Methods for treating water, sediment and / or sludge

Abstract

The present invention relates to a method for treating water, sediment and / or sludge using alkaline earth metal peroxides, in particular calcium peroxide, and cable bacteria, to a kit comprising a composition and cable bacteria, the composition comprising at least one alkaline earth metal peroxide, and to the use of a composition comprising at least one alkaline earth metal peroxide in combination with cable bacteria.

Description

Technical Field

[0001] The present invention relates to a method for treating water, sediment and / or sludge using alkaline earth metal peroxides, in particular calcium peroxide, and cable bacteria, to a kit comprising a composition and cable bacteria, the composition comprising at least one alkaline earth metal peroxide, and to the use of a composition comprising at least one alkaline earth metal peroxide, in particular in combination with cable bacteria. Background Art

[0002] In lakes and water bodies, a consequence of high phosphorus pollution (eutrophication) is the accelerated formation of sludge consisting of particulate organic matter (POM), such as dead algae and incompletely mineralized plant parts.

[0003] The accumulation of organic matter leads to a severe oxygen depletion. Up to the upper edge of the sediment layer, the overlying water is also oxygen-free. In the lower layers of the sediment, the organic matter is mineralized anaerobically, with other inorganic and oxidized substrates acting as electron acceptors. According to the principle of competition, microorganisms that are able to utilize the electron acceptors with the highest redox potential prevail. Under these conditions, what occurs is the sequential reduction of nitrates, manganese (IV) oxides, iron (III) oxides and sulfates. In the absence of these substrates, the organic matter is degraded by acetogenesis and methanogenesis.

[0004] The layer of water above the upper edge of the sediment, which is already devoid of oxygen, actually blocks out microorganisms that can use oxygen. This unnaturally shortens the circulation of substances. The shortening of the mineralization of the water body is part of the "vicious cycle" of eutrophication.

[0005] Due to the continuous accumulation of silt, the amount of water in the water column decreases, and not only the habitat becomes smaller according to natural laws, but also the habitat for fish, macrofauna and plankton is reduced due to chemical / physical consequences. The number of species decreases, and the density of organisms also decreases. In addition, the sulphides formed in the sediments are phytotoxic, which means that aquatic plants can no longer develop.

[0006] The accumulation of silt in bodies of water is a global problem and leads to various usage restrictions as well as increased release of climate-damaging methane in aquatic sediments.

[0007] Due to these occurrences and consequences of eutrophication, lakes and water bodies may be damaged, so it is necessary to treat them.

[0008] For example, EP 1080042 A1 discloses the use of calcium peroxide (CaO2) to treat sludge. It describes in particular the binding of o-phosphates to heavy metals and the increase in bacterial enzyme activity.

[0009] One of the advantages of calcium peroxide is that hydrolysis can continue for about 7-8 weeks, during which time molecular oxygen is uniformly released into the environment and is available for in situ degradation of organic matter by heterotrophic bacteria.

[0010] The organic mass that can be converted is thus quantitatively proportional to the mass of oxygen released. Given that the oxygen availability can be calculated from the mass of calcium peroxide (Equation 1), the oxygen required for mineralization of the "average biomass composition" [Uhlmann & Horn 2001] can also be determined according to Equation 2.

[0011] CaO2+2H2O→2Ca(OH)2+O2 (Equation 1)

[0012] C 106 H 180 O 45 N 16 P+118.5O2→106CO2+66H2O+16NH3+PO4 3- + Energy (Equation 2)

[0013] Therefore, 1.56 g of oxygen is required for the mineralization of each gram of organic matter. 3 Oxidation of 1% of the dry residue of sludge to a depth of 1 cm requires 7.0 g of oxygen per square meter. This requires the application of 49 g of pure calcium peroxide per square meter.

[0014] In the case of water bodies containing a large amount of silt, for example with an organic fraction of between 10% and 40% of the dry matter, it is necessary to use relatively large application rates.

[0015] Furthermore, in cases where the thickness of the sludge is high, calcium peroxide is usually applied as a suspension into the deposit using a spray gun in order to achieve the effect within the layer.

[0016] Since calcium peroxide is insoluble in water and good distribution requires at least one injection per square meter of surface, this requires considerable effort in cases where the deposit surface is large.

[0017] It has been found to be beneficial to add heterotrophic microorganisms to the CaO2 to allow a rapid utilization of the released oxygen within a short-term activity of 8 weeks. These microorganisms are active directly at the interface between the CaO2 and the sediment. This means that an active surface is formed which, in the absence of any injected application, is capped by the CaO2 layer. The released oxygen is also released into the water column, since free diffusion is possible in this direction.

[0018] Therefore, there is a need for improved methods of treating water bodies, sediments and sludge having high silt content and / or low or even anoxic areas.

[0019] Surprisingly, it was found that the effectiveness of the CaO2 application can be significantly increased if the application is designed in such a way that an environment is created in which so-called cable bacteria establish. Summary of the invention

[0020] In a first aspect, the present invention provides a method for treating water, such as standing water and flowing water and wastewater; sediment and / or sludge, especially sediment and / or sludge in a body of water, comprising:

[0021] (a) introducing and / or applying a composition comprising at least one alkaline earth metal peroxide into water, sediment and / or sludge; and

[0022] (b) Introduction of cable bacteria into water, sediment and / or sludge.

[0023] In a second aspect, a method for treating water, sediment and / or sludge, in particular sediment and / or sludge in a body of water, is disclosed, comprising:

[0024] (i) testing water, sediment and / or sludge for the presence of cable bacteria; and

[0025] (ii-a) introducing and / or applying a composition comprising at least one alkaline earth metal peroxide into water, sediment and / or sludge, and

[0026] If no or substantially no cable bacteria are found during the testing of the water, sediment and / or sludge, introducing cable bacteria into the water, sediment and / or sludge; or

[0027] (ii-b) If cable bacteria are found during the detection of water, sediment and / or sludge, a composition comprising at least one alkaline earth metal peroxide is introduced and / or applied to the water, sediment and / or sludge.

[0028] In some cable bacteria with low density (e.g. <10 1 In embodiments where the number of cells / cm2 is greater than 1%, a small dose of calcium peroxide may be administered first to allow for initial in situ culture before a second administration, for example, at the earliest after 2 months.

[0029] The present invention also provides a kit comprising a composition and cable bacteria, wherein the composition comprises at least one alkaline earth metal peroxide, and also provides the use of the composition comprising at least one alkaline earth metal peroxide in combination with cable bacteria in treating water, sediment and / or sludge, especially sediment and / or sludge in a water body.

[0030] Also disclosed are the use of a composition comprising at least one alkaline earth metal peroxide in combination with cable bacteria for promoting the development of aquatic plants, the use of a composition comprising at least one alkaline earth metal peroxide in combination with cable bacteria for water body remediation, the use of a composition comprising at least one alkaline earth metal peroxide in combination with cable bacteria for sludge degradation and reservoir capacity restoration, and the use of a composition comprising at least one alkaline earth metal peroxide in combination with cable bacteria for detoxifying biological communities in sediments and / or sludge. Also disclosed are the use of alkaline earth metal peroxides, especially calcium peroxide, or mixtures comprising alkaline earth metal peroxides, especially calcium peroxide, as solid electron acceptors for temporarily establishing sediment biological communities including cable bacteria, such as occurring in undisturbed water bodies.

[0031] Advantageous embodiments and developments become apparent from the further dependent claims and from the description with reference to the drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] The accompanying drawings are intended to provide a further understanding of the embodiments of the present invention. The accompanying drawings illustrate embodiments and together with the description are used to explain the principles and concepts of the present invention. Other embodiments and many of the advantages noted will become apparent with reference to the accompanying drawings. The elements of the accompanying drawings are not necessarily shown in true proportion to each other.

[0033] In the figures, identical elements, features and components having the same function and having the same effect are provided with the same reference signs, unless otherwise indicated.

[0034] Figure 1 An exemplary method according to the invention according to the first aspect is schematically illustrated.

[0035] Figure 2 An exemplary method according to the invention according to the second aspect is schematically illustrated. DETAILED DESCRIPTION

[0036] definition

[0037] First, in the context of this patent application, the following terms should be understood as follows:

[0038] Unless defined otherwise, technical and scientific expressions used herein have the same meanings as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0039] Cable bacteria are multicellular bacteria that are linked together in chains to form long aggregates in the form of cables, allowing electrons to be transported over centimeters. Cable bacteria belong to the deltaproteobacterial family Desulfobulbaceae, which is known to contain sulfate-reducing or sulfur-disproportionating species. Based on the 16S rRNA of cable bacteria, cable bacteria currently form two genera, "Candidatus Electrothrix" and "Candidatus Electrothrix". Cable bacteria have an "anodic end" deep in the sediment and a "cathodic end" at the phase boundary with the electron acceptor, which can bridge the hypoxic zone and oxidize, for example, sulfide to sulfate in the anoxic zone. For example, at the "cathodic end" (as a cathode), oxygen is reduced, which leads to an increase in the pH there. In this article, cable bacteria allow long-distance electron transport. It is worth noting that these cable bacteria are usually not stable enough to grow out of the sediment surface to contact the oxygen dissolved in the water. Therefore, cable bacteria cannot work in the strongly reducing sediments of eutrophic water bodies. Cable bacteria spatially bridge the gap between the substrate and the electron acceptor due to their electron transport. This means that they have a clear advantage over other organisms that can only metabolize directly at the boundary layer of redox potential.

[0040] Cable bacteria therefore cannot naturally "function" in water bodies with accumulated silt due to eutrophication, since there oxygen as electron acceptor does not enter the upper sediment layers. With the help of calcium peroxide, these normally natural organisms can eliminate the known principle of competition, which is based on the highest redox potential of a specific electron acceptor; the cable bacteria directly connect to any highest available redox potential, thus avoiding competition with microorganisms that are restricted to metabolism at / within phase boundaries.

[0041] Oxidation of sulfides eliminates their phytotoxic effects, thus allowing underwater aquatic plants to colonize and grow. The loss of macrophyte vegetation in water bodies is a known and unwelcome consequence of eutrophication.

[0042] Another advantage of cable bacteria is that they are mobile and can orient themselves, for example in sludge and / or sediment or even on particles, in order to be able to carry out redox reactions in different environments.

[0043] Cable bacteria are described, for example, in KUKjeldsen et al., "On the evolution and physiology of cable bacteria", PNAS, 2019, www.pnas.org / cgi / doifl073 / pnas.1903514116, and reference may be made to the article for cable bacteria, the content of which is incorporated herein by reference.

[0044] In the context of the present invention, water is understood to mean all water or water bodies, for example ponds, lakes, rivers, reservoirs, coastal waters, fjords, lagoons, bays, seawater, fish and other marine animal breeding stations, water in reservoir systems and aquifers of agricultural or drinking water reservoirs, and the above-mentioned water may also contain soil, sediment and / or silt and sediment and suspended matter. In the context of the present invention, sediment is understood to mean the solid present in water, for example ponds, lakes and rivers. For example, silt can come from sewage treatment plants, wastewater filters, etc., and / or be present at the bottom of the water. Preferred water is fresh water containing sediment and / or silt sediment, for example ponds, lakes, etc., which has hypoxia and / or anoxic zones and can be destroyed rapidly, but can be effectively processed with this method.

[0045] Unless stated otherwise or clear from the context, the amounts specified in the context of the present invention are based on weight %.

[0046] In a first aspect, the present invention provides a method for treating water, such as standing water and flowing water and wastewater; sediment and / or sludge, especially sediment and / or sludge in a body of water, comprising:

[0047] (a) introducing and / or applying a composition comprising at least one alkaline earth metal peroxide into water, sediment and / or sludge; and

[0048] (b) Introduction of cable bacteria into water, sediment and / or sludge.

[0049] In a second aspect, the present invention relates to a method for treating water, sediment and / or sludge, in particular sediment and / or sludge in a body of water, comprising:

[0050] (i) testing water, sediment and / or sludge for the presence of cable bacteria; and

[0051] (ii-a) introducing and / or applying a composition comprising at least one alkaline earth metal peroxide into water, sediment and / or sludge, and

[0052] If no or substantially no cable bacteria are found during the testing of the water, sediment and / or sludge, introducing cable bacteria into the water, sediment and / or sludge; or

[0053] (ii-b) If cable bacteria are found during the detection of water, sediment and / or sludge, a composition comprising at least one alkaline earth metal peroxide is introduced and / or applied to the water, sediment and / or sludge.

[0054] In the method of the second aspect, in certain cable bacteria having low density (e.g. <10 1 In embodiments where the number of cells / cm2 or <100 cells / m2) is less than 100, a small dose of calcium peroxide may be administered first to allow for initial in situ culture prior to a second administration, for example, at the earliest 2, 3 or 4 months later.

[0055] In the method of the first aspect and the method of the second aspect, the composition comprising at least one alkaline earth metal peroxide and the cable bacteria are the same.

[0056] The introduction of cable bacteria is not subject to any particular restrictions. For example, they can be introduced as a suspension with water as solvent. Since cable bacteria are able to multiply very efficiently, especially under sufficient substrate conditions (O2 / S 2- ), the concentration required for effective inoculation is not very high; for example, using 10 2 Up to 10 5 Cells / ml, a few liters of relevant preliminary culture, for example 2, 3, 4, 5, 6, 7, 8, 9 or 10 liters or more, are sufficient for 1 hectare of water surface. Higher starting concentrations or amounts shorten the establishment time. Cable bacteria are likewise not subject to any particular restrictions and can be tailored, for example, to the type of water body. For example, they can be provided from a preliminary culture that can be cultivated in the laboratory or in the field, in a part of a water body or in the entire area.

[0057] In the method of the first aspect, steps (a) and (b) can be performed independently of each other or simultaneously, and step (a) can be performed before or after step (b). However, in some embodiments, step (b) of introducing cable bacteria is performed before step (a), so that the cable bacteria can immediately start to utilize the oxygen released by at least one alkaline earth metal peroxide (especially calcium peroxide) and / or other electron acceptors provided thereby (e.g., alkaline earth metal peroxide itself, such as calcium peroxide). In this context, the time interval between steps (b) and (a) is not subject to any particular restrictions, but can be, for example, at most one week, preferably at most 3 days, 2 days, 1 day or less, such as 12 hours or less or 8 hours or less. In some embodiments, step (a) is performed before step (b), so that the oxygen released from at least one alkaline earth metal peroxide (especially calcium peroxide) and / or other electron acceptors provided thereby (e.g., alkaline earth metal peroxide itself, such as calcium peroxide) is already available to the cable bacteria. Herein, the time interval between steps (a) and (b) is not subject to any particular limitation, but may be, for example, at most one week, preferably at most 3 days, 2 days, 1 day or less, for example 12 hours or less or 8 hours or less.

[0058] Cable bacteria prefer a pH-neutral environment. Since the pH of the uppermost layer will temporarily increase immediately after the application of calcium peroxide, it is preferred to monitor the pH at the sediment phase boundary, for example, before introducing cable bacteria, until it is normalized to a value between 8.7 and 7.4.

[0059] Calcium peroxide may be used as a product to treat undesirable pH increases caused during the introduction of the composition, such as described above, which facilitates the practical implementation of the present invention.

[0060] However, the composition comprising at least one alkaline earth metal peroxide and the cable bacteria are preferably introduced into the water, sediment and / or sludge at substantially the same point or at the same point to minimize diffusion processes and improve the efficiency of the treatment. In the present context, it becomes particularly evident that the synergy between the oxygen released by at least one alkaline earth metal peroxide, in particular calcium peroxide, and / or other electron acceptors derived from alkaline earth metal peroxides, such as calcium peroxide, and its utilization by the cable bacteria is described in more detail above and below.

[0061] In certain embodiments, the cable bacteria are introduced in such a way that they can accumulate on the material to be degraded, such as sludge, sediment, general sludge, sediment, etc. in a body of water, thereby allowing the hypoxic and / or anoxic areas of the material to be degraded to come into contact with oxygen released by at least one alkaline earth metal peroxide (particularly calcium peroxide) and / or by some other solid electron acceptor derived therefrom (e.g., the alkaline earth metal peroxide itself, such as CaO2).

[0062] In step (ii-a) of the method of the second aspect, if no or substantially no cable bacteria are found during the detection of the water, sediment and / or sludge, introducing and / or applying a composition comprising at least one alkaline earth metal peroxide into the water, sediment and / or sludge and introducing cable bacteria into the water, sediment and / or sludge can be carried out simultaneously or in a staggered manner.

[0063] However, in certain embodiments, the step of introducing the cable bacteria is performed before the step of introducing and / or applying the composition comprising at least one alkaline earth metal peroxide, in particular calcium peroxide, so that the cable bacteria can immediately start to utilize the oxygen released by the at least one alkaline earth metal peroxide, in particular calcium peroxide, and / or other electron acceptors provided thereby (e.g., the alkaline earth metal peroxide itself, such as calcium peroxide). In this context, the time interval between the two steps (e.g., the introduction of the cable bacteria before the introduction and / or application of the composition comprising at least one alkaline earth metal peroxide, in particular calcium peroxide) is also not subject to any particular restrictions, but may be, for example, at most one week, preferably at most 3 days, 2 days, 1 day or less, such as 12 hours or less or 8 hours or less. In certain embodiments, the step of introducing and / or applying the composition comprising at least one alkaline earth metal peroxide, in particular calcium peroxide, is performed before the step of introducing the cable bacteria, so that the oxygen released from the at least one alkaline earth metal peroxide, in particular calcium peroxide, and / or other electron acceptors provided thereby (e.g., the alkaline earth metal peroxide itself, such as calcium peroxide) is already available to the cable bacteria. In this context, the time interval between the two steps (e.g., applying and / or introducing a composition comprising at least one alkaline earth metal peroxide, in particular calcium peroxide, before the cable bacteria) is not subject to any particular restrictions, but may be, for example, at most one week, preferably at most 3 days, 2 days, 1 day or less, for example 12 hours or less or 8 hours or less.

[0064] However, the composition comprising at least one alkaline earth metal peroxide and the cable bacteria are preferably introduced into the water, sediment and / or sludge at substantially the same point or at the same point to minimize diffusion processes and improve the efficiency of the treatment. It becomes particularly evident in this context that the synergy between the oxygen released by the at least one alkaline earth metal peroxide (especially calcium peroxide) and / or other electron acceptors provided thereby (e.g. the alkaline earth metal peroxide itself, such as calcium peroxide) and its utilization by the cable bacteria is described in more detail above and below.

[0065] In certain embodiments, the cable bacteria are introduced in such a way that they can accumulate on the material to be degraded, such as sludge, sediment, general sludge, sediment, particles, etc. in a body of water, thereby allowing low oxygen and / or anoxic areas of the material to be degraded to contact with oxygen released by at least one alkaline earth metal peroxide (especially calcium peroxide) and / or other electron acceptors provided thereby (e.g., alkaline earth metal peroxide itself, such as calcium peroxide).

[0066] The introduction and / or application of the composition comprising at least one alkaline earth metal peroxide, in particular calcium peroxide, is not subject to any particular restrictions. In certain embodiments, the composition comprising at least one alkaline earth metal peroxide is introduced into the water, sludge and / or sediment in solid form or as an aqueous slurry or solution, and / or is applied directly to the water, sludge and / or sediment, manually or by a suitable metering system. This is easy to carry out and allows distribution, so that approximately the same concentration of alkaline earth metal peroxide, in particular calcium peroxide, can be obtained in the water, on the sludge and / or on the sediment - even over a long period of time - and the optimal function of the cable bacteria can be ensured.

[0067] In certain preferred embodiments, the composition comprising at least one alkaline earth metal peroxide comprises only one alkaline earth metal peroxide, especially calcium peroxide. In certain embodiments, more than one alkaline earth metal peroxide may be present in the composition.

[0068] In certain embodiments, the composition comprising at least one alkaline earth metal peroxide is present in solid form and the water to be treated flows around it. As a result, at least one alkaline earth metal peroxide, especially calcium peroxide, can release oxygen uniformly over a long period of time, which means that relatively long introduction intervals are possible.

[0069] In certain embodiments, the composition comprising at least one alkaline earth metal peroxide is incorporated into the sediment and / or sludge by a forward mixer, a rotary tiller or other mechanical metering system and / or method. As a result, the sediment and / or sludge can be loosened and its surface can be enlarged for docking with cable bacteria, thereby making effective degradation possible.

[0070] In the method of the second aspect, the detection of the presence of cable bacteria in water, sediment and / or sludge is not subject to any particular restrictions, but is carried out before the introduction and / or application step, and since it varies according to the test results, it is usually necessary to wait for the test results. For example, the detection can be carried out by collecting a sample containing solids (e.g., suspended matter, sludge and sediment) and performing a microbial detection of cable bacteria on the sample, for example by using cable bacteria-specific markers, for example, using optical methods such as in the case of FISH (fluorescence in situ hybridization), by genetic sequencing of genes or genomes present in the sample, etc. The microbial detection is not subject to any particular restrictions, for example, various preparation steps may also be included, such as purification and / or concentration steps.

[0071] If, in the method of the second aspect, cable bacteria are found in the sample, then it is no longer necessary to introduce cable bacteria, and step (ii-b) is performed. However, if there is substantially no cable bacteria, e.g. <10 1 cells / cm2 or <100 cells / m2, or if cable bacteria are not found, cable bacteria must also be introduced and step (ii-a) must be performed.

[0072] exist Figure 1 and 2 , the method of the first aspect and the method of the second aspect are schematically compared.

[0073] exist Figure 1 In the schematically illustrated method of the first aspect, no preliminary detection is performed here, which means that rapid action is possible. However, it is also possible to introduce cable bacteria despite the presence of cable bacteria in order to better utilize the amount of CaO2 applied during the active period. However, in the case of water, sediments and / or sludge with low oxygen or particularly anoxic areas, for example, such rapid action may be desirable. Figure 1 As shown by way of example, first a composition comprising at least one alkaline earth metal peroxide, in particular calcium peroxide, is introduced and / or applied in step 1, and then the cable bacteria are introduced in step 2. It goes without saying that these steps can also be reversed or carried out simultaneously, for example the composition comprising at least one alkaline earth metal peroxide, in particular calcium peroxide, can therefore also comprise cable bacteria (in step ii-a of the first and second methods).

[0074] exist Figure 2 In the method of the second aspect shown schematically, firstly, in step 3, the presence of cable bacteria in water, sediment and / or sludge is detected. In the case where there is no or a small amount of cable bacteria in the test sample, step (ii-a) is performed, such as Figure 1As shown, this involves the introduction and / or application of a composition comprising at least one alkaline earth metal peroxide, in particular calcium peroxide, in step 1 and the introduction of cable bacteria in step 2, wherein these steps can also be reversed or carried out simultaneously.

[0075] However, if cable bacteria are present, especially in sufficient concentrations, e.g. ≥10 1 cells / cm2 or ≥100 cells / m2, only a composition comprising at least one alkaline earth metal peroxide, in particular calcium peroxide, is introduced in step 1 and no cable bacteria are introduced here.

[0076] Suitable alkaline earth metal peroxides are, for example, magnesium and calcium peroxides and mixtures thereof, preferably calcium and magnesium peroxides or mixtures thereof. Particularly preferred is calcium peroxide, the calcium being replaced by magnesium in a proportion of 0.02% to 50%, preferably up to 30%, by weight, based on CaO2. Particularly preferred is calcium peroxide which can release oxygen over a long period of time. In commercial products, alkaline earth metal peroxides are usually present in admixture with the corresponding carbonates and hydroxides.

[0077] In certain embodiments, the composition comprising at least one alkaline earth metal peroxide further comprises at least one alkaline earth metal carbonate and / or at least one alkaline earth metal hydroxide and / or one alkaline earth metal sulfate. For example, in addition to calcium peroxide, calcium carbonate, calcium hydroxide and / or magnesium sulfate may also be present. Examples of compositions comprising these ingredients are, for example, Solvay's 75C. Examples of suitable compositions comprising alkaline earth metal peroxides are also given by GmbH and plus.

[0078] In certain embodiments, at least one alkaline earth metal peroxide is used in a mixture with an alkali metal carbonate peroxyhydrate. 3 Alkali metal carbonate peroxyhydrates are known to have a direct oxygen-increasing effect when used in dosages of 20 to 400 mg / L, wherein no biocidal effect has yet occurred. Alkali metal carbonate peroxyhydrates are addition products of alkali metal carbonates with H2O2, such as Me2CO3×H2O2, such as 2Me2CO3·3H2O2 (Me=alkali metal, such as Na, K, Rb, Cs, especially Na). They are also known as alkali metal percarbonates and are commercially available. Sodium carbonate peroxyhydrate has been found to be particularly suitable for immediately increasing low oxygen levels in water bodies in terms of economics and ecology.

[0079] In certain embodiments, the composition comprising at least one alkaline earth metal peroxide further comprises at least one alkali metal carbonate peroxyhydrate, in particular Na2CO3×H2O2, preferably 2Na2CO3·3H2O2, or a mixture of Na2CO3 and H2O2. In certain embodiments, the method according to the present invention further comprises introducing and / or applying at least one alkali metal carbonate peroxyhydrate, in particular Na2CO3×H2O2, preferably 2Na2CO3·3H2O2, or a mixture of Na2CO3 and H2O2.

[0080] The alkaline earth metal peroxide and the alkali metal carbonate peroxyhydrate are preferably used in a ratio of 1:1 to 1:0.03.

[0081] If lanthanum ions are added to the system to be treated, an increase in phosphate precipitation can be achieved. This combination is particularly useful if phosphate precipitation is required anyway to reduce eutrophication. When the lanthanum in the active sediment barrier is reduced again after treatment with CaO2, the efflux of phosphorus from the sediment is reduced.

[0082] In certain embodiments, for carrying out the method according to the invention, the substances used, i.e. the alkaline earth metal peroxide and optionally the alkali metal carbonate peroxyhydrate and other optional ingredients, are present in an amount of 2 to 700, preferably 4 to 500, in particular 5 to 300, particularly preferably 10 to 150 g / m 2 In the case of sediment and / or sludge treatment, the generally higher amount of oxidizable substances means that the amount of substance used according to the invention can be added in many times the amount to be added to the water. In these cases, repeated applications are possible.

[0083] Using this new method, it is also possible to reduce levels of heavy metals and damaging anions such as NO2 - , S 2- NH4 + wait.

[0084] Due to such efficient detoxification of the pore water, the normal development of other organisms in the hypoxic and oxic sediment zones is allowed, so that the activation of all sediment zones above the cable bacteria activity space additionally occurs as a synergistic effect.

[0085] The at least one alkaline earth metal peroxide used according to the invention and the optionally used further components can be added to the system to be treated as individual substances or in the form of a mixture with other substances in a solid, aqueous solution or aqueous slurry.

[0086] Silicates, such as phyllosilicates or tectosilicates, preferably selected from zeolites and bentonites, are particularly suitable as such solids. For practical reasons, it is particularly useful to compact the materials in solid form and use them as, for example, granules, pills or tablets. In certain embodiments, the composition comprising at least one alkaline earth metal peroxide therefore additionally comprises at least one silicate, such as phyllosilicates or tectosilicates, preferably selected from zeolites and bentonites.

[0087] Depending on the water quality and sediment quality, e.g. carbonate content, pH, etc., it may be appropriate to add further compounds to improve the water quality and / or sediment quality. Examples of such compounds include Ca(OH)2, CaO, CaCO3, CaCl2, Ca(NO3)2, CaS04, MgSO4, Ca2SiO4, other similar magnesium compounds and mixtures of the above. Depending on the conditions of the raw water, it may be necessary to treat the water with alkali or alkaline earth metal salts, especially oxides, hydroxides, carbonates and / or bicarbonates, e.g. to control the pH

[0088] In certain embodiments, the compounds used according to the invention are combined with a mixture of CaCO3, CaCl2 and / or Ca(NO3)2 and optionally a magnesium salt and NaHCO3 and optionally KHCO3, wherein CaCO3 and CaCl2 and / or Ca(NO3)2 and optionally a magnesium salt are present in a molar ratio of 0.01:1 to 2:1, and CaCl2 and / or Ca(NO3)2 and optionally a magnesium salt and NaHCO3 and optionally KHCO3 are present in a molar ratio of 1:3 to 2:1. Such mixtures and their suitability for treating water and sediments are described, for example, in European patent application EP 737 169. In certain embodiments, the composition comprising at least one alkaline earth metal peroxide is additionally used with a mixture of CaCO3, CaCl2 and / or Ca(NO3)2 and optionally a magnesium salt and NaHCO3 and optionally KHCO3, wherein the CaCO3 and the CaCl2 and / or Ca(NO3)2 and optionally a magnesium salt are present in a molar ratio of 0.01:1 to 2:1, and the CaCl2 and / or Ca(NO3)2 and optionally a magnesium salt and NaHCO3 and optionally KHCO3 are present in a molar ratio of 1:3 to 2:1.

[0089] The presence of, for example, salts and / or oxides, hydroxides, bicarbonates, carbonates, sulfates, nitrates, chlorides and / or fluorides of iron and / or aluminum can support the effectiveness of the method. Effectiveness can be increased in particular by doping metallic iron and / or aluminum and / or lanthanum into a compound, which is used in such an amount that the water quality is not adversely affected (depending on, for example, preliminary tests of the water quality). In certain embodiments, therefore, additional iron ions and / or aluminum ions and / or lanthanum ions are introduced, for example also in a composition comprising at least one alkaline earth metal peroxide.

[0090] The method according to the invention can be used for the treatment of water sediments, sludge and / or water / wastewater in open and closed aquatic systems, such as seawater, brackish water and freshwater, for example in reservoirs, artificial or natural lakes, bathing or fishing water, ornamental ponds and fish farms, and in process waters, such as wastewater from sewage treatment plants, wastewater treatment plants, recycling plants, cooling water plants and heat exchanger plants, chemical production plants, or for the treatment of water produced in decomposition and condensation processes (for example, landfill leachate or condensate from thermal waste treatment plants) or leaching processes (for example, water seeping from contaminated soil, water sediments or sludge).

[0091] The method according to the invention can be carried out by directly metering the added components manually and / or by means of technical equipment or auxiliary devices such as metering systems. The material can be metered directly into the water, sludge and / or sediment to be treated and / or also via a container containing the material in solid form and the water to be treated flowing through it, such as a filter cartridge, a fixed bed reactor or a fluidized bed reactor.

[0092] Also disclosed is a kit comprising a composition comprising at least one alkaline earth metal peroxide and cable bacteria.

[0093] Here, the composition comprising at least one alkaline earth metal peroxide and the cable bacteria are the same as in the method according to the invention, so reference is made here to the relevant paragraphs in the discussion of the method according to the invention. In the kit, the composition comprising at least one alkaline earth metal peroxide and the cable bacteria can be present separately, or the cable bacteria can be included in the composition comprising at least one alkaline earth metal peroxide. Other possible components of the kit are described above in conjunction with the method according to the invention.

[0094] The kit according to the invention can be used in particular in the method according to the invention. Therefore, such use of the kit is also disclosed.

[0095] In addition, the use of a composition comprising at least one alkaline earth metal peroxide in combination with cable bacteria for treating water, sediments and / or sludge is disclosed. Here, the composition comprising at least one alkaline earth metal peroxide and the cable bacteria are also as described above in conjunction with the method according to the invention, and here, the composition comprising at least one alkaline earth metal peroxide and the cable bacteria can also be used alone or together.

[0096] Also disclosed is the use of a composition comprising at least one alkaline earth metal peroxide in combination with cable bacteria in promoting the development of aquatic plants. Here, the aquatic plants are not subject to any particular restrictions, but are preferably those aquatic plants that cannot grow in a low oxygen or anoxic environment.

[0097] Also disclosed is the use of a composition comprising at least one alkaline earth metal peroxide in combination with cable bacteria in the remediation of water bodies.

[0098] The invention further provides for the use of a composition comprising at least one alkaline earth metal peroxide in combination with cable bacteria for sludge degradation in reservoir capacity restoration. This is particularly important for such water bodies.

[0099] Also disclosed is the use of a composition comprising at least one alkaline earth metal peroxide in combination with cable bacteria for detoxifying biota in sediments and / or sludge. In this context, the toxins and environmental hazards described above and below can be degraded.

[0100] Also disclosed is the use of alkaline earth metal peroxides, especially calcium peroxide, or mixtures containing alkaline earth metal peroxides, especially calcium peroxide, as solid electron acceptors for temporarily establishing a sediment biome including cable bacteria, such as occurs in an undisturbed body of water. Thus, it is possible to establish or introduce an "artificial" biome to restore the natural environment in a body of water, sludge or sediment.

[0101] The above-mentioned embodiments and developments can be combined with each other as required, which is meaningful. Other possible embodiments, developments and implementations of the present invention also include combinations of features of the present invention described above or below with respect to the exemplary embodiments, which are not explicitly mentioned. In particular, those skilled in the art will also add separate aspects as improvements or supplements to a specific basic form of the present invention.

[0102] The present invention will be described in more detail below with reference to various embodiments of the present invention. However, the present invention is not limited to these embodiments.

[0103] Example

[0104] Five different water bodies containing water sediments were treated with a composition comprising calcium peroxide, and an increase in effectiveness was observed in three water bodies. Here, cable bacteria were found in sediment samples of three water bodies, while cable bacteria were not found in the other two water bodies. Cable bacteria were detected here by FISH using a specific fluorescent marker for cable bacteria.

[0105] The results show that cable bacteria in the sediments of water bodies can record an unexpectedly high degradation effect of CaO2. For example, in the Kleiner ruweiher water body in Eschenbach, CaO2 was applied to 17 hectares of land in low doses after higher doses in previous years did not show a significant effect. Using 450 kg / ha of the composition, corresponding to 150 kg of CaO2 / ha of water surface, 2200 cubic meters of silt per hectare were degraded. Here, a silt layer of about 22 cm was removed within a period of 5 months. It was found that, with this measurement, phosphorus was mainly bound to iron in the remaining sediment. It was surprisingly found that the mass of organic silt degraded in the presence of cable bacteria was many times higher than expected by stoichiometry.

[0106] Therefore, due to Fe 2 Diffusion to the water / sediment interface and oxidation to Fe there or en route 3 , Fe 2 The active migration of Fe leads to a synergistic enhancement of the formation of an upper sediment barrier for phosphorus. 3 is a natural binding partner for phosphate. It can be assumed here that the phosphorus barrier is generated by iron ions, which can be released after oxidation by the cable bacteria from deposits such as iron sulfide or iron sulfite. Here, the cable bacteria continue to use the oxygen introduced by calcium peroxide and / or other electron acceptors provided thereby for redox reactions.

[0107] Sediment testing confirmed an increase in iron-bound phosphate in the sediment.

[0108] It was also found that in water bodies containing cable bacteria, the oxygen concentration in the water column increased only initially, or even decreased, after the application of calcium peroxide. Here, this demonstrates that the cable bacteria also utilize oxygen from the water column after the oxygen-free water layer above the upper edge of the sediment has been eliminated by CaO2. Normally, in the absence of cable bacteria, the oxygen concentration increases by diffusion. In contrast, the projects without cable bacteria showed a rise in the O2 concentration in the water column, which is also expected from the point of view of diffusion control.

[0109] According to patent EP1080042 A1, the P-binding properties of CaO2 play no role in this process.

[0110] Tablets are used, because they can be applied precisely, and / or granules or powders, which are preferably metered as a suspension, because this is the only way to achieve uniform distribution under water. What is important is an application proportionate to the area.

[0111] The presence of cable bacteria generally results in an increase in the water content of the treated sediments, a decrease in the organic fraction (which can be measured by loss on ignition or TOC (total organic carbon)), an increase in the Fe-P content in the P fraction of the sediments, and an increase in the mass transfer of oxygen from the water column to / into the sediment surface.

[0112] Then, an increase in macrophyte vegetation could be recorded in treated lakes containing cable bacteria. Therefore, this method is suitable for the recolonization of aquatic plants in eutrophic water bodies.

[0113] Cable bacteria detoxify (sulfide) in the method according to the invention, allowing macrophyte vegetation to grow, it mobilizes Fe-II, creates a P barrier below the CaO2 layer, it bypasses the competition principle, thereby eliminating itself from the competition for electron acceptors. CaO2 alone has limited effect, and cable bacteria alone cannot obtain electron acceptors. Both have a reinforcing effect in each direction at the same time.

Claims

1. A method for treating water, sediment and / or sludge, comprising: (a) applying a composition comprising at least one alkaline earth metal peroxide to water, sediment and / or sludge; and (b) introducing cable bacteria into said water, sediment and / or sludge.

2. A method for treating water, sediment and / or sludge, comprising: (i) Detection of the presence of cable bacteria in water, sediment and / or sludge; and (ii-a) applying a composition comprising at least one alkaline earth metal peroxide to said water, sediment and / or sludge, and If cable bacteria are not found during the detection of the water, sediment and / or sludge, introducing cable bacteria into the water, sediment and / or sludge; or (ii-b) if cable bacteria are found during the detection of said water, sediment and / or sludge, applying a composition comprising at least one alkaline earth metal peroxide to said water, sediment and / or sludge.

3. The method according to claim 1 or 2, characterized in that: The alkaline earth metal peroxide used is calcium peroxide, magnesium peroxide or a mixture thereof.

4. The method according to claim 1 or 2, characterized in that: The composition comprising at least one alkaline earth metal peroxide further comprises at least one alkaline earth metal carbonate and / or at least one alkaline earth metal hydroxide and / or one alkaline earth metal sulfate.

5. The method according to claim 1 or 2, characterized in that: The composition comprising at least one alkaline earth metal peroxide further comprises at least one alkali metal carbonate peroxyhydrate.

6. The method according to claim 1 or 2, characterized in that: The composition comprising at least one alkaline earth metal peroxide further comprises sodium carbonate peroxyhydrate.

7. The method according to claim 1 or 2, characterized in that: The composition comprising at least one alkaline earth metal peroxide further comprises 2Na2CO3·3H2O2.

8. The method according to claim 1 or 2, characterized in that: The composition comprising at least one alkaline earth metal peroxide further comprises a mixture of Na2CO3 and H2O2.

9. The method according to claim 1 or 2, characterized in that: Further comprising applying at least one alkali metal carbonate peroxyhydrate.

10. The method according to claim 1 or 2, characterized in that: Further comprising applying sodium carbonate peroxyhydrate.

11. The method according to claim 1 or 2, characterized in that: Further comprising applying 2Na2CO3·3H2O2.

12. The method according to claim 1 or 2, characterized in that: Further comprising applying a mixture of Na2CO3 and H2O2.

13. The method according to claim 1 or 2, characterized in that: The composition comprising at least one alkaline earth metal peroxide is additionally used with a mixture of CaCO3, CaCl2 and / or Ca(NO3)2 and optionally a magnesium salt and NaHCO3 and optionally KHCO3, wherein the molar amount of CaCO3 is present in a ratio of 0.01:1 to 2:1 with the molar amount of CaCl2 and / or Ca(NO3)2 and optionally a magnesium salt, and the molar amount of CaCl2 and / or Ca(NO3)2 and optionally a magnesium salt is present in a ratio of 1:3 to 2:1 with the molar amount of NaHCO3 and optionally KHCO3.

14. The method according to claim 1 or 2, characterized in that: The composition comprising at least one alkaline earth metal peroxide further comprises at least one silicate.

15. The method according to claim 1 or 2, characterized in that: The composition comprising at least one alkaline earth metal peroxide further comprises a layered silicate or a framework silicate.

16. The method according to claim 1 or 2, characterized in that: The composition comprising at least one alkaline earth metal peroxide further comprises zeolite and bentonite.

17. The method according to claim 1 or 2, characterized in that: Iron ions and / or aluminum ions, fluoride ions and / or lanthanum ions are additionally applied.

18. The method according to claim 1 or 2, characterized in that: The composition comprising at least one alkaline earth metal peroxide is applied directly to the water, the sludge and / or the sediment in solid form or as an aqueous slurry or solution, either manually or by means of a suitable metering system.

19. The method according to claim 1 or 2, characterized in that: The composition comprising at least one alkaline earth metal peroxide is present in solid form and the water to be treated flows around it.

20. The method according to claim 1 or 2, characterized in that: The composition comprising at least one alkaline earth metal peroxide is incorporated into the sediment and / or the sludge by means of a forward mixer, a rotary tiller or other mechanical metering system and / or method.

21. A kit comprising a composition comprising at least one alkaline earth metal peroxide and cable bacteria.

22. Use of a composition comprising at least one alkaline earth metal peroxide in combination with cable bacteria for the treatment of water, sediments and / or sludge.

23. Use of a composition comprising at least one alkaline earth metal peroxide in combination with cable bacteria for treating sediments and / or sludge in a body of water.

24. Use of a composition comprising at least one alkaline earth metal peroxide in combination with cable bacteria for promoting the development of aquatic plants.

25. Use of a composition comprising at least one alkaline earth metal peroxide in combination with cable bacteria for the remediation of water bodies.

26. Use of a composition comprising at least one alkaline earth metal peroxide in combination with cable bacteria for sludge degradation and reservoir capacity restoration.

27. Use of a composition comprising at least one alkaline earth metal peroxide in combination with cable bacteria for detoxifying biological communities in sediments and / or sludge.

28. Use of alkaline earth metal peroxides, or mixtures comprising alkaline earth metal peroxides, as solid electron acceptors for the temporary establishment of sediment biota including cable bacteria.

29. The use according to claim 28, characterized in that It occurs in undisturbed bodies of water.

30. Use of calcium peroxide as a solid electron acceptor for the temporary establishment of sediment biota including cable bacteria.

31. The use according to claim 30, characterized in that It occurs in undisturbed bodies of water.

32. Use of a mixture comprising calcium peroxide as a solid electron acceptor for temporarily establishing a sediment biocommunity comprising cable bacteria.

33. The use according to claim 32, characterized in that It occurs in undisturbed bodies of water.

Images