CN102553905A - Method for remediating cadmium contaminated soil of vegetable field in situ by compounding bio-charcoal and organic fertilizer - Google Patents
Method for remediating cadmium contaminated soil of vegetable field in situ by compounding bio-charcoal and organic fertilizer Download PDFInfo
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Abstract
The invention relates to a method for remediating cadmium contaminated soil of a vegetable field in situ by compounding bio-charcoal and an organic fertilizer. The method comprises the following steps of: applying a passivation material obtained by compounding the bio-charcoal and the organic fertilizer in a mass ratio of 1:1 to a surface layer of soil of a cadmium contaminated vegetable field, fully and uniformly mixing the passivation material and the soil in a plowing layer with the thickness of 0 to 20cm, judging the contamination level of the soil according to environmental quality standard for soils GB15618-1995, and ensuring that the application rate of the passivation material is not less than 0.5 percent of the weight of dry soil, namely 750kg/mu when the cadmium concentration of the soil is 1.0 to 2.9mg/kg. The invention has the advantages that: raw materials of the passivation material are wide in source and low in cost, the application method is simple and has a remarkable effect of remediating the cadmium in the soil in a passivation way, and the risk of secondary contamination is avoided; and the bio-charcoal is applied into the soil, so the passivation material has the effects of reducing the discharge of greenhouse gas of farmland ecosystems, increasing the content of organic carbon of the soil, improving soil structures and the like, and has huge popularization and application value.
Description
Technical field
The present invention relates to heavy-metal contaminated soil improvement technology, the composite original position of specifically a kind of applying biological charcoal and fertilizer is repaired the method that vegetable field soil cadmium (Cd) pollutes.
Technical background
Heavy metal pollution is one type of important polluter in agricultural soil environment and the agricultural product.China receives the cultivated area of heavy metal pollution to surpass 2,000 ten thousand hm
2More than, account for 1/5 of cultivated area.At China 1,400,000 hm
2In the dirty irrigated area, have 64.8% soil to suffer heavy metal pollution, wherein slight pollution accounts for 46.7%, and intermediate pollution accounts for 9.7%, and severe contamination accounts for 8.4%.Cd, Hg, Pb, As, Cu etc. exceed standard serious and general in grain and the vegetables, and agricultural has been caused enormous economic loss.About 1,200 ten thousand t of grain of the annual output heavy metal pollution of China in 320 emphasis contaminated areas of 24 provinces (city) of investigation, have 60.6 ten thousand hm
2Land for growing field crops crop pollution thing exceed standard, account for the investigation gross area 20%, wherein be that content of beary metal exceeds standard more than 80%, especially Cd, Pb, Hg, Cu and combined pollution thereof are the most outstanding.China vegetable field soil Cd content overproof rate is up to 24.1%, and more than 10,000 hectare of vegetable plot, the suburbs, Shenyang City generally receives heavy metal pollution, and Cd content overproof rate is up to 100% in the Chinese cabbage of output.In March, 2011, State Council formally gave an written reply " heavy metal pollution integrated control " 12 " planning " that State Bueau of Environmental Protection proposes.This shows how effectively the remediating heavy metal agricultural land soil that exceeds standard is kept the sustainable use in soil, has become the outstanding environmental problem that needs to be resolved hurrily.
The original position reparation is a kind of very efficient ways as heavy metal pollution of soil improvement technology, receives people's generally attention, is particularly useful for repairing in the large tracts of land, the agricultural land soil of slight heavy metals exceeding standard.In soil, applying passivator is the in-situ treatment method of a kind of less expensive of restoration of soil polluted by heavy metal.Through applying passivator such as clay mineral (sepiolite, bentonite and attapulgite etc.), lime, phosphate and industry byproduct thing (stove slag, ground granulated blast furnace slag and red mud etc.) etc.; Change soil pH and chemical form and the occurrence status of heavy metal element in soil; Increase adsorption site position and the processes such as co-precipitation that promote heavy metal ion and other component of soil (comprising the passivator material); Make the biological available state of heavy metal-polluted soil be converted into biological form not capable of using; Thereby suppress the animal migration of heavy metal in soil and biological effectiveness, reduction heavy metal contaminants toxicity, reach the purpose of restoration of soil polluted by heavy metal environmental organism.For the soil of heavy metal pollution, can in soil, there be a characteristic according to heavy metal, in soil, apply some chemical improvement agent and adsorbent, like lime, phosphate, compost, blast furnace slag and clay mineral etc., reach the soil of repairing heavy metal pollution.But undeniable is in soil, to add chemical substances such as white lime, calcium silicates, calcium magnesium silicate and calcium carbonate, brings influence in various degree all can for soil physico-chemical property and growth of microorganism environment.And the main component SiO of natural clay mineral
2, the MgO equal size will greatly restrict its exchange suction-operated to the heavy metal-polluted soil ion, in practical application, generally need carry out activation processing and improve adsorption capacity heavy metal to the natural clay mineral.The activation processing of clay mineral also can increase the mineral resources of heavy metal pollution of soil rehabilitation cost and consume valuable, and therefore needing further, cheap, efficient, stable, the safe passivator of exploitation comes restoration of soil polluted by heavy metal.Research in recent years shows; Use fertilizers such as agricultural crop straw, husk, poultry manure, cow dung and can reduce the animal migration and the heavy metal available state content of heavy metal-polluted soil ion and increase adsorption capacity, thereby alleviate heavy metal enrichment in plant heavy metal ion.But because organic matter is prone to decomposed by microorganism, the heavy metal ion that is adsorbed after fixing possibly discharged again again, causes secondary pollution, and is therefore, unstable to the heavy metal pollution repairing effect in directly organic matter being manured into soil.In order to address the above problem; Can consider agricultural wastes such as agricultural crop straws composite through charcoal and fertilizer that pyrolysis charring forms under the situation of anoxic wholly or in part; Porous, high-specific surface area, strong surface adsorption, height chemical inertness and charcoal apparent height aromatization structure and the functional groups such as part of hydroxyl, phenolic hydroxyl group and carbonyl that utilize on the one hand charcoal are to characteristics such as organic and inorganic pollution height are affine; The passivation renovation agent that can be used as pollutant in soil is united nutrients such as the performance required N of crop that fertilizer provided, P, K simultaneously, improves soil nutrient; Improve soil quality; Realize to promote plant growth again, improve crop quality both to the passivation repair of heavy metal-polluted soil; On the other hand charcoal is applied to the farmland, can reduces the farmland ecosystem greenhouse gas emission, increase the carbon base in soil carbon fixation.Therefore, applying biological charcoal and fertilizer are composite can effectively repair cadmium pollution problem in the vegetable field soil, and simultaneously, this passivating material is applied to the problem that the farmland can solve the numerous restriction agricultural productions of degradation under agricultural wastes processing, climate change, the soil fertility in the lump.
Summary of the invention
The object of the invention is exactly for overcoming the deficiency of prior art, administer technical barrier to heavy metal pollution of soil, providing a kind of economy, efficient, stable, safe original position to repair the method for vegetable field soil cadmium pollution.
The present invention realizes through such technical scheme: the composite original position of applying biological charcoal and fertilizer is repaired the method for vegetable field soil cadmium pollution; It is characterized in that; In the vegetable field soil of polluted by heavy metal cadmium, will impose on upper soll layer by charcoal and the composite passivating material that forms of fertilizer, then in the arable layer of 0-20cm with passivating material and the abundant mixing of soil; According to soil environment quality standard GB 15618-1995; Judge the soil pollution rank, wherein the heavy metal-polluted soil secondary standard is for ensureing agricultural production, safeguarding the soil limits value of health; When the soil cadmium concentration surpasses soil environment quality secondary standard value, then need administer and repair cadmium pollution soil, just can be used for kind of a plant after the reparation; When the soil cadmium concentration is between 1.0-2.9 mg/ kg, the passivating material amount of application be no less than dry ground heavy 0.5%, i.e. 750 kg/ mus, charcoal in the said passivating material and fertilizer are composite the forming of ratio of 1:1 in mass ratio; Said method comprises the steps:
A) charcoal in the preparation passivating material: charcoal is formed by agricultural crop straw pyrolysis charring under 350 ℃ of anoxia conditions, and after grinding, crossing the aperture again is the screen cloth acquisition of 2mm;
B) fertilizer in the preparation passivating material: fertilizer is selected chicken manure for use, and the chicken manure that the chicken farm provides is dried under 100 ℃ of temperature, and after grinding, crossing the aperture again is the screen cloth acquisition of 2mm;
C) in mass ratio the composite passivating material that forms of ratio of 1:1 with charcoal and fertilizer;
D) measure heavy metal-polluted soil cadmium content to be repaired, confirm soil recoverable scope be the soil cadmium concentration between 1.0-2.9 mg/kg, again vegetable field soil is turned over, break up the clods, smooth;
E) according to soil cadmium actual levels of pollution; In cadmium pollution soil to be repaired, use passivating material, earlier passivating material imposed on upper soll layer, again with passivating material at the arable layer plowed soils; Make the abundant mixing of passivating material and cadmium pollution soil; Field water divides the moisture state that keeps 70% maxmun field capacity, and balance gets final product planting vegetable after 2 weeks, and the field water management is consistent with normal agricultural production.
The present invention has following beneficial effect:
(1) remarkable to Cadmium Pollution in Soils passivation repairing effect.Passivating material among the present invention is by charcoal and fertilizer is composite by a certain percentage forms; Through passivating material and soil cadmium adsorb, reaction such as complexing, ion-exchange, co-precipitation; Significantly reduce its biological effectiveness and transportable property, thereby resistance control cadmium is to crops edible part migration enrichment; Simultaneously,, be difficult for being decomposed by microorganism because charcoal is relatively stable in soil, stable to absorption, the fixation of heavy metal contaminants, can not produce the risk of secondary pollution.
(2) raw material sources in the passivating material are abundant, and are with low cost.Wherein the raw material of charcoal is selected agricultural wastes straw for use, and China is large agricultural country, and stalk resource is quite abundant.Stalk obtains charcoal through low temperature pyrogenation under anoxic or the anaerobic condition, has realized agricultural wastes targets such as " minimizing, innoxious, resources " simultaneously; And fertilizer is selected for use is chicken manure, can directly provide from the chicken farm, and the source is sufficient, and is cheap.
(3) the passivating material method for using is simple, is easy to apply.The composite original position of applying biological charcoal and fertilizer is repaired vegetable field soil cadmium (Cd) and is polluted, and method for using is simple, is easy to accepted by vast farmers; Passivating material is applied to the farmland can improve the utilization rate of crop to soil nutrient, strengthens the moisture-retaining capacity of soil, increases soil organic carbon and improves effect such as soil texture, has huge application value.
Description of drawings
Fig. 1 is soil available cadmium (Cd) content sketch map under the different passivation repair process conditions;
Fig. 2 is rape edible part cadmium (Cd) content sketch map under the different passivation repair process conditions.
The specific embodiment
Understand the present invention for clearer, describe in detail in conjunction with accompanying drawing and embodiment:
Adopt the principle of this method repairing heavy metal pollution vegetable field soil to be: the charcoal in the passivating material has porous and high-specific surface area, strong surface adsorption, height chemical inertness, its surface are generally height aromatization structure and functional groups such as part of hydroxyl, phenolic hydroxyl group and carbonyl; To characteristics such as organic and inorganic pollution height are affine, the animal migration that can strong adsorption also influences heavy metal in soil with reduce the heavy metal biological utilizability; The fixing heavy metal ion of also having fertilizer in the passivating material limits the effect of its migration.Passivating material adds in the soil; Can with effects such as the absorption of available state cadmium (Cd) ion generation obligate, ion-exchange, metal complex and co-precipitation in the soil liquid; Cause the form of cadmium (Cd) to change; In the soil soluble state with can extract attitude cadmium biological attitudes capable of using such as (Cd) to the low biology of activity form transformation not capable of using; Thereby reduce the biological effectiveness and the transportable property of cadmium (Cd), the cadmium (Cd) in the resistance control soil reaches the purpose of reparation to crops edible part migratory concentration.
Vegetable field soil cadmium (Cd) pollutes original position and repairs instance:
Repairing test is chosen in dirty irrigated area, the Dongli District Da Bi village, Tianjin, and dirty irrigated area vegetable field soil cadmium (Cd) concentration is up to 2.9 mg kg
-1, surpassing soil environment quality secondary standard value (pH＞7.5,1.0 mg/kg), therefore need carry out just being used for kind of a plant after contaminated soil is administered and repaired.Investigate the repairing effect of the different administration amount of passivating material to Cadmium Pollution in Soils, passivating material is provided with three and uses level, its quality be respectively dry ground heavy 0.5%, 1% and 2%, promptly be equivalent to 750 kg/ mus, 1500 kg/ mus and 3000 kg/ mus respectively.Divide 6 experimental plots in dirty irrigated area, a kind of repair process method is adopted in each experimental plot, is provided with 6 kinds of repair process methods altogether:
Any passivation passivating material is not added for contrast (CK) in experimental plot 1, and CK is Control Check abbreviation;
Apply 1% fertilizer (representing that with 1%PM 1500 kg/ mus are with the dry ground restatement) in the soil of experimental plot 2, PM is Poultry Manure abbreviation, down together;
Apply 1% charcoal (representing that with 1%BC 1500 kg/ mus are with the dry ground restatement) in the soil of experimental plot 3, BC is the Bio-char abbreviation, down together;
Apply 0.5% in the soil of experimental plot 4 by charcoal and the composite passivating material that forms of fertilizer (representing that with 0.5%BC-PM 750 kg/ mus are with the dry ground restatement);
Apply 1% in the soil of experimental plot 5 by charcoal and the composite passivating material that forms of fertilizer (representing that with 1%BC-PM 1500 kg/ mus are with the dry ground restatement);
Apply 2% in the soil of experimental plot 6 by charcoal and the composite passivating material that forms of fertilizer (representing that with 2%BC-PM 3000 kg/ mus are with the dry ground restatement).
Each experimental plot area is 10m
2Every kind of repair process method repeats 4 times in the test.Before kind of plant, earlier vegetable field soil to be repaired is turned over, then passivating material is evenly spread fertilizer over the fields in soil surface; Once more with passivating material at the arable layer mixing of raking the soil level; The degree of depth is about 20cm, and field water divides the moisture state that keeps 70% maxmun field capacity, balance planting vegetable after 2 weeks.The Crop Planting Management Agriculture Expert measure is consistent with ordinary production.Growth of rape is gathered in the crops sampling after 60 days, rape edible part and rape root cadmium (Cd) content adopt nitric acid-H
2O
2Micro-wave digestion, soil cadmium (Cd) available state content adopt DTPA (pH=7.3) extraction to extract.Cadmium in each sample (Cd) concentration adopts atomic absorption spectroscopy determination.
Fig. 1 is the influences of different passivation repair processes to vegetable field soil cadmium (Cd) available state content.Can know that by Fig. 1 soil adds fertilizer, charcoal and both composite passivating materials that forms all can reduce soil cadmium (Cd) available state content, and charcoal and the composite effect of fertilizer are superior to charcoal and the single effect of fertilizer.After soil applied 1% fertilizer (1%PM) and 1% charcoal (1%BC) respectively, soil cadmium (Cd) available state content was compared photograph (CK does not add any passivating material) respectively and is reduced by 15% and 27%; When soil applies 0.5% by charcoal and the composite passivating material that forms of fertilizer (0.5%BC-PM), soil cadmium (Cd) available state content and contrast (CK does not add any passivating material) are compared, and descend 43%, and reach the level of signifiance (
P<0.05); When charcoal in the soil and the composite passivating material amount of application that forms of fertilizer reach 2% (2%BC-PM), the comparison of soil cadmium (Cd) available state content is according to reducing more than 53%, and reach the level of signifiance (
P<0.05).Soil heavy metal cadmium available state content reduces, and the amount that crop absorbs heavy metal is also few, for the vegetables safety in production provides safeguard.This shows that the composite passivating material that forms of charcoal and fertilizer can effectively reduce soil cadmium (Cd) available state content, and all be superior to charcoal or the single processing of fertilizer.
Fig. 2 for vegetable field soil adds different passivating materials to the influence of rape edible part cadmium (Cd) content.Can know by Fig. 2; Soil adds fertilizer, charcoal and both composite passivating materials that forms all can reduce rape edible part cadmium (Cd) content, is the composite passivating material＞charcoal of charcoal and fertilizer＞fertilizer in proper order to the influence of rape edible part cadmium (Cd) enrichment.When soil applies 0.5% by charcoal and the composite passivating material that forms of fertilizer (0.5%BC-PM), rape edible part cadmium (Cd) content is 0.166 mg/kg (in fresh weight), and comparison is according to reducing by 55%, and reach the level of signifiance (
P<0.05); When charcoal in the soil and the composite passivating material amount of application that forms of fertilizer reach 2% (2%BC-PM), native rape edible part cadmium (Cd) content is 0.138 mgkg (in fresh weight), and comparison is according to reducing more than 62%, and reach the level of signifiance (
P<0.05).China food hygienic standard GB2762-2005 regulation, leaf vegetables cadmium (Cd) content limit value is 0.2 mgkg (in a fresh weight).Can find out by Fig. 2, polluted in the vegetable field soil by cadmium (Cd), apply the composite passivating material that forms of charcoal and fertilizer after, rape edible part cadmium (Cd) content all is lower than national food hygienic standard limit value (0.2 mg/kg), can supply safe edible.Therefore; Material charcoal and fertilizer composite effectively passivation soil cadmium (Cd) pollutes; Reduce the biological effectiveness and the transportable property of soil cadmium (Cd); Resistance control soil toxic heavy metal cadmium (Cd) is to the migration of vegetables edible part, accumulation, thereby the food hygiene quality of raising vegetables ensures the safety in production of vegetables.
According to above-mentioned explanation, can realize scheme of the present invention in conjunction with art technology.
Claims (1)
1. the composite original position of applying biological charcoal and fertilizer is repaired the method for vegetable field soil cadmium pollution; It is characterized in that; In the vegetable field soil of polluted by heavy metal cadmium, will impose on upper soll layer by charcoal and the composite passivating material that forms of fertilizer, then in the arable layer of 0-20cm with passivating material and the abundant mixing of soil; According to soil environment quality standard GB 15618-1995; Judge the soil pollution rank, wherein the heavy metal-polluted soil secondary standard is for ensureing agricultural production, safeguarding the soil limits value of health; When the soil cadmium concentration surpasses soil environment quality secondary standard value, then need administer and repair cadmium pollution soil, just can be used for kind of a plant after the reparation; When the soil cadmium concentration is between 1.0-2.9 mg/ kg, the passivating material amount of application be no less than dry ground heavy 0.5%, i.e. 750 kg/ mus, charcoal in the said passivating material and fertilizer are composite the forming of ratio of 1:1 in mass ratio; Said method comprises the steps:
Charcoal in the preparation passivating material: charcoal is formed by agricultural crop straw pyrolysis charring under 350 ℃ of anoxia conditions, and after grinding, crossing the aperture again is the screen cloth acquisition of 2mm;
Fertilizer in the preparation passivating material: fertilizer is selected chicken manure for use, and the chicken manure that the chicken farm provides is dried under 100 ℃ of temperature, and after grinding, crossing the aperture again is the screen cloth acquisition of 2mm;
With charcoal and fertilizer is the composite passivating material that forms of ratio of 1:1 in mass ratio;
Measure heavy metal-polluted soil cadmium content to be repaired, confirm soil recoverable scope be the soil cadmium concentration between 1.0-2.9 mg/kg, again vegetable field soil is turned over, break up the clods, smooth;
According to soil cadmium actual levels of pollution; In cadmium pollution soil to be repaired, use passivating material, earlier passivating material imposed on upper soll layer, again with passivating material at the arable layer plowed soils; Make the abundant mixing of passivating material and cadmium pollution soil; Field water divides the moisture state that keeps 70% maxmun field capacity, and balance gets final product planting vegetable after 2 weeks, and the field water management is consistent with normal agricultural production.
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