CN111270647B

CN111270647B - Service ocean breakwater ecologization method

Info

Publication number: CN111270647B
Application number: CN201911210463.XA
Authority: CN
Inventors: 吕建福; 汪明军
Original assignee: Harbin Engineering University
Current assignee: Harbin Engineering University
Priority date: 2019-12-02
Filing date: 2019-12-02
Publication date: 2021-07-13
Anticipated expiration: 2039-12-02
Also published as: CN111270647A

Abstract

The invention relates to a breakwater ecologization technology, in particular to a method for ecologizing a serving ocean breakwater, belonging to the crossing field of ocean sessile organisms and ocean ecological engineering disciplines. The invention comprises the following steps: (1) surveying the sea area of the building position of the concrete structure; (2) preparing a concrete adhesive base. (3) Quantitatively collecting oyster seedlings and culturing. (4) Cleaning the surface of the breakwater; (5) coating and maintaining the paint; (6) the oyster attaching base is placed on site. (7) Larvae attachment was monitored. (8) And (5) adding and managing nutrient substances. The invention aims to quickly attach compact oysters to the breakwater in service by cleaning and washing the breakwater in service and fixedly placing the attaching base attached with the oysters around the breakwater in service, and utilizes the characteristics of the oysters as ecological engineers and the functions of purifying water and improving water areas to highly ecologize the breakwater in service and realize the aims of ecologization and long-term service of the breakwater.

Description

Service ocean breakwater ecologization method

Technical Field

The invention relates to a breakwater ecologization technology, in particular to a method for ecologizing a serving ocean breakwater, belonging to the crossing field of ocean sessile organisms and ocean ecological engineering disciplines.

Background

Because of the rapid development of coastal economy in recent decades and no attention to environmental protection, large-scale damage to coastal ecology is caused, and huge influence is caused on coastal ecology and economy in China. At present, a series of relevant policies of China emerge, the ocean engineering construction of China also faces a peak period, and simultaneously, the ocean engineering constructed in a large scale and the breakwater which ensures the stability of the surrounding sea area further destroy the originally fragile ecosystem of the ocean. Without proper protection of ecological environment, the method brings about greater disaster to the ecology along the shore of the ocean. Meanwhile, most coastal infrastructures cannot be dismantled, and the ecology in the sea area needs to be restored, so that people gradually realize the application of ecological technology on a large number of infrastructures, and the ecology in the sea area can be effectively improved or restored. Therefore, it is very important and urgent to construct a breakwater having good ecological effects, or to ecologize the existing breakwater, so as to improve the offshore ecological environment.

In order to reduce the damage of ocean engineering to the ocean ecological environment, people have been trying to improve the ocean environment by various methods in recent years. From the engineering perspective, CN208039153U discloses an ecological breakwater capable of keeping water flow smooth, which adopts a culvert designed at the bottom, biological attachment made of rubber blocks, and a riprap levee body structure, so as to realize certain ecological functions on the basis of wave prevention and wave absorption; the university of Wuhan's rational engineering discloses a method for manufacturing a plant ecological floating breakwater, which is provided with a floating platform, the main structure of the floating platform adopts reinforced concrete, mangrove plants are planted on the reinforced concrete, and the floating breakwater has certain ecological effect and is mainly characterized by having good landscape effect and meeting the beautiful requirements of yacht wharves and the like on the breakwater; sydney university has studied two concrete surface grooving modes, and after grooving, the oyster attachment rate is improved by 50%, and the biomass inside the groove is 3 times of that of the raised part. In addition, france has studied a new breakwater structure consisting of a number of columns, placed at a distance of hundreds of metres from the shore or from the existing breakwater. The calm weather allows the waves to pass freely, and the extreme weather upright post reflects the impact force of the waves, so that the aim of protecting the coastline is fulfilled. In addition, the new york gulf has built a 'living' breakwater, which is designed comprehensively, and increases marine biomass by macroscopic design, surface texture and the use of low-alkali cement to make concrete members. Can improve wave-absorbing ability and ecological effect.

So far, only research has focused on the influence of the structural change of the breakwater on the sea ecosystem, and individual research aims at the influence of the low alkalinity of concrete and the texture of members on biological enrichment. The oysters are ecological engineers and are mainly concentrated in a tidal range area and within 30 meters underwater, and meanwhile, the oysters are likely to be attached to the shells of the same kind to form a thick oyster reef, so that the oysters are attached to the breakwater compactly, and the ecology of the breakwater can be realized. In addition, researches show that biological glue secreted by oysters and barnacles can block capillary pores on the surface layer of concrete, block the entrance and exit of ions and gas, improve the impermeability of the concrete and further improve the durability of the concrete, and the more compact the attachment of sessile organisms, the more obvious the protection effect is. The marine periphyton is used for protecting a marine concrete structure such as a marine breakwater, so that the marine periphyton has the characteristics of initiative, economy and environmental protection, and the limitation of the current concrete corrosion prevention technology in a tidal range area and an underwater area is made up. The method is a cross between the subjects of marine concrete and marine sessile biology, and opens up a new research field of reinforced concrete structure corrosion prevention.

In a word, the compact adhesion of the oysters on the breakwater can not only realize the ecology of the breakwater, but also improve the durability of the concrete for the breakwater, prolong the service life of the ecological breakwater and improve the use value and the economic benefit of the ecological breakwater. Obviously, how to make oysters compactly attached to the breakwater and timely metamorphosis and rapid growth are the key to promote the development and application of the field. At present, relevant researches on oyster attachment and metamorphosis at home and abroad are as follows:

first, the influence of ions on the attachment and metamorphosis of marine periphyton larva

The research on the marine periphyton larva attachment and metamorphosis induction at home and abroad mainly focuses on the influence of the ion concentration in the solution, and the deeply researched ions and substances have K⁺、NH₃、Ca²⁺And Cu²⁺The first three ions or substances can promote the adhesion or metamorphosis of oyster at proper concentration, but Cu²⁺The promoting effect is not obvious, and even the death rate of larvae is increased at a large concentration. K⁺Inducing larval metamorphosis by affecting the behavior of cell membranes; NH (NH)₃It is intracellular, leading to an increase in intracellular pH, which subsequently causes depolarization of neurons that are behavioral pathways, thereby inducing sessile metamorphosis. Although the study on the attachment and metamorphosis of more sessile organisms on the surfaces of different substances such as polyethylene plates, shells, tiles and the like is carried out in solution, the method is not easy to realize or has high cost when being applied to the actual marine concrete engineering.

At present, with the great application of concrete in ocean engineering, particularly recent oyster reef repair engineering and the like, the concrete becomes a substrate material which is most commonly attached by marine periphyton. But the concrete material is different from the traditional seashells, limestone, rubber tires, plastic plates and the like. The concrete has high alkalinity and high calcium ion, also contains rich other ions, such as potassium and sodium ions, and has great influence on the attachment and growth of the oysters. At present, although some oyster reef repair projects and the like adopt newly manufactured concrete members, waste concrete and the like as repair substrates, the effect is not ideal.

Second, the influence of concrete of different types of cement on marine plants and sessile organisms

At present, portland cement concrete is almost adopted in ocean concrete engineering and has high alkalinity (the pH value of a pore solution is generally 12.0-13.0), and the pH value of seawater is generally 7.9-8.4. Because of the alkali concentration gradient, the concrete contacted with the seawater can continuously release alkali, thereby improving the pH value of the seawater in the sea area and damaging a local ecological system. Has a great inhibiting effect on the attachment growth of sessile organisms on the surface of the biological filter, and particularly has great influence on alkalinity sensitive organisms. The current domestic and foreign research shows that: the artificial fish reef made of different cement types has obvious difference on the biological adhesion effect, the aluminate cement and the fly ash portland cement have good biological adhesion effect, and the alkalinity is lower than that of common portland cement concrete^[1]. Similarly, the cement concrete has better ecological effect by adding 40-60% of fly ash and slag powder. In addition, the types and the quantity of the attachment organisms on the travertine gelled material concrete are more than those on the cement concrete, and the higher the content of the travertine gelled material is, the better the ecological effect is. The ecological concrete engineering for building American ecological concrete adopts low-alkalinity cement concrete, such as aluminate cement, in particular slag portland cement, wherein the replacement amount of slag powder reaches 50%, and the ecological effect of enriching marine plants, animals and the like is better^[2,3]. By adopting cement with lower alkalinity to prepare concrete, biomass (mainly marine plants) sensitive to alkali can be effectively improved, but the improvement of the attachment amount and the attachment density of oysters is limited.

Third, the influence of calcium substances on the adhesion of marine sessile organisms

The research at home and abroad shows that the chemical element composition of the attaching substrate obviously influences the attachment, metamorphosis and later growth of oyster larvae. The most commonly used calcium-containing substrates (limestone and concrete) are effective in inducing adhesion of oyster larvae with an inducing effect comparable to that of shells. This indicates that calcium is a vital role in the attachment, metamorphosis and growth of oyster larvae.

Recently, in addition to conventional substrates, studies have been made on the adhesion of oyster larvae by adding calcium to cement-based materials and increasing the content of calcium in concrete. Literature reference^[1,2]In the method, 80-mesh cattle bone powder, calcium carbonate powder and gypsum powder (the mixing amount is 62.5 percent and 375 percent of the weight of cement) are singly mixed into mortar to carry out an oyster attachment experiment, and the sequence of the inducing capacity of the calcium excipient for the adhesion of oyster larvae under the same condition is obtained: os bovis Seu Bubali powder>Calcium carbonate is calcium sulfate; the calcium carbonate powder is 5-60% of the mortar (41.7-500.0% of the cement), and the effect is best when the calcium carbonate powder is 20% (166.7% of the cement). Although the attachment amount of the oysters can be increased by adding the bovine bone meal, the calcium carbonate powder and the gypsum powder, the added proportion is too large (the weight of the calcium powder is more than 41.7 percent of that of the cement and even reaches 500.0 percent), the mechanical property and the durability of the concrete are seriously influenced, and the oyster shell cement is not suitable for being used in concrete engineering in marine environment. In addition, although the bovine bone meal has a good effect of inducing adhesion of oysters, when the amount of the bovine bone meal exceeds 10% of the cement, the concrete is mildewed. Therefore, at present, although calcium substances such as bovine bone meal, calcium carbonate and the like are doped into concrete, the influence of marine environment on the durability of a concrete structure is not considered, so that the concrete cannot be applied to severe marine environment at all.

In CN104529286 patent: from the aspect of waste utilization, oyster shell fragments of 5 mm-8 mm with the mass of 10% -20% of cement are mixed into the artificial fish reef, and the concrete which does not influence biological attachment and does not pollute the environment is obtained. CN104938384 is to mix 150-200 mesh biological calcium carbonate powder (fishbone, coral, egg shell and shell are 1:1:1:1) and shell fragment which are 10-20% of the cement mass into the artificial fish reef, which shows that the induced biomass is gradually increased along with the increase of the calcium carbonate mixing amount, and the biomass (marine plant and marine organism) induced by the biological calcium carbonate is the most when the mixing amount is the maximum (20% of the cement weight). In order to reduce the alkalinity of the surface of the concrete artificial fish reef, microorganisms and algae are easier to attach, the biomass and the population quantity are increased, and the fish collecting effect is better. The biological calcium carbonate cement mortar coating layer educt is harmless to the environment and the organism. Although the biological calcium carbonate powder, the oyster shell fragments and the like are doped into concrete for artificial fish reef manufacturing and biological attachment experiments, the biological calcium carbonate powder indeed enhances the biological enrichment effect, but mainly enriches marine plants and microorganisms.

In a word, the calcium content is important for the attachment of oyster larvae, and the current experimental results also prove that the addition of a proper amount of calcium carbonate substances in the cement-based material can promote the attachment and growth of the oyster larvae. However, cement concrete contains a large amount of calcium ions, the pH value of a pore solution is generally greater than 12.5, and the pH value of a saturated calcium hydroxide solution is about 12 at normal temperature, so that the concentration of the calcium ions in the concrete pore solution is about 5 mmol/L; the solubility of calcium carbonate is very low, and is only 9.5X 10 at 25 DEG C^-5mol/L(9.5×10^-2mmol/L). At present, the optimal range of calcium ion concentration for inducing shellfish adhesion is considered to be 10-25 mmol/L, and even if oyster larvae are placed in saturated calcium carbonate solution, enough Ca is not available²⁺The concentration of Ca is suitable for providing proper Ca for the adhesion of oysters²⁺And (4) concentration. Further, Ca (OH) in the inside of the cement concrete₂Can be released more quickly, while the dissolution of calcium carbonate takes longer. Therefore, it was confirmed that incorporation of calcium carbonate material into concrete promotes adhesion of oyster larvae, Ca²⁺Not the dominant role.

In addition, the doping amount of the shell powder is too large, the weight ratio of the shell powder to the cement is more than 10%, and some shell powder even reaches 500%, so that the durability of the concrete is greatly influenced. Although the proper amount of calcium carbonate material can prevent the concrete from being reduced in impermeability or better, the excessive amount of calcium carbonate material is very unfavorable for the concrete to resist the corrosion of sulfuric acid and sulfate in seawater.

Therefore, the problem of marine sessile organism larva induced adhesion by doping calcium substances such as biological calcium carbonate, bovine bone meal, calcium carbonate powder and the like into concrete still exists, and particularly the problems of concrete performance caused by excessive doping of the calcium substances, mildew caused by doping of the bovine bone meal and the like exist.

Fourth, the influence of color on the adhesion of marine periphyton

The color of the substrate has certain influence on the attachment, metamorphosis and growth of the larvae of the marine periphyton. In foreign countries, it has been reported that in sea areas with low temperature, dark bottom substances can promote the growth of oysters. Domestic research shows that oyster larvae have certain selectivity on color. The color selectivity of the crassostrea hongkongensis larvae on the plastic anchoring base is as follows: black > white > red. Crassostrea gigas larvae prefer to attach to black and gray plastic plates and it is believed that black and gray may be a protective color for oyster larvae to avoid natural enemy attacks. Barnacles prefer to adhere to red substrates. Pearl oyster also prefers dark (black, red), non-reflective substrates, showing non-photosensitive behavior. And the bacterium alteromonas melellii attracts oyster larvae by producing a compound that participates in melanin synthesis.

At present, the research on the influence of the color of the substrate on the adhesion of marine periphyton larvae is limited to organic polymer plates such as plastic plates and polyethylene plates, asbestos plates and the like. The concrete is used as a most potential substitute substrate, is particularly used for oyster reef repair, artificial ecological engineering construction and marine reinforced concrete corrosion prevention at present, and the influence of the color on the attachment amount of sessile organism larvae is not referred to related data.

Fifth, the influence of roughness on the adhesion of marine periphyton larvae

Generally, the roughness of the surface of the substrate has a certain influence on the adhesion of oysters and barnacle larvae. Domestic and foreign researches show that under the same other conditions, oysters and barnacle larvae attached to the rough surface are more than those attached to the smooth surface. The rough surface provides better tactile stimulation for the crawling and attachment of oyster and barnacle larvae so as to help the larvae to stay on the substrate; the presence of cracks and pits can protect the larvae from predators; and a larger area, and potentially a richer, diverse microbial environment than a smooth surface. Recent studies have shown that textured concrete surfaces adhere to more marine organisms than smooth surfaces, promoting the attachment and metamorphosis of larvae. However, some studies have shown that coarseness has no significant effect on attachment metamorphosis of larvae.

In summary, different substrates, as well as the effects of color and roughness on marine periphyton attachment, are currently being investigated. There are also some studies relating to the effect of calcareous materials in concrete on marine biofouling. However, due to the knowledge of related subjects such as marine organisms, marine microorganisms, marine chemistry, marine concrete engineering materials and structures, the subject directions are greatly different, so that many problems are encountered in the cross research, such as the above-mentioned problems that the cement-based material has an unclear water-cement ratio, the mechanism of inducing oyster adhesion by calcium carbonate materials is unclear, the calcium carbonate materials are too much to be added into the cement, the durability of the concrete is poor, and the added bovine bone meal is easy to mildew. In addition, the current research idea of inducing oyster adhesion is more suitable for newly building an ocean breakwater, and is not feasible for a concrete breakwater in service, because the project cannot be dismantled and rebuilt to change the concrete substrate for the breakwater, a novel method is needed to be adopted for solving the problem.

Disclosure of Invention

The invention aims to attach more compact oysters to a breakwater in service, and realize high ecology of the breakwater by utilizing the characteristics of the oysters as ecological engineers and the effects of purifying water and improving water areas. The specific technical scheme is as follows:

(1) surveying the sea area of the building position of the concrete structure: investigating the species of the oyster in the sea area and whether the oyster is attached, and performing temperature, seawater temperature, dissolved oxygen, plankton, total dissolved inorganic nitrogen, active phosphate, active silicate and Ca on the sea area in different seasons²⁺，Zn²⁺，K⁺The like, and the times, the intensity and the like of typhoon in the past year;

(2) preparing a concrete adhesive base: and manufacturing the lightweight concrete oyster attaching base with a rough surface, wherein the shape of the lightweight concrete oyster attaching base is one of a plate-shaped attaching base, a wave-shaped attaching base and a cylindrical attaching base.

(3) Quantitatively collecting and breeding oyster seedlings: oyster in local sea areaThe planktonic larvae are intensively attached and metamorphosis stage, and the attaching base is placed in a fry collecting area of a nearby sea area, and when the attaching amount of the oyster larvae is 15-25 per 100cm²Stopping seedling collection; then the fish is moved to a sea area with rich bait for floating cultivation.

(4) And (3) cleaning the surface of the breakwater: after the tide is removed, shoveling and cleaning marine sessile organisms and marine plants on the surface of the concrete structure, and then flushing by adopting a high-pressure water gun;

(5) coating and maintaining the paint: coating a cement-based coating for inducing sessile organisms on the surface of ocean engineering on the surface of the concrete block, and maintaining for 1-3 days;

(6) placing the oyster attaching base on site: and (4) fixing the oyster base with the gonad development stage of the oysters in the step (3) as the maturation stage on a fixing frame at the tidal range area.

(7) Monitoring larva attachment: monitoring the attachment condition of oyster larvae on the surface of concrete, and determining the attachment condition of oyster larvae to be 30-40/100 cm²In this case, the oyster adherance was removed to areas where there was less oyster spat.

(8) Nutrient addition and management: by monitoring the area periodically for plankton, nutrients and Ca²⁺And the like, a nutrition barrel which can be automatically controlled is placed, the amount of plankton is enriched, and the support of calcium ions and the like is provided for the growth of the oysters.

(2) The light concrete adhesive base with the rough surface, which is prepared by the specific measures in the specification, comprises the following material components: the cementing material, the light coarse aggregate, the light fine aggregate, water, the dark pigment, the biological calcium powder, the calcium carbonate powder, the trace elements, the chopped fiber and the superplasticizer are sequentially mixed according to the weight ratio: 21.8% -34.5%, 24.6% -37.5%, 15.8% -29.6%, 8.4% -16.4%, 0.6-3.0%, 0.4% -2.0%, 0.2% -1.8%, 0.15% -1.5% and 0.03% -0.18%.

Preferably, the dark color pigment is: one or two of iron oxide black, aniline black, carbon black, antimony sulfide, iron oxide red and organic pigment red.

Preferably, the dark color pigment is: according to the influence degree on the performance of concrete, the pigments are modified by adopting one of transparent resin, organic silicon, dimethyl siloxane and super-hydrophobic materials.

Preferably, the biological calcium powder is: the biological calcium carbonate powder is one or a plurality of compounds of oyster shell powder, fishbone powder, egg shell powder and coral powder, and the fineness of the biological calcium carbonate powder is 100-1000 meshes.

Preferably, the biological calcium powder is: treating 100-500 mesh egg shell powder, coral powder, oyster shell powder and fishbone powder with acid selected from one or two of acetic acid, silicic acid and sulfurous acid; and treating the 100-500-mesh bovine bone powder by using one or two of diluted phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid.

Preferably, the calcium carbonate powder is: calcite, chalk, limestone, marble, aragonite, travertine powder, and one or more of light calcium carbonate, activated calcium carbonate, calcium carbonate whisker and superfine light calcium carbonate which are processed, and the fineness is more than 200 meshes.

Preferably, the trace elements of zinc, iron, potassium and phosphorus can be selected from natural minerals, industrial products or chemical reagents, including one or more of zinc sulfate, calcium phosphate, zinc phosphate, potassium sulfate, potassium nitrate, ferric sulfate, ammonium nitrate, potassium phosphate, ammonium phosphate and iron phosphate, and are modified to realize slow release of corresponding ions and reduce or eliminate adverse effects on the performance of concrete. However, nitrogen and phosphorus are not selected for the eutrophic area.

Preferably, the cementing material is one of silicate cement, sulphoaluminate cement and alkali-activated cementing material doped with mineral admixture. Wherein the mineral admixture in the silicate cement doped with the mineral admixture comprises one or more of silica fume, slag powder and fly ash; the sulphoaluminate cement comprises one or two of quick-hardening sulphoaluminate cement, high-strength sulphoaluminate cement and expansion sulphoaluminate cement; the alkali-activated cementing material comprises one of alkali-activated slag, alkali-activated slag and fly ash.

Preferably, the chopped fibers are inorganic fibers (with the length of 12-20 mm) and comprise one or more of basalt fibers, alkali-resistant glass fibers and carbon fibers.

Preferably, the lightweight coarse aggregate is: one or two of crushed light porous basalt and light ceramsite with the maximum grain size of less than 20 mm.

Preferably, the lightweight fine aggregate is: one or two of the crushed zeolite and the light ceramic sand have the grain diameter of 0.2 mm-5 mm.

A preparation method of a cement concrete oyster attaching base with a rough surface comprises the following steps:

s1: designing different roughness according to the characteristics of the oyster larvae which favor to attach to the rough surface, and then manufacturing forming templates with different roughness;

s2: weighing a cementing material, a light coarse aggregate, a light fine aggregate, water, a dark pigment, biological calcium powder, calcium carbonate powder, trace elements, chopped fibers and a superplasticizer;

s3: firstly, putting the light coarse aggregate and the light fine aggregate into a concrete mixer to be mixed for 0.5-1 minute; then adding a cementing material, a dark pigment, biological calcium powder, calcium carbonate powder and trace elements, and continuously stirring for 1-2 minutes; then adding chopped fibers, water and a superplasticizer and stirring for 2-6 minutes; and after the mixture is uniformly stirred, pouring and vibrating.

S4: placing the concrete sample after the form removal in high-concentration CO according to the condition₂And curing in a curing box for 0.5 to 5 hours, reducing the alkalinity of the cement test piece, and then performing standard curing for 28d or curing according to actual conditions.

The cement concrete oyster attaching base with rough surface and good induction effect can be prepared.

(2) The light concrete ecological adhesive base is provided with a circular hole with the diameter of 3-5 mm during molding, and the size of the plate-shaped adhesive base is 10 multiplied by 2-3 cm.

(3) The specific measures of the method are that the floating larvae of the oysters are intensively attached and metamorphosis, wherein the north is generally 5-8 months, and the south is generally 4-10 months.

(5) The cement coating for inducing sessile organisms on the surface of ocean engineering is provided by the specific measures in the specification. The specific technical scheme is as follows:

the material components are as follows: the weight ratio of the cementing material, the sand, the water, the dark pigment, the biological calcium powder, the calcium carbonate powder, the trace elements, the lignocellulose, the dispersible rubber powder and the superplasticizer is as follows in sequence:

1:(0.35～0.7):(0.20～0.60):(0.02～0.10):(0.02～0.10):(0.02～0.10):(0.01～0.08):(0.04～0.12):(0.05～0.15):(0.001～0.010)。

Preferably, the sand is one or more of river sand with the particle size of 0.16-2.36 mm, machine-made sand (mother rock can be limestone, basalt or granite) and sea sand.

Preferably, the superplasticizer is one of polycarboxylic acid and naphthalene series.

A cement-based paint for inducing sessile organisms on the surface of ocean engineering and a preparation method thereof comprise the following steps:

s1: weighing a cementing material, sand, water, a dark pigment, biological calcium powder, calcium carbonate powder, trace elements, lignocellulose, dispersible rubber powder and a superplasticizer;

s2: placing the cementing material, the deep color pigment, the biological calcium powder, the calcium carbonate powder and the trace elements into a mixer, wherein the rotating speed is 1000-1500 rpm, the mixing time is 2-5 minutes, and the materials are uniformly mixed;

s3: then placing the sand, the lignocellulose and the dispersible rubber powder into a stirrer, wherein the rotating speed is 500 plus 1000 revolutions per minute, and the mixing time is 5-10 minutes;

s4: fully dissolving the powdery superplasticizer into water, then placing the mixed materials into a high-speed stirrer together at the rotating speed of 200 plus materials of 500 rpm, and stirring for 5-10 minutes.

Thus obtaining the cement coating with good induction effect for inducing sessile organisms on the surface of ocean engineering.

(6) The rope is one of a palm rope, a glass fiber rope and a basalt fiber rope.

(7) According to the specific measures, the nutrition barrel is added with carbonate, bicarbonate, biological calcium powder, calcium carbonate powder, trace elements and the like according to the needs of marine plankton, and different substances are selected to be combined and placed in the breakwater according to the actual marine conditions.

The invention has the beneficial effects that:

the invention aims to quickly attach compact oysters to the breakwater in service by cleaning and washing the breakwater in service and fixedly placing the attaching base attached with the oysters around the breakwater in service, and utilizes the characteristics of the oysters as ecological engineers and the functions of purifying water and improving water areas to highly ecologize the breakwater in service and realize the aims of ecologization and long-term service of the breakwater.

Drawings

FIG. 1 shows the surface mildew (under standard curing) of concrete mixed with 10% of bovine bone meal at different mixing ratios;

FIG. 2 shows different mixing ratios of modified 10% bovine bone meal with fineness greater than 200 meshes;

FIG. 3 is a schematic diagram of a sea adhesion experiment 210 d;

FIG. 4 is a schematic diagram of a sea adhesion experiment 300 d;

FIG. 5 is a schematic diagram of a concrete oyster attachment base;

FIG. 6 is a schematic diagram of a concrete oyster attachment base;

fig. 7 is a schematic diagram of a concrete oyster attachment base.

Detailed Description

The present invention is described in detail below with reference to examples, which are provided only for illustrating the present invention and do not limit the scope of the present invention.

The specific technical scheme of the engineering scheme comprises the following steps:

example 1:

(1) concrete structure construction siteSurvey in sea areas: researching the oyster dominant species of the sea area and whether oysters are attached, researching the typhoon frequency and strength of the past year, and looking up the meteorological and hydrological data of the sea area of the construction area for many years; simultaneously applying each season to air temperature, sea water temperature, dissolved oxygen, plankton, total dissolved inorganic nitrogen, active phosphate, active silicate and Ca in the sea area²⁺、Zn²⁺、K⁺Testing and recording ions, and analyzing feasible methods and solving measures for the construction of the marine concrete engineering structure;

(2) preparing a concrete adhesive base: ecological concrete is adopted to prepare a lightweight concrete oyster attachment base with a rough surface, the size of the attachment base is 10cm multiplied by 2cm, and after the mould is removed, CO is immediately carried out for 1 hour under 10 atmospheric pressures₂Curing is followed by standard curing 28 d.

(3) And (3) regular and quantitative collection and cultivation of oyster fries: in 7 months, placing lightweight coarse concrete attaching base in the seedling collecting area of nearby sea area, and allowing the oyster larvae to attach at a rate of 20/100 cm²Stopping collecting seedlings, and then moving the seedlings to a sea area with rich baits for floating culture;

(4) and (3) cleaning the surface of the breakwater: after the tide is subsided in the evening, the marine sessile organisms and marine plants on the surface of a part of concrete structure in a tidal range area are eradicated and cleaned, and then a high-pressure water gun is adopted for washing;

(5) coating and maintaining the paint: coating a cement-based coating for inducing sessile organisms on the surface of ocean engineering on the surface of the concrete block during saturated surface drying, and maintaining for 3 d;

(6) placing the oyster attaching base on site: ensuring the engineering implementation time in the planktonic larvae concentrated attachment metamorphosis period of the oysters. And (4) transporting the oyster base with good attachment to the oyster base on the concrete surface (the gonad development stage is the mature stage) to the sea area for constructing the breakwater. Placing a lightweight concrete oyster attaching base with a rough surface every 20 meters along the breakwater, and fixing the oyster attaching base on the area fixing frame; and feeding chlorella concentrated bait according to the plankton condition in the local sea area. Meanwhile, the feeding amount is increased from 2.5 ten thousand cells/mL, 4 ten thousand cells/mL and 6 ten thousand cells/mL to 8 ten thousand cells/mL according to the development condition of the oyster larvae.

(7) Monitoring larva attachment: monitoring the attachment condition of oyster larvae on the surface of concrete, and when the attachment density reaches 45/100 cm²And removing the oyster attaching base to the area with less oyster seedlings.

Example 2:

(1) surveying the sea area of the building position of the concrete structure: researching the oyster dominant species of the sea area and whether oysters are attached, researching the typhoon frequency and strength of the past year, and looking up the meteorological and hydrological data of the sea area of the construction area for many years; simultaneously, the temperature of the sea area, the temperature of the sea water, dissolved oxygen, plankton, total dissolved inorganic nitrogen, active phosphate, active silicate and Ca are measured in each quarter²⁺，Zn²⁺，K⁺Testing and recording ions, and analyzing feasible methods and solving measures for the construction of the marine concrete engineering structure;

(2) preparing a concrete adhesive base: ecological concrete is adopted to prepare a lightweight concrete oyster attachment base with a rough surface, the size of the attachment base is 10cm multiplied by 3cm, and after the mould is removed, CO is immediately carried out for 1.5 hours under 10 atmospheric pressures₂Curing is followed by standard curing 28 d.

(3) And (3) regular and quantitative collection and cultivation of oyster fries: in 6 months, placing lightweight coarse concrete attaching base in the seedling collecting area of nearby sea area, and allowing the oyster larvae to attach at a rate of 30/100 cm²Stopping collecting seedlings, and then moving the seedlings to a sea area with rich baits for floating culture.

(5) coating and maintaining the paint: when the saturated surface is dry, the surface of the concrete block is coated with a cement-based coating for inducing sessile organisms on the surface of ocean engineering, and the curing is carried out for 3d

(6) Placing the oyster attaching base on site: ensuring the engineering implementation time in the planktonic larvae concentrated attachment metamorphosis period of the oysters. And (4) transporting the oyster base with good attachment to the oyster base on the concrete surface (the gonad development stage is the mature stage) to the sea area for constructing the breakwater. Placing a lightweight concrete oyster attaching base with a rough surface every 30 meters along the breakwater, and fixing the oyster attaching base on the area fixing frame; and feeding chlorella concentrated bait according to the plankton condition in the local sea area. Meanwhile, the feeding amount is increased from 3 ten thousand cells/mL, 5 ten thousand cells/mL and 7 ten thousand cells/mL to 9 ten thousand cells/mL according to the development condition of the oyster larvae.

(7) Monitoring larva attachment: monitoring the attachment condition of oyster larvae on the surface of concrete, and when the attachment density reaches 50/100 cm²And removing the oyster attaching base to the area with less oyster seedlings.

The mixing ratio of the oyster attaching base and the cement-based paint described in example 1 and example 2 was as follows:

a concrete mixing proportion of lightweight concrete oyster attaching base (1-26) with rough surface, a mixing proportion of cement-based paint (27-36) for inducing sessile organisms on the surface of ocean engineering,

1: the common Portland cement concrete comprises the following components in parts by weight: 29.37%, 33.57%, 24.48%, 12.59%, 0.03%.

Wherein the light coarse aggregate is one or two of crushed light porous basalt with the maximum grain size of less than 20mm and light ceramsite. The light fine aggregate is one or two of crushed zeolite and light ceramic sand, the particle size of the light fine aggregate is 0.2-5 mm, and the light fine aggregate is good in gradation. The water meets the concrete water standard (JGJ63-2006), the Cl-content is less than 1000mg/L, the PH value is more than 4.5, and the influence on the initial setting time difference, the final setting time, the strength and the permeability of the cement is small. The materials selected in examples 1 to 25 are the same.

2: the reference concrete has the following weight proportions of ordinary portland cement, silica fume, blast furnace slag powder, light coarse aggregate, light fine aggregate, water and polycarboxylic acid water reducer powder: 17.62%, 1.47%, 10.28%, 33.57%, 24.48%, 12.59%, 0.03%.

3: the weight proportions of the unmodified dark pigment, the ordinary Portland cement, the silica fume, the blast furnace slag powder, the light coarse aggregate, the light fine aggregate, the water and the polycarboxylic acid water reducer powder are as follows in sequence: 0.87%, 17.62%, 1.36%, 9.52%, 33.57%, 24.48%, 12.59%, 0.03%.

4: the weight proportions of the unmodified dark pigment, the ordinary Portland cement, the silica fume, the blast furnace slag powder, the light coarse aggregate, the light fine aggregate, the water and the polycarboxylic acid water reducer powder are as follows in sequence: 1.47%, 17.62%, 1.28%, 8.99%, 33.57%, 24.48%, 12.59%, 0.03%.

5: the weight proportions of the unmodified dark pigment, the ordinary Portland cement, the silica fume, the blast furnace slag powder, the light coarse aggregate, the light fine aggregate, the water and the polycarboxylic acid water reducer powder are as follows in sequence: 2.35%, 17.62%, 1.18%, 8.23%, 33.57%, 24.48%, 12.59%, 0.03%.

6: the modified dark pigment (iron oxide black: nigrosine mixture mass ratio is 1:1), ordinary portland cement, silica fume, blast furnace slag powder, light coarse aggregate, light fine aggregate, water and polycarboxylic acid water reducing agent powder are sequentially mixed according to the weight ratio: 0.87%, 17.62%, 1.36%, 9.52%, 33.57%, 24.48%, 12.59%, 0.03%.

7: the modified dark pigment (iron oxide black: nigrosine mixture mass ratio is 1:1), ordinary portland cement, silica fume, blast furnace slag powder, light coarse aggregate, light fine aggregate, water and polycarboxylic acid water reducing agent powder are sequentially mixed according to the weight ratio: 1.47%, 17.62%, 1.28%, 8.99%, 33.57%, 24.48%, 12.59%, 0.03%.

8: the modified dark pigment (iron oxide black: nigrosine mixture mass ratio is 1:1), ordinary portland cement, silica fume, blast furnace slag powder, light coarse aggregate, light fine aggregate, water and polycarboxylic acid water reducing agent powder are sequentially mixed according to the weight ratio: 2.35%, 17.62%, 1.18%, 8.23%, 33.57%, 24.48%, 12.59%, 0.03%.

The modified dark color pigment is prepared by mixing 196 transparent resin, 3% of curing agent and 1.5% of accelerator with the pigment, wherein the volume ratio of the pigment to the resin is as follows: 1: 0.2; curing at normal temperature for 4h, curing at 60 deg.C for 4h, then breaking, and grinding with vibration mill to obtain the final product with fineness greater than 400 mesh.

9: the weight proportions of the calcium carbonate powder, the ordinary Portland cement, the silica fume, the blast furnace slag powder, the light coarse aggregate, the light fine aggregate, the water and the polycarboxylic acid water reducer powder are as follows in sequence: 0.87%, 17.62%, 1.36%, 9.52%, 33.57%, 24.48%, 12.59%, 0.03%.

10: the weight proportions of the calcium carbonate powder, the ordinary Portland cement, the silica fume, the blast furnace slag powder, the light coarse aggregate, the light fine aggregate, the water and the polycarboxylic acid water reducer powder are as follows in sequence: 1.47%, 17.62%, 1.28%, 8.99%, 33.57%, 24.48%, 12.59%, 0.03%.

11: the weight proportions of the calcium carbonate powder, the ordinary Portland cement, the silica fume, the blast furnace slag powder, the light coarse aggregate, the light fine aggregate, the water and the polycarboxylic acid water reducer powder are as follows in sequence: 2.35%, 17.62%, 1.18%, 8.23%, 33.57%, 24.48%, 12.59%, 0.03%.

12: the modified dark pigment (iron oxide black: aniline black mixture mass ratio is 1:1), calcium carbonate powder, ordinary portland cement, silica fume, blast furnace slag powder, light coarse aggregate, light fine aggregate, water and polycarboxylic acid water reducing agent powder are sequentially mixed according to the weight ratio: 1.47%, 0.87%, 17.62%, 1.18%, 8.23%, 33.57%, 24.48%, 12.59%, 0.03%.

13: the modified dark pigment (iron oxide black: aniline black mixture mass ratio is 1:1), calcium carbonate powder, ordinary portland cement, silica fume, blast furnace slag powder, light coarse aggregate, light fine aggregate, water and polycarboxylic acid water reducing agent powder are sequentially mixed according to the weight ratio: 1.47%, 17.62%, 1.10%, 7.71%, 33.57%, 24.48%, 12.59%, 0.03%.

14: the modified dark pigment (iron oxide black: aniline black mixture mass ratio is 1:1), calcium carbonate powder, ordinary portland cement, silica fume, blast furnace slag powder, light coarse aggregate, light fine aggregate, water and polycarboxylic acid water reducing agent powder are sequentially mixed according to the weight ratio: 1.47%, 2.35%, 17.62%, 0.99%, 6.94%, 33.57%, 24.48%, 12.59%, 0.03%.

15: the weight proportions of the unmodified bovine bone meal, the ordinary portland cement, the silica fume, the blast furnace slag powder, the light coarse aggregate, the light fine aggregate, the water and the polycarboxylic acid water reducer powder are as follows in sequence: 0.87%, 17.62%, 1.36%, 9.52%, 33.57%, 24.48%, 12.59%, 0.03%.

16: the weight proportions of the unmodified bovine bone meal, the ordinary portland cement, the silica fume, the blast furnace slag powder, the light coarse aggregate, the light fine aggregate, the water and the polycarboxylic acid water reducer powder are as follows in sequence: 1.47%, 17.62%, 1.28%, 8.99%, 33.57%, 24.48%, 12.59%, 0.03%.

17: the weight proportions of the unmodified bovine bone meal, the ordinary portland cement, the silica fume, the blast furnace slag powder, the light coarse aggregate, the light fine aggregate, the water and the polycarboxylic acid water reducer powder are as follows in sequence: 2.35%, 17.62%, 1.18%, 8.23%, 33.57%, 24.48%, 12.59%, 0.03%.

18: the modified bovine bone meal, the ordinary portland cement, the silica fume, the blast furnace slag powder, the light coarse aggregate, the light fine aggregate, the water and the polycarboxylic acid water reducer powder are sequentially mixed according to the weight ratio: 0.87%, 17.62%, 1.36%, 9.52%, 33.57%, 24.48%, 12.59%, 0.03%.

19: the modified bovine bone meal, the ordinary portland cement, the silica fume, the blast furnace slag powder, the light coarse aggregate, the light fine aggregate, the water and the polycarboxylic acid water reducer powder are sequentially mixed according to the weight ratio: 1.47%, 17.62%, 1.28%, 8.99%, 33.57%, 24.48%, 12.59%, 0.03%.

20: the modified bovine bone meal, the ordinary portland cement, the silica fume, the blast furnace slag powder, the light coarse aggregate, the light fine aggregate, the water and the polycarboxylic acid water reducer powder are sequentially mixed according to the weight ratio: 2.35%, 17.62%, 1.18%, 8.23%, 33.57%, 24.48%, 12.59%, 0.03%.

The method for modifying the bovine bone meal comprises the following steps: adding 100-mesh bovine bone meal into 2% phosphoric acid solution, wherein the weight ratio of the bovine bone meal to the phosphoric acid solution is 1:3, the temperature is 20-30 ℃, the mixture is stirred for 30 minutes in a stirrer with the rotating speed of 200-500 rpm, a centrifugal machine with the rotating speed of 3000-5000 rpm is adopted for centrifugation for 3 minutes, supernatant is poured off, solid matters of the centrifuged solid matters are washed for 2-3 times by water, and washing water does not show acidity any more; and (3) drying the centrifuged solid substance in vacuum at 40 ℃, and grinding the dried bovine bone meal and 1:4 of slag powder to the fineness of more than 200 meshes by using a vibration mill for later use.

21: calcium carbonate powder, zinc sulfate, modified dark color pigment (black iron oxide: nigrosine mixture mass ratio is 1:1), ordinary portland cement, blast furnace slag powder, silica fume, light coarse aggregate, light fine aggregate, water and polycarboxylic acid water reducer powder are sequentially mixed according to the weight ratio: 2.35%, 0.5%, 1.47%, 17.62%, 0.93%, 6.50%, 33.57%, 24.48%, 12.59%, 0.03%.

22: calcium carbonate powder, zinc sulfate, modified dark color pigment (black iron oxide: nigrosine mixture mass ratio is 1:1), ordinary portland cement, blast furnace slag powder, silica fume, light coarse aggregate, light fine aggregate, water and polycarboxylic acid water reducer powder are sequentially mixed according to the weight ratio: 2.35%, 1.2%, 1.47%, 17.62%, 0.84%, 5.89%, 33.57%, 24.48%, 12.59%, 0.03%.

23: zinc sulfate, modified dark color pigment (black iron oxide: nigrosine mixture mass ratio is 1:1), modified biological calcium powder (modified bovine bone powder: oyster shell powder: 2:1), calcium carbonate powder, ordinary portland cement, silica fume, blast furnace slag powder, macadam, sand, water and polycarboxylic acid water reducing agent powder in sequence: 0.5%, 1.47%, 0.87%, 17.62%, 0.93%, 6.50%, 33.57%, 24.48%, 12.59%, 0.03%.

24: zinc sulfate, modified dark color pigment (black iron oxide: nigrosine mixture mass ratio is 1:1), modified biological calcium powder (modified bovine bone powder: oyster shell powder: 2:1), calcium carbonate powder, ordinary portland cement, silica fume, blast furnace slag powder, macadam, sand, water and polycarboxylic acid water reducing agent powder in sequence: 0.6%, 1.47%, 0.87%, 17.62%, 0.84%, 5.89%, 33.57%, 24.48%, 12.59%, 0.03%.

The modification method of zinc sulfate comprises the following steps: selecting diatomite SiO₂Adding 150g of water and 100g of zinc sulfate into diatomite with the content of more than 90 percent and the fineness of 600 meshes in a stirrer at the temperature of 60 ℃, and stirring until the mixture is completely dissolved for later use; and then 150g of the diatomite is heated to 60 ℃, added into the solution, stirred for 10 minutes in a stirrer with the rotating speed of 200-500 rpm, and then dried in a drying box with the drying temperature of 100 ℃ to obtain the modified zinc sulfate.

25: the weight ratio of zinc sulfate, modified dark color pigment, modified biological calcium powder (modified bovine bone powder: oyster shell powder: 2:1), calcium carbonate powder, ordinary portland cement, silica fume, blast furnace slag powder, broken stone, sand, water, short-cut fiber and polycarboxylic acid water reducer powder is as follows in sequence: 0.5%, 1.47%, 0.87%, 17.62%, 0.93%, 6.50%, 33.07%, 24.18%, 12.59%, 0.8%, 0.03%

26: the concrete oyster attachment base adopts the concrete and is designed into concrete oyster attachment bases with different shapes, which are shown in figures 5-7.

27: the weight ratio of the cementing material to the sand to the water to the modified dark pigment (black iron oxide: nigrosine mixture is 1:1), the modified biological calcium powder (modified bovine bone meal: oyster shell powder is 2:1), the calcium carbonate powder to the zinc sulfate to the lignocellulose to the dispersible gelatine powder to the superplasticizer is 1:0.5:0.4:0.03:0.03:0.03:0.02:0.06:0.06: 0.005.

28: the weight ratio of the cementing material to the sand to the water to the modified dark color pigment (black iron oxide: nigrosine mixture is 1:1), the weight ratio of the modified biological calcium powder (modified bovine bone powder: oyster shell powder is 2:1), the calcium carbonate powder, the zinc sulfate, the lignocellulose to the dispersible rubber powder to the superplasticizer are as follows in sequence: 1:0.5:0.4:0.05:0.05:0.05:0.02:0.06:0.06:0.005.

29: the weight ratio of the cementing material to the sand to the water to the modified dark color pigment (black iron oxide: nigrosine mixture is 1:1), the weight ratio of the modified biological calcium powder (modified bovine bone powder: oyster shell powder is 2:1), the calcium carbonate powder, the zinc sulfate, the lignocellulose to the dispersible rubber powder to the superplasticizer are as follows in sequence: 1:0.5:0.4:0.05:0.05:0.05:0.04:0.08:0.09:0.005.

30: the weight ratio of the cementing material to the sand to the water to the modified dark color pigment (black iron oxide: nigrosine mixture is 1:1), the weight ratio of the modified biological calcium powder (modified bovine bone powder: oyster shell powder is 2:1), the calcium carbonate powder, the zinc sulfate, the lignocellulose to the dispersible rubber powder to the superplasticizer are as follows in sequence: 1:0.5:0.4:0.08:0.08:0.08:0.04:0.08:0.09:0.005. .

31: the weight ratio of the cementing material to the sand to the water to the modified dark color pigment (black iron oxide: nigrosine mixture is 1:1), the weight ratio of the modified biological calcium powder (modified bovine bone powder: oyster shell powder is 2:1), the calcium carbonate powder, the zinc sulfate, the lignocellulose to the dispersible rubber powder to the superplasticizer are as follows in sequence: 1:0.5:0.4:0.08:0.08:0.08:0.06:0.10:0.12:0.005.

32: the weight ratio of the cementing material to the sand to the water to the modified dark pigment (black iron oxide: nigrosine mixture is 1:1), the modified biological calcium powder (modified bovine bone meal: oyster shell powder is 2:1), the calcium carbonate powder to the zinc sulfate to the lignocellulose to the dispersible gelatine powder to the superplasticizer is 1:0.5:0.4:0.03:0.03:0.03:0.04:0.06:0.06: 0.005.

33: the weight ratio of the cementing material to the sand to the water to the modified dark color pigment (black iron oxide: nigrosine mixture is 1:1), the weight ratio of the modified biological calcium powder (modified bovine bone powder: oyster shell powder is 2:1), the calcium carbonate powder, the zinc sulfate, the lignocellulose to the dispersible rubber powder to the superplasticizer are as follows in sequence: 1:0.5:0.4:0.05:0.05:0.05:0.04:0.06:0.06:0.005.

34: the weight ratio of the cementing material to the sand to the water to the modified dark color pigment (black iron oxide: nigrosine mixture is 1:1), the weight ratio of the modified biological calcium powder (modified bovine bone powder: oyster shell powder is 2:1), the calcium carbonate powder, the zinc sulfate, the lignocellulose to the dispersible rubber powder to the superplasticizer are as follows in sequence: 1:0.5:0.4:0.05:0.05:0.05:0.02:0.08:0.09:0.005.

35: the weight ratio of the cementing material to the sand to the water to the modified dark color pigment (black iron oxide: nigrosine mixture is 1:1), the weight ratio of the modified biological calcium powder (modified bovine bone powder: oyster shell powder is 2:1), the calcium carbonate powder, the zinc sulfate, the lignocellulose to the dispersible rubber powder to the superplasticizer are as follows in sequence: 1:0.5:0.4:0.08:0.08:0.08:0.06:0.08:0.09:0.005. .

36: the weight ratio of the cementing material to the sand to the water to the modified dark color pigment (black iron oxide: nigrosine mixture is 1:1), the weight ratio of the modified biological calcium powder (modified bovine bone powder: oyster shell powder is 2:1), the calcium carbonate powder, the zinc sulfate, the lignocellulose to the dispersible rubber powder to the superplasticizer are as follows in sequence: 1:0.5:0.4:0.03:0.03:0.03:0.06:0.10:0.12:0.005.

The method for modifying the dark pigment comprises the following steps: 196 transparent resin is adopted, 3 percent of curing agent and 1.5 percent of accelerating agent are added and mixed with pigment, and the volume ratio of the pigment to the resin is as follows: 1: 0.2; curing at normal temperature for 4h, curing at 60 deg.C for 4h, then breaking, and grinding with vibration mill to obtain the final product with fineness greater than 400 mesh.

Comparison document 1: living breakwater _ New York coastal green infrastructure _ Sun-Crane

The construction of the "living" breakwater, the macroscopic design, the surface texture and the use of low-alkali cement for the concrete member, increase the marine biomass, but the increase includes marine plants and marine sessile organisms, and is mainly marine plants, is performed in the comparison document 1.

In the invention, besides low alkalization is carried out on cement, dark pigment, biological calcium powder, calcium carbonate powder, trace elements and modified carbonate (hydrogen) are added into concrete for inducing oyster larvae, the induction has the characteristics of rapidness and compactness, the effect is good, and the ecological environment of sea areas can be improved to a great extent.

Compared with the comparison document 2 (a bionic concrete artificial fish reef and a preparation method 2015CN104938384A), the differences are that:

(1) the object in the present invention is different from comparative document 2: in comparison document 2, although a layer of cement mortar mixed with ground oyster shells is coated on the surface of concrete, the purpose is mainly achieved by surface bionic property, fish, microorganisms and algae are collected, the number of microorganisms is increased, and the water environment is improved, and oyster is not mentioned. The cement-based coating of the present invention is intended to induce oyster adhesion.

(2) The comparison document 2 indicates that in cement mortar, the biological calcium carbonate powder (150-200 meshes) with the cement mass of less than 10% is not obvious in induced adhesion. However, in the research process, the modified bovine bone powder and the biological calcium carbonate powder are mixed with the cement-based coating (the fineness is 100-1000 meshes), and the optimal mixing amount of the bovine bone powder and the biological calcium carbonate powder is within 10 percent of the cementing material.

(3) By modifying the bovine bone powder and the biological calcium carbonate powder, in particular to egg shell powder, coral powder, oyster shell powder and fishbone powder of 100 meshes to 500 meshes which are treated by the following acids, including one or two of acetic acid, silicic acid, sulfurous acid and the like; bovine bone meal of 100 to 500 mesh was treated with an acid comprising diluted phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid.

(4) The contrast document is difficult to construct by embedding oyster shells on the concrete surface, and the method can not be adopted on the surface of each project, so that the feasibility is low. The invention can achieve the effect of inducing sessile organisms by coating a layer of cement-based paint on the surface of concrete, does not need to be embedded with oyster shells, has simple construction and can greatly increase the attachment of the oysters.

(5) In the marine environment, the phenomenon that the artificial fish reef is seriously corroded for many times in recent years appears, and the serious corrosion is mainly caused by the combined action of biological sulfuric acid secreted by anaerobic microorganism thiobacillus, acid substances secreted by other bacteria and the like. Calcium carbonate is weak in acid corrosion resistance, and therefore, excessive calcium carbonate with a large fineness causes severe acid corrosion.

Compared to reference 3 (Vanreilin. influence of matrix type on oyster attachment, growth, population establishment and reef development [ D ]), the differences are:

(1) in comparison document 3, 80-mesh bovine bone powder, calcium powder and gypsum powder were used, each separately added to concrete. The fineness of all the calcium materials in the invention is more than 100 meshes and more than that of the materials in the comparison document 3. The bovine bone meal is also added, modified, and the grading of the coating and concrete particles and the induction capability of the coating and concrete particles are considered.

(2) Grinding the bovine bone powder by using a vibration mill at normal temperature, wherein when the fineness is more than 80 meshes, the bovine bone powder contains a large amount of collagen and is seriously agglomerated, so that the bovine bone powder cannot be continuously ground. The invention adopts dilute acid modification technology and is compounded with other substances and ground to obtain the modified biological calcium powder with small particle size and fineness of more than 200 meshes. The prepared biological calcium powder keeps the original substances of the biological calcium, increases the release rate of substances which induce oyster larvae to adhere to the biological calcium powder, and reduces the doping amount of the biological calcium powder, thereby reducing the influence on the performance of the coating and the concrete.

(3) Because the bovine bone meal contains rich organic substances such as collagen, the great amount of the substances can cause the strength and impermeability of the coating and concrete to be reduced, particularly after the content of the organic substances exceeds 5 percent, the mixing amount is increased, the strength of the coating and concrete is rapidly reduced, the impermeability is obviously reduced, and the surface of the coating and concrete can grow mildewed under standard curing conditions. FIG. 1 shows the mildew formation of a concrete specimen. FIG. 2 shows the surface condition of the modified concrete.

As can be seen from FIG. 1, the mold on the concrete surface appeared white flocculent, covering almost the entire concrete surface; the concrete surface in figure 2 has no mildew due to the same amount of bovine bone meal, age and curing conditions.

According to the invention, by controlling and adopting the dilute acid modification and composite grinding technology, the induction capability of the bovine bone meal is fully exerted, the mixing amount of the bovine bone meal is greatly reduced, and the anti-corrosion treatment and modification are carried out, so that the composite inducer mainly comprising the bovine bone meal is realized, the mixing amount is small, the strength and the permeability of the coating and the concrete are hardly influenced, the oyster larva attachment capability is very strong, the problem of mildew of the coating and the concrete is solved, and the oyster larva attachment number of the concrete doped with the inducer is obviously increased compared with the concrete not doped with the inducer, which is shown in figure 3 in particular.

The comparison documents and the reference documents show that: the calcium content is important for the attachment of oyster larvae, and the addition of a proper amount of calcium carbonate substances into the cement-based material is also proved by some current experimental results to promote the attachment and growth of the oyster larvae. However, cement paint and cement concrete contain a large amount of calcium ions, the pH value of the pore solution is generally larger than 12.5, and the pH value of the saturated calcium hydroxide solution is about 12 at normal temperature, so the concentration of the calcium ions in the concrete pore solution is about 5 mmol/L; the solubility of calcium carbonate is very low, and is only 9.5X 10 at 25 DEG C^-5mol/L(9.5×10^-2mmol/L). At present, the optimal range of calcium ion concentration for inducing oyster attachment is considered to be 10-25 mmol/L, and even if oyster larvae are placed in saturated calcium carbonate solution, enough Ca is not available²⁺The concentration provides a suitable ionic concentration for adhesion of the oysters. Further, Ca (OH) in the interior of cement coating and concrete₂Can be released more quickly, while the dissolution of calcium carbonate takes longer. Therefore, it was confirmed that incorporation of calcium carbonate material in paints and concrete promotes adhesion of oyster larvae, Ca²⁺Not the dominant role. Early attachment, metamorphosis and HCO of oyster₃ ^-Related to Ca in allergy²⁺Together generating a secondary shell of calcium carbonate. After calcium carbonate is added, the calcium carbonate is mixed with CO₂Reacting with water to form Ca (HCO)₃)₂The later participation in the attachment is the fundamental mechanism for promoting the attachment of oyster larvae.

The calcium carbonate doping amount in the cement-based material has an optimal doping amount, which can be explained from the following three aspects:

1) for equivalent substituted cement, as the calcium carbonate content is increased, the alkali in the coating and concrete is diluted, the total alkalinity is reduced, but as the calcium carbonate content is increased, the dissolution probability of the calcium carbonate in the coating and concrete is increased, and the HCO in the solution is increased₃ ^-The content is increased, so that the attachment and metamorphosis of oysters are promoted; however, when the amount of the carbonate is too large, the permeability of the coating and the concrete is increased rapidly, alkali and carbonate in the coating and the concrete are exuded rapidly, so that the negative effect of the alkali is obvious, and the critical or negative effect of the carbonate is obvious, so that the adhesion is reduced;

2) for the same amount of substituted aggregate, the permeability of the coating and concrete is reduced along with the increase of the mixing amount, and calcium ions and OH are caused^-The bleeding of (2) is reduced, but the permeation rate of carbonate ions is gradually increased, and when reaching a certain value, the adhesion of the oyster reaches the maximum value; as the doping amount continues to increase, the calcium ions decrease greatly, carbonate ions may decrease, and the concentration of the calcium ions can limit the attachment of oyster larvae, which is expressed as the decrease of the attachment amount;

3) for the same amount of mineral-substituted admixtures, the permeability is increased along with the increase of the admixture, and the HCO required for oyster adhesion is increased due to the increase of calcium carbonate₃ ^-The concentration reaches a proper range, which is shown as the attachment of oyster larvae is increased; as the amount of the mineral admixture continues to increase, the amount of the mineral admixture is reduced, so that the amount of alkali exuded increases, carbonate increases, but excess alkali and HCO₃ ^-The ions inhibit adhesion of oyster larvae.

Compared with a comparison document 4 (plum true, public, green, heavy, et. bio-adhesion effect of concrete artificial fish reef of different cement types [ J ] fishery science progress, 2017,38(5):57-63.), the difference is that:

in comparative document 4, composite portland cement, slag portland cement, pozzolanic portland cement, fly ash portland cement, and aluminate cement were used: the invention adopts the composite doping of ordinary portland cement and mineral admixture to realize low-alkalinity cement; the silica fume is one of mineral admixtures, has high activity, has obvious effect of improving the durability of reinforced concrete in the marine environment by proper mixing amount, and can obtain low-alkalinity cement with excellent strength and durability through optimized design and experiments. Meanwhile, by utilizing the characteristic of high impermeability of the silica fume concrete, a large amount of oyster larvae are attached, distorted and grown even if the alkalinity inside the concrete is higher. And the alkalinity of the cement concrete is regulated and controlled by adopting the composition of the low-alkalinity sulphoaluminate cement, so that a proper pH value is provided for the adhesion of oyster larvae. In addition, marine plants and sessile organisms such as oysters and barnacles have different alkali resistance and different environments required in the attachment period and later period, such as the attachment, metamorphosis and later growth of barnacles and oysters, need a large amount of calcium ions.

The concrete in the comparison document 4 is used for enriching marine organisms, mainly in view of the size and diversity of attached biomass, and the main attached organisms are various algae and the like. The aim of the research in the invention is to induce oyster adhesion, but the tolerance of oysters and barnacles to alkalinity is higher than that of algae, and a large amount of calcium ions are needed for adhesion and metamorphosis of oysters, so that two kinds of concrete look the same and are greatly different. Fig. 4 and 5 are comparison results of biological adhesion after the experiment of the comparison document 3 for about 210d and the experiment of the invention for 300d, respectively.

The concrete in the comparison document 4 is used for enriching marine organisms, mainly in view of the size and diversity of attached biomass, and the main attached organisms are various algae and the like. The aim of the research in the invention is to induce oyster adhesion, but the tolerance of oysters and barnacles to alkalinity is higher than that of algae, and a large amount of calcium ions are needed for adhesion and metamorphosis of oysters, so that two kinds of concrete look the same and are greatly different.

Therefore, since this part of knowledge relates to marine periphyton, the intersection of marine plants and marine concrete engineering disciplines, no matter those skilled in concrete and engineering fields or marine life fields, the technical feature of the present invention that relates the balance between concrete alkalinity reduction and calcium ion concentration to the attachment of marine periphyton can be obtained by comparing document 3.

In addition, the unique characteristics and the beneficial effects of the invention are as follows:

deep colour pigment

By utilizing the light-resistant characteristic of oyster eyespot larvae, dark pigments (one or two of black iron oxide, nigrosine, carbon black, antimony sulfide, red iron oxide and organic pigment red) are doped into the concrete, the color of the concrete is changed, the color of the concrete is darkened, the oyster larvae are considered as a dark environment, the oyster larvae are induced to arrive at the dark concrete surface, the contact probability of the larvae and the concrete surface is increased, and the oyster larva induced attachment rate is increased. The method specifically comprises the following steps:

the researchers of marine organisms, in order to breed and proliferate or in order to eliminate undesirable populations, consider the study of the adhesion of marine periphyton with different colored substrates, belonging to the subject of marine biology. The discipline of marine concrete engineering or concrete materials is quite different and is two big disciplines. By crossing the marine sessile organisms with the concrete discipline, the oyster larva induced attachment by adopting the dark-color coating and the concrete is obtained. In the invention, the oyster larvae are promoted to attach by adding the dark pigment and deepening the color of the coating and the concrete. The incorporation of other materials into coatings and concrete can affect their performance. The invention considers that the concrete with different cement has different surface colors. Therefore, the amount of the dark color substance is determined according to the type and amount of the cement. Dark pigments also affect the properties of coatings and concrete. Most importantly, the deep color pigment is added, and alkali and Ca in the coating and concrete are not controlled²⁺When the permeation rate is equal, the released alkali can influence the attachment, metamorphosis and growth of sessile organism larvae, and when the mixing amount is more than a certain value, the attachment amount of the larvae is reduced. The impermeability of the concrete is designed and controlled, and the main measures are as follows: selecting the type of the dark pigment, controlling the adding amount and modifying. Along with the increase of the mixing amount of the dark substances, the youngThe attachment rate of the larvae is increased firstly, when the addition amount is 0.5-6% of the cementing material, the attachment amount of the larvae is maximum, but then the attachment amount is slightly increased or kept unchanged.

Trace elements

According to the enrichment of a large amount of zinc in the oyster body, the zinc is far higher than the seawater where the oyster lives, and meanwhile, the oyster body also contains more Fe, P and K elements. At the same time, the appropriate Zn in the solution²⁺，K⁺The concentration can promote early stage attachment and metamorphosis of oyster larva. Therefore, zinc phosphate, potassium phosphate, ammonium phosphate, zinc sulfate, potassium nitrate, ferric sulfate, ammonium nitrate, iron phosphate and calcium phosphate are used as trace elements to be doped into the concrete, and the strength and the impermeability of the concrete are basically kept unchanged through modifying the substances, so that the induced attachment rate of oyster larvae is greatly increased. The method specifically comprises the following steps:

the marine organism researchers, in order to clarify the oyster attachment mechanism and the purpose of breeding and proliferation, research the attachment and metamorphosis of different ions to marine periphyton, belong to the marine biology subject. The discipline of marine concrete engineering or concrete materials is quite different and is two big disciplines. Through the crossing of marine sessile organisms and concrete disciplines, the method is obtained by adding corresponding substances into the coating and the concrete to induce the adhesion of oyster larvae on the surface of the concrete. Because the soluble salts greatly affect the performance of the concrete, such as the early workability, the setting time and the later strength and impermeability, the invention adopts the diatomite as the carrier, fixes the inorganic salts in the diatomite, reduces the performance influence of the soluble salts on the coating and the concrete, and simultaneously utilizes the effect of the diatomite on improving the performance of the coating and the concrete to realize that the good performance of the coating and the concrete can still be maintained when the inducing substances are added. In addition, the diatomite has a slow release effect as a carrier, so that the soluble salt is slowly released, and particularly, after the diatomite is soaked in seawater for a certain time, the release rate is maintained at a small rate. Therefore, this part of knowledge also relates to the intersection of marine periphyton, chemistry and marine concrete engineering disciplines, and neither those skilled in the concrete and engineering fields nor marine life fields can, by the present background, obtain the technical features of the present invention of incorporating trace elements into coatings and concrete, altering the ionic content of trace elements on the surface of coatings and concrete and controlling the permeability of coatings and concrete in close association with coatings and concrete having a high ability to induce oyster larvae attachment.

Coating and concrete penetration

The strength and permeability of coatings and concrete are the two most important properties of coatings and concrete. When considering that different substances are added to promote adhesion, metamorphosis and later growth of oyster larvae, the strength and permeability of the oyster larvae cannot be greatly influenced by the oyster larvae, and then raw materials are selected according to the compatibility of various raw materials. However, in the related research, although the influence of the calcium content on the adhesion of the oyster larvae is considered, the permeability of the coating and the concrete is changed to change the alkali and ion leakage rate inside the coating and the concrete, and the poorer the impermeability of the coating and the concrete, the larger the alkali and ion leakage rate inside the coating and the concrete is, and the increase of the alkali and ion leakage rate may be exponential, regardless of the performance of the concrete itself. Thus, these released alkalis and ions have a great influence on the larvae, and there may be cases where the adhesion is promoted to be inhibited, which is more serious particularly when the cement is contained in a large amount. Therefore, the inducer is added into the coating and the concrete, and the permeability resistance of the coating and the concrete must be ensured to be changed within a controllable range, such as the change is not more than 10%. The induction effects of these can only be compared, otherwise the influence of the single or compound addition of the inducer on the induction effect of the oyster larvae cannot be evaluated.

Only the optimum environment required by the adhesion, metamorphosis and later growth of marine periphyton is mastered, and the coating and the concrete can be designed based on the high impermeability of the coating and the concrete, rather than neglecting the impermeability change of the coating and the concrete due to the consideration of the mixing amount of various raw materials. Therefore, this part of knowledge also relates to the intersection of marine periphyton, chemistry and marine concrete engineering disciplines, and no one skilled in the concrete and engineering fields or marine biology field can obtain the technical characteristics of the present invention that the overall control of the impermeability of the coating and concrete is closely linked to the ability of the inducer to promote the efficient induced adhesion of oysters by the existing background.

Therefore, since this part of knowledge relates to the intersection of marine periphytons, marine plants and marine concrete engineering disciplines, no matter the concrete and engineering fields or those skilled in the marine life field, the technical characteristics of color change, bovine bone meal modification, milling technology and control of paint and concrete permeability in the present invention in close association with paint and concrete having high efficiency of inducing oyster attachment ability and high durability cannot be obtained by the comparison of documents 2 to 3. And the technical feature of the present invention that the balance between the concrete alkalinity decrease and the calcium ion concentration is closely linked to the attachment of marine periphyton cannot be obtained by comparison with document 4.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims

1. An in-service ocean breakwater ecologization method is characterized by comprising the following steps:

(1) surveying the sea area of the building position of the concrete structure: investigating the species of the oyster in the sea area and whether the oyster is attached, and performing temperature, seawater temperature, dissolved oxygen, plankton, total dissolved inorganic nitrogen, active phosphate, active silicate and Ca in different seasons on the sea area²⁺、Zn²⁺、K⁺The mixture is subjected to a research and a study,and the number of typhoon times and intensity in the past year are investigated;

(2) preparing a concrete adhesive base: manufacturing a lightweight concrete oyster attaching base with a rough surface, wherein the shape of the lightweight concrete oyster attaching base is one of a plate-shaped attaching base, a wave-shaped attaching base and a cylindrical attaching base;

(3) quantitatively collecting and breeding oyster seedlings: in the local sea area, the floating larvae of the oysters are intensively attached and metamorphosis, and the attaching base is placed in a fry collecting area of the nearby sea area, when the attaching amount of the larvae of the oysters is 15-25 per 100cm²Stopping seedling collection; then moving the fish to a sea area with rich baits for floating culture;

(5) coating and maintaining the paint: coating a cement-based coating for inducing sessile organisms on the surface of ocean engineering on the surface of the concrete structure, and maintaining for 1-3 days;

(6) placing the oyster attaching base on site: fixing the oyster base with gonad development stage of the oyster in the step (3) as maturation stage on a fixing frame at the position of the tidal range area;

(7) monitoring larva attachment: monitoring the attachment condition of oyster larvae on the surface of a concrete structure, and when the number of oyster larvae is 30-40/100 cm²When the oyster attaching base is removed, the oyster attaching base is moved to an area with less oyster seedlings;

(8) nutrient addition and management: by monitoring the area periodically for plankton, nutrients and Ca²⁺A nutrition barrel capable of being automatically controlled is placed to enrich the amount of plankton and provide calcium ion support for the growth of oysters;

the oyster attaching base is prepared from a cementing material, a light coarse aggregate, a light fine aggregate, water, a dark color pigment, biological calcium powder, calcium carbonate powder, trace elements, short fibers and a superplasticizer, wherein the cementing material, the light coarse aggregate, the light fine aggregate, the water, the dark color pigment, the biological calcium powder, the calcium carbonate powder, the trace elements, the short fibers and the superplasticizer are sequentially prepared from the following components in parts by weight: 21.8% -34.5%, 24.6% -37.5%, 15.8% -29.6%, 8.4% -16.4%, 0.6-3.0%, 0.4% -2.0%, 0.2% -1.8%, 0.1% -1.0% and 0.03% -0.15%;

in the raw materials of the oyster attaching base, the dark color pigment is as follows: one or two of iron oxide black, aniline black, carbon black, antimony sulfide, iron oxide red and organic pigment red; according to the influence degree on the performance of concrete, the pigments are modified by adopting one of transparent resin, organic silicon, dimethyl siloxane and super-hydrophobic materials;

the biological calcium carbonate powder is prepared by compounding oyster shell powder, fishbone powder, egg shell powder and coral powder, and the fineness of the biological calcium carbonate powder is 100-1000 meshes; treating 100-500 mesh egg shell powder, coral powder, oyster shell powder and fishbone powder with acid selected from one or two of acetic acid, silicic acid and sulfurous acid; and treating 100-500 mesh bovine bone powder with one or two of diluted phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid;

the calcium carbonate powder is as follows: calcite, chalk, limestone, marble, aragonite, travertine powder, and several of active calcium carbonate, calcium carbonate whisker and superfine light calcium carbonate which are processed, and the fineness is more than 200 meshes;

the trace elements are as follows: zinc, iron, potassium and phosphorus, which can be selected from natural minerals or industrial products, including one or more of zinc sulfate, calcium phosphate, zinc phosphate, potassium sulfate, potassium nitrate, ferric sulfate, ammonium nitrate, potassium phosphate, ammonium phosphate and ferric phosphate, and are modified to realize the slow release of corresponding ions and reduce or eliminate the adverse effect on the performance of concrete; however, nitrogen and phosphorus elements are not selected for eutrophic areas;

the cementing material is as follows: one of silicate cement, sulphoaluminate cement and alkali-activated cementing material which are mixed with mineral admixture; wherein the mineral admixture in the silicate cement doped with the mineral admixture comprises one or more of silica fume, slag powder and fly ash; the sulphoaluminate cement comprises one or two of quick-hardening sulphoaluminate cement, high-strength sulphoaluminate cement and expansion sulphoaluminate cement; the alkali-activated cementing material is one of alkali-activated slag, alkali-activated slag and fly ash;

the light coarse aggregate is one or two of crushed light porous basalt with the maximum grain size of less than 20mm and light ceramsite;

the light fine aggregate is one or two of crushed zeolite and light ceramic sand, and the particle size of the light fine aggregate is 0.2-5 mm;

the chopped fibers are inorganic fibers with the length of 12-20 mm and comprise several of basalt fibers, alkali-resistant glass fibers and carbon fibers;

the preparation method comprises the following steps:

s3: firstly, putting the light coarse aggregate and the light fine aggregate into a concrete mixer to be mixed for 0.5-1 minute; then adding a cementing material, a dark pigment, biological calcium powder, calcium carbonate powder and trace elements, and continuously stirring for 1-2 minutes; then adding chopped fibers, water and a superplasticizer and stirring for 2-6 minutes; after being stirred evenly, pouring and vibrating are carried out;

s4: immediately placing the concrete sample after the form removal in high-concentration CO₂Curing in a curing box for 0.5 to 5 hours, reducing the alkalinity of the cement test piece, and then performing standard curing for 28 d;

2. The ecological method for the marine breakwater in service of claim 1, wherein the cement-based coating is prepared from a cementing material, sand, water, a dark pigment, biological calcium powder, calcium carbonate powder, trace elements, lignocellulose, dispersible rubber powder and a superplasticizer, and the cementing material, the sand, the water, the dark pigment, the biological calcium powder, the calcium carbonate powder, the trace elements, the lignocellulose, the dispersible rubber powder and the superplasticizer are sequentially prepared from the following components in parts by weight:

3. the method for ecologizing the working ocean breakwater according to claim 2, wherein the raw materials of the cement-based paint comprise the following dark pigments: one or two of iron oxide black, aniline black, carbon black, antimony sulfide, iron oxide red and organic pigment red; according to the influence degree on the performance of concrete, the pigments are modified by adopting one of transparent resin, organic silicon, dimethyl siloxane and super-hydrophobic materials;

the biological calcium powder comprises: the bovine bone powder, the biological calcium carbonate powder comprises a plurality of compounds of oyster shell powder, fishbone powder, egg shell powder and coral powder, and the fineness of the biological calcium carbonate powder is 100-1000 meshes;

the biological calcium powder modification method comprises the following steps: treating 100-500 mesh egg shell powder, coral powder, oyster shell powder and fishbone powder with acid selected from one or two of acetic acid, silicic acid and sulfurous acid; and treating the 100-500-mesh bovine bone powder by using one or two of diluted phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid;

the sand is as follows: river sand, machine-made sand or desalinated sea sand;

the superplasticizer comprises one of polycarboxylic acid and naphthalene;

the preparation method of the cement-based coating comprises the following steps:

s4: fully dissolving the powdery superplasticizer into water, then placing the mixed materials into a high-speed stirrer together at the rotating speed of 200 plus materials of 500 rpm, and stirring for 5-10 minutes;

thus obtaining the cement-based coating with good induction effect for inducing sessile organisms on the surface of ocean engineering.

4. The method for ecologizing the active marine breakwater according to claim 3, wherein the method comprises the following steps: a circular hole with the diameter of 3-5 mm is reserved on the oyster attaching base during molding, and the size of the plate-shaped attaching base is 10 multiplied by 2-3 cm.

5. The method for ecologizing the marine breakwater in service according to claim 4, wherein the method comprises the following steps: the nutrition barrel is added with carbonate, bicarbonate, biological calcium powder, calcium carbonate powder and trace elements according to the needs of marine plankton, and different substances are selected to be combined and placed in the breakwater according to the actual marine condition.