A kind of nitrate nitrogen contamination method of heavy metals in farmland pollution
Technical field
The present invention relates to a kind of method of nitrate nitrogen contamination heavy metals in farmland pollution, especially for without the heavy metal lain fallow
The in-situ remediation method of polluted agricultural land, belongs to heavy metal pollution of soil farmland Treatment process field.
Background technology
In recent years, with industrialization, the quickening of urbanization process, China's environmental pollution states are presented aggravation situation, overall
Situation allows of no optimist, particularly particularly problematic in terms of heavy metal pollution of soil, and it is not only to ecological environment, food security
Being constituted a serious threat with health, and also result in crops cannot grow situation about being accumulated in crop with heavy metal.It is many
Well known, soil is material base for the survival of mankind, is indispensable, the non-renewable natural resources of the mankind.Not only
Because it has the function of production green plants, while being also the place that various pollutants are naturally purified.Due to for soil ring
Border protection work payes attention to not enough, and the development for causing Heavy Metal Pollution Control to work is more delayed, nowadays, Soil Pollution Control row
Dynamic plan (referred to as " ten, soil ") is formally put into effect in May, 2016, and from country to place, the control of soil pollution is all having
Carry out to sequence.
Due to the disguise that heavy metals in farmland pollutes the complexity to be formed, long-term cumulative bad, occurs, cause in farmland weight
It is difficult in the governance process of metal.The current research on soil restoring technology mainly includes heavy metal pollution of soil, dilution method, steady
Fixed/technique for fixing, glass method, in-situ passivation, thermal desorption (volatilization heavy metal), electro reclamation, chemical leaching, phytoremediation and micro-
Biological prosthetic etc., in these methods, in-situ passivation recovery technique is a kind of relatively comparatively ideal technology, can be used to repair big face
Product contaminated soil.Heavy metal pollution of soil, dilution method, stabilization/immobilization technology, in-situ passivation and phytoremediation are in-situ immobilization soil,
But in actual application, although the easily engineering operation of heavy metal pollution of soil and dilution method, rehabilitation cost is high, it is difficult to big face
Product popularization and application;After immobilization technology rehabilitating soil, soil is cured, and crop is difficult to grow in the soil do not repaired;Plant
It is long that recovery technique typically repairs the time limit time, and climate and edaphic condition influence are larger.
Therefore, passivation and plant combined reparation skill are typically with for heavy metal pollution farmland feasibility method higher
Based on art, by the activating agent being added in soil, the physicochemical properties of soil are adjusted, handed over by absorption, precipitation, ion
Change, humification, the series reaction such as oxidationreduction, the toxic heavy metal in soil is fixed up, or heavy metal is converted
Into the inactive form of chemical property, its biological effectiveness is reduced, so as to prevent heavy metal from soil by plant root to agriculture
The migration accumulation of crop overground part, so as to reach the requirement of farmland reparation.
Be presently used for heavy metal passivation material (passivator) have natural clay mineral, phosphate, silicate, carbonate,
Organic compost and microbial material etc., but prior art is likely to cause the secondary pollution of soil.
Therefore it provides a kind of simple production process, running cost be low, high adsorption rate, high selectivity, can provide increment dynamic
Adsorption of Heavy Metals ion and do not produce the farmland restorative procedure of secondary pollution just to turn into the skill that the technical field is badly in need of solving
Art problem.
The content of the invention
An object of the present invention be to provide low a kind of simple production process, running cost, high adsorption rate, high selectivity,
The dynamic Adsorption of Heavy Metals ion of increment can be provided and the nitrate nitrogen contamination that the heavy metals in farmland of secondary pollution pollutes is not produced
Use composition.
Above-mentioned purpose of the invention reaches by the following technical programs:
A kind of nitrate nitrogen contamination composition of heavy metals in farmland pollution, its proportioning is as follows:The purpose of first stage 50~200
The weight portion of charcoal powder 3~10, the weight portion of Candida 2~8, the weight portion of brewer's yeast 2~8, the weight of bacillus subtilis 2~8
Part, the weight portion of Rhodopseudomonas palustris 2~8, the weight portion of microorganism mixed culture medium 10;The weight of second stage Candida 2~8
Part, the weight portion of brewer's yeast 2~8, the weight portion of bacillus subtilis 2~8, the weight portion of Rhodopseudomonas palustris 2~8, microorganism
The weight portion of mixed culture medium 10.
Preferably, Candida, brewer's yeast, bacillus subtilis and natural pond in the first stage and the second stage
The microbial composite bacteria of damp red pseudomonas composition amounts to consumption and is 8-32 weight portions.
Preferably, the charcoal powder is the powdered carbon that agricultural crop straw, forestry residue are made, or using timber, plant
Residuum by under conditions of HTHP anoxic formed, and by fineness after crushing 50~200 mesh carbon dust.
Preferably, described candidiasis, brewer's yeast, bacillus subtilis, Shao Ze red pseudomonas are strain guarantor
The industrial producing strain at Tibetan center.
Preferably, described microbial composite bacteria, candidiasis, brewer's yeast, bacillus subtilis, Shao Ze are red false single
Born of the same parents bacterium total amount is 10 weight portions.
Preferably, the microorganism mixed culture medium be steamed beef soup peptone, glucose, soluble starch and analysis for soybean powder,
Its ratio is 0.5~1%, 2~3%, 1~2.85%, 0.2~1.5%, and remainder water is supplied.
Preferably, the candidiasis:Brewer's yeast:Bacillus subtilis:Ratio between Shao Ze red pseudomonas
It is 3:3:3:1,2:2:3:3,4:4:1:1,3:3:2:3 or 2:3:4:3.
Preferably, the brewer's yeast is industrial strain, culture presevation number:CICC1928;Candida industrial strain, bacterium
Plant deposit number:CICC1268;Rhodopseudomonas palustris, culture presevation numbering:CICC 23812;Bacillus subtillis R31
(Bacillus subtilis R31, culture presevation numbering:CCTCC M209261.
It is a further object of the present invention to provide application of the combinations of the above thing in farmland.
Foregoing invention purpose of the invention reaches by the following technical programs:
Application of the described composition in the nitrate nitrogen contamination that heavy metals in farmland pollutes.
Another object of the present invention is to overcome the deficiencies in the prior art, there is provided a kind of continuable, dynamic equilibrium control agriculture
The ecological restoring method of field heavy metal pollution.
The purpose of the present invention is achieved through the following technical solutions:
A kind of nitrate nitrogen contamination method of heavy metals in farmland pollution, its step is as follows:
(1) before Planting Crops, with Soil tillage, during charcoal powder, microorganism mixed bacteria liquid are manured into soil;
(2) in the mid-term of plant growth, by microorganism mixed bacteria liquid and microorganism mixed culture medium, by the shape for spraying
Formula, applies earth's surface.
Preferably, soil described in the step (1) is the soil of 0~25cm.
Preferably, microorganism mixed bacteria liquid described in the step (1) includes part viable bacteria and fermentation wastes.
Preferably, microorganism mixed culture medium described in the step (2) is steamed beef soup peptone, glucose, solubility
Starch and analysis for soybean powder, ratio be 0.5~1 weight %, 2~3 weight %, 1~2.85 weight %, 0.2~1.5 weight %, remaining
Part water is supplied.
Preferably, the addition of charcoal powder described in the step (1) is 3~10kg/ mus;Microorganism mixed bacteria liquid plus
Enter amount for 5~15kg/ mus.
Preferably, the addition of microorganism mixed bacteria liquid described in the step (2) is 5~15kg/ mus;The microorganism
The addition of mixed culture medium is 10L/ mus.
Preferably, charcoal powder described in the step (1) is the carbon dust that agricultural crop straw, forestry residue are made, or
Using timber, plant residue by under conditions of HTHP anoxic formed, and by fineness after crushing 50~200 mesh carbon
Powder.
Preferably, the bacterium in microorganism mixed bacteria liquid described in the step (1) and the step (2) is Candida
Bacterium, brewer's yeast, bacillus subtilis and Shao Ze red pseudomonas.
Preferably, the bacterium in microorganism mixed bacteria liquid described in the step (1) and the step (2) is Candida
The content of the effective active gemma of bacterium, brewer's yeast, bacillus subtilis and Shao Ze red pseudomonas is more than 10~2,000,000,000 work
Spermatium/gram.
Preferably, the candidiasis:Brewer's yeast:Bacillus subtilis:Weight between Shao Ze red pseudomonas
Than being 4:2:1:1~2:4:3:3.
Preferably, the candidiasis:Brewer's yeast:Bacillus subtilis:Weight between Shao Ze red pseudomonas
Than being 3:3:3:1,2:2:3:3,4:4:1:1,3:3:2:3 or 2:3:4:3.
Preferably, the brewer's yeast is that current industrial strain (number by culture presevation:CICC1928), Candida
Industrial strain (number by culture presevation:CICC1268), Rhodopseudomonas palustris (number by culture presevation:CICC 23812), withered grass
Bacillus R31 culture presevation is numbered:CCTCC NO:M209261.
Compared with current heavy metal pollution recovery technique, advantage of the invention is that:
1) can effectively accumulation of the ground resistance control heavy metal in crop within whole effectively growth period;
2) the method material therefor is biomaterial, can be degradable in nature, does not result in the secondary of soil
Pollution, while can increase the fertility of soil after microbial degradation, kills two birds with one stone;
3) the method belongs to Agro-ecology reparation in situ, saving of labor, laborsaving, can quickly realize the obstruct of heavy metal.
Below by specific embodiment, the present invention is described in detail.It should be understood that described embodiment is only
It is related to the preferred embodiments of the invention, in the case of the spirit and scope of the present invention are not departed from, the change of various composition and content
It is all possible to change and improve.
Specific embodiment
A kind of nitrate nitrogen contamination composition of heavy metals in farmland pollution, its proportioning is as follows:
(1) before Planting Crops:3~10kg/ of charcoal powder mus of 50~200 mesh, 1~4kg/ of Candida mus, beer ferment
1~4kg/ mus of mother, 1~4kg/ of bacillus subtilis mus, 1~4kg/ of Rhodopseudomonas palustris mus, microbial composite bacteria is amounted to be used
It is 10kg to measure;
(2) in the mid-term of plant growth:1~4kg/ of Candida mus, 1~4kg/ of brewer's yeast mus, withered grass gemma
1~4kg/ of bacillus mus, 1~4kg/ of Rhodopseudomonas palustris mus, it is 10kg that microbial composite bacteria amounts to consumption, micro-
Biological mixed culture medium 10L/ mus.
Charcoal powder is the carbon dust that is made of agricultural crop straw, forestry residue in life, or home-use discarded work
Property charcoal by after crushing, or formed by under conditions of HTHP anoxic using timber, plant residue, it is by after crushing
Fineness is the carbon dust of 50~200 mesh, 3~10kg of mu consumption.
Candidiasis, brewer's yeast, bacillus subtilis, Shao Ze red pseudomonas are raw for the industry of DSMZ
Produce bacterial strain.
Microbial composite bacteria:Candidiasis, brewer's yeast, bacillus subtilis and Shao Ze red pseudomonas total amounts are
10kg/ mus.
Microorganism mixed culture medium is:Steamed beef soup peptone+glucose+soluble starch+analysis for soybean powder, its ratio is 0.5
~1 weight %, 2~3 weight %, 1~2.85 weight %, 0.2~1.5 weight %, balance of water.
Need to coordinate fungi liquid culture medium and the fluid nutrient medium of bacterium to use in application process, wherein, steamed beef soup egg
White peptone and analysis for soybean powder are used to cultivate bacterium, and glucose and soluble starch are used to cultivate fungi;Microorganism is set to play absorption weight
Bred while metal, the total number of microorganism is increased with this, for the absorption and fixation of heavy metal provide a kind of dynamic
Balance.
A kind of nitrate nitrogen contamination method of heavy metals in farmland pollution of the invention is further described below:
(1) before Planting Crops, with Soil tillage, by charcoal powder, microorganism mixed bacteria liquid, (part viable bacteria and fermentation are useless
Gurry beer yeast slurry, Candida medicinal extract) and microorganism mixed culture medium (steamed beef soup peptone+glucose+soluble starch
+ analysis for soybean powder, 0.5~1 weight %, 2~3 weight %, 1~2.85 weight %, 0.2~1.5 weight %, balance of water makes training
Support base 10L) 0~25cm that is manured into soil soil in, using biomaterial suction-operated be passivated heavy metal in soil available state
Ion
(2) in the mid-term of plant growth, complex microorganism (viable bacteria) mixed liquor will have been cultivated, add steamed beef soup peptone+
Glucose+soluble starch+analysis for soybean powder, 0.5~1 weight %, 2~3 weight %, 1~2.85 weight %, 0.2~1.5 weight %
Ratio, balance of water makes culture medium 10L, by the form for spraying, applies earth's surface, by the way of then being irrigated using small water,
During its nutrient solution poured into soil layer, in case of rained, then without watering.
Embodiment 1
In the plot of heavy metals in farmland pollution, can turn over spreading fertilizer over the fields according to the consumption of following table before planting
The early stage nitrate nitrogen contamination heavy metal-polluted soil preferred proportion of table 1
Material |
1 (kg) of formula |
2 (kg) of formula |
3 (kg) of formula |
4 (kg) of formula |
5 (kg) of formula |
Charcoal powder |
10 |
7 |
5 |
3 |
10 |
Candida |
3 |
2 |
4 |
3 |
2 |
Brewer's yeast |
3 |
2 |
4 |
2 |
3 |
Shao Ze red pseudomonas |
3 |
3 |
1 |
2 |
2 |
Bacillus subtilis |
1 |
3 |
1 |
3 |
3 |
Wherein, brewer's yeast is that current industrial strain (number by culture presevation:CICC1928), the industrial bacterium of Candida
(culture presevation is numbered for strain:CICC1268), Rhodopseudomonas palustris (number by culture presevation:CICC23812), Bacillus subtillis
R31 (number by culture presevation:CCTCC M209261).
Embodiment 2
In the growth medium of crop, sprayed by according to following formula, control soil in heavy metal it is effective
State.
The plant growth mid-term nitrate nitrogen contamination heavy metal-polluted soil preferred proportion of table 2
Material |
1 (kg) of formula |
2 (kg) of formula |
3 (kg) of formula |
4 (kg) of formula |
5 (kg) of formula |
Candida |
3 |
2 |
4 |
3 |
2 |
Brewer's yeast |
3 |
2 |
4 |
2 |
3 |
Shao Ze red pseudomonas |
3 |
3 |
1 |
2 |
2 |
Bacillus subtilis |
1 |
3 |
1 |
3 |
3 |
Wherein, brewer's yeast is that current industrial strain (number by culture presevation:CICC1928), the industrial bacterium of Candida
(culture presevation is numbered for strain:CICC1268), Rhodopseudomonas palustris (number by culture presevation:CICC23812), Bacillus subtillis
R31 (number by culture presevation:CCTCC M209261).
Embodiment 3
For examination soil be located at Zhongshan City, Guangdong Province suburb nearby vegetable plot, test area amount to 1 mu of ground, be equally divided into 5 it is small
Area, while planting water spinach, Chinese cabbage, capsicum, four kinds of crops of tomato, and harvests in complete stool after 60 days, in measure whole plant
Content of beary metal, wherein the soil for processing is the first stage to use mesh 10kg/ mus of charcoal powder 50, candidiasis 3kg/ mus, beer
Brewer yeast 3kg/ mus, bacillus subtilis 2kg/ mus, red Pseudomonas alba 2kg/ mus of Shao Ze;Second stage candidiasis 3kg/
Mu, brewer's yeast 3kg/ mus, bacillus subtilis 2kg/ mus, red Pseudomonas alba 2kg/ mus of Shao Ze and mixing liquid culture medium
(steamed beef soup peptone+glucose+soluble starch+analysis for soybean powder, 0.5 weight %, 3 weight %, 1.5 weight %, 1.5 weight %)
10L;The content of the effective active gemma of wherein every kind of microorganism more than 10~2,000,000,000 viable spores/gram.
The measure of plant sample heavy metal species content, weighs 0.5g dry-eye diseases in digester, every kind of sample set 3 it is parallel
The hydrogen peroxide of sample, each addition 10ml concentrated nitric acids and 1mL30%, predigestion, 180 DEG C of high temperature disappear in being then placed in micro-wave oven counteracting tank
Change 15min, make acid treatment volume to final volume about 0.5ml.Pb, Cd using GFAAS determine, Cu, Zn,
Cr is determined using inductively coupled plasma atomic emission.
The nitrate nitrogen contamination of table 3 compares four kinds of vegetables repairing effects
Embodiment 4
In radio and television system downstream, the rice terrace of acidic mine waste water irrigating region lays sampling point collection paddy rice soil sample 6 at random
It is individual, 0-20cm topsoil samples are gathered using " S " type in the range of 5 ㎡ per sampling point, with PE-PP composite waterproofing membrane, wherein processing
Soil for the first stage use mesh 10kg/ mus of charcoal powder 200, candidiasis 2kg/ mus, brewer's yeast 2kg/ mus, withered grass bud
Red Pseudomonas alba 3kg/ mus of 3kg/ mus of spore bacillus, Shao Ze;2kg/ mus of second stage candidiasis, brewer's yeast 2kg/ mus,
Bacillus subtilis 3kg/ mus, red Pseudomonas alba 3kg/ mus of Shao Ze and mixing liquid culture medium 10L;It is untreated soil to compare
Earth.
Analysis soil pH value and Cd, Zn, Pb and Cu bio-available Zn concentration, take the levigate whole of a small amount of soil sample and cross 100 mesh sieves in addition,
It is used to determine Cd, Zn, Pb and Cu total amount after before processing.
Analysis method:Pedotheque Cd, Zn, Pb and Cu bio-available Zn concentration 0.1mol.L-1HCl is determined after extracting, sample
Clearing up for total amount uses HF-HCIO4-HNO3Mixed acid is determined after being digested in polytetrafluoroethylene (PTFE) crucible.With ICP-OES (Optima
5300DV, Perkin-Elmer Instruments, USA) determine Cd, Zn, Pb and Cu content.Test data is 3 repetitions
Average value.
The paddy soil heavy metal bio-available Zn concentration of table 4 changes afterwards before treatment
Embodiment 5
For examination soil selection Guangzhou Fanyu Battery Plant near, be the heavier plot of heavy metal pollution, we by
Rice cultivation early stage is by using 10kg/ mus of 50 mesh charcoal powder, candidiasis 3kg/ mus, brewer's yeast 3kg/ mus, withered grass bud
Red Pseudomonas alba 2kg/ mus of 2kg/ mus of spore bacillus, Shao Ze, mid-term using candidiasis 3kg/ mus, brewer's yeast 3kg/ mus,
Bacillus subtilis 2kg/ mus, the red modes for Pseudomonas alba 2kg/ mus, being sprayed of Shao Ze, carry out Tiny ecosystem adsorption by soil,
Fixing process 90 days, is below our analyze data
The paddy soil heavy metal bio-available Zn concentration of table 5 changes afterwards before treatment
Interpretation of result:
Microbial bacterial agent heavy metal ion has stronger suction-operated, and the present invention have selected centering heavy metal and carry out biology
Enrichment, and adsorption rate is up to more than 70%, greatly removes cadmium ion, but as the concentration of heavy metal ion constantly increases
Plus, microbial bacterial agent adsorption capacity declines, and illustrates that the concentration increase of heavy metal ion inhibits the growth of microorganism, so,
The present invention is effective in the farmland of the moderate heavy metal pollution in farmland, but to the party cannot be used in the soil of severe pollution level
Method.
Farmland of the invention is repaired to be carried out with farming operation, and effect is good, can be used with scale, and what is particularly used is micro-
It is active bacteria that biological compound fungi agent is most of, can be bred in soil environment, can continue absorption and the network of heavy metal
Close, and charcoal powder by being used and microorganism etc. are biomaterial, can degradable be organic matter, are inhaled by plant
Receive, secondary pollution is not caused to soil, therefore, the method is for current, and advantage is particularly evident.
Farmland restorative procedure of the invention, while application passivating technique, it is to avoid the secondary pollution of soil, the present invention
The main mode being combined there is provided biological adsorption and passivation, the farmland lighter for administering heavy metal pollution degree.
Complex microbial inoculum used includes discarded object, bacterium, fungi and the agriculture by-product of plant in the present invention
The biomaterials such as thing all have the ability for separating metal ion in soil.Its principle is biomolecule surface Adsorption of Heavy Metals ion
Accumulate both modes in vivo with heavy metal ion;Wherein, biological adsorption is extracellular polymer, functional group etc. and weight
Metal ion is combined;Heavy metal ion and cell some enzymes are combined transport to intracellular and be stored in cell, are such as rich in bacterium
Carboxyl anion and phosphate anion so that bacterium surface has the property of anion, it is easy to reacted with metal, thus
Metal is readily incorporated into the surface of bacterium.In addition, many researchs also indicate that the metal of bacterium and its metabolite to solubilised state
Ion has very strong complexing power, and this is mainly due to unique chemical composition on its surface, is inhaled by the surface of biological substance
Attached, two homeostasis processes of cylinder accumulation.After thalline death, thalline can remain a period of time in soil, can after degraded
Application as plant is utilized once again.Therefore, the method for the present invention is so that its simple production process, running cost be low, suction high
The advantages of attached rate, high selectivity, can providing increment dynamic Adsorption of Heavy Metals ion, and not produce secondary pollution, is particularly suitable for
In the lighter agricultural land soil of transformation heavy metal pollution.
The above, is only highly preferred embodiment of the present invention and control case study on implementation, not makees other forms to the present invention
Limitation, any those of ordinary skill in the art are changed or are modified as equivalent change using the technology contents of the disclosure above
The Equivalent embodiments of change.In every case it is, without departing from technical solution of the present invention content, to implement to more than according to technical spirit of the invention
Any modification, equivalent variations and remodeling that example is made, still fall within the protection domain of technical solution of the present invention.