Process-based modeling for ecosystem service provisioning: Non-linear responses to restoration efforts in a quarry lake under climate change.

Healthy freshwater ecosystems can provide vital ecosystem services (ESs), and this capacity may be hampered due to water quality deterioration and climate change. In the currently available ES modeling tools, ecosystem processes are either absent or oversimplified, hindering the evaluation of impacts of restoration measures on ES provisioning. In this study, we propose an ES modeling tool that integrates lake physics, ecology and service provisioning into a holistic modeling framework. We applied this model to a Dutch quarry lake, to evaluate how nine ESs respond to technological-based (phosphorus (P) reduction) and nature-based measures (wetland restoration). As climate change might be affecting the future effectiveness of restoration efforts, we also studied the climate change impacts on the outcome of restoration measures and provisioning of ESs, using climate scenarios for the Netherlands in 2050. Our results indicate that both phosphorus reduction and wetland restoration mitigated eutrophication symptoms, resulting in increased oxygen concentrations and water transparency, and decreased phytoplankton biomass. Delivery of most ESs was improved, including swimming, P retention, and macrophyte habitat, whereas the ES provisioning that required a more productive system was impaired (sport fishing and bird watching). However, our modeling results suggested hampered effectiveness of restoration measures upon exposure to future climate conditions, which may require intensification of restoration efforts in the future to meet restoration targets. Importantly, ESs provisioning showed non-linear responses to increasing intensity of restoration measures, indicating that effectiveness of restoration measures does not necessarily increase proportionally. In conclusion, the ecosystem service modeling framework proposed in this study, provides a holistic evaluation of lake restoration measures on ecosystem services provisioning, and can contribute to development of climate-robust management strategies.

Comparison of dredging, lanthanum-modified bentonite, aluminium-modified zeolite, and FeCl2 in controlling internal nutrient loading.

The eutrophic Bouvigne pond (Breda, The Netherlands) regularly suffers from cyanobacterial blooms. To improve the water quality, the external nutrient loading and the nutrient release from the pond sediment have to be reduced. An enclosure experiment was performed in the pond between March 9 and July 29, 2020 to compare the efficiency of dredging, addition of the lanthanum-modified bentonite clay Phoslock® (LMB), the aluminum-modified zeolite Aqual-P™ (AMZ) and FeCl2 to mitigate nutrient release from the sediment. The treatments improved water quality. Mean total phosphorus (TP) concentrations in water were 0.091, 0.058, 0.032, 0.031, and 0.030 mg P L-1 in controls, dredged, FeCl2, LMB and AMZ treated enclosures, respectively. Mean filterable P (FP) concentrations were 0.056, 0.010, 0.009, 0.005, and 0.005 mg P L-1 in controls, dredged, FeCl2, LMB and AMZ treatments, respectively. Total nitrogen (TN) and dissolved inorganic nitrogen (DIN) were similar among treatments; lanthanum was elevated in LMB treatments, Fe and Cl in FeCl2 treatments, and Al and Cl in AMZ treatments. After 112 days, sediment was collected from each enclosure, and subsequent sequential P extraction revealed that the mobile P pool in the sediments had reduced by 71.4%, 60.2%, 38%, and 5.2% in dredged, AMZ, LMB, and FeCl2 treatments compared to the controls. A sediment core incubation laboratory experiment done simultaneously with the enclosure experiment revealed that FP fluxes were positive in controls and cores from the dredged area, while negative in LMB, AMZ and FeCl2 treated cores. Dissolved inorganic nitrogen (DIN) release rate in LMB treated cores was 3.6 times higher than in controls. Overall, the applied in-lake treatments improved water quality in the enclosures. Based on this study, from effectiveness, application, stakeholders engagement, costs and environmental safety, LMB treatment would be the preferred option to reduce the internal nutrient loading of the Bouvigne pond, but additional arguments also have to be considered when preparing a restoration.

Compounds to mitigate cyanobacterial blooms affect growth and toxicity of Microcystis aeruginosa.

Numerous products and techniques are used to combat harmful cyanobacterial blooms in lakes. In this study, we tested nine products, the phosphate binders Phoslock® and Aqual-PTM, the coagulant chitosan, the phosphorus binder and coagulant aluminum salts (aluminum sulphate and sodium aluminate), the copper-based algicides SeClear, Captain® XTR and CuSO4·5H2O, the antibiotic Streptomycin and the oxidant hydrogen peroxide (H2O2) on their efficiency to manage the cyanobacterium Microcystis aeruginosa (M. aeruginosa). To this end, 7 days of laboratory experiments were conducted and effects were determined on chlorophyll-a, photosystem II efficiency (PSII), soluble reactive phosphorus (SRP) and intracellular and extracellular microcystin (MC) concentrations. The algicides, chitosan and H2O2 were the most powerful in reducing cyanobacteria biomass. Biomass reductions compared to the controls yielded: Chitosan (99.8%) > Hydrogen peroxide (99.6%) > Captain XTR (98.2%) > SeClear (98.1%) > CuSO4·5H2O (97.8%) > Streptomycin (86.6%) > Phoslock® (42.6%) > Aqual-PTM (28.4%) > alum (5.5%). Compounds that caused the largest reductions in biomass also strongly lowered photosystem II efficiency, while the other compounds (Phoslock®, Aqual-PTM, aluminum salts) had no effect on PSII, but strongly reduced SRP. Intracellular MC concentration followed the biomass patterns, extracellular MC was generally lower at higher doses of algicides, chitosan and H2O2 after one week. Recovery of PSII was observed in most algicides and chitosan, but not at the highest doses of SeClear and in all streptomycin treatments. Our results revealed that M. aeruginosa can be killed rapidly using several compounds, that in some treatments already signs of recovery occurred within one week. P fixatives are efficient in reducing SRP, and thus acting via resource suppression, which potentially may provide an addition to fast-acting algicides that kill most of the cells, but allow rapid regrowth as sufficient nutrients remain.

Phosphorus control and dredging decrease methane emissions from shallow lakes.

Freshwater ecosystems are an important source of the greenhouse gas methane (CH4), and their emissions are expected to increase due to eutrophication. Two commonly applied management techniques to reduce eutrophication are the addition of phosphate-binding lanthanum modified bentonite (LMB, trademark Phoslock©) and dredging, but their effect on CH4 emissions is still poorly understood. Here, this study researched how LMB and dredging affected CH4 emissions using a full-factorial mesocosm design monitored for 18 months. The effect was tested by measuring diffusive and ebullitive CH4 fluxes, plant community composition, methanogen and methanotroph activity and community composition, and a range of physicochemical water and sediment variables. LMB addition decreased total CH4 emissions, while dredging showed a trend towards decreasing CH4 emissions. Total CH4 emissions in all mesocosms were much higher in the summer of the second year, likely because of higher algal decomposition and organic matter availability. First, LMB addition lowered CH4 emissions by decreasing P-availability, which reduced coverage of the floating fern Azolla filiculoides, and thereby prevented anoxia and decreased surface water NH4+ concentrations, lowering CH4 production rates. Second, dredging decreased CH4 emissions in the first summer, possibly it removed the methanogenic community, and in the second year by preventing autumn and winter die-off of the rooted macrophyte Potamogeton cripsus. Finally, methanogen community composition was related to surface water NH4+ and O2, and porewater total phosphorus, while methanotroph community composition was related to organic matter content. To conclude, LMB addition and dredging not only improve water quality, but also decrease CH4 emissions, mitigating climate change.

Combining lanthanum-modified bentonite (LMB) and submerged macrophytes alleviates water quality deterioration in the presence of omni-benthivorous fish.

Bioturbation by omni-benthivorous fish often causes sediment resuspension and internal nutrient loading, which boosts phytoplankton growth and may lead to a shift of clear water lakes to a turbid state. Removal of large-sized omni-benthivorous individuals is a lake restoration measure that may revert lakes from a turbid to a clear water state, yet the rapid reproduction of small omni-benthivorous fish in tropical and subtropical shallow lakes may impede such lake recovery. In lake restoration, also a combination of lanthanum-modified bentonite (LMB) and planting submerged macrophytes has been used that may synergistically improve lake water quality. How the combined effect works in the presence of small omni-benthivorous fish has not been studied, which is needed given the high abundances of small omni-benthivorous fish in (sub)tropical lakes. We conducted a two-by-two factorial mesocosm experiment with and without the submerged macrophytes Vallisneria natans and with and without LMB, all in the presence of small crucian carp. At the end of the experiment, turbidity in the V. natans, LMB and combined LMB + V. natans treatments had decreased by 0.8%, 30.3% and 30.9%, respectively, compared with the controls. In addition, the nitrogen (N) and phosphorus (P) release from the sediment in the combined LMB + V. natans treatments had decreased substantially, by 97.4% and 94.3%, respectively, compared with the control. These N and P fluxes were also significantly lower in the combined LMB + V. natans treatments than in the sole LMB treatment (88.1% and 82.3%) or the V. natans treatment (93.2% and 90.3%). Cyanobacteria in the overlying water in the combined LMB + V. natans treatments significantly decreased by 84.1%, 63.5% and 37.0%, respectively, compared with the control and the sole LMB and V. natans treatments. Our results show that LMB and submerged macrophytes complement each other in effectively improving the water quality, even in the presence of small omni-benthivorous fish.

Towards climate-robust water quality management: Testing the efficacy of different eutrophication control measures during a heatwave in an urban canal.

Harmful algal blooms are symptomatic of eutrophication and lead to deterioration of water quality and ecosystem services. Extreme climatic events could enhance eutrophication resulting in more severe nuisance algal blooms, while they also may hamper current restoration efforts aimed to reduce nutrient loads. Evaluation of restoration measures on their efficacy under climate change is essential for effective water management. We conducted a two-month mesocosm experiment in a hypertrophic urban canal focussing on the reduction of sediment phosphorus (P)-release. We tested the efficacy of four interventions, measuring phytoplankton biomass, nutrients in water and sediment. The measures included sediment dredging, water column aeration and application of P-sorbents (lanthanum-modified bentonite - Phoslock® and iron-lime sludge, a by-product from drinking water production). An extreme heatwave (with the highest daily maximum air temperature up to 40.7 °C) was recorded in the middle of our experiment. This extreme heatwave was used for the evaluation of heatwave-induced impacts. Dredging and lanthanum modified bentonite exhibited the largest efficacy in reducing phytoplankton and cyanobacteria biomass and improving water clarity, followed by iron-lime sludge, whereas aeration did not show an effect. The heatwave negatively impacted all four measures, with increased nutrient releases and consequently increased phytoplankton biomass and decreased water clarity compared to the pre-heatwave phase. We propose a conceptual model suggesting that the heatwave locks nutrients within the biological P loop, which is the exchange between labile P and organic P, while the P fraction in the chemical P loop will be decreased. As a consequence, the efficacy of chemical agents targeting P-reduction by chemical binding will be hampered by heatwaves. Our study indicates that current restoration measures might be challenged in a future with more frequent and intense heatwaves.

Influence of temperature and pH on phosphate removal efficiency of different sorbents used in lake restoration.

Phosphorus sorbents (PS) are viewed as a powerful tool to manage eutrophication. Here, we tested three commercially available PS - lanthanum-modified bentonite (LMB), aluminium-modified zeolite (AMZ) and aluminium salts (Al) on their capacity to chemically inactivate soluble reactive phosphorus (SRP) at six different temperatures (5 to 35 °C) and five pH values (6 to 10). We also evaluated if the SRP bound at a neutral pH would be released if pH increases to pH 10. Results showed that temperature affected the SRP binding behavior differently for each PS. For instance, the highest SRP binding capacities of LMB, AMZ and Al were 14.0, 29.9 and 251.1 mg P g-1 at 30 °C, 35 °C and 30 °C, respectively; and the lowest was at 35 °C for LMB, 25 °C for AMZ and 20 °C for Al (6.3, 4.0 and 205.2 mg P g-1, respectively). The pH also affected the SRP binding differently. When pH increased from pH 6 to pH 10, LMB and Al decreased their binding capacity from 10.0 to 4.9 and from 571.7 mg P g-1 to 21.3 mg P g-1, respectively. The SRP adsorption capacity of AMZ was similar at pH 7 and 10 (6.3 and 6.2 mg P g-1). We observed that in high pH, LMB did not release the SRP precipitated. In contrast, AMZ and Al desorbed around 39%, and 71% of the SRP adsorbed when pH changed from 7 to 10. Abiotic factors such as pH should be considered when selecting the most promising material in lake restoration.

Lanthanum modified bentonite behaviour and efficiency in adsorbing phosphate in saline waters.

Lanthanum-modified bentonite (LMB, commercially called Phoslock®) has been widely applied in freshwater systems to manage eutrophication. Little is known, however, about its behaviour and efficiency in binding filterable reactive phosphorus (FRP) in saline environments. We assessed if LMB would adsorb phosphate over a range of salinities (0-32 ppth) comparing the behaviour in seawater salts and equivalent concentrations of NaCl. Lanthanum release from the bentonite matrix was measured and the La species prevailing in saline environments were evaluated through chemical equilibrium modelling. We demonstrated that LMB was able to adsorb FRP in all the salinities tested. Filterable lanthanum (FLa) concentrations were similarly low (<5 µgL-1) at all seawater salinities but considerably elevated, on occasion >2000 times greater in equivalent NaCl salinities. Mineralogical analysis indicates that La present in the clay interlayer was (partially) replaced by Na/Ca/Mg present in the seawater and a possible secondary P-reactive phase was formed, such as kozoite (LaCO3OH) or lanthanite (La2(CO3)3·8H2O) that may be physically dissociated from the LMB. Geochemical modelling also indicates that most FLa dissociated from LMB would be precipitated as a carbonate complex. In light of the identification of reactive intermediate phases, further studies including ecotoxicologial assays are required to assess any deleterious effects from the application of LMB to saline waters.

Lanthanum in Water, Sediment, Macrophytes and chironomid larvae following application of Lanthanum modified bentonite to lake Rauwbraken (The Netherlands).

Lanthanum Modified Bentonite (LMB; Phoslock®) is used to mitigate eutrophication by binding phosphate released from sediments. This study investigated the fate of lanthanum (La) from LMB in water, sediment, macrophytes, and chironomid larvae in Lake Rauwbraken (The Netherlands). Before the LMB application, water column filterable La (FLa) was 0.02 µg L-1, total La (TLa) was 0.22 µg L-1. In sediment the total La ranged 0.03-1.86 g m-2. The day after the application the maximum FLa concentration in the water column was 44 µg L-1, TLa was 528 µg L-1, exceeding the Dutch Maximum Permissible Concentrations (MPC) of 10.1 µg L-1 by three to fourfold. TLa declined below the MPC after 15 days, FLa after 75 days. After ten years, FLa was 0.4 µg L-1 and TLa was 0.7 µg L-1. Over the post-application years, FLa and TLa showed statistically significant downward trends. While the LMB settled homogeneously on sediment, after 3 years it redistributed to 0.2-5.4 g La m-2 within shallow zones, and 30.7 g m-2 to 40.0 g La m-2 in deeper zones. In the upper 20 cm of sediment, La concentrations were 7-6702 mg kg -1 dry weight (DW) compared to 0.5-7.0 mg kg-1 before application. Pre-application anaerobic sediment release of FLa was 0.006 mg m-2 day-1. Three months after the application it was 1.02 mg m-2 day-1. Three years later it was 0.063 mg m-2 day-1. Before application La in plants was 0.8-5.1 mg La kg-1 DW, post-application values were up to 2925 mg La kg-1 DW. In chironomid larvae, La increased from 1.7 µg g-1 DW before application to 1421 µg g-1 DW after one month, 3 years later it was 277 µg g-1 DW. Filtration experiments indicate FLa is not truly dissolved free La3+ cations.

Intraspecific variability in response to phosphorus depleted conditions in the cyanobacteria Microcystis aeruginosa and Raphidiopsis raciborskii.

Phosphorus loading plays an important role in the occurrence of cyanobacterial blooms and understanding how this nutrient affects the physiology of cyanobacteria is imperative to manage these phenomena. Microcystis aeruginosa and Raphidiopsis raciborskii are cyanobacterial species that form potentially toxic blooms in freshwater ecosystems worldwide. Blooms comprise numerous strains with high trait variability, which can contribute to the widespread distribution of these species. Here, we explored the intraspecific variability in response to phosphorus depleted conditions (P-) testing five strains of each species. Strains could be differentiated by cell volume or genetic profiles except for those of the same species, sampling location and date, though these presented differences in their response to (P-). Although differently affected by (P-) over 10 days, all strains were able to grow and maintain photosynthetic activity. For most M. aeruginosa and R. raciborskii strains growth rates were not significantly different comparing (P+) and (P-) conditions. After ten days in (P-), only one M. aeruginosa strain and two R. raciborskii strains showed reduction in biovolume yield as compared to (P+) but in most strains chlorophyll-a concentrations were lower in (P-) than in (P+). Reduced photosystem II efficiency was found for only one R. raciborskii strain while all M. aeruginosa strains were affected. Only two M. aeruginosa and one R. raciborskii strain increased alkaline phosphatase activity under (P-) as compared to (P+). Variation in P-uptake was also observed but comparison among strains yielded homogeneous groups comprised of representatives of both species. Comparing the response of each species as a whole, the (P-) condition affected growth rate, biovolume yield and chlorophyll yield. However, these parameters revealed variation among strains of the same species to the extent that differences between M. aeruginosa and R. raciborskii were not significant. Taken together, these results do not support the idea that R. raciborskii, as a species, can withstand phosphorus limitation better than M. aeruginosa and also point that the level of intraspecific variation may preclude generalizations based on studies that use only one or few strains.

Composition of dissolved organic matter controls interactions with La and Al ions: Implications for phosphorus immobilization in eutrophic lakes.

Applications of aluminium (Al) salt or lanthanum (La) modified bentonite (LMB) have become popular methodologies for immobilizing phosphorus (P) in eutrophic lakes. The presence of humic substances, has been shown to inhibit this form of treatment due to the complexation with La/Al. However, the effects of other dissolved organic matter (DOM), especially that derived from phytoplankton (the dominant source in eutrophic lakes) are unknown. In this study, the interaction with La/Al of Suwannee River Standard Humic Acid Standard II (SRHA) and algae-derived DOM (ADOM) were investigated and compared. Differed to SRHA which was dominated by polyphenol-like component (76.8%, C1-SRHA), majority in ADOM were protein-like substance, including 41.9% tryptophan-like component (C2-ADOM) and 21.0% tyrosine-like component (C3-ADOM). Two reactions of complexation and coprecipitation were observed between SRHA/ADOM and La/Al. Complexation dominated at low metal inputs less than 10 µM and coprecipitation was the main reaction at higher metal inputs. For ADOM, the tryptophan-like component (C2-ADOM) was the important component to react with metal. The reaction rate for C2-ADOM with La were about two-third of that for C1-SRHA, indicating that the influence of C2-ADOM was significant during the P immobilization by La/Al-based treatment in eutrophic lakes. The P removal data in the presence of ADOM confirmed the significant inhibition of ADOM. In addition, based on the composition of coprecipitates and relatively biodegradable character of tryptophan-like substances (C2-ADOM), the coprecipitation of ADOM was assumed to reduce the stability of precipitated P in eutrophic lakes. The release of P from the potential biodegradation of the coprecipitates and thus the possible decline of the performance of P immobilization by La/Al-based treatments is an important work in the future.

Human health risk associated with the management of phosphorus in freshwaters using lanthanum and aluminium.

The use of geo-engineering materials to manage phosphorus in lakes has increased in recent years with aluminium and lanthanum based materials being most commonly applied. Hence the potential impact of the use of these compounds on human health is receiving growing interest. This review seeks to understand, evaluate and compare potential unintended consequences on human health and ecotoxicological risks associated with the use of lanthanum- and aluminium-based materials to modify chemical and ecological conditions in water bodies. In addition to their therapeutic use for the reduction of intestinal phosphate absorption in patients with impaired renal function, the phosphate binding capacity of aluminium and lanthanum also led to the development of materials used for water treatment. Although lanthanum and aluminium share physicochemical similarities and have many common applications, their uptake and kinetics within the human body and living organisms importantly differ from each other which is reflected in a different toxicity profile. Whilst a causal role in the development of neurological pathologies, skeletal lesions, hematopoietic disorders and respiratory effects has unequivocally been demonstrated with increased exposure to aluminium, studies until now have failed to find such a clear association after exposure to lanthanum although caution is warranted. Our review indicates that lanthanum and aluminium have a distinctly different profile with respect to their potential effects on human health. Regular monitoring of both aluminium and lanthanum concentrations in lanthanum-/aluminium-treated water by the responsible authorities is recommended to avoid acute accidental or chronic low level accumulation.

The Impact of Warming and Nutrients on Algae Production and Microcystins in Seston from the Iconic Lake Lesser Prespa, Greece.

Lake Lesser Prespa and its adjacent pond, Vromolimni in Greece, is a shallow freshwater system and a highly protected area hosting an exceptional biodiversity. The occurrence of microcystins (MCs) producing cyanobacterial blooms in these waters during recent years can be harmful to the wildlife. We tested the hypothesis that both cyanobacterial biomass and MCs are strongly influenced by nutrients (eutrophication) and warming (climate change). Lake and pond water was collected from two sites in each water body in 2013 and incubated at three temperatures (20 °C, 25 °C, 30 °C) with or without additional nutrients (nitrogen +N, phosphorus +P and both +N and +P). Based on both biovolume and chlorophyll-a concentrations, cyanobacteria in water from Lesser Prespa were promoted primarily by combined N and P additions and to a lesser extent by N alone. Warming seemed to yield more cyanobacteria biomass in these treatments. In water from Vromolimni, both N alone and N+P additions increased cyanobacteria and a warming effect was hardly discernible. MC concentrations were strongly increased by N and N+P additions in water from all four sites, which also promoted the more toxic variant MC-LR. Hence, both water bodies seem particularly vulnerable to further N-loading enhancing MC related risks.

Effects of polyaluminum chloride and lanthanum-modified bentonite on the growth rates of three Cylindrospermopsis raciborskii strains.

In tropical and subtropical lakes, eutrophication often leads to nuisance blooms of Cylindrospermopsis raciborskii. In laboratory experiments, we tested the combined effects of flocculant polyaluminum chloride (PAC) and lanthanum-modified bentonite (LMB) on the sinking and growth rates of three C. raciborskii strains. We tested the hypothesis that the combination of PAC and LMB would (1) effectively sink C. raciborskii in a test tube experiment and (2) impair C. raciborskii growth, irrespective of the biomass of the inoculum (bloom) and the strain in the growth experiment. We tested the recommended (LMB1) and a three-times higher dose of LMB (LMB3). The combined addition of PAC and LMB enhanced the sedimentation of all C. raciborskii strains. Moreover, both the PAC and LMB doses decreased the phosphate concentration. PAC and LMB1 decreased the growth rate of all strains, but the efficacy depended on the biomass and strain. The combined addition of PAC and LMB3 inhibited the growth of all strains independently of the biomass and strain. We conclude that a low dose of PAC in combination with the recommended dose of LMB decreases C. raciborskii blooms and that the efficiency of the technique depends on the biomass of the bloom. A higher dose of LMB is needed to obtain a more efficient control of C. raciborskii blooms.

Bioavailable phosphorus (P) reduction is less than mobile P immobilization in lake sediment for eutrophication control by inactivating agents.

Phosphorus (P) immobilization by inactivating agents in the sediment of eutrophic lakes to reduce immediately available P in lake water is often crucial for mitigating nuisance eutrophication symptoms, such as cyanobacterial blooms. Macrophytes and phytoplankton, however, can directly utilize P from the sediment for growth. Accordingly, a comprehensive analysis of the P bioavailability in lake sediment amended with two promising P-inactivation agents, namely Phoslock® and drinking water treatment residue (DWTR), was investigated in both short- and long-term studies (20 and 180 d). Phosphorus-availability was assessed using six chemical extraction methods and Hydrilla verticillata and Microcystis aeruginosa growth tests. The results showed that Phoslock® and DWTR significantly reduced mobile P (NH4Cl and Na2S2O4/NaHCO3 extractable P) in lake sediment, while P bioavailability that was assessed by different methods showed considerable deviations. Interestingly, appropriate bioavailable P chemical extraction methods were determined based on linear correlation analysis, and further comparison indicated that reduction of bioavailable P by DWTR (<55% for macrophyte available P) and Phoslock® (<17% for cyanobacteria available P) were clearly less than the mobile P immobilization (>75%) at recommended dosages, which was probably caused by the capability of macrophyte and cyanobacteria to utilize various fractions of P (except the residual P) in amended sediment under proper illumination. Therefore, DWTR and Phoslock® can effectively reduce P release from lake sediment, but the potential bioavailable P may pose uncertainties for eutrophication control in lakes that typically have regular sediment re-suspension. Overall, an evaluation of the bioavailable P pool in the lake ecosystem should be essential for successful lake geo-engineering.

Editorial - A critical perspective on geo-engineering for eutrophication management in lakes.

Eutrophication is the primary worldwide water quality issue. Reducing excessive external nutrient loading is the most straightforward action in mitigating eutrophication, but lakes, ponds and reservoirs often show little, if any, signs of recovery in the years following external load reduction. This is due to internal cycling of phosphorus (P). Geo-engineering, which we can here define as activities intervening with biogeochemical cycles to control eutrophication in inland waters, represents a promising approach, under appropriate conditions, to reduce P release from bed sediments and cyanobacteria accumulation in surface waters, thereby speeding up recovery. In this overview, we draw on evidence from this special issue Geoengineering in Lakes, and on supporting literature to provide a critical perspective on the approach. We demonstrate that many of the strong P sorbents in the literature will not be applicable in the field because of costs and other constraints. Aluminium and lanthanum modified compounds are among the most effective compounds for targeting P. Flocculants and ballast compounds can be used to sink cyanobacteria, in the short term. We emphasize that the first step in managing eutrophication is a system analysis that will reveal the main water and P flows and the biological structure of the waterbody. These site specific traits can be significant confounding factors dictating successful eutrophication management. Geo-engineering techniques, considered collectively, as part of a tool kit, may ensure successful management of eutrophication through a range of target effects. In addition, novel developments in modified zeolites offer simultaneous P and nitrogen control. To facilitate research and reduce the delay from concept to market a multi-national centre of excellence is required.

Responses in sediment phosphorus and lanthanum concentrations and composition across 10 lakes following applications of lanthanum modified bentonite.

A combined field and laboratory scale study of 10 European lakes treated between 2006 and 2013 with a lanthanum (La) modified bentonite (LMB) to control sediment phosphorus (P) release was conducted. The study followed the responses in sediment characteristics including La and P fractions and binding forms, P adsorption capacity of discrete sediment layers, and pore water P concentrations. Lanthanum phosphate mineral phases were confirmed by solid state (31)P MAS NMR and LIII EXAFS spectroscopy. Rhabdophane (LaPO4 · nH2O) was the major phase although indications of monazite (LaPO4) formation were also reported, in the earliest treated lake. Molar ratios between La and P in the sediments were generally above 1, demonstrating excess La relative to P. Lanthanum was vertically mixed in the sediment down to a depth of 10 cm for eight of the ten lakes, and recovery of La in excess of 100% of the theoretical aerial load indicated translocation of the LMB towards the deepest areas of the lakes. Lanthanum was generally recovered from bed sediment samples following sequential chemical extraction from the HCl fraction. Soluble reactive P (SRP) release experiments on intact sediment cores indicated conditions of P retention (with the exception of two lakes) by sediments, indicating effective control of sediment P release, i.e. between two and nine years after treatment.

Assessment of changes in potential nutrient limitation in an impounded river after application of lanthanum-modified bentonite.

With the advent of phosphorus (P)-adsorbent materials and techniques to address eutrophication in aquatic systems, there is a need to develop interpretive techniques to rapidly assess changes in potential nutrient limitation. In a trial application of the P-adsorbent, lanthanum-modified bentonite (LMB) to an impounded section of the Canning River, Western Australia, a combination of potential P, nitrogen (N) and silicon (Si) nutrient limitation diagrams based on dissolved molar nutrient ratios and actual dissolved nutrient concentrations have been used to interpret trial outcomes. Application of LMB resulted in rapid and effective removal of filterable reactive P (FRP) from the water column and also effectively intercepted FRP released from bottom sediments until the advent of a major unseasonal flood event. A shift from potential N-limitation to potential P-limitation also occurred in surface waters. In the absence of other factors, the reduction in FRP was likely to be sufficient to induce actual nutrient limitation of phytoplankton growth. The outcomes of this experiment underpins the concept that, where possible in the short-term, in managing eutrophication the focus should not be on the limiting nutrient under eutrophic conditions (here N), but the one that can be made limiting most rapidly and cost-effectively (P).

Geo-engineering experiments in two urban ponds to control eutrophication.

Many urban ponds experience detrimental algal blooms as the result of eutrophication. During a two year field experiment, the efficacy of five in situ treatments to mitigate eutrophication effects in urban ponds was studied. The treatments targeted the sediment phosphorus release and were intended to switch the ponds from a turbid phytoplankton-dominated state to a clear-water state with a low phytoplankton biomass. Two eutrophic urban ponds were each divided into six compartments (300-400 m(2); 210-700 m(3)). In each pond the following treatments were tested: dredging in combination with biomanipulation (involving fish biomass control and the introduction of macrophytes) with and without the addition of the flocculant polyaluminiumchloride, interception and reduction of sediment phosphorus release with lanthanum-modified bentonite (Phoslock(®)) in combination with biomanipulation with and without polyaluminiumchloride; biomanipulation alone; and a control. Trial results support the hypothesis that the combination of biomanipulation and measures targeting the sediment phosphorus release can be effective in reducing the phytoplankton biomass and establishing and maintaining a clear-water state, provided the external phosphorus loading is limited. During the experimental period dredging combined with biomanipulation showed mean chlorophyll-a concentrations of 5.3 and 6.2 µg L(-1), compared to 268.9 and 52.4 µg L(-1) in the control compartments. Lanthanum-modified bentonite can be an effective alternative to dredging and in combination with biomanipulation it showed mean chlorophyll-a concentrations of 5.9 and 7.6 µg L(-1). Biomanipulation alone did not establish a clear-water state or only during a limited period. As the two experimental sites differed in their reaction to the treatments, it is important to choose the most promising treatment depending on site specific characteristics. In recovering the water quality status of urban ponds, continuing attention is required to the concurrent reduction of external phosphorus loading and to maintaining an appropriate fish community.

A meta-analysis of water quality and aquatic macrophyte responses in 18 lakes treated with lanthanum modified bentonite (Phoslock(®)).

Lanthanum (La) modified bentonite is being increasingly used as a geo-engineering tool for the control of phosphorus (P) release from lake bed sediments to overlying waters. However, little is known about its effectiveness in controlling P across a wide range of lake conditions or of its potential to promote rapid ecological recovery. We combined data from 18 treated lakes to examine the lake population responses in the 24 months following La-bentonite application (range of La-bentonite loads: 1.4-6.7 tonnes ha(-1)) in concentrations of surface water total phosphorus (TP; data available from 15 lakes), soluble reactive phosphorus (SRP; 14 lakes), and chlorophyll a (15 lakes), and in Secchi disk depths (15 lakes), aquatic macrophyte species numbers (6 lakes) and aquatic macrophyte maximum colonisation depths (4 lakes) across the treated lakes. Data availability varied across the lakes and variables, and in general monitoring was more frequent closer to the application dates. Median annual TP concentrations decreased significantly across the lakes, following the La-bentonite applications (from 0.08 mg L(-1) in the 24 months pre-application to 0.03 mg L(-1) in the 24 months post-application), particularly in autumn (0.08 mg L(-1) to 0.03 mg L(-1)) and winter (0.08 mg L(-1) to 0.02 mg L(-1)). Significant decreases in SRP concentrations over annual (0.019 mg L(-1) to 0.005 mg L(-1)), summer (0.018 mg L(-1) to 0.004 mg L(-1)), autumn (0.019 mg L(-1) to 0.005 mg L(-1)) and winter (0.033 mg L(-1) to 0.005 mg L(-1)) periods were also reported. P concentrations following La-bentonite application varied across the lakes and were correlated positively with dissolved organic carbon concentrations. Relatively weak, but significant responses were reported for summer chlorophyll a concentrations and Secchi disk depths following La-bentonite applications, the 75th percentile values decreasing from 119 µg L(-1) to 74 µg L(-1) and increasing from 398 cm to 506 cm, respectively. Aquatic macrophyte species numbers and maximum colonisation depths increased following La-bentonite application from a median of 5.5 species to 7.0 species and a median of 1.8 m to 2.5 m, respectively. The aquatic macrophyte responses varied significantly between lakes. La-bentonite application resulted in a general improvement in water quality leading to an improvement in the aquatic macrophyte community within 24 months. However, because, the responses were highly site-specific, we stress the need for comprehensive pre- and post-application assessments of processes driving ecological structure and function in candidate lakes to inform future use of this and similar products.