, width of uncultivated buffer strips, and the vegetation of buffer strips. A random stratified procedure in geographical information system (GIS) was used to select two replicate stream reaches covering different stream orders, channelized vs. naturally meandering channels, width of uncultivated buffer strips (≤ 2 m and ≥ 10 m), and buffer strips with different vegetation types. Thirty-six 100-m stream reaches with 180 bank plots and a total of 3000 erosion pins were established in autumn 2006, and readings were conducted during a 3-yr period (2006-2009). The results show that neither stream size nor stream disturbance measured as channelization of channel or the width of uncultivated buffer strip had any significant ( < 0.05) influence on bank erosion and P losses during each of the 3 yr studied. In buffer strips with natural trees bank erosion was significantly ( < 0.05) lower than in buffer strips dominated by grass and herbs. Gross and net P input from bank erosion amounted to 13.8 to 16.5 and 2.4 to 6.3 t P, respectively, in the River Odense catchment during the three study years. The net P input from bank erosion equaled 17 to 29% of the annual total P export and 21 to 62% of the annual export of P from diffuse sources from the River Odense catchment. Most of the exported total P was found to be bioavailable (71.7%) based on a P speciation of monthly suspended sediment samples collected at the outlet of the river basin. The results found in this study have a great importance for managers working with P mitigation and modeling at catchment scale.

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.

A comparative study of phosphate sorption in lowland soils under oxic and anoxic conditions.

Phosphate (P(i)) release due to Fe(III) oxide dissolution is well documented for soils undergoing reduction. The P(i) sorption properties of soils in anoxic conditions are, however, still under consideration. In this investigation, P(i) sorption to strictly anoxic soils was compared with oxic conditions to assess the potential of lowland soils to function as traps for P(i) when flooded with drainage water. Batch sorption experiments were performed on seven minerogenic soils. Sorption to the anoxic soils was conducted after anoxic incubation, resulting in reduction of 36 to 93% of the dithionite-extractable Fe(III) (Fe(BD)). Langmuir fitted P(i) sorption isotherms showed a P(i) release of up to 1.1 mmol kg(-1) in six soils when P(i) concentrations in the matrix (P(sol)) were lower than 10 microM. Phosphate desorption was attributed to dissolution of amorphous iron oxides, and higher pH under anoxic conditions. The point of zero net sorption (EPC(0)) increased 2- to 10-fold on reduction. Five soils showed higher P(i) sorption capacities in the anoxic than in the oxic state at higher P(sol) concentrations. Solubility calculations indicated that precipitation of vivianite or similar Fe(II) phosphates may have caused the higher sorption capacities. Use of maximum sorption capacity (S(max)) is therefore misleading as a measure of P(i) sorption at low P(sol) concentrations. The results demonstrate that none of the strongly anoxic soils, irrespective of the initial Fe(III) oxide content, the P saturation, and the degree of Fe(III) oxide reduction, could retain P(i) at natural P(sol) concentrations in agricultural drainage water.

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).