Chelant extraction of heavy metals from contaminated soils.

The current state of the art regarding the use of chelating agents to extract heavy metal contaminants has been addressed. Results are presented for treatability studies conducted as worst-case and representative soils from Aberdeen Proving Ground's J-Field for extraction of copper (Cu), lead (Pb), and zinc (Zn). The particle size distribution characteristics of the soils determined from hydrometer tests are approximately 60% sand, 30% silt, and 10% clay. Sequential extractions were performed on the 'as-received' soils (worst case and representative) to determine the speciation of the metal forms. The technique speciates the heavy metal distribution into an easily extractable (exchangeable) form, carbonates, reducible oxides, organically-bound, and residual forms. The results indicated that most of the metals are in forms that are amenable to soil washing (i.e. exchangeable+carbonate+reducible oxides). The metals Cu, Pb, Zn, and Cr have greater than 70% of their distribution in forms amenable to soil washing techniques, while Cd, Mn, and Fe are somewhat less amenable to soil washing using chelant extraction. However, the concentrations of Cd and Mn are low in the contaminated soil. From the batch chelant extraction studies, ethylenediaminetetraacetic acid (EDTA), citric acid, and nitrilotriacetic acid (NTA) were all effective in removing copper, lead, and zinc from the J-Field soils. Due to NTA being a Class II carcinogen, it is not recommended for use in remediating contaminated soils. EDTA and citric acid appear to offer the greatest potential as chelating agents to use in soil washing the Aberdeen Proving Ground soils. The other chelating agents studied (gluconate, oxalate, Citranox, ammonium acetate, and phosphoric acid, along with pH-adjusted water) were generally ineffective in mobilizing the heavy metals from the soils. The chelant solution removes the heavy metals (Cd, Cu, Pb, Zn, Fe, Cr, As, and Hg) simultaneously. Using a multiple-stage batch extraction, the soil was successfully treated passing both the Toxicity Characteristics Leaching Procedure (TCLP) and EPA Total Extractable Metal Limit. The final residual Pb concentration was about 300 mg/kg, with a corresponding TCLP of 1.5 mg/l. Removal of the exchangeable and carbonate fractions for Cu and Zn was achieved during the first extraction stage, whereas it required two extraction stages for the same fractions for Pb. Removal of Pb, Cu, and Zn present as exchangeable, carbonates, and reducible oxides occurred between the fourth- and fifth-stage extractions. The overall removal of copper, lead, and zinc from the multiple-stage washing were 98.9%, 98.9%, and 97.2%, respectively. The concentration and operating conditions for the soil washing extractions were not necessarily optimized. If the conditions had been optimized and using a more representative Pb concentration (approximately 12000 mg/kg), it is likely that the TCLP and residual heavy metal soil concentrations could be achieved within two to three extractions. The results indicate that the J-Field contaminated soils can be successfully treated using a soil washing technique.     

A kinetic study of chelant-assisted remediation of contaminated dredged sediment

A study on the remediation of a real heavy metal-contaminated sediment was conducted using the four chelating agents ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), citric acid and the S,S-isomer of the ethylenediaminedisuccinic acid ([S,S]-EDDS). Different chelant washing experiments were carried out at a chelant/total metal content of 1 and 10 mol/mol for treatment durations from 0.5 to 48 h to study the extraction kinetics of trace metals and major cations. The objective was to evaluate the removal efficiency of conventional chelating agents as compared to innovative, biodegradable species. Among the target contaminants, Cd, Cu, Pb and Zn were found to be adequately removed by both EDTA and EDDS, while NTA and citric acid yielded unsatisfactory results in some cases. It was also found that As was a critical contaminant which would require an additional specific treatment step, since the residual concentrations after the washing treatment were still far above the regulatory limit values.     

Influence of EDTA washing on the species and mobility of heavy metals residual in soils

Aiming to estimate the potential risk of ethylenediaminetetraacetic acid (EDTA)-enhanced soil washing, the heavy metal species and their mobility in the washed soil under different combinations were investigated by batch leaching tests and the sequential extraction procedure. Results demonstrate that the metal removal efficiency was rather low (less than 12%), partially due to the significant Ca dissolution and strong bonding between metals and the soil as well as the insufficient EDTA dosage. The washing combination of 0.0005 M EDTA and half-an-hour washing can enhance the instant mobility of Ni, Zn and Pb possibly owing to the slow detachment of EDTA-destabilized metals. Metal fractionation also exhibits the corresponding increase in their labile exchangeable fractions. Therefore, a more concentrated EDTA solution for a longer duration often decreased their mobility. The increase in some fractions of a curtain metal implies the redistribution of this metal during the EDTA soil washing. The pathway of such a redistribution may vary for different metals, but the redistribution to organic matter is often a slow process, while that to carbonates or Fe/Mn oxides is a faster one and even may occur in a half hour washing with 0.0005 M EDTA solution. These redistribution processes may also increase the metal chemical availability. Therefore, we should prudently control the chelating reagent concentration and washing duration to finally minimize the mobility and availability of the remaining heavy metals when designing the soil washing for the remediation of metal-contaminated soils.     

Electrochemical EDTA recycling after soil washing of Pb, Zn and Cd contaminated soil

Recycling of chelant decreases the cost of EDTA-based soil washing. Current methods, however, are not effective when the spent soil washing solution contains more than one contaminating metal. In this study, we applied electrochemical treatment of the washing solution obtained after EDTA extraction of Pb, Zn and Cd contaminated soil. A sacrificial Al anode and stainless steel cathode in a conventional electrolytic cell at pH 10 efficiently removed Pb from the solution. The method efficiency, specific electricity and Al consumption were significantly higher for solutions with a higher initial metal concentration. Partial replacement of NaCl with KNO₃ as an electrolyte (aggressive Cl⁻ are required to prevent passivisation of the Al anode) prevented EDTA degradation during the electrolysis. The addition of FeCl₃ to the acidified washing solution prior to electrolysis improved Zn removal. Using the novel method 98, 73 and 66% of Pb, Zn and Cd, respectively, were removed, while 88% of EDTA was preserved in the treated washing solution. The recycled EDTA retained 86, 84 and 85% of Pb, Zn and Cd extraction potential from contaminated soil, respectively.     

Influence of indigenous and added iron on copper extraction from soil

Experimental tests of copper leaching from a low permeability soil are presented and discussed. The objective of the experiments was to investigate the influence of indigenous and added iron in the soil towards copper mobilization. Metals’ leaching was performed by flushing (column tests) or washing (batch tests) the soil with an aqueous solution of ethylenediaminetetraacetic acid, EDTA. An excess of EDTA was used in flushing tests (up to a EDTA:Cu molar ratio of about 26.2:1), while, in washing tests, the investigated EDTA vs. copper molar ratios were in the range between 1 (equimolar tests) and 8.Copper extraction yield in flushing tests (up to about 85%) was found to depend upon contact time between the soil and the leaching solution and the characteristics of the conditioning solution. The saturation of the soil with a NaNO₃ solution before the treatment, favoured the flushing process reducing the time of percolation, but resulted in a lower metal extraction during the following percolation of EDTA.The indigenous iron was competitive with copper to form EDTA complexes only when it was present in the organic and oxides–hydroxides fractions. Artificial iron addition to the soil resulted in an increase of both the exchangeable iron and the iron bonded to the organic fraction of the soil, thus increasing the overall amount of iron available to extraction.In both batch and continuous tests, the mechanism of copper extraction was found to involve the former dissolution of metal salts, that lead to an initial high concentration of both copper and selected competitive cations (essentially Ca²⁺), and the following EDTA exchange reaction between calcium and copper complexes. The initial metal salts dissolution was found to be pH-dependant.     

Copper leaching from a sandy soil: mechanism and parameters affecting EDTA extraction

A series of 24h batch tests of copper extraction from a sandy soil were performed by washing the soil with aqueous solution of ethylenediaminetetraacetic acid, EDTA. EDTA versus copper molar ratio were in the range between 1 (equimolar tests) and 13.3. The tests were performed at three selected liquid/solid ratio, 5, 12.5 and 25. Results show that decreasing the pH of the washing solution an higher copper extraction yield was achieved: an almost complete copper extraction was achieved after 23 h of mixing at a L/S = 5, and after 5 h of mixing at an L/S = 12.5. The mechanism of copper extraction was found to involve two sequential processes: the former dissolution of metal salts, that lead to an initial high concentration of both copper and some competitive cations (essentially Ca(2+)), and the following EDTA exchange reaction between calcium and copper complexes, which corresponded an increase of pH in the washing solution. A negligible extraction of Fe(3+) was also observed at the investigated operative conditions.     

Application of EDTA decontamination on soils affected by mining activities and impact of treatment on the geochemical partition of metal contaminants

Two soil samples were collected at mining areas located in southern Hunan Province, China. EDTA extraction of Pb, Zn, Cu and Cd from these two tailing soils was studied using column leaching experiments. The redistributions of heavy metals (HMs) were determined using the modified BCR (Community Bureau of Reference) sequential extraction procedure, before and after EDTA extraction. The results indicated that EDTA was an effective extractant because of its strong chelating ability for various HMs. The proportions of Pb, Zn, Cu and Cd in the four fractions varied largely after EDTA extraction. The extraction efficiency of EDTA of the acid-extractable fraction (AEX) was significant in shallow soil column, while in deeper soil column, decrease of the extraction efficiency of reduced (RED), oxidizable (OX) and residual fractions (RES) was obtained, which was mainly due to the decrease of EDTA concentration.     

Removal of Pb by EDTA-washing in the presence of hydrophobic organic contaminants or anionic surfactant

Heavy metals and organic contaminants often coexist in contaminated soils, of which the remediation requires a combined or sequential use of surfactant and chelant in chemical-enhanced soil washing. This study investigated the Pb removal by EDTA-washing in the presence of the coexisting hydrophobic organic contaminants (marine diesel fuel, MDF) or anionic surfactant (sodium dodecyl sulfate, SDS). The results of batch experiments indicated a negative impact of MDF on Pb removal, whereas a positive or negative influence of SDS depending on the molar ratio of [EDTA]:[Pb]. The surface of MDF-contaminated soil was partially covered by free-phase MDF limiting the interaction between EDTA and sorbed Pb, especially at [EDTA]:[Pb]=1:1. Despite the ability of SDS itself for extracting Pb to some extent, probably through electrostatic interaction and dissolution of soil organic matter (SOM), the addition of SDS into EDTA solution only slightly enhanced Pb removal at [EDTA]:[Pb]=1:1 but inhibited at [EDTA]:[Pb]=2:1. This may be attributed to the SOM dissolution and the potential formation of ternary surface complexes, respectively. Along the same line of reasoning, it was not surprising that the optimal sequence for Pb removal was EDTA- followed by SDS-washing rather than the reverse sequence or simultaneous EDTA- and SDS-washing.     

Assessment of single extraction methods for the prediction of bioavailability of metals to Brassica juncea L. Czern. (var. Vaibhav) grown on tannery waste contaminated soil

Various single extractant (DTPA, EDTA, NH(4)NO(3), CaCl(2), and NaNO(3)) was used to evaluate the bioavailability of heavy metals from tannery wastewater contaminated soil and translocation of metals to the plant of Brassica juncea L. Czern. (var. Vaibhav). The extraction capacity of the metals was found in the order: EDTA>DTPA>NH(4)NO(3)>CaCl(2)>NaNO(3). Cluster analysis between different extractants showed close relationship between DTPA, CaCl(2), NH(4)NO(3) except EDTA and NaNO(3), which showed dispersed relationship. Principal components analysis (PCA) applied to metals extracted with EDTA showed different grouping of metals (i) Na, Co, Pb, Ni and (ii) K, Mn, Zn, Cr, in the loading plot which showed similar availability from contaminated soil. PCA applied on metals accumulation data in the plants also exhibited different grouping of variables (i) Cu, Co, Ni, Cd and (ii) Mn, Zn, Pb, Fe showed almost similar accumulation pattern in the plants. The data displayed positive loading for Mn and negative loading for Cr with PC(2). Cd and Zn have shown high loadings in PC(1) and PC(2), respectively. The translocation of most of the tested metals (Pb, Mn, Cd, Ni, Fe) in the shoot of the plant was found better except Cr, Cu, Co and K. The correlation analysis between different extractable metals and metal accumulation in the shoot of the plant showed significant positive correlation with Pb and Cr. Overall, extraction capacity and cluster analysis augmented that EDTA was found suitable extractant for tannery wastewater contaminated soil to B. juncea.     

Distribution of heavy metals in Lakes Doirani and Kerkini, Northern Greece

The distribution of heavy metals in two lakes of high ecological significance, Doirani and Kerkini, located in Northern Greece was studied. Eight metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn) were determined in water, total suspended solids, fine and coarse sediments. Moreover, the modified BCR fractionation scheme was employed in sediments and suspended solids to determine soluble, oxidisable, reducible and residual fractions of metals. The Lake Doirani presents higher metal concentrations in aqueous phase than Lake Kerkini; Cd, Cu, Ni, Pb and Zn are above the chronic freshwater quality criteria for aquatic life. In both lakes, Fe and Mn are the most abundant elements in total suspended solids whereas Cd the less abundant. The Lake Kerkini exhibits higher concentrations of all the examined metals in sediments comparing to the Lake Doirani, however the concentrations are lower than the sediment quality guidelines. Cd in sediments is mainly in soluble fraction, Pb and Cu exhibit significant oxidisable fractions whereas, Cr and Fe associated mainly with residual fraction.     

Removal of metals from landfill leachate by sorption to activated carbon, bone meal and iron fines

Sorption filters based on granular activated carbon, bone meal and iron fines were tested for their efficiency of removing metals from landfill leachate. Removal of Al, As, Ca, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn, Mo, Ni, Pb, Sr and Zn were studied in a laboratory scale setup. Activated carbon removed more than 90% of Co, Cr, Cu, Fe, Mn and Ni. Ca, Pb, Sr and Zn were removed but less efficiently. Bone meal removed over 80% of Cr, Fe, Hg, Mn and Sr and 20-80% of Al, Ca, Cu, Mo, Ni, Pb and Zn. Iron fines removed most metals (As, Ca, Co, Cr, Cu, Fe, Mg, Mn, Pb, Sr and Zn) to some extent but less efficiently. All materials released unwanted substances (metals, TOC or nutrients), highlighting the need to study the uptake and release of a large number of compounds, not only the target metals. To remove a wide range of metals using these materials two or more filter materials may need to be combined. Sorption mechanisms for all materials include ion exchange, sorption and precipitation. For iron fines oxidation of Fe(0) seems to be important for metal immobilisation.     

Remediation of heavy metal contaminated soil washing residues with amino polycarboxylic acids

Removal of Cu, Pb, and Zn by the action of the two biodegradable chelating agents [S,S]-ethylenediaminedisuccinic acid (EDDS) and methylglycinediacetic acid (MGDA), as well as citric acid, was tested. Three soil samples, which had previously been treated by conventional soil washing (water), were utilized in the leaching tests. Experiments were performed in batches (0.3 kg-scale) and with a WTC-mixer system (Water Treatment Construction, 10 kg-scale). EDDS and MGDA were most often equally efficient in removing Cu, Pb, and Zn after 10–60 min. Nonetheless, after 10 d, there were occasionally significant differences in extraction efficiencies. Extraction with citric acid was generally less efficient, however equal for Zn (mainly) after 10 d. Metal removal was similar in batch and WTC-mixer systems, which indicates that a dynamic mixer system could be used in full-scale. Use of biodegradable amino polycarboxylic acids for metal removal, as a second step after soil washing, would release most remaining metals (Cu, Pb and Zn) from the present soils, however only after long leaching time. Thus, a full-scale procedure, based on enhanced metal leaching by amino polycarboxylic acids from soil of the present kind, would require a pre-leaching step lasting several days in order to be efficient.     

Effect of metal spiking on different chemical pools and chemically extractable fractions of heavy metals in sewage sludge

A laboratory experiment was conducted to study the effect of metal spiking and incubation on some properties and sequentially extractable chemical pools of some heavy metals (F1, two extractions with 0.1 M Sr(NO3)2; F2, one extraction with 1 M NaOAc (pH 5.0); F3, three extractions with 5% NaOCl (pH 8.5) at 90-95 degrees C; F4, three extractions with 0.2 M oxalic acid + 0.2 M ammonium oxalate + 0.1 M ascorbic acid (pH 3.0); and F5, dissolution of sample residue in HF-HClO4 (residual fraction,) and also 1 M CaCl2 and 0.005 M DTPA extractable heavy metals in sewage sludge. Metal spiking and incubation decreased pH and easily oxidizable organic C content of sludge but increased electrical conductivity. Metal spiking and incubation increased F1 fraction of all heavy metals, F2 fraction of Ni, Pb, Cu, and Cd, F3 fraction of Pb, Cu, and Cd, F4 or reducible fraction of Ni, Cu, and Cd and residual fraction of Zn and Pb, but decreased F2 fraction of Zn, F3 of Zn and Ni, F4 fraction of Zn and F5 fraction of Ni, Cu, and Cd. Metal spiking and incubation increased 1 M CaCl2 and 0.005 M DTPA extractable amounts of all heavy metals in sludge except for 0.005 M DTPA extractable Zn, which registered only very marginal decrease.     

Recycling of lead-contaminated EDTA wastewater.

Ethylene diaminetetraacetic acid (EDTA) is one of the chelating agents used in the soil washing process for the decontamination of lead-contaminated soil. Lead-EDTA complexes in the wastewater from the soil washing process must be removed before the wastewater can be safely discharged. This study outlines a method to recycle Pb-EDTA wastewater by substituting the Pb complexed with EDTA with Fe(III) ions at low pH, followed by precipitation of Pb ions with phosphate or sulfate ions. Fe(III) ions complexed with EDTA were then precipitated at high pH using sodium hydroxide. The resulting solution (Fe-precipitated solution) was tested on three lead-contaminated soils. The Fe-precipitated EDTA solution was found to have similar extraction capabilities as fresh EDTA solution. Experimental results showed that the recycled EDTA solution may be recycled several times without losing its extractive power. Recycled EDTA wastewater with phosphate precipitation was found to be slightly more effective than recycled EDTA solution using sulfate precipitation. The recycling procedure may be applied to wastewater generated during soil washing of lead-contaminated soil, resulting in a reduction in wastewater generated and savings in the amount of EDTA used.     

Geochemical speciation and risk assessment of heavy metals in the river estuarine sediments--a case study: Mahanadi basin, India

Sequential extraction technique was used to study the mobility and dynamics of operationally determined chemical forms of heavy metals in the sediments and their ecological risk on the biotic species. The results reveal that high environmental risk of Cd, Ni, Co and Pb, are due to their higher availability in the exchangeable fraction. Substantial amount of Cd, Co, Mn, Cu, Zn, Ni and Pb, is observed as carbonate bound, which may result due to their special affinity towards carbonate and their co-precipitation with its minerals. Colloids of Fe-Mn oxides act as efficient scavengers for the heavy metals like Zn, Pb, Cu, Cr, Co, and Ni. Toxic metals like Ni, Pb and Cd are of concern, which occasionally may be associated with adverse biological effects based on the comparison with sediment quality guidelines (SQGs). The risk assessment code (RAC) suggests that the highest mobility of Cd poses a higher environmental risk and also threat to the aquatic biota. Factor analysis reveals that the enrichment of heavy metals in bioavailable fraction is mostly contributed from anthropogenic sources. These contributing sources are highlighted by cluster analysis.     

Fractionation of metals in street sediment samples by using the BCR sequential extraction procedure and multivariate statistical elucidation of the data

The concentrations of metals (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) in street sediment samples were determined by flame atomic absorption spectrometry (FAAS) using the modified BCR (the European Community Bureau of Reference) sequential extraction procedure. According to the BCR protocol for extracting the metals from the relevant target phases, 1.0 g of specimen of the sample was treated with 0.11 M acetic acid (exchangeable and bound to carbonates), 0.5M hydroxylamine hydrochloride (bound to iron- and manganese-oxides), and 8.8M hydrogen peroxide plus 1M ammonium acetate (bound to sulphides and organics), sequentially. The residue was treated with aqua regia solution for recovery studies, although this step is not part of the BCR procedure. The mobility sequence based on the sum of the BCR sequential extraction stages was: Cd approximately Zn ( approximately 90%)>Pb ( approximately 84%)>Cu ( approximately 75%)>Mn ( approximately 70%)>Co ( approximately 57%)>Ni ( approximately 43%)>Cr ( approximately 40%)>Fe ( approximately 17%). Enrichment factors as the criteria for examining the impact of the anthropogenic emission sources of heavy metals were calculated, and it was observed that the highest enriched elements were Cd, Pb, and Zn in the dust samples, average 190, 111, and 20, respectively. Correlation analysis (CA) and principal component analysis (PCA) were applied to the data matrix to evaluate the analytical results and to identify the possible pollution sources of metals. PCA revealed that the sampling area was mainly influenced from three pollution sources, namely; traffic, industrial, and natural sources. The results show that chemical sequential extraction is a precious operational tool. Validation of the analytical results was checked by both recovery studies and analysis of the standard reference material (NIST SRM 2711 Montana Soil).     

Time saving modified BCR sequential extraction procedure for the fraction of Cd, Cr, Cu, Ni, Pb and Zn in sediment samples of polluted lake

The mobility, availability and persistence of heavy metals (Cd, Cr, Cu, Ni, Pb and Zn) in contaminated lake sediment samples were evaluated by means of sequential extraction scheme, proposed by the Community Bureau of Reference protocol (BCR). The metal content in the extracts was measured by atomic absorption spectrometry. The precision and accuracy of the proposed procedure were evaluated by using a certified reference material BCR 701. The maximum recoveries for heavy metals (HMs) were observed for all three steps of BCR protocol at 32h total shaking period instead of previously reported 51h, with p>0.05. The lixiviation tests (DIN 38414-S4) were used to evaluate the leaching of HMs from sediment samples and it was observed that levels of water extractable HMs were low as compared to those values obtained by acid-soluble fraction of the BCR protocol.     

Assessment of heavy metal contamination and its mobilization from municipal solid waste open dumping site

Influence of heavy metals was investigated by conducting various tests on the samples collected from Nonthaburi dumpsite in Thailand. The heavy metal concentration in the solid waste and its mobility potential based on its binding forms was studied. The sequential extraction method was used to determine the binding forms of metals. From the analysis, Zn was found to be highest concentrated heavy metal compared to Mn, Cu, Cr, Cd, Pb, Ni and Hg in the solid waste. From the sequential extraction, Mn, Zn and Cd mostly found in reducible form, showed its susceptibility to be leached easily. Cu and Cr were found predominantly in oxidizable form and stable under anaerobic condition. Pb and Ni were present in residual form, which is inert. The estimated individual contamination factor (C(f)(i)), showed Zn with highest affinity to leach. The concentration level of all the heavy metals in the leachate except for Cr was noticed to be below the National effluent standards. Though, indicated to be safe for disposal, its effect in any concentration proved toxic to the plant life from the seed germination toxicity test using synthetic chelate ethylene diamine tetraacetic acid (EDTA).     

Extraction of heavy metals from MSW incinerator fly ashes by chelating agents

An extraction process has been studied on a laboratory scale for the pretreatment of municipal solid waste (MSW) incinerator fly ash to remobilize Cr, Cu, Pb, and Zn. Five different types of fly ashes were treated with HCl, nitrilotriacetic acid (NTA), ethylendiaminetetraacetate (EDTA), or diethylenetriaminepentaacetate (DTPA) in a batch process in the pH range 2.5-10. The extraction of heavy metals by HCl was dependent on pH, increasing with increasing acid concentration. The efficiency of the chelating agents was independent of pH. By the treatment with 3.0% EDTA or DTPA, 20-50% of Cr, 60-95% of Cu, 60-100% of Pb, and 50-100% of Zn were extracted in the pH range 3-9. NTA was also effective in extracting Cr, Cu, and Zn. The maximum extraction of Cr, Cu, Pb, and Zn was obtained at 0.3-1.0% concentration of the chelating agents. NTA was effective in extracting Pb at a concentration as low as 0.1%. Extraction behavior of other elements during the treatment was also studied. The leaching test on the residues after the treatment with chelating agents showed that the fly ashes were successfully detoxified to meet the guideline for landfilling.     

The effect of grain size of rock phosphate amendment on metal immobilization in contaminated soils

When rock phosphates (RP) are used to remediate Pb-contaminated soils, their effectiveness is likely affected by their grain size. In this study, the effect of grain size of rock phosphate on the effectiveness of heavy metal immobilization in two contaminated soils was measured in pot experiment. Rock phosphate was used with four different grain sizes: <35, 35-72, 72-133 and 133-266microm. The application rate of rock phosphate in two soils was determined based on P/metals (Pb, Zn, Cu and Cd) molar ratio of 5.0 in the soils. The results showed that rock phosphate of the smallest grain size (<35microm) was superior to all of other grain sizes more than 35microm for reducing uptake in plant (Brassica oleracea L.) shoots for Cd (19.6-50.0%), Pb (21.9-51.4%) and Zn (22.4-34.6%), respectively, as compared with the soil without application of rock phosphate. Sequential extraction analysis indicated that rock phosphate was most effective for soil Pb to induced transformation from non-residual fractions to a residual fraction than that for Zn and Cd. Such transformation was probably through dissolution of Pb associated with exchangeable (EX), organic fraction (OC), acidic fraction (AC) and amorphous Fe and Al oxides-bound (OX) fraction and precipitation of pyromorphite-like minerals. Results suggested that the rock phosphate with small grain size was superior to that with large grain size for in situ remediation technology.