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.

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.

Controlling cyanobacterial blooms through effective flocculation and sedimentation with combined use of flocculants and phosphorus adsorbing natural soil and modified clay.

Eutrophication often results in blooms of toxic cyanobacteria that hamper the use of lakes and reservoirs. In this paper, we experimentally evaluated the efficacy of a metal salt (poly-aluminium chloride, PAC) and chitosan, alone and combined with different doses of the lanthanum modified bentonite Phoslock(®) (LMB) or local red soil (LRS) to sediment positively buoyant cyanobacteria from Funil Reservoir, Brazil, (22°30'S, 44°45'W). We also tested the effect of calcium peroxide (CaO2) on suspended and settled cyanobacterial photosystem efficiency, and evaluated the soluble reactive P (SRP) adsorbing capacity of both LMB and LRS under oxic and anoxic conditions. Our data showed that buoyant cyanobacteria could be flocked and effectively precipitated using a combination of PAC or chitosan with LMB or LRS. The SRP sorption capacity of LMB was higher than that of LRS. The maximum P adsorption was lowered under anoxic conditions especially for LRS ballast. CaO2 addition impaired photosystem efficiency at 1 mg L(-1) or higher and killed precipitated cyanobacteria at 4 mg L(-1) or higher. A drawback was that oxygen production from the peroxide gave positive buoyancy again to the settled flocs. Therefore, further experimentations with slow release pellets are recommended.