CN103918437A - Method for adopting eluting solution to restore sewage irrigation area soil heavy metal - Google Patents
Method for adopting eluting solution to restore sewage irrigation area soil heavy metal Download PDFInfo
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Abstract
The invention discloses a method for adopting an eluting solution to restore sewage irrigation area soil heavy metal. The eluting solution is composed of nitrilotriacetic acid which is a chelating agent and sodium dodecyl sulfate which is a surfactant, and mole ratio of nitrilotriacetic acid and sodium dodecyl sulfate is 5-15mmol kg-1:1mmol kg-1. On the basis of an optimal experiment, restored soil is eluted by using simulated acid rain, the objective of eluting restoration of lawn planting system sewage irrigation area soil heavy metal pollution is achieved, and the sewage irrigation area soil heavy metal after reaching the standard can continue to be applied to agricultural production.
Description
Technical field
The invention belongs to environmental protection technical field, relate to the method that adopts compound leacheate to repair dirty Irrigated Area Soils heavy metal.
Background technology
China's water resource is also faced with various pollution problems, and water resource lacks has become one of key factor of restriction China economic development.Reasonably use wastewater irrigation can alleviate the problem of water resource anxiety, can also saving water resource, alleviate the pollution to environment.Dirty filling refers to be carried out after harmless treatment city domestic sewage and industrial wastewater, directly or indirectly recharges for Sewage Irrigation in Farmland, gardens wastewater irrigation and underground reservoir.China starts to build wastewater irrigation engineering in nineteen fifty-seven after the founding of the state, lasts so far over half a century, and China has also passed through relevant dirt filling principle, policy and standard during this period.
The shortage of water resource has been alleviated in wastewater irrigation to a certain extent, still fills with the expansion of scale along with dirt, more and more obvious on the impact of soil.Change physicochemical property, Organic Pollution and the heavy metal pollution of soil.Wastewater irrigation is one of important sources of heavy metal-polluted soil, has in 7 heavy metal higher than background value, and have the trend increasing gradually in the dirty Irrigated Area Soils of the cool phoenix in Beijing; The dirty Irrigated Area Soils in Baiyin city is subject to heavy metal ion severe contamination, need to be through many kinds of measures comprehensive regulation ability pollution remission situation.
The wastewater irrigation of China is broadly divided into 3 stages: nineteen fifty-seven was spontaneous use wastewater irrigation period in the past, since the forties in 20th century, starts someone and utilize waste water irrigation farmland near Beijing; Nineteen fifty-seven wastewater irrigation is put into national scientific research plan, has obtained initial development to dirty filling of China during 1972; So far wastewater irrigation in 1972 develops rapidly.Since the beginning of the sixties, the dirty area of filling with of China expands rapidly, the famous dirty irrigated areas such as Beijing, Tianjin, Baoding, Shenyang, Shijiazhuang, Zhengzhou that distributed, combined task, the north, these areas account for dirty the more than 90% of area of filling with in the whole nation, and the dirt of south and highlands filling area is relatively little.Because sewage treatment facility efficiency is low, somewhat expensive etc., a large amount of raw sewerages are as direct irrigated farmland, water source.
Also there are a lot of countries and regions to adopt sewage to irrigate farmland abroad.The U.S. utilizes sewage country early in the world, and what the whole America urban sewage was used for irrigating at present accounts for 60% of total amount, and the handling rate of urban sewage reaches 100%.Japan just reclaims sewage since early 1960s, at present first by after waste water treatment, introduces farmland after making indices up to standard again and irrigates.Extremely Israel's wastewater treatment rate of lack of water has reached more than 90%, and availability also has 70%, wherein after 57% sewage purification for watering agricultural and meadow, gardens.France is used a century around of wastewater irrigation, government's Efforts To Develop waste water treatment research on the one hand, government takes much count of the impact of wastewater irrigation on agricultural byproducts quality on the other hand, the special Liao Wuguan health guidance association that sets up, regularly publish relevant information and wastewater irrigation situation is exercised supervision, government also instructs people by the irrigation of classifying of dissimilar sewage.The history of Germany's wastewater irrigation has more than 100 year, and 12 Ge Wuguan farms have just been set up in nineteen twenty-eight in surrounding area, Berlin city, and area reaches 10,000 hm
2.Although Berlin city has now built complete urban sewage treatment system, these wastewater irrigation farms are as an important component part of municipal sewage treatment.Also have the countries such as Brazil, Argentina, Greece, Chile also to have a large amount of practical experiences at sewage aspect utilizing.
The shortage of water resource has been alleviated in wastewater irrigation to a certain extent, still fills with the expansion of scale along with dirt, more and more obvious on the impact of soil.Change physicochemical property, Organic Pollution and the heavy metal pollution of soil.Wastewater irrigation is one of important sources of heavy metal-polluted soil, has in 7 heavy metal higher than background value, and have the trend increasing gradually in the dirty Irrigated Area Soils of the cool phoenix in Beijing; The dirty Irrigated Area Soils in Baiyin city is subject to heavy metal ion severe contamination, need to be through many kinds of measures comprehensive regulation ability pollution remission situation.
In sewage, contain a large amount of heavy metal elements, in soil, accumulation can affect absorption and the utilization of plant to nutrient, also the metabolic balance that can upset plant carries out field experiment in Beijing suburb, result shows the dirty plant height, the leaf area index that have affected summer corn of filling with, and its output and dry matter are obviously reduced.The pollution main manifestations of dirty irrigated area crop quality is that in agricultural product, content of beary metal exceeds standard and the change of nutrient component.There are some researches show, use each index of quality of wastewater irrigation mud field rice all to irrigate the obvious decline that has in mud field than clear water.Also have research to detect the agricultural product such as the terraneous potato of soil, beet of wastewater irrigation, result shows that wherein in Cd content and the soil solution, Cd content is linear correlation.
Agriculture environmental protection place is investigated the agricultural product of more than 300 contaminated area of 24 provinces and cities in the whole nation for 1997, and result shows that wheat, corn heavy metals exceeding standard rate are 15.5%, 14.0%, and heavy metal pollution is mainly taking mercury, chromium, cadmium, arsenic etc. as main.Wastewater irrigation also can make the protein content of wheat and paddy rice reduce, and along with the prolongation of sewage irrigation duration, the quality of crop can decline year by year.Dirty filling also can significantly be reduced Vitamin C content in vegetables, and the content of other nutrient components is to have to increase to have to subtract.
Heavy metal in sewage is mainly enriched between the 0-20 cm of dirty Irrigated Area Soils top layer.Soil has reduced heavy metal to underground migration to the absorption of heavy metal.There are some researches show long-term dirty area of filling with, local underground water is not subject to the pollution of heavy metal, and in most cases, the heavy metal of dirt in pouring water can't significantly affect underground water generates.Also there are some researches show, the heavy metal in soil especially Cd can show with the increase of leaching time the trend of downward migration, thereby underground water is threatened.In a word, in dirty sewage of filling with, some pollutant is by adsorption by soil, and another part can move to soil lower floor, finally phreatic water is affected.
Wastewater irrigation causes soil and pollution of agricultural products on the one hand, makes pollutant in crop or the middle accumulation of winning, and then enters people by food chain, then causes the incidence of disease of various chronic diseases to rise; Long-term dirt filling can cause Groundwater body pollution on the other hand, also can endanger human and livestock health after the daily drinking-water of people or livestock consumption; Also have long wastewater irrigation, peasant's health of direct contact is also had to impact.Edible such agricultural product for a long time as having indivedual areas, 19 areas such as the Shaoguan in the Ganzhou in Jiangxi and Dayu and Guangdong and the Qujiang River, Hunan, Shaanxi produce the situations of " cadmium rice ", if can work the mischief to the healthy of people.
Owing to directly irrigating with a large amount of raw sewerages, overproof water quality, the dirty area of filling with blindly expands again, causes the pollution of soil and crop and underground water, and wastewater irrigation has been the one of the main reasons that causes China's Rural Water Environment to worsen.Wastewater irrigation major part is that peasant is spontaneous, and their majority is in the situation that can not get clear water, and spontaneous introducing city life and industry waste water is as source of irrigation water, and this suburb nearby in northern China big and medium-sized cities is very general.
Traditional heavy metal pollution of soil recovery technique has casting landfill method, dilution method, elution method, physical partition method and chemical method etc.Compared with traditional processing mode, the major advantage of phytoremediation is that cost is low, and treatment facility is simple, is applicable to large-scale application, is beneficial to the maintenance of soil ecosystem, little to environmental perturbation, and the feature such as possess aesthetic value.
In the biological restoration of heavy metal pollution of soil, application is phytoremediation technology early, more widely.Phytoremediation is exactly the heavy metal contaminants utilizing in plant absorption, accumulation and fixing soil, is transferred to root or acrial part, then gathers in the crops at suitable vegetative stage, and after treatment, ashing is reclaimed heavy metal or carried out landfill.The result of study that ciliate desert-grass can a large amount of enrichment As of having reported for work first such as Chen Tongbin, analyzed the enriching quantity of this plant Different Organs to heavy metal simultaneously, the content of finding As in ciliate desert-grass Different Organs tissue is accessory pinna > petiole > root system, As easily upwards transport and enrichment in this plant corpus is described, demonstrating ciliate desert-grass has extremely strong patience and unique accumulation ability to As.Sun etc. study discovery, be grown in containing Cd content in the Sedum alfredii Hance plants stems in Cd slag soil and leaf apparently higher than root, the Sedum alfredii Hance plant root Cd content that is grown in non-Cd mining area is apparently higher than the content in cauline leaf, thereby confirms that Sedum alfredii Hance also has stronger enrichment to Cd.Tian Shengni etc. are by being preced with relatively thinking of grass with goose, and vetiver is that Cu, Pb, Zn Single Pollution or combined pollution are all had to good repair function.Ye Chun and studied reparation and the activating mechanism of alfalfa to Pb contaminated soil, finds out from X-ray micro-zone analysis result, space between cells Pb content is the highest, and cell wall and vacuole take second place, minimum in kytoplasm; Pb mainly exists with the form of indissoluble in alfalfa body, and alfalfa is relevant with the formation of plant complexing element to the tolerance of Pb.Because biomass of alfalfa is high, so it is the desirable rehabilitation plant of one that P in soil b pollutes that alfalfa can be used as.Secretions from plant roots can change rhizosphere soil environment, can make Cr, the Hg of multivalence state, valence state and the form of As change, and affects its poisonous effect.The root hair of plant can directly increase root table from soil exchange adsorption heavy metal to be fixed.But the growth cycle of the super enriching plant for restoration of soil polluted by heavy metal having is grown, biomass is relatively little, and low for the bioaccumulation efficiency of the low heavy metal of some biological effectiveness, this is restricted single use phytoremediation.
In reality, pollutant in soil is of a great variety, combined pollution is general, and pollution level and difference in thickness are large, and epidermic soil types is many simultaneously, the area differentiation of its composition, character, condition is obvious, and after repairing, the space planning of soil recycling formula requires different.Therefore, individual event recovery technique is toward being difficult to reach reparation target, and exploitation complex repairation pattern just becomes the main direction of studying that soil pollution is repaired.
The main Types that starts now the complex repairation technology that drops into application has the reparation of plant/microbial association, animal/plant combined reparation and chemistry/materialization-Co-bioremediation.The mechanism of plant/microbial association reparation is that higher plant and edaphon often exist synergy in process of growth, on the one hand plant can provide the edaphon required carbon source of growing, simultaneously again through base of leaf to root delivering oxygen, be formed with the microenvironment that is beneficial to oxidation, promote the decomposition of aerobic microbiological to pollutant.Chemistry/materialization-Co-bioremediation can be brought into play the advantage of short, instant effect of the cycle that chemistry or physics repairs, and in conjunction with nondestructive biological restoration feature, development is contaminated soil restorative procedure the most with potential applications based on chemical-biological recovery technique.As utilize the coordination stripping of organic complexing agent, and increase heavy metal concentration in the soil solution, improve the absorption efficiency of plant, thereby realize the reparation of strengthening Enhanced phytoextraction.Therefore, improve the method that plant absorbs enriching heavy metal, except using and continuing to find accumulation ability is strong and biomass is large super enriching plant, we can add artificial or natural chelating agent and other enhancements and improve the ability of plant absorption enriching heavy metal in phytoremediation process.
Chelating agent inducing plant extracts remediating heavy metal, and it can increase the solvability of heavy metal in soil on the one hand, can improve on the other hand heavy metal rhizosphere diffusivity, can also promote heavy metal to transport to overground part from root system.Pealosa etc. have studied the factor that several promotion lupine repairing heavy metal in soil pollute, found that, chelating agent NTA can promote metal ion (Fe, Mn, Cu, Zn, Cd) migration, impel the contained concentration of metal ions of lupine to raise, especially As, Cd and the increase of Pb concentration are more obvious.Qian Meng etc. plant elsholtzia splendens on Cu, Zn, Pb, Cd combined contamination soil, use 5 mmolkg
-1after EDTA, the concentration of Cu, Zn, Pb, Cd improves 27.4,3.2,17.6 and 89.5 times than contrast respectively.The researchs such as Stanhope show, along with the increase of EDTA concentration, the ratio that in soil, the content of Cu, Zn, Cd, Pb, Ni soluble state heavy metal accounts for total content of beary metal is linear raising.In chelation evoked phytoremediation process, the service time of chelating agent is very important, generally to gather in the crops in first 1 ~ 2 week and add plant, now growth and development of plants maturation, less on amount of growth impact after processing in the short time, the total metals of plant extract can significantly increase.
By green house potted plant experiment, research chelating agent and surfactant is independent or the effect of the auxiliary golden good fortune mushroom restoration of soil polluted by heavy metal of Combined Processing.Result shows, the EDTA of high concentration makes the biomass of Jin Fugu reduce than contrast, the concentration of fruit body Pb, Cu and Cd improves 15 ~ 88 times, 0.8 ~ 3.3 times and 0.5 ~ 0.6 times than contrast respectively. while adding surfactant separately, each biomass of processing does not have significant difference with contrasting, and heavy metal concentration amplitude of variation there is no to add separately the processing of EDTA large.But the complexing agent of this routine has stronger bio-toxicity.Therefore, the application of novel renovation agent attracts wide attention.
Most reports and research at present all shows that China's wastewater irrigation soil has heavy metal pollution in various degree, this also has the mankind's harm to environment is apparent, and at present the achievement in research in laboratory also temporarily can not be applied to land for growing field crops, find feasible, to be applicable to repair dirty method or technology of filling with native heavy metal very necessary.Heavy metal pollution of soil has the features such as the poly-property of complexity, irreversibility and table, single improvement method is difficult to be removed clean, the recovery technique that two or more recovery technique combines, can better bring into play advantage separately, is more beneficial to the reparation of heavy metal pollution of soil.Combination recovery technique is that Recent study is more concerned recovery technique.
Dirty filling civil engineering Lawn planted plant, add degradable chelating agent, respectively again using surfactant as auxiliary, make the heavy metal of turf establishment system reach the object that drip washing is repaired, this not only can be avoided heavy metal to enter food chain harm humans, also turf volume can be applied to urban afforestation, the stronger reviviscence of lawn plant is also suitable for repairing in addition simultaneously.After the native content of beary metal of dirty filling is up to standard, can continue to be applied to agricultural production.
Summary of the invention
The object of the present invention is to provide a kind of method that adopts compound leacheate to repair dirty Irrigated Area Soils heavy metal.The present invention, on the basis of Optimal Experimental, by using Simulated Acid Rain to carry out drip washing to the soil after repairing, reaches the object of the drip washing reparation of turf establishment system wastewater irrigation district heavy metal pollution of soil.For realizing this object, the invention provides following technical scheme:
A kind of compound leacheate, is characterized in that it is made up of chelating agent nitrilotriacetic acid and surfactant dodecyl sodium sulfate, and wherein the mol ratio of chelating agent nitrilotriacetic acid and surfactant dodecyl sodium sulfate is 5-15mmolkg
-1nTA:1 mmolkg
-1dodecyl sodium sulfate.
The present invention further discloses compound leacheate and repair the method for dirty Irrigated Area Soils heavy metal, it is characterized in that being undertaken by following step:
(1) processing of material:
Select the more common perennial Festuca Arundinacea of northern China (
festuca arundinaceal
.) be experiment material;
Chelating agent is selected nitrilotriacetic acid, and surfactant is selected dodecyl sodium sulfate;
Take from dirty irrigated area, Xiqing District, Tianjin for examination soil, by dividing on transparent plastic cloth after the soil removal grass roots of collection, stone, be positioned over ventilation, after natural air drying 2 ~ 3 d, cross 2 mm sieves for subsequent use.Soil organic matter content 3.62%, total nitrogen content 0.19%, full phosphorus amount 5.4 gkg
-1, full potassium amount 787.3 mgkg
-1, pH7.28, soil moisture content 4.13%, electrical conductivity 0.44 mscm
-1.In soil, the content of Cd, Cu and Zn is respectively 7.13,146.31 and 795.56 mgkg
-1, be respectively 23.8,1.5 and 3.2 times of soil environment quality secondary standard (GB156182-1995).
The preparation of artificial rainwater: being 5.59 according to the Tianjin whole city precipitation pH annual mean of monitoring out, is acid precipitation.(NH for this experiment
4)
2sO
4, Na
2sO
4, K
2sO
4, MgSO
4, Ca (NO
3)
2, Mg (NO
3)
2, H
2sO
4make SO
4 2-, NO
3 -, Cl
-, NH
4 +, Mg
2+, Ca
2+, K
+, Na
+concentration is respectively 14.96,6.54,1.68,3.71,0.82,1.38,0.64 and 0.78 mgL
-1rainwater, and with HCl allotment pH be 5.59.
(2) experimental technique:
Be 3 cm to diameter, in the pvc pipe of high 30 cm, add 220g for examination soil, 0.3g Festuca Arundinacea grass seeds is then planted in cotton and nylon wire sealing for bottom in each pipe, pvc pipe is sling and fixed, lower end is joined and is put conical flask and access effusion, and lawn plant is cultivated and carries out in laboratory, and often reversing of position is consistent to ensure illumination, 12 ~ 28 DEG C of indoor temperatures between culture period, relative moisture 34 ~ 56%, normal water supply between establishment period, to maintain plant normal growth.Plant growth 30 d, respectively the NTA of respective concentration or dodecyl sodium sulfate are pressed to required dosage according to experimental design, the disposable stromal surface that puts on respective handling group, processes after 10d and gathers in the crops lawn plant acrial part, cradle second day, carry out acid rain drip washing for the first time, each 30ml(is equivalent to 42mm precipitation), every 7 days are once, altogether drip washing three times, finally collect leacheate, finally measure content of beary metal in digestive juice with TAS-990 atomic absorption spectrophotometer; Wherein the NTA of respective concentration or dodecyl sodium sulfate refer to wherein one below:
5-15?mmol·kg
-1NTA；
5 mmolkg
-1nTA+1 mmolkg
-1dodecyl sodium sulfate;
10 mmolkg
-1nTA+1 mmolkg
-1dodecyl sodium sulfate;
15 mmolkg
-1nTA+1 mmolkg
-1dodecyl sodium sulfate.
3, the method that described in claim 2, compound leacheate is repaired dirty Irrigated Area Soils heavy metal, heavy metal wherein refers to Cd, Cu, Zn content.
The present invention further discloses method that compound leacheate repairs dirty Irrigated Area Soils heavy metal in the application increasing aspect heavy metal drip washing repair ability.Wherein said compound leacheate refers to 5 mmolkg
-1nTA:1 mmolkg
-1dodecyl sodium sulfate or 10 mmolkg
-1nTA:1 mmolkg
-1dodecyl sodium sulfate
The conclusion that the present invention reaches by test: under acid rain leaching, common processed group leaching liquor Cd, the Cu using of NTA and dodecyl sodium sulfate, Zn concentration are all than being improved of contrast and organize with concentration NTA, there are some researches show that in addition acid rain can accelerate soil acidification, the increased activity that makes heavy metal, result shows: the use of NTA and dodecyl sodium sulfate has also increased heavy metal drip washing repair ability in activation heavy metal.
materials and methods
1.1 experiment material
Select the more common perennial Festuca Arundinacea of northern China (
festuca arundinaceal
.) be experiment material.
Chelating agent is selected nitrilotriacetic acid (NTA), and molecular formula is N (CH
2cOOH)
3, be purchased from Chemical Reagent Co., Ltd., Sinopharm Group, pure for analyzing.
Surfactant is selected dodecyl sodium sulfate, and molecular formula is C
12h
25naO
3s, is purchased from Beijing chemical reagents corporation, pure for analyzing.
Take from dirty irrigated area, Xiqing District, Tianjin for examination soil, by dividing on transparent plastic cloth after the soil removal grass roots of collection, stone, be positioned over ventilation, after natural air drying 2 ~ 3 d, cross 2 mm sieves for subsequent use.Soil organic matter content 3.62%, total nitrogen content 0.19%, full phosphorus amount 5.4 gkg
-1, full potassium amount 787.3 mgkg
-1, pH7.28, soil moisture content 4.13%, electrical conductivity 0.44 mscm
-1.In soil, the content of Cd, Cu and Zn is respectively 7.13,146.31 and 795.56 mgkg
-1, be respectively 23.8,1.5 and 3.2 times of soil environment quality secondary standard (GB156182-1995).
The preparation of artificial rainwater: being 5.59 according to the Tianjin whole city precipitation pH annual mean of monitoring out, is acid precipitation.(NH for this experiment
4)
2sO
4, Na
2sO
4, K
2sO
4, MgSO
4, Ca (NO
3)
2, Mg (NO
3)
2, H
2sO
4make SO
4 2-, NO
3 -, Cl
-, NH
+, Mg
2+, Ca
2+, K
+, Na
+concentration is respectively 14.96,6.54,1.68,3.71,0.82,1.38,0.64 and 0.78 mgL
-1rainwater, and with HCl allotment pH be 5.59.
1.2 experiments are processed
Experimental design: do not add the contrast (I) of NTA and dodecyl sodium sulfate; 5 mmolkg
-1nTA(II); 10 mmolkg
-1nTA(III); 15 mmolkg
-1nTA(IV); 5 mmolkg
-1nTA+1 mmolkg
-1dodecyl sodium sulfate (V); 10 mmolkg
-1nTA+1 mmolkg
-1dodecyl sodium sulfate (VI); 15 mmolkg
-1nTA+1 mmolkg
-1dodecyl sodium sulfate (VII).Each processing repeats for 3 times.
1.3 lawn plants are cultivated
Be 3 cm to diameter, add 220g for examination soil in the pvc pipe of high 30 cm, 0.3g Festuca Arundinacea grass seeds is then planted in cotton and nylon wire sealing for bottom in each pipe, pvc pipe is sling and fixed, and lower end is joined and put conical flask and access effusion.Lawn plant is cultivated and carries out in laboratory, and often reversing of position is consistent to ensure illumination, 12 ~ 28 DEG C of indoor temperatures between culture period, relative moisture 34 ~ 56%.Normal water supply between establishment period, to maintain plant normal growth.Plant growth 30 d, are dissolved in distilled water by the NTA of respective concentration or dodecyl sodium sulfate by required dosage respectively according to experimental design, the disposable stromal surface that puts on respective handling group; The distilled water pouring of equivalent for contrast.After processing 10d, gather in the crops lawn plant acrial part.Cradle second day, carry out acid rain drip washing for the first time, each 30ml(is equivalent to 42mm precipitation), every 7 days are once, altogether drip washing three times.Finally collect leacheate.
1.4 index determining
The mensuration of content of beary metal: get leacheate 5mL, use nitric acid and perchloric acid to digest at 120-140 DEG C, gained solution is settled to 10mL with distilled water.Finally measure heavy metal (Cd, Cu, Zn) content in digestive juice with TAS-990 atomic absorption spectrophotometer.
1.5 data analysis processing
Adopt SPSS17.0 software to carry out statistical analysis to data.
2 development results analyses
As can be seen from Table 1,15 mmolkg
-1cd, Cu, the Zn concentration of NTA associating dodecyl sodium sulfate group effusion reach maximum, are respectively 2.35,2.00,5.83 times of contrast.Compared with the NTA group of NTA associating dodecyl sodium sulfate processed group and same concentration, Cd, Cu, Zn concentration are all improved.According to country, about the regulation in groundwater quality standard (GB/T14848-93), III class standard, taking health a reference value as foundation, is mainly applicable to centralized Drinking Water water source and work, agricultural water.The concentration of Groundwater Environmental Quality III class standard Cd, Cu, Zn will be not more than 0.01,1.0,1.0mgL, and in this experiment, in percolate, the concentration of Cd all exceedes III class standard, but Cu, Zn concentration do not exceed III class standard.
The concentration of heavy metal (ug/mL) in effusion under table 1 different disposal
| Process | Cd | Cu | Zn |
| Do not add NTA and dodecyl sodium sulfate | 0.017±0.003e | 0.213±0.027d | 0.047±0.012d |
| 5 mmol·kg -1NTA | 0.024±0.002de | 0.260±0.071cd | 0.126±0.017c |
| 10 mmol·kg -1NTA | 0.028±0.007cd | 0.298±0.107cd | 0.189±0.026b |
| 15 mmol·kg -1NTA | 0.045±0.008b | 0.374±0.073bc | 0.268±0.057a |
| 5 mmol·kg -1NTA+ dodecyl sodium sulfate | 0.037±0.007bc | 0.435±0.028b | 0.182±0.026bc |
| 10 mmol·kg -1NTA+ dodecyl sodium sulfate | 0.036±0.005bc | 0.427±0.073b | 0.205±0.016b |
| 15 mmol·kg -1NTA+ dodecyl sodium sulfate | 0.057±0.004a | 0.638±0.063a | 0.274±0.050a |
With the different letter representation significant differences of column data (P<0.05)
3 development conclusions
In this technology, under acid rain leaching, common processed group leaching liquor Cd, the Cu using of NTA and dodecyl sodium sulfate, Zn concentration are all than being improved of contrast and organize with concentration NTA, there are some researches show that in addition acid rain can accelerate soil acidification, the increased activity that makes heavy metal, result shows: the use of NTA and dodecyl sodium sulfate has also increased heavy metal drip washing repair ability in activation heavy metal.After the native content of beary metal of dirty filling is up to standard, can continue to be applied to agricultural production.
Embodiment:
Below in conjunction with specific embodiment, the present invention will be further described, and following each embodiment is not only limitation of the present invention for the present invention is described.Wherein chemical reagent used all has commercially available.
Embodiment 1
Compound leacheate is repaired the method for dirty Irrigated Area Soils heavy metal, it is characterized in that being undertaken by following step:
(1) processing of material:
Select the more common perennial Festuca Arundinacea of northern China (
festuca arundinaceal
.) be experiment material;
Chelating agent is selected nitrilotriacetic acid, and surfactant is selected dodecyl sodium sulfate;
Take from dirty irrigated area, Xiqing District, Tianjin for examination soil, by dividing on transparent plastic cloth after the soil removal grass roots of collection, stone, be positioned over ventilation, after natural air drying 2 ~ 3 d, cross 2 mm sieves for subsequent use.Soil organic matter content 3.62%, total nitrogen content 0.19%, full phosphorus amount 5.4 gkg
-1, full potassium amount 787.3 mgkg
-1, pH7.28, soil moisture content 4.13%, electrical conductivity 0.44 mscm
-1.In soil, the content of Cd, Cu and Zn is respectively 7.13,146.31 and 795.56 mgkg
-1, be respectively 23.8,1.5 and 3.2 times of soil environment quality secondary standard (GB156182-1995).
The preparation of artificial rainwater: being 5.59 according to the Tianjin whole city precipitation pH annual mean of monitoring out, is acid precipitation.(NH for this experiment
4)
2sO
4, Na
2sO
4, K
2sO
4, MgSO
4, Ca (NO
3)
2, Mg (NO
3)
2, H
2sO
4make SO
4 2-, NO
3 -, Cl
-, NH
4 +, Mg
2+, Ca
2+, K
+, Na
+concentration is respectively 14.96,6.54,1.68,3.71,0.82,1.38,0.64 and 0.78 mgL
-1rainwater, and with HCl allotment pH be 5.59.
(2) experimental technique:
Be 3 cm to diameter, in the pvc pipe of high 30 cm, add 220g for examination soil, 0.3g Festuca Arundinacea grass seeds is then planted in cotton and nylon wire sealing for bottom in each pipe, pvc pipe is sling and fixed, lower end is joined and is put conical flask and access effusion, and lawn plant is cultivated and carries out in laboratory, and often reversing of position is consistent to ensure illumination, 15 DEG C of indoor temperatures between culture period, relative moisture 35%, normal water supply between establishment period, to maintain plant normal growth.Plant growth 30 d, respectively the NTA of respective concentration or dodecyl sodium sulfate are pressed to required dosage according to experimental design, the disposable stromal surface that puts on respective handling group, after processing 10d, gather in the crops lawn plant acrial part, cradle second day, carry out acid rain drip washing for the first time, each 30ml(is equivalent to 42mm precipitation), every 7 days once, drip washing three times altogether, finally collect leacheate, finally measure heavy metal Cd, Cu, Zn content in digestive juice with TAS-990 atomic absorption spectrophotometer; Wherein respective concentration: 5 mmolkg
-1nTA+1 mmolkg
-1dodecyl sodium sulfate;
Embodiment 2
Compound leacheate is repaired the method for dirty Irrigated Area Soils heavy metal, it is characterized in that being undertaken by following step:
(1) processing of material:
Select the more common perennial Festuca Arundinacea of northern China (
festuca arundinaceal
.) be experiment material;
Chelating agent is selected nitrilotriacetic acid, and surfactant is selected dodecyl sodium sulfate;
Take from dirty irrigated area, Xiqing District, Tianjin for examination soil, by dividing on transparent plastic cloth after the soil removal grass roots of collection, stone, be positioned over ventilation, after natural air drying 2 ~ 3 d, cross 2 mm sieves for subsequent use.Soil organic matter content 3.62%, total nitrogen content 0.19%, full phosphorus amount 5.4 gkg
-1, full potassium amount 787.3 mgkg
-1, pH7.28, soil moisture content 4.13%, electrical conductivity 0.44 mscm
-1.In soil, the content of Cd, Cu and Zn is respectively 7.13,146.31 and 795.56 mgkg
-1, be respectively 23.8,1.5 and 3.2 times of soil environment quality secondary standard (GB156182-1995).
The preparation of artificial rainwater: being 5.59 according to the Tianjin whole city precipitation pH annual mean of monitoring out, is acid precipitation.(NH for this experiment
4)
2sO
4, Na
2sO
4, K
2sO
4, MgSO
4, Ca (NO
3)
2, Mg (NO
3)
2, H
2sO
4make SO
4 2-, NO
3 -, Cl
-, NH
4 +, Mg
2+, Ca
2+, K
+, Na
+concentration is respectively 14.96,6.54,1.68,3.71,0.82,1.38,0.64 and 0.78 mgL
-1rainwater, and with HCl allotment pH be 5.59.
(2) experimental technique:
Be 3 cm to diameter, in the pvc pipe of high 30 cm, add 220g for examination soil, 0.3g Festuca Arundinacea grass seeds is then planted in cotton and nylon wire sealing for bottom in each pipe, pvc pipe is sling and fixed, lower end is joined and is put conical flask and access effusion, and lawn plant is cultivated and carries out in laboratory, and often reversing of position is consistent to ensure illumination, 25 DEG C of indoor temperatures between culture period, relative moisture 45%, normal water supply between establishment period, to maintain plant normal growth.Plant growth 30 d, respectively the NTA of respective concentration or dodecyl sodium sulfate are pressed to required dosage according to experimental design, the disposable stromal surface that puts on respective handling group, after processing 10d, gather in the crops lawn plant acrial part, cradle second day, carry out acid rain drip washing for the first time, each 30ml(is equivalent to 42mm precipitation), every 7 days once, drip washing three times altogether, finally collect leacheate, finally measure heavy metal Cd, Cu, Zn content in digestive juice with TAS-990 atomic absorption spectrophotometer; Wherein respective concentration: 10 mmolkg
-1nTA+1 mmolkg
-1dodecyl sodium sulfate.
Claims (5)
1. a compound leacheate, is characterized in that it is made up of chelating agent nitrilotriacetic acid and surfactant dodecyl sodium sulfate, and wherein the mol ratio of chelating agent nitrilotriacetic acid and surfactant dodecyl sodium sulfate is 5-15mmolkg
-1nTA:1 mmolkg
-1dodecyl sodium sulfate.
2. a method that adopts compound leacheate claimed in claim 1 to repair dirty Irrigated Area Soils heavy metal, is characterized in that being undertaken by following step:
(1) processing of material:
Select the more common perennial Festuca Arundinacea of northern China (
festuca arundinaceal
.) be experiment material;
Chelating agent is selected nitrilotriacetic acid, and surfactant is selected dodecyl sodium sulfate;
Take from dirty irrigated area, Xiqing District, Tianjin for examination soil, by dividing on transparent plastic cloth after the soil removal grass roots of collection, stone, be positioned over ventilation, after natural air drying 2 ~ 3 d, cross 2 mm sieves for subsequent use;
The preparation of artificial rainwater: being 5.59 according to the Tianjin whole city precipitation pH annual mean of monitoring out, is acid precipitation;
(NH for this experiment
4)
2sO
4, Na
2sO
4, K
2sO
4, MgSO
4, Ca (NO
3)
2, Mg (NO
3)
2, H
2sO
4make SO
4 2-, NO
3 -, Cl
-, NH
4 +, Mg
2+, Ca
2+, K
+, Na
+concentration is respectively 14.96,6.54,1.68,3.71,0.82,1.38,0.64 and 0.78 mgL
-1rainwater, and with HCl allotment pH be 5.59;
(2) experimental technique:
Be 3 cm to diameter, in the pvc pipe of high 30 cm, add 220g for examination soil, 0.3g Festuca Arundinacea grass seeds is then planted in cotton and nylon wire sealing for bottom in each pipe, pvc pipe is sling and fixed, lower end is joined and is put conical flask and access effusion, and lawn plant is cultivated and carries out in laboratory, and often reversing of position is consistent to ensure illumination, 12 ~ 28 DEG C of indoor temperatures between culture period, relative moisture 34 ~ 56%, normal water supply between establishment period, to maintain plant normal growth;
Plant growth 30 d, respectively the NTA of respective concentration or dodecyl sodium sulfate are pressed to required dosage according to experimental design, the disposable stromal surface that puts on respective handling group, processes after 10d and gathers in the crops lawn plant acrial part, cradle second day, carry out acid rain drip washing for the first time, each 30ml(is equivalent to 42mm precipitation), every 7 days are once, altogether drip washing three times, finally collect leacheate, finally measure content of beary metal in digestive juice with TAS-990 atomic absorption spectrophotometer; Wherein the NTA of respective concentration or dodecyl sodium sulfate refer to wherein one below:
5-15?mmol·kg
-1NTA；
5 mmolkg
-1nTA+1 mmolkg
-1dodecyl sodium sulfate;
10 mmolkg
-1nTA+1 mmolkg
-1dodecyl sodium sulfate;
15 mmolkg
-1nTA+1 mmolkg
-1dodecyl sodium sulfate.
3. the method that described in claim 2, compound leacheate is repaired dirty Irrigated Area Soils heavy metal, heavy metal wherein refers to Cd, Cu, Zn content.
4. the method that described in claim 2, compound leacheate is repaired dirty Irrigated Area Soils heavy metal is in the application increasing aspect heavy metal drip washing repair ability.
5. application claimed in claim 4, wherein said compound leacheate refers to 5 mmolkg
-1nTA:1 mmolkg
-1dodecyl sodium sulfate or 10 mmolkg
-1nTA:1 mmolkg
-1dodecyl sodium sulfate.
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