CN102764756B - Method for remediation of lead pollution on beach soil - Google Patents
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- CN102764756B CN102764756B CN201210242394.2A CN201210242394A CN102764756B CN 102764756 B CN102764756 B CN 102764756B CN 201210242394 A CN201210242394 A CN 201210242394A CN 102764756 B CN102764756 B CN 102764756B
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Abstract
The invention discloses a method for remediation of lead pollution on beach soil. The method disclosed by the invention comprises the following steps of: carrying out alternate drying and wetting treatment on the beach soil, regulating and controlling soil oxidation-reduction potential, thus oxidizable and reducible lead in the beach soil is released and is changed into soluble or exchangeable lead; and carrying out complexing, strengthening and analyzing on the released lead by utilizing chloride ion in sea water, soaking and washing the soil, and washing the lead away from soil body at a surface layer, thus the lead pollution on the soil at the surface layer is remediated. The method disclosed by the invention has the advantages that removal rate of pollutant is high, no chemical agent is required to be added and no secondary harm can be caused to the soil and also has the advantage that beach inning and pollution remediation can be carried out at the same time.
Description
Technical field
The present invention relates to the recovery technique field of heavy-metal contaminated soil, be specifically related to a kind of method that beach Lead Pollution in Soil is repaired.
Background technology
term
(1) lead
Lead is human body and plant non-essential element, seldom with free state, is present in nature.Plumbous main infringement nerve system of human body, digestive system, hemopoietic system and kidney.Lead in soil can enter human body by food chain.
(2) chemical form of Lead In Soil
The chemical form classification of heavy metal-polluted soil press Tessier continuous extraction conventionally, is divided into exchangeable species, carbonate in conjunction with state, reducible state (claim that iron and manganese oxides in conjunction with state not only), oxidable state (but also title combination state) and residual.
Heavy metal pollution of soil reparation mainly comprises two approach: 1. passivation and stabilisation, passivation reduces animal migration and the activity of heavy metal by changing chemical property, make it to be not easy by bio-absorbable, conventional interpolation material comprises lime, zeolite, clay, red mud, organic matter, plant residue, phosphate fertilizer etc.The shortcoming of this technology is that heavy metal still stays in soil, once soil physical chemistry environmental change, heavy metal likely reactivates and produces harm.Stabilisation is that pollutant is wrapped up in to limit in certain medium, as cement solidification, vitrification, under high temperature (more than 1500 ℃), contaminated soil is melted for glass or the nature of glass and mixed crystal, although the possibility that the soil heavy metal of these technical finesses of process reactivates is very little, but its shortcoming is soil property to be changed completely, can not continue to use as soil.2. separated removal activates heavy metal separation by physics, chemistry, microorganism, plant or soil animal method, and shifts out soil from soil, and heavy metal content in soil is significantly declined.
Phytoremediation technology, mainly to utilize heavy metal super-enriched plant or high enriching plant, as held back blue dish, Indian mustard, ramie, cordate houttuynia, Tephrosia candida etc., the heavy metal in soil is absorbed to enrichment, thereby heavy metal is accumulated to from soil to plant, then reaches by the mode of results plant the object of removing heavy metal-polluted soil.The shortcoming of this technology is that heavy metal hyperaccumulative/enriching plant of finding mostly at present is wild plant, yields poorly, and repair time is long, generally needs the several years; And plant growth has very strong region, not necessarily adapt to various weathers and edaphic condition; In addition, also there is no ripe cultivation management technology, the plant treatment after results also has problems.Microorganism is due to can only activating soil heavy metal, but cannot be in engineering separated soil particle and microorganism, therefore, generally microorganism is combined with plant, for improving phytoremediation efficiency, fortification of plants reparation.Soil animal method is mainly with the heavy metal in soil animal absorption, the enrichment soil such as earthworm, then that earthworm is separated with soil.
Technology is removed in physics, Chemical Decomposition, because the heavy metal in soil is easy to be adsorbed by soil particle, water-soluble state content of beary metal is extremely low, therefore, existing conventional physics, Chemical Decomposition method all need that chemical agent dissolves, the heavy metal in complexing or replacement soil, make it to become water-soluble state heavy metal, then by methods such as water wash or electrode adsorptions, remove.As chemical leaching method: a large amount of water and chemical reagent are poured in soil, and so that the pollutant in soil is cleared out, conventional chemical agent has HCl, EDTA, CaCl
2deng.Motorized learns a skill: use acidic buffer solution to keep the low pH value of soil, dissolve heavy metal, again electrode is inserted in soil, pass into low intensive direct current, make charged heavy metal ion produce towards the direction of both ends of electrode and move under the effect of electric field, and it is neighbouring to collect to be gathered in electrode.The shortcoming of these methods is, the artificial chemical agent adding as the serious change of meeting such as acids, EDTA soil property, cause secondary pollution, and EDTA mainly can only complexing exchangeable species heavy metal as complexing agent; Also can only the replace heavy metal of exchangeable species of neutral salt.As the method for a license ZL200810026052.0 leaching and repairing cadmium polluted coast saline soil, adopt flue gas desulfurization byproduct CaSO
4replace the cadmium of soil exchange state, being applicable to take exchange state is main cadmium pollution reparation, but is not suitable for take reducible state and oxidable state content is main lead contamination reparation.
Beach soil is that river mouth or strand water body deposit are constantly accumulated and a class special soil of formation, and Tidal Flat Reclamation is to set up dyke by engineering measure, beach and seawater is isolated, so that beach utilization.2,080,000 hectares of China's beach areas, because annual a large amount of river loads inflows are marine, constantly form beach, make Tidal Flat Reclamation just become since ancient times the main path that coastal area beach utilizes.For carry out beach soil pollution reparation by Tidal Flat Reclamation, provide condition.
Beach soil salt content is very high, is not suitable for the growth of heavy metal rehabilitation plant and reparation animal.Our early-stage Study also finds, the plumbous chemical form of lead contamination beach soil be take reducible state and oxidable state content as main.Simultaneously, owing to only having the environmental quality of beach topsoil just can exert an influence to Tidal Flat Reclamation and ecology, and the underground water of beach soil is that soil pore water is connected with seawater, salt content is very high, lack use value, therefore, using beach soil deep as topsoil, repair the storage site of after stain thing, can not cause any ecological risk.These characteristics of beach soil, make existing many heavy metal-polluted soil recovery techniques not be suitable for the reparation of beach Lead Pollution in Soil, but also for some new technology developments provide condition.
In mudflat seawater, contain a large amount of sodium chloride, chlorion wherein has stronger complexing power, the heavy metal of exchange state part in soil can be resolved and form complex compound, sodium ion can with soil in exchange state part heavy metal generation replacement effect.Because seawater and beach soil salt content are all very high, so can significantly not change soil property with Seawater Treatment beach soil.(salt water soaks the removal effect to the mouth of the Zhujiang River Tidal Flat Reclamation heavy metal-polluted soil to document, Cui Zhihong etc., China Environmental Science, the 30th the 2nd phase of volume, 246-250 page, in February, 2010) disclosing a kind of salt water that utilizes soaks the method that heavy metal-polluted soil is enclosed and cultivated in centrifugal removal.The method completes in centrifuge tube, adopts NaCl parsing and replacement heavy metal-polluted soil to enter water, then adopts centrifugal method by water separated with soil (rotating speed 4000r/min).Result shows, soak time reaches maximum material removal rate while being 60d, NaCl soak can effectively remove exchange state, carbonate in conjunction with state and iron and manganese oxides the heavy metal in conjunction with state, and not obvious to the heavy metal action effect of organic and residual form.Owing to polluting the chemical form of beach Lead In Soil, take reducible state (iron and manganese oxides is in conjunction with state) and oxidable state content (combination state) as main, therefore, in the method, the highest clearance of lead only has 9.4%.In addition, the method adopts centrifuge centrifugal that dissolubility heavy metal is separated with soil, needs lot of energy and cost, is not suitable for implementing in beach original place large area.
Summary of the invention
The object of the invention is to according to the concrete feature of above shortcomings in prior art and lead contamination beach soil, method by beach soil being carried out to specific alternation of wetting and drying processing, coordinating sea water immersion drip washing to carry out repair process, significantly reduces beach upper soll layer 20cm lead contamination degree.
Above-mentioned purpose of the present invention is achieved by the following technical programs:
The method that beach Lead Pollution in Soil is repaired, comprises the steps:
(1), in conjunction with Tidal Flat Reclamation engineering or utilize existing project of cultivation that beach is enclosed and cultivated, make beach soil and seawater isolation.
(2) when low tide, utilize the draining of natural water level drop, beach soil shone to dry-cure 10～30 days, during top layer 20cm soil is carried out to fragmentation 1 time, to improve the touch opportunity of Soil and air.
(3) utilize high tide level at the incoming tide, that puts into that sea water immersion dried encloses and cultivates beach soil, and immersion way is that batch (-type) soaks, and soaks below depth of water 5cm at every turn, puts into seawater after soaking the complete seepage of water again.With guarantee soil redox potential-more than 100mV.Soak time 5～10 days.
(4) adjust and soak the depth of water to more than 20cm, soil redox potential is reduced to-below 200mV, continue to soak after 20～30 days draining when low tide.
As a kind of preferred version, after having operated step (1) ~ (4), above-mentioned steps (1) ~ (4) can be repeated once.
Know-why of the present invention is as follows:
The present invention is mainly applicable to lead contamination beach soil.This soil has following features: (1) plumbous chemical form be take reducible state and oxidable state content as main; (2) be subject to seawater influence, its underground water is that soil pore water is connected with seawater, and salt content is very high, lacks use value, and beach soil deep can be used as the storage site that topsoil is repaired after stain thing, can not cause any ecological risk; (3) its height is between high tide level and low tide, can natural drainage during low tide, can natural waterflooding during high tide level, and waterflooding and draining are controlled by project of cultivation.
Reducible state in heavy metal-polluted soil chemical form is mainly that high price iron and manganese oxides is mainly that organic matter and sulfide are in conjunction with state in conjunction with state, oxidable state.Except residual heavy metal, the heavy metal of other form can promote Forms Transformation by changing soil environment condition.Chlorion can form stable water soluble complex with lead ion, accelerates the plumbous parsing of ADSORPTION STATE (exchangeable species).Present technique is according to the These characteristics of lead contamination beach soil, beach soil is dried to break process, improve soil redox potential, make organic matter and sulfide partial oxidation in soil, thereby the plumbous part of the oxidable state of being combined with organic matter and sulfide is discharged, become soluble state or exchangeable species plumbous.Then, soaking washed off soil at the incoming tide with seawater batch (-type), the lead that in seawater, the chlorion of high-load can discharge oxidable state carries out complexing, and is gone out the top layer soil body to soil deep by seepage drip washing.Afterwards, by raising, soak the degree of depth of seawater, significantly reduce soil redox potential, part high price iron and manganese oxides is reduced, the reducible state lead of combination is released with it, also becomes soluble state or exchangeable species plumbous, under the complexing strengthening of seawater chlorion is resolved, the lead discharging from reducible state is also gone out the top layer soil body by seepage drip washing, thereby topsoil lead contamination is repaired.The lead that drip washing goes out is mainly accumulated in lower soil.
Compared with prior art, tool of the present invention has the following advantages and effect:
(1) compare with existing conventional physics, Chemical Decomposition method, they all need, and chemical agent dissolves, complexing or the heavy metal of replacement in soil, makes it to become water-soluble state heavy metal, then by methods such as water wash or electrode adsorptions, removes.The shortcoming of these methods is that the artificial chemical agent adding can seriously change soil property or cause secondary pollution; Advantage of the present invention is not need to apply any chemical agent, to soil, can not produce any secondary harm.Can only the replace heavy metal of exchangeable species of neutral salt isolation technics, and the chemical form that can not replace to take reducible state and oxidable state content be main heavy metal, thereby be not suitable for this type of lead-contaminated soil reparation.
(2) compare with phytoremediation technology, current both at home and abroad conventional and disclosed Lead Pollution in Soil phytoremediation technology----blue dish, Indian mustard, ramie, cordate houttuynia, Tephrosia candida etc. held back, because can not adapt to the highly-saline growing environment of beach soil, and be not suitable for the reparation of beach Lead Pollution in Soil yet.
(3) (salt water soaks the removal effect to the mouth of the Zhujiang River Tidal Flat Reclamation heavy metal-polluted soil with document, Cui Zhihong etc., China Environmental Science, the 30th the 2nd phase of volume, 246-250 page, in February, 2010) disclosedly a kind ofly utilize salt water to soak centrifugal removal to enclose and cultivate heavy metal-polluted soil method and compare, the present invention can make the lead content clearance of beach top layer 0～20cm soil layer reach 16.3%～38.4%, far above the clearance of document lead the highest 9.4%.Meanwhile, utilize tidal water potential difference to soak drip washing, than the centrifugal method of document, significantly reduce costs and energy consumption.
The specific embodiment
Below in conjunction with embodiment, further explain the present invention, but embodiment does not limit in any form to the present invention.
embodiment 1
Rehabilitating soil is the mouth of the Zhujiang River beach soil.The plumbous average content of 0～20cm topsoil is 77 mg/kg.Repair object for reducing as far as possible the plumbous average content of topsoil.In conjunction with Tidal Flat Reclamation engineering, beach is enclosed and cultivated, make beach soil and seawater isolation.To enclosing and cultivating, beach soil dries after draining when the low tide, break process 10 days, and then batch (-type) sea water immersion, soaks maximum water depth 5cm, after the complete seepages of immersion water such as each immersion, puts into seawater, 5 days immersion treatment time again.Adjust and soak the depth of water to 20cm, continue to soak draining after 20 days.After reparation finishes, the plumbous average content of 0～20cm topsoil is 64.4 mg/kg, plumbous clearance 16.3%.
embodiment 2
Rehabilitating soil is the mouth of the Zhujiang River beach soil.The plumbous average content of 0～20cm topsoil is 77 mg/kg.Repair object for reducing as far as possible the plumbous average content of topsoil.In conjunction with Tidal Flat Reclamation engineering, beach is enclosed and cultivated, make beach soil and seawater isolation.To enclosing and cultivating, beach soil dries after draining when the low tide, break process 30 days, and then batch (-type) sea water immersion, soaks maximum water depth 5cm, after the complete seepages of immersion water such as each immersion, puts into seawater, 10 days immersion treatment time again.Adjust and soak the depth of water to 20cm, continue to soak draining after 30 days.After reparation finishes, the plumbous average content of 0～20cm topsoil is 55.7 mg/kg, plumbous clearance 27.7%.
embodiment 3
Rehabilitating soil is the mouth of the Zhujiang River beach soil.The plumbous average content of 0～20cm topsoil is 77 mg/kg.Repair object for reducing as far as possible the plumbous average content of topsoil.In conjunction with Tidal Flat Reclamation engineering, beach is enclosed and cultivated, make beach soil and seawater isolation.To enclosing and cultivating, beach soil dries after draining when the low tide, break process 10 days, and then batch (-type) sea water immersion, soaks maximum water depth 5cm, after the complete seepages of immersion water such as each immersion, puts into seawater, 5 days immersion treatment time again.Adjust and soak the depth of water to 20cm, continue to soak draining after 20 days.Repeat 1 time said process.After reparation finishes, the plumbous average content of 0～20cm topsoil is 52.7 mg/kg, plumbous clearance 31.5%.
embodiment 4
Rehabilitating soil is the mouth of the Zhujiang River beach soil.The plumbous average content of 0～20cm topsoil is 77 mg/kg.Repair object for reducing as far as possible the plumbous average content of topsoil.In conjunction with Tidal Flat Reclamation engineering, beach is enclosed and cultivated, make beach soil and seawater isolation.To enclosing and cultivating, beach soil dries after draining when the low tide, break process 30 days, and then batch (-type) sea water immersion, soaks maximum water depth 5cm, after the complete seepages of immersion water such as each immersion, puts into seawater, 10 days immersion treatment time again.Adjust and soak the depth of water to 20cm, continue to soak draining after 30 days.Repeat 1 time said process.After reparation finishes, the plumbous average content of 0～20cm topsoil is 47.4 mg/kg, plumbous clearance 38.4%.
Claims (3)
1. the method that beach Lead Pollution in Soil is repaired, is characterized in that described method comprises the steps:
(1) beach is enclosed and cultivated, make beach soil and seawater isolation;
(2) when low tide, utilize the draining of natural water level drop, beach soil shone to dry-cure 10 ~ 30 days, during the soil of top layer 20cm is carried out to fragmentation 1 time, to improve the touch opportunity of Soil and air;
(3) utilize high tide level at the incoming tide, that puts into that sea water immersion dried encloses and cultivates beach soil, immersion way is that batch (-type) soaks, each immersion depth of water is below 5cm, soak after water permeates completely and put into again seawater, with guarantee soil redox potential-more than 100mV, soak time is 5 ~ 10 days;
(4) adjust and soak the depth of water to more than 20cm, soil redox potential is reduced to-below 200mV, continue to soak after 20 ~ 30 days draining when low tide.
2. the method that beach Lead Pollution in Soil according to claim 1 is repaired, is characterized in that having operated behind step (1) ~ (4), then repeats once.
3. the method that beach Lead Pollution in Soil according to claim 1 is repaired, is characterized in that: the plumbous chemical form of (1) lead contamination beach soil be take reducible state and oxidable state content as main; (2) lead contamination beach soil is subject to seawater influence, and its underground water is that soil pore water is connected with seawater, and salt content is high; (3) lead contamination beach soil height is between high tide level and low tide, natural drainage during low tide, and nature waterflooding during high tide level, waterflooding and draining are controlled by project of cultivation.
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