CN103894403A - Method for restoring heavy metal polluted farmland soil with tourmaline as modifying agent - Google Patents

Method for restoring heavy metal polluted farmland soil with tourmaline as modifying agent Download PDF

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CN103894403A
CN103894403A CN201210593272.8A CN201210593272A CN103894403A CN 103894403 A CN103894403 A CN 103894403A CN 201210593272 A CN201210593272 A CN 201210593272A CN 103894403 A CN103894403 A CN 103894403A
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tourmaline
soil
heavy metal
modifying agent
absorption
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CN201210593272.8A
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王翠苹
王宝琳
李歆
孙红文
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Nankai University
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Nankai University
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Abstract

The invention provides a method for restoring heavy metal polluted farmland soil with tourmaline as a modifying agent. Less than or equal to 5% of tourmaline is added into soil to be restored, and a stable compound is formed through adsorption, ion exchange and other reactions of the tourmaline and heavy metals; the bio-availability and the mobility of the heavy metals are remarkably reduced, and absorption and accumulation of plants to the heavy metals are alleviated; Ca, Mg and K, released in the restoring process, can improve soil fertility and promote plant growth; the tourmaline improved soil has stable adsorption effect on the heavy metals and desorption and release are difficult. The method has the advantages of simplicity in operation, low cost, rapidness in restoring and no secondary pollution.

Description

Tourmaline is the reparation of modifying agent to heavy metal pollution agricultural land soil
Technical field
The present invention relates to soil remediation technology, specifically a kind of method taking tourmaline as modifying agent repairing heavy metal pollution agricultural land soil.
Background technology
Heavy metal can not be biodegradable, once enter soil, will extended residual, constantly accumulation, the food chain that enters absorbed by crops, is detrimental to health.According to State Environmental Protection Administration, at present there is nearly 2,000 ten thousand hectares of the farmland area of the heavy metal pollutions such as cadmium, lead, arsenic in China, accounts for 1/5 of total cultivated area.Along with the quickening of process of industrialization, the soil erosion of heavy metal pollution is increasing, pollution level increases the weight of day by day.Therefore it is significant that, the recovery technique of heavy metal pollution agricultural land soil is set up in exploitation.
At present, the recovery technique of heavy-metal contaminated soil mainly comprises: (1) engineering reparation, to dig etc. as soil moved in to improve the original, soil removal and replacement and deep ploughing, and the method quantities is large, and investment cost is high, is not suitable for the improvement of pollution in wide area soil; (2) physics reparation, as electronic reparation and electric heating reparation, to the soil remediation successful polluting heavily, area is little, but easily causes soil texture to destroy and fertility decline, and the contaminated soil larger to area need to consume a large amount of manpower and materials; (3) biological restoration, repairs and phytoremediation as microorganism, and wherein microorganism recovery technique is also confined to scientific research and laboratory level, case study is few, cannot spread, phytoremediation generally needs more than 10 years, the cycle is long, is not suitable for the reparation of farmland pollution soil; (4) chemistry is repaired, as chemical leaching, chemical passivation etc.Chemical passivation reparation is in soil, to add modifying agent to change physics, the chemical property of soil, the effects such as absorption by it to heavy metal, precipitation, ion-exchange, complexing, change the existence of heavy metal in soil, reduce its biological effectiveness and animal migration.Chemical passivation recovery technique is with low cost with it, reparation is quick, simple operation and other advantages comes into one's own, and is suitable for the reparation of large area heavy-metal contaminated soil.
Conventional modifying agent comprises basic matterial, phosphorated material, is rich in mineral and the organic materials etc. of iron and manganese oxides.Conventional modifying agent has limitation separately, and as lime is only applicable to subacidity soil as soil conditioner, and long-term use easily causes soil compaction; Chronic administration phosphorated material, as modifying agent, can make soil be strong basicity, and brings out the eutrophication of water body.Be rich in the mineral of iron and manganese oxides because cost is relatively high, exist again Fe, the Mn murder by poisoning risk to crop, limited its application in production practices simultaneously.The fertilizers such as ight soil can reduce the validity of heavy metal in the time being just manured into soil, but along with the mineralising of organic substance is decomposed, likely cause the heavy metal ion being adsorbed again to discharge at the 2nd year or the 3rd year.In the time of restoration of soil polluted by heavy metal, there are serious problems in these modifying agents.
2012, people's first Application tourmaline such as Wang Baolin are repaired Dagu, Tianjin polluted river heavy metal pollution agricultural land soil, tourmaline can make soil pH still keep neutral, promote the growth of crops, significantly reduce biological effectiveness and the transportable property of heavy metal in soil, reduce the absorption and accumulation of crops to heavy metal, and tourmaline is stable to heavy metal adsorption, fixation, can not produce secondary pollution.
Summary of the invention
The object of the invention is to solve some problems that exist in conventional modifying agent technology, a kind of technical method of new material-tourmaline restoration of soil polluted by heavy metal is provided.
For achieving the above object, reparation heavy metals in farmland pollution method provided by the invention be by tourmaline and soil respectively according to mass ratio be 0,1%, 2%, 5% (W tourmaline: W soil) addition manner repairs.
The present invention adds cheap natural minerals tourmaline in contaminated soil to, with cadmium, copper generation chemical reaction (ion-exchange, absorption etc.), forms stable compound, reduces the biological effectiveness of Cadmium in Soil, copper; Tourmaline adds soil meeting release of trace elements, Promoting plant growth to simultaneously; After tourmaline Adsorption of Heavy Metal Ions, difficult release.
Concrete detailed description in detail:
Stock:
Tourmaline (tourmaline) 325 order technical grade reagent, buy in Lingshou County, Hebei province health care stone processing factory, and the place of production is Xinjiang.
Contaminated soil picks up from farmland, polluted river bank, Dagu, Tianjin 0~20cm soil, pH is 7.45, be alkalescent, cadmium content is 4.62mg/kg, copper content is 120.16mg/kg, all exceeding national soil environment quality secondary standard (GB15618-1995), is slight heavy-metal composite pollution agricultural land soil.Soil is crossed 2mm sieve, for subsequent use.
The foundation of improvement system:
By adding respectively in soil for examination, mass ratio is 0,1%, 2%, 5% tourmaline, fully mixes, and packs plastic flowerpot into, every basin fills native 1000g, each processing repeated 3 times, adds water and is adjusted to 60% left and right that water content is soil maxmun field capacity, regularly waters deionized water, after ageing two weeks, sowing romaine lettuce seed, and add a certain amount of urea and potassium dihydrogen phosphate as base manure, be placed in hot-house culture, every basin final singling 6 strains after emerging, gather in the crops after growth 60d.The romaine lettuce aerial part of results, a small amount of blade is for chlorophyll content analysis, and 105 DEG C of remainders complete half an hour, measure dry weight, and Cd, Cu content are analyzed to mensuration after 70 DEG C of oven dry.
Investigate various dose tourmaline to Growth of Lettuce and the impact on heavy metal absorption and accumulation thereof; Set forth the impact of tourmaline on soil available heavy metal and micronutrient levels; Evaluate the stability of tourmaline to heavy metal-polluted soil improvement.
Brief description of the drawings
The impact of Fig. 1 tourmaline on soil available Cd, Cu content
The impact of Fig. 2 tourmaline on romaine lettuce absorption and accumulation Cd, Cu content
Fig. 3 tourmaline is to Cd 2+analytical dynamics
Detailed description of the invention
Below in conjunction with implementing further detailed description of the present invention, but working of an invention mode is not limited to this.
1. the impact of various dose tourmaline on Growth of Lettuce
For adding a certain proportion of tourmaline in examination soil, ageing, after two weeks, is carried out romaine lettuce pot experiment.Experimental result shows: tourmaline Different adding amount all can effectively promote the growth of romaine lettuce, is embodied as the raising (table 1) of romaine lettuce biomass and chlorophyll content.Wherein 5% tourmaline processing makes romaine lettuce dry weight increase by 107.69%, is 2.08 times of check experiment, and chlorophyll content increases by 31.03%.
The impact of table 1 tourmaline on Growth of Lettuce
Figure BSA00000833814800031
2. the impact of various dose tourmaline on content of beary metal in soil and plant
In order to investigate the effect of tourmaline to soil, take processing in the same manner as in Example 1, tourmaline and soil are fully mixed, adding water to water content is 60% of soil maxmun field capacity, incubated at room temperature two months, gets pedotheque, air-dry, crosses 100 mesh sieves.Soil pH is measured, and with diethyl pentetic acid (DTPA) lixiviate soil available cadmium, Cu content.
From pH measurement result, add 1%, 2%, 5% tourmaline in soil for examination after pH between 7.36-7.50, compared with original soil, change in 0.1 unit, substantially do not change the acid-base value of native soil, for plant normal growth provides safeguard.
Each processing on the impact of soil available Cd, Cu content as shown in Figure 1, along with the increase of tourmaline addition, in upper earth, available heavy metal content is remarkable downward trend, in the time that tourmaline addition is 5%, soil available Cd, Cu content reduce 22.45%, 19.10% than contrast respectively.
Different disposal on the impact of romaine lettuce edible part Cd, Cu content as shown in Figure 2.Along with the increase of tourmaline addition, romaine lettuce edible part content of beary metal is remarkable downward trend.In the time that tourmaline addition is 5%, Cd, Cu content reduce 51.28%, 30.97% than contrast respectively.China food hygienic standard GB2762-2005 regulation, leaf vegetables Cd content limit value is 0.2mg/kg, as seen from Figure 2, uses after 5% tourmaline in heavy-metal contaminated soil, romaine lettuce edible part Cd content, lower than national food hygienic standard limit value, can supply safe edible
From above-mentioned case study, tourmaline adds heavy-metal contaminated soil to, can reduce heavy metal and shift, accumulates to plant edible part, improves the food hygiene quality of crops, ensures the safety in production of crops.
3. the impact of various dose tourmaline on microelement contents of soil
In order to set forth the mechanism of tourmaline to Influence To Soil and Promoting plant growth, hereby investigate the variation of soil water soluble trace elements in tourmaline-soil system.Each processing is as shown in table 2 on the impact of water soluble trace elements content in soil, and along with the increase of tourmaline addition, micronutrient levels is remarkable increase trend.Water soluble trace elements in soil can be absorbed and used by plants, Promoting plant growth.Therefore, the interpolation of tourmaline not only can reduce the murder by poisoning risk of heavy metal on plants, also has the potentiality that promote crop growth, has very big application value.
The impact (mg/kg) of table 2 tourmaline on soil water dissolubility micronutrient levels
Figure BSA00000833814800041
4. the absorption stability of tourmaline to heavy metal
Discharge risk for evaluating tourmaline as stability or the short time of modifying agent counterweight metal function, the present invention selects Cd 2+carry out resolving experimental study in the aqueous solution for representative, evaluate it to heavy metal adsorption stability.
By Cd (NO 3) 2it is 4.0 that solution is adjusted to pH, 25 DEG C of adsorption temps, and tourmaline consumption is 6g/L, Cd 2+solion initial concentration is 100mg/L, and liquor capacity is 20ml, carries out Cd 2+adsorption test, after absorption 24h, centrifugal 15min under 3000r/min, supernatant is crossed 0.22 μ m filter membrane to be measured in the centrifuge tube of 15ml acidifying, will remain and adsorb Cd 2+in the centrifuge tube of tourmaline, add 20ml HCl to regulate the distilled water that pH is 4, shake up, be placed in the constant incubator of 25 DEG C, carry out analytical dynamics experiment.Parsing reaches certain hour takes out, and centrifugal, mistake film, with Cd in WFX-210 type atomic absorption spectrophotometer mensuration filtrate 2+concentration.
Under the acid condition of pH=4, the Cd that is 100mg/L to initial concentration with tourmaline 2+adsorb, in the time of 24h, adsorption rate reaches 58.02%, and therefore, tourmaline is to Cd in strongly acidic solution 2+high adsorption rate, for tourmaline restoration of soil polluted by heavy metal has been established good theoretical foundation.To absorption Cd 2+tourmaline carries out 3 times and resolves experiment, and as seen from Figure 3, tourmaline is to Cd 2+resolution factor very low, resolve from starting to 48h at every turn, resolution factor is basicly stable, the resolution factor of resolving for the first time when 48h is 9% left and right, secondary resolve resolution factor be 5% left and right, three times resolve resolution factor be 3% left and right.This explanation tourmaline is stable to heavy metal ion adsorbed effect, and parsing amount is few.Therefore, the reparation by tourmaline for heavy metal pollution agricultural land soil, does not have and discharges the risk that heavy metal generation is polluted again.
To sum up, tourmaline can discharge the trace element useful to plant growth, promotes Growth of Lettuce; Reduce soil available content of beary metal, thereby reduce the absorption and accumulation of romaine lettuce to heavy metal; Tourmaline is high to heavy metal adsorption rate, absorption fixation is stable, and parsing amount is few, do not have modifying agent and discharge the risk of heavy metal.Be the present invention confirm tourmaline can be well for the reparation of heavy metal pollution agricultural land soil.

Claims (3)

1. a tourmaline recovery technique for heavy metal pollution agricultural land soil, is characterized in that, in polluted farmland soil to be repaired, add a certain amount of tourmaline, fully mix, regulate 60% left and right that soil moisture content is maximum water-holding capacity, after balance two weeks, get final product Planting Crops.
2. tourmaline claimed in claim 1 is repaired feature:
Tourmaline can significantly reduce biological effectiveness and the transportable property of heavy metal; Reduce the absorption and accumulation of plant to heavy metal; Improve soil fertility, Promoting plant growth; The heavy metal ion of tourmaline absorption is difficult to resolve to be analysed, non-secondary pollution risk.
3. tourmaline recovery technique according to claim 1, it is characterized in that, tourmaline used is powder, the addition of tourmaline can be definite according to heavy metals in farmland pollution level, and recommendation amount is that quality (dry weight) ratio of modifying agent described in claim 1 and agricultural land soil is 1%-5%.
CN201210593272.8A 2012-12-27 2012-12-27 Method for restoring heavy metal polluted farmland soil with tourmaline as modifying agent Pending CN103894403A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109694713A (en) * 2018-11-09 2019-04-30 天津天绿健科技有限公司 A kind of soil-repairing agent and preparation method thereof handling cadmium pollution soil
CN111957734A (en) * 2020-07-03 2020-11-20 广东省生态环境技术研究所 Method for in-situ remediation of soil heavy metal pollution
CN114749141A (en) * 2022-05-16 2022-07-15 南开大学 Environmental heavy metal pollution repairing agent and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1320581A (en) * 2001-05-18 2001-11-07 李献 Functional tourmaline fertilizer and its preparing process
KR20100029410A (en) * 2008-09-08 2010-03-17 강원대학교산학협력단 Method for treating soils contaminated by heavy metals using ostershell and soil treatment agent

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1320581A (en) * 2001-05-18 2001-11-07 李献 Functional tourmaline fertilizer and its preparing process
KR20100029410A (en) * 2008-09-08 2010-03-17 강원대학교산학협력단 Method for treating soils contaminated by heavy metals using ostershell and soil treatment agent

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
李文龙等: "电气石矿物材料的特性", 《功能材料》, 31 December 2007 (2007-12-31), pages 3545 - 3548 *
王宝琳等: "电气石、沸石对重金属污染农田土壤的修复效果研究", 《第六届海峡两岸土壤和地下水污染与整治研讨会论文集》, 28 August 2012 (2012-08-28), pages 125 - 127 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109694713A (en) * 2018-11-09 2019-04-30 天津天绿健科技有限公司 A kind of soil-repairing agent and preparation method thereof handling cadmium pollution soil
CN111957734A (en) * 2020-07-03 2020-11-20 广东省生态环境技术研究所 Method for in-situ remediation of soil heavy metal pollution
CN114749141A (en) * 2022-05-16 2022-07-15 南开大学 Environmental heavy metal pollution repairing agent and preparation method and application thereof

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Application publication date: 20140702