Lead Bioaccessibility in Soil and Mine Wastes After Immobilization with Phosphate

The immobilization of lead by the reaction with phosphate bearing materials is a promising remediation method for contaminated soils. Low soluble neo-formed lead-phosphate phases similar to chloropyromorphite [Pb₅(PO₄)₃Cl], can control availability and mobility of lead in the environment, and consequently reduce human exposure, if soils are the main contamination pathway. We used three phosphate source materials [NaH₂(PO₄)₃, commercial superphosphate and phosphate rock] to study lead immobilization in soil and mining waste samples. Products were examined after 1, 3 and 6 months of contact. The samples are from a contaminated area by former Pb mining and smelting activities, in southeastern Brazil, where epidemiological studies showed high lead blood levels in local population. The PBET (physiological based extraction test) bioaccessibility test was used to measure changes in the amount of soluble lead after sample treatment. Results show that the most efficient phosphate source was NaH₂(PO₄)₃, which reduced lead solubility to 92% in acidic gastric conditions after the first month of contact. Superphosphate and phosphate rock also diminished Pb solubility, but the effect was more time dependent. None specific Pb–phosphate phases could be identified by XRD in whole treated samples, but the Pb–Ca–P elemental associations, observed on SEM images and EDS spectra of portions of the samples, combined with the reduced solubility, indicate that more insoluble lead phases were formed after the treatment. Based in these results, the in site phosphate application on soils to induce lead immobilization should be considered as a possible alternative to reduce human exposure at the area.     

不同洗涤蜂窝煤灰渣对污染土壤中铅的稳定作用研究

蜂窝煤灰渣具有稳定污染土壤中铅的作用,但可增大土壤pH和电导率（EC）。将蜂窝煤灰渣经过水洗和稀盐酸酸洗后加入铅污染土壤（1 000 mg·kg-1 Pb）,研究了不同处理灰渣对铅有效性和土壤性质的影响。结果表明,灰渣经水洗和酸洗后,其pH（分别下降1.94、3.70）和电导率（0.785、0.890 mS·cm-1）明显下降,重金属有效性和全量也有一定程度的下降。水洗和酸洗灰渣加入土壤后,土壤磷有效性有一定的上升。污染土壤在未加磷条件下加入原灰渣、水洗灰渣和酸洗灰渣后,DTPA-Pb含量分别下降67.2、195、117 mg·kg-1,加磷情况下加入这3种灰渣土壤DTPA-Pb含量分别降低102、91.8、86.8 mg·kg-1,各处理与对照的差异均达到0.05的显著水平。连续提取的结果表明,不同处理对土壤铅形态的影响不明显。     

Extraction and Analysis of Soil Solution of Phosphate Rock and Acid Treated Soil

Abstract

Increasing basic phosphate rock (PR) rates and acid loads were applied to an acidic sandy soil in a laboratory experiment. ‘Total’ amounts of potentially toxic elements in the soil and PR samples were determined by inductively coupled plasma (ICP) spectrometry after acidic, microwave digestion. Soil solution was extracted from wet soil by centrifugation with a speed corresponding to the suction power exerted by plants at the conventional wilting point. Addition of PR generally decreased rather than increased metal concentrations in the soil solution because of its pH elevating, immobilizing effect. Except for Pb, the extreme acid treatment compensated for the immobilizing effect of PR. Release of Cd (expressed as soil solution concentration in percentage of the total amount in soil+PR) was generally highest among elements at every treatment, and Cr was the least mobile metal. The one‐time, high rate of PR application did not make a direct environmental risk probable.     

Soil Immobilization of Heavy Metal Using Soil Amendments in a Greenhouse Study

ABSTRACT

The application of soil amendments to immobilize heavy metals is a promising technology to meet the requirements for environmentally sound and cost-effective remediation. The present work was carried out to evaluate the effect of phosphogypsum (PG) used alone and in combination with compost (CP) at a mix ratio of 1:1 wet weight ratio (PG+CP) at 10 and 20 g dry weight kg^?1 dry soil, on heavy metal immobilization in contaminated soil, and on canola growth (Brassica napus). The results were then compared with untreated soil (control). The results revealed that the Pb, Cd, and Zn uptake of canola plants was reduced by the application of PG alone and when it was mixed with CP. At an application rate of 10 g dry weight kg^?1 dry soil of (PG+CP), the dry weight of canola plants increased by 66.8%, which was increased in comparison on its weight in the untreated soil (control). The addition of PG alone resulted in more pronounced immobilization of heavy metals as compared to PG mixed with CP. Plant growth was improved with CP addition but heavy metals immobilization was greatest in PG alone treatments. Results suggest that PG may be useful for the immobilization of heavy metals in contaminated soils.     

Amendment-Induced Immobilization of Lead in a Lead-Spiked Soil: Evidence from Phytotoxicity Studies

Lead immobilization was evaluated on soils spiked with increasingconcentrations of Pb (as Pb-acetate) using the following soilamendments: bentonite, zeolite, cyclonic ash, compost, lime,steelshot, and hydroxyapatite. The immobilization efficacy of theamendments was evaluated according to the following criteria:Ca(NO₃)₂-extractable Pb as an indicator of Pbphytoavailability, morphological and enzymatic parameters of beanplants (Phaseolus vulgaris) as indicator of phytotoxicity, and Pb concentration in edible tissue of lettuce (Lactuca sativa). The lowest reductions in Ca(NO₃)₂-extractablesoil Pb occurred when bentonite and steelshot were applied. Phytotoxicity from application of steelshot was confounded by toxic amounts of Fe and Mn released from the by-product which killed the lettuce seedlings. Addition of zeolite induced poorplant growth independent of Pb concentration due to its adverseeffect on soil structure. Substantial reductions in Ca(NO₃)₂-extractable Pb were observed when cyclonic ash, lime, compost and hydroxyapatite were applied. In general,these amendments reduced Pb phytotoxicity concomitant with reduced Pb concentration in lettuce tissue. Cyclonic ash, limeand compost further improved plant growth and reduced oxidativestress at low soil Pb concentrations due to soil pH increase mitigating Al or Mn toxicity.     

膨润土对轻度镉污染土壤钝化修复效应研究

通过盆栽和大田小区试验,研究了膨润土对Cd污染土壤修复效应。结果表明,盆栽和大田条件下施用膨润土后土壤Cd交换态含量分别较对照降低了41.3%~86.1%和7.9%~24.6%,铁锰氧化物结合态(OX)和残渣态(RES)Cd含量则有所上升。水稻各部分Cd含量总体上随膨润土投加量的增加而降低,与对照相比,盆栽条件下根、茎、叶、糙米中Cd含量最大降幅分别达到46.0%、49.8%、54.2%和71.8%,大田小区条件下水稻各部分Cd含量最大降幅分别达到35.3%、48.8%、36.0%和40.9%。投加不同浓度膨润土后,水稻幼苗叶片SOD酶活性和可溶性蛋白含量在一定程度上有所促进,而POD酶活性和MDA含量则表现为明显的抑制效应(P0.05)。在盆栽和大田实验中,施用膨润土显著提高土壤过氧化氢酶活性(P0.05),与之相反,在盆栽实验中,土壤Cd蔗糖酶活性较对照处理显著降低(P0.05),降幅达44.3%~52.3%,而大田条件下各处理间差异不显著(P0.05);脲酶活性随膨润土施加量的增加呈现出先降低后增加的趋势。     

施用不同磷肥对海泡石钝化修复镉污染土壤影响的研究

通过油菜盆栽试验研究了添加不同剂量磷肥对重金属Cd污染土壤海泡石钝化修复效应的影响。结果表明:海泡石(S)、海泡石钝化的基础上施钙镁磷肥(S+CMP)和普钙(S+SSP)均显著降低了油菜地上部位和根部中Cd含量(P0.05),其中地上部位中Cd含量的降低率分别为74.73%、8.80%~62.63%和67.58%~70.33%;根部中Cd含量的降低率分别为84.40%、33.67%~79.37%和73.79%~92.16%,S处理和S+CMP处理均能显著的增加油菜的生物量(P0.05),但S+SSP处理对油菜生物量影响不明显。与CK相比,S、S+SSP和S+CMP处理均显著提高了土壤pH值,且显著降低了TCLP(Toxicity characteristic leaching procedure,TCLP)浸提态Cd含量(P0.05),其降低率分别为43.86%、36.84%~52.63%和26.32%~31.58%。S处理和S+CMP处理显著的增加了土壤脲酶活性,且S、S+SSP和S+CMP处理均不同程度的增加了土壤过氧化氢酶活性,在一定程度上改善了土壤环境质量。     

生物质炭对单一与复合污染土壤中铜、铅、铬的钝化作用

外源投加重金属硝酸盐制得铜、铅、铬单一和复合三级污染土壤(800 mg kg~(-1)、1000 mg kg~(-1)、800 mg kg~(-1)),以热解制备的生物炭为钝化剂,根据重金属钝化率对钝化剂投加量进行优化,并通过改进的BCR(European Communities Bureau of Referent)分级提取方法研究最佳钝化剂投加量下土壤中重金属形态变化。结果表明:施入生物质炭后,单一与复合污染土壤重金属有效浓度均显著降低,确定2%和10%为单一和复合最佳投加量。最佳投加量下,单一与复合过程Cu、Pb、Cr钝化率分别为26.2%、10.9%、36.5%与12.7%、6.0%、37.6%。生物质炭的施入能促进金属离子从可交换态向残渣态和可还原态转变,比较单一与复合污染,Cu、Pb、Cr可交换态减少量分别从18.4%、20.5%、37.5%变为10.5%、18.2%、46.5%,残渣态增加量分别从138.1%、64.2%、41.6%变为37.4%、58.5%、48.2%。生物炭对土壤中Cr的钝化效果最佳,在复合污染土壤中更为明显。     

磷酸盐、石灰和膨润土降低冶炼厂污染石灰性土壤重金属活性的研究

通过土壤培养试验探讨了磷酸盐配合石灰或膨润土对铅冶炼污染石灰性土壤(全铅和全镉含量分别为497和5.22 mg kg-1)中铅、镉等重金属的稳定效果。石灰和膨润土均可使土壤pH明显上升,而磷酸盐使土壤pH下降。各处理措施均使土壤EC上升。膨润土、石灰有利于土壤磷有效性下降。稳定剂施用后30 d时,与对照相比,磷酸盐单独施用、石灰单独施用、膨润土单独施用、磷酸盐配合膨润土施用处理土壤DTPA-Pb含量分别下降了5.92%、16.7%、9.24%和17.9%;培养60 d时,以上处理DTPA-Pb含量与对照相比下降比例分别为6.15%、17.6%、14.5%和16.4%,而磷酸盐施用30 d后再施用一半石灰的处理DTPA-Pb含量下降14.2%。与铅相比,稳定措施对镉的有效性影响较小,仅有石灰单独施用和磷酸盐施用30 d后再施用一半石灰处理DTPA-Cd含量显著低于对照(P 0.05),降低比例分别为2.54%和5.51%。以上结果表明,对于铅冶炼污染石灰性土壤,磷酸盐配合膨润土施用、磷酸盐施用后一段时间再施用石灰均可促进镉、铅的稳定,磷酸盐配合石灰施用可降低土壤磷的风险。     

Maize Inbreds' Response to Riecito Phosphate Rock and Triple Superphosphate on an Acidic Soil

Abstract

Tropical acidic soils require large inputs of nitrogen (N) and phosphorus (P) fertilizers to sustain crop production. Attempts to use phosphate rock (PR) as a cheaper P source have shown limited success because of low rock solubility. The objective of this study was to evaluate growth and P nutrition of aluminum (Al)‐tolerant maize inbreds fertilized with PR. Twelve Al‐tolerant inbreds from CIMMYT were planted in 2‐kg pots filled with an acidic soil very low in available P and fertilized with 0, 40, or 100 mg kg^?1 of Riecito PR or triple superphosphate (SP). Plant shoots were harvested 35 days after planting, and biomass, root length, P uptake, and soil residual P were determined. Inbreds were able to sustain growth when fertilized with PR. There was indication that various mechanisms were involved in the responses to PR fertilization. Cultivars combining high uptake and conversion efficiencies should improve maize utilization of PR.     

水分调控和钝化剂处理对水稻土镉的钝化效应及其机理

采用盆栽试验,研究了水分管理和钝化剂处理对红壤性水稻土重金属镉的钝化效应及其作用机理。结果表明,在土壤镉含量为0．75mg·kg。下,添加海泡石复配磷肥可以显著提高土壤pH值,长期淹水、常规管理水分条件下,土壤交换态cd分别降低了20．4％和15．7％,碳酸盐结合态cd分别下降了15．5％和14．1％,糙米cd分别降低了52．3％和46．O％。未添加钝化剂条件下,长期淹水处理的根表Fe（Ⅱ）含量比常规处理增加了1．2倍,根表cd含量则是常规处理的82．6％。土壤经钝化处理后,长期淹水和常规管理水分条件下,根表Fe（Ⅱ）分别增加了40．1％和70．0％,而根表cd分别降低了35．3％和42．4％。糙米cd含量与根表Fe（Ⅱ）含量呈显著负相关,与根表cd含量呈显著正相关。土壤Fe“和cd“对水稻根表吸附点位的竞争以及土壤镉较低的生物有效性是钝化处理组糙米镉含量下降的主要原因。     

In Situ Acidulation of Rock Phosphate

This study was undertaken to study the impact of adding <75 μm elemental sulfur (ES) on P availability from a range of <250 μm ground rock phosphates (RP) namely; Minjingu (Mi) from Tanzania, Khouribga from Morocco (Mo) and Duchess (D) from Australia. Italian ryegrass (Lolium multiflorum, Thumpa tetraploid) grown in a glasshouse was used as the test crop and tops were harvested 5 times over 27 weeks. Co-granulating RP and 10.7% ES yielded 30–70% more ryegrass tops than RP alone, with the greatest effect with Mi. Fertilizer P recovery in the tops from the RP was 5.2% with D and 6.5% and 7.8% from Mi and Mo, respectively. ES addition increased this by 51% from Mo, 98% from D and 194% from Mi. Co-granulation of RP with ES has been shown to be an effective means of releasing plant available P to crops from RP with minimal fertilizer processing.     

Bioresource Efficacy of Phosphate Rock,Sulfur, and Thiobacillus Inoculum in Improving Soil Phosphorus Availability

In order to improve the effectiveness of phosphate rock as phosphorus fertilizer, elemental sulfur and Thiobacillus have been evaluated as amendments. First, Thiobacillus was isolated from different soil samples. Then, a greenhouse pot experiment was conducted using a completely randomized factorial design with three factors included: elemental sulfur at four levels of 0, 1000, 2000, and 5000 mg kg^?1; phosphate rock at three levels of 0, 1000 and 2000 mg kg^?1; four Thiobacillus inoculums (T₁, T₂, T₃, T₄) and without inoculation (T₀) in three replications. Results showed that all the four Thiobacillus inoculums increased significantly extractable soil-P. Combined application of phosphate rock and sulfur in equal proportion (1:1) along with inoculum Thiobacillus had a significant effect in improving phosphorus availability in soil. Combined application of sulfur (at rates of 1000 and 2000 mg kg^–1) and Thiobacillus significantly increased phosphorus uptake by plants as compared to the control.     

Application of Ground Phosphate Rock to Dimmish the Effects of Simulated Acid Rain on Soil Properties

The effects of simulated acid rain retained in soil on the properties of acid soil and its diminishing by application of ground phosphate rock were investigated by using the sorption method.Results show as follows:(1)For yellow brown soil,the effect of simulated acid rain on the properties of soil with a pH value of 5.9 was relatively small,except a great quantity of acid rain deposited on it.(2) for red soil,the effect of simulated acid rain on the properties of soil was significant.With the increase of the amount of acid deposition,the pH value of soil was declined,but the contents of exchangeable H^ ,Al^3 and Mn^2 and the amount of SO4^1- retention were increased.(3) Many properties of acid soils could be improved by applying ground phosphate rock.For example,pH value of soils and the amounts of available P and exchangeable Ca^2 and Mg^2 were increased,and the amounts of exchangeable H^ and Al^3 and SO4^2- retained was reduced.The application of ground posphate rock could effctively diminish the pollution of acid rain to soil.     

Agronomic Effectiveness of Partially Acidulated Phosphate Rock

Laboratorial incubation and field experiments were conducted on soils ranging in texture from sandy loam to clay and in pH from 3.6 to 9.0 to determine the agronomic effectiveness of single superphosphate (SSP).fused magnesium phosphate(FMP) and partially acidulated phosphate rock(PAPR) on 8 field crops.The results showed that the pattern of available P released from SSP was fixing-releasing-fixing-steady state,while that of PAPR was shortly fixing-slowly releasing-fixing steady state.And the PAPR,SSP and FMP were equally effective as judged by yield Puptake by phants and extractable P in soils after crop harvesting,The PAPR used as basal fertilizer was more effective than that as top dressing,and its residual effect was also obvious.     

草酸活化磷矿粉对矿区污染土壤中Cd的钝化效果

通过盆栽莴苣试验,研究施加草酸活化磷矿粉对矿区农田土壤Cd污染钝化修复的效果。结果表明：施加南漳磷矿粉后,供试土壤交换态Cd的含量比对照降低了12.5%～20.3%;施加不同浓度经草酸活化过的南漳磷矿粉后,交换态Cd的含量与对照相比最高降低了39.5%。施加保康磷矿粉后,随着施加量的增加,与对照相比,交换态Cd的含量变化不显著;施加经草酸活化保康磷矿粉,土壤交换态Cd含量比对照最高降低了21.5%。同时,与对照相比,施加南漳磷矿粉后,残渣态Cd含量最大值是对照的2.03倍,施加经草酸活化的南漳磷矿粉后,残渣态Cd含量最大值是对照的2.61倍;施加保康磷矿粉和活化磷矿粉后,残渣态Cd含量与对照也有显著增加。施加磷矿粉和活化磷矿粉可以显著降低莴苣各部分对Cd的吸收,减少Cd在莴苣植株的累积。在施加两种活化磷矿粉后,与对照相比,莴苣地上部分Cd含量分别最多可降低41.4%、59.3%,根部Cd含量最多降低47.7%、55.1%。因此,低品位磷矿粉经草酸活化后施于Cd污染土壤,可以更好地钝化固定土壤中的Cd。     

pH和磷对铅胁迫下芥菜生长和土壤酶活性的影响

采用盆栽试验研究不同pH和磷酸盐浓度对铅污染土壤种植的芥菜生物量和铅吸收的影响,及铅浓度与土壤酶活性的关系.结果表明,芥菜地下部分铅含量明显高于芥菜地上部分.土壤酸化有可能导致土壤中铅的溶出释放,在试验中,土壤pH为5.0时,土壤中铅的释放最多,芥菜生长和土壤酶活性受到的影响最大.土壤中铅与磷酸结合成难溶性的磷酸铅,当土壤中施加的磷浓度为300mg/kg时,土壤中铅的释放量最少,芥菜生长和土壤酶活性受到的影响最小;土壤中铅的释放溶出与土壤酶活性相关性较大,同时二者易受土壤pH和磷含量的影响,因此把土壤中铅的释放溶出与土壤酶活性结合起来作为判断土壤铅污染程度指标更合适.     

Not All Phosphate Fertilizers Immobilize Lead in Soils

The effects of six phosphate (P) fertilizers in mobilizing and immobilizing water-soluble lead (Pb) were determined in a contaminated soil (Alfisol from Shaoxing) from China and four Australian soils (an Oxisol from Twonsville Queensland and three South Australian soils from Cooke Plains (Typic Palexeralf)), Inman Valley (Vertisol), and Two Wells (Natric Palexeralf). The fertilizers tested were single superphosphate (SSP), triple superphosphate (TSP), monoammonium phosphate (MAP), diammonium phosphate (DAP), monocalcium phosphate (MCP), and dicalcium phosphate (DCP) to produce an initial P concentration of 1,000 mg/L. The Chinese soil contained 16,397 mg/kg total Pb, but the Australian soils were uncontaminated. The four Australian soils were each spiked with 1,000 mg Pb/kg soil (as Pb(NO₃)₂) and incubated for a month. Single superphosphate treatments decreased total soluble Pb in soil solution to 2–14 % of those of the nil-P (0P) treatment in the four Pb-spiked soils and to 48 % in the Chinese Pb-contaminated soil. The DAP treatment followed by the MAP treatment greatly increased the total soluble Pb in soil solution up to 135–500 % of the 0P treatment, except in the Two Wells soil. MCP could decrease the total soluble Pb in Cooke Plains, Inman Valley, Shaoxing, and Two Wells soils while increase it in the Queensland soil; DCP decreased the total soluble Pb in Cooke Plains and Queensland soils while increased it in the Shaoxing and Inman Valley soils. There were close relationships between the total soluble Pb, total soluble Al, and total soluble Fe in the water extracts of each. Soluble Al and Fe ions in soil solution increased soluble Pb concentrations. We conclude that not all phosphate fertilizers immobilize Pb in soils equally well. SSP and TSP are excellent Pb-immobilizing fertilizers, while MAP and DAP are strong Pb-mobilizing fertilizers. MCP and DCP are either Pb-immobilizing fertilizers or Pb-mobilizing fertilizers depending on their reactions with individual soils.     

Analysis of Phosphate Rock Dissolution Determining Factors Using Principal Component Analysis in Some Acid Indonesian Soils

Abstract

Dissolution of phosphate rock (PR) materials and its subsequent phosphorus (P) availability to plants depend upon soil characteristics, PR characteristics, type of crops, and environmental conditions. Agronomic effectiveness of the PR sources has frequently been investigated in the field or in the greenhouse. This is time consuming and not cost‐effective. Therefore, identification of the soil characteristics influencing the dissolution of PR is very important for direct application of P sources. The principal component analysis was used to summarize the characteristics of acid soils in an incubation system into a number of factors that may affect PR dissolution. Three major factors were selected in this study: 1) soil texture, 2) soil acidity, and 3) fertilization. Using the scores of the individual factors as independent variables, a stepwise regression analysis was performed to derive a PR dissolution function. The coefficient of determination (R²) reached 0.91**, and the magnitude of the different factors affect PR dissolution following the order of soil texture (54%)>soil acidity (43%)>fertilizer (3%). Fertilizer was not significant as a PR dissolution factor.