Speciation and mobility of lead in shooting range soils

The mobility and bioavailability of lead (Pb) in seven military shooting range soils found in eastern and north eastern Botswana were studied using sequential extraction procedure. The different forms of Pb and their reactivity in the soil help explain their speciation, mobility and bioavailability in the environment. Mobility of Pb in the berm soils in all the seven shooting ranges was found to be over 90% implying high Pb lability. The bioavailability index of Pb was in the range 60–90%, an indication that most of the Pb can be available for plant uptake. Sequential extraction studies indicate that the partitioning of Pb was mostly confined to the carbonate compartment in all the shooting ranges. All the seven shooting ranges failed the Synthetic Precipitation Leaching Procedure (SPLP) with SPLP Pb concentrations exceeding United States Environmental Protection Agency (USEPA) 0.015 mg/kg critical level of hazardous waste, posing a pollution threat to surface and groundwater.     

A Comprehensive Approach to Speciation of Lead and Its Contamination of Firing Range Soils: A Review

Lead pollution of shooting range soils has received tremendous attention in the past few years due to its adverse effects to the environment. High total Pb concentrations have been reported in shooting range soils. Soil physicochemical properties such as pH, organic matter, cation exchange capacity (CEC) and soil moisture have been found to have a strong influence on the transformation of Pb shots. Therefore, it is imperative that the soil physicochemical properties are well understood when investigating the environmental effects of Pb. Total Pb concentration gives a measure of the amount of Pb stored in soil but does not give a true picture of the environmental pollution risk. In their quest to control pollution of shooting range soils from Pb, scientists have applied soil remedial methods such as soil washing, chemical stabilisation and phytoremediation. This review examines the pollution status of shooting range soils from Pb, the effect of soil properties on Pb mobility and bioavailability, the importance of Pb chemical speciation in understanding Pb mobility and shooting range management strategies applied in the control and management of Pb pollution of shooting range soils. This is a holistic review covering literature from 1983 to 2018, a period of 35 years.     

Distribution and mobility of lead in soils at an outdoor shooting range

The distribution of total Pb in surface and subsurface soil horizons at an outdoor shooting range in southeastern Michigan was determined by single extraction elemental analysis (AAS and ICP‐AES). Significant Pb enrichment of the site's soils coincides closely with Pb vapor and particulate matter produced from shot shell primers and the downfall of Pb/Sb pellets associated with the recreational shooting of skeet and trap. Surface concentrations in these locations are 10 to 100 times greater than the background concentration found on adjacent properties. The distribution of Pb in the subsurface soil horizons corresponds to the distribution of Pb at the surface, which suggests the Pb is mobilizing and migrating downward through the vadose zone. This mobilization appears to be occurring despite the clay‐rich nature of the soils, and may be due to the transformation of metallic Pb into soluble Pb compounds of carbonate and sulfate: Both compounds appear to be present in crust material found coating many of the pellets found at the site. The downward migration of soluble Pb is a potential threat to groundwater that is present at the site at a depth of less than 1 m. The protection of surface water quality is also a concern because Pb pellets from the shooting range have been found in the bed sediments of a nearby stream.     

Characterization of Lead in Soils of a Rifle/Pistol Shooting Range in Central Florida,USA

The distribution of lead in soil samples collected from both surface (0 to 10?cm) and profile (O 0 to 10?cm, E 11 to 30?cm, Eb 31 to 50?cm, Bw 51 to 100?cm, and C 181 to 200?cm) at a 14-year-old rifle/pistol shooting range located in central Florida were determined using EPA Method 3051a (microwave, HNO₃/HCl=3:1, v/v). In addition to total lead analysis, Toxicity Characteristic Leaching Procedure (TCLP) analysis was performed on corresponding samples to determine whether the soils would require special handling as hazardous waste if the soils were to be removed from the range. Total lead in surface soils varied from 330 to 17 850?mg Pb kg^?1, with the greatest concentration in the middle of the backstop berm. The TCLP tests indicated that lead in all surface soils exceeded the 5?mg Pb L^?1 critical level of federal regulation for solid wastes and hazardous wastes provided by the Resource Conservation and Recovery Act (RCRA) and would be characterized as hazardous waste. Sequential fractionation and X-ray diffraction (XRD) analyses revealed that lead carbonate existed predominantly (91.3%) in the berm soil. The weathering of lead bullets in the soil environments formed primarily as hydrocerussite (Pb₃(CO₃)₂(OH)₂), with small amounts of massicot (PbO) and cerussite (PbCO₃). However, the elevated soil pH, caused by the oxidization and transformation process of elemental lead in lead bullets, could be a significant factor in limiting the migration of lead in the soil.     

Metal Distribution and Characterization of Cultivable Lead-Resistant Bacteria in Shooting Range Soils

Shooting ranges represent about 10% of polluted sites in Switzerland. This pollution, mainly consisting of lead (Pb) and antimony (Sb), can spread into the local groundwater, wildlife and plants. In this study, shooting range stop butt soils (elevated soil mount behind the target) of three sites (Versoix, Cartigny and Nyon, Western Switzerland) were investigated for metal contamination and culturable lead-resistant bacteria in contaminated soils. The inductively coupled plasma mass spectrometry analysis of surface stop butt soils (0–5 cm) indicated high metal concentrations especially for Pb and Sb, e.g., the Pb concentration ranging from 61,135 to 395,651, 23,821 to 201,268 and 120 to 27,517 mg kg^?1 in the soil from the sites of Versoix, Cartigny and Nyon, respectively. Molecular analysis of 16S rRNA gene demonstrates the presence of bacteria from diverse classes: Flavobacteriia, α-Proteobacteria, γ-Proteobacteria, Actinobacteria and Bacilli that exhibited high Pb minimum inhibitory concentration value from 1,036 to 2,694 mg kg^?1. The isolated strains could be the subject of further studies to evaluate their role in bioremediation of lead-contaminated soil.     

Effect of Phosphate Treatment on Pb Leachability in Contaminated Shooting Range Soils

A cost-effective way to reduce lead released into the environment is through immobilization with readily available soil amendments. Leaching of Pb from four shooting range soils treated with two phosphate sources was evaluated in soil columns. Phosphate was applied at a P/Pb molar ratio of 4:1 with two-thirds of the P supplied from phosphate rock (PR) and one-third from phosphoric acid (PA). The soils were incubated for 18 hr and leached with toxicity characterization leaching procedure (TCLP) and synthetic precipitation leaching procedure (SPLP) fluids, respectively. PR/PA treatment reduced Pb in TCLP leachate to below regulatory limit of 5 mg/L after 18 hr of incubation. Reduction of Pb leached was more dependent on clay content than total Fe. PR/PA treatment had no effect on pH of TCLP leached soils, while it led to a drastic lowering of pH that mobilized Pb in SPLP leached soils. However, leaching of Pb reduced with time in SPLP leached soils because pH increased gradually. PR/PA treatment was more effective in SPLP leached soils with low total soil Pb because they received lower amounts of PA. PR/PA treatment may be more efficient when applied as split applications in soils with a low to medium Pb loading and a high buffering capacity.     

Firing range soils yield a diverse array of fungal isolates capable of organic Acid production and pb mineral solubilization

Anthropogenic sources of lead contamination in soils include mining and smelting activities, effluents and wastes, agricultural pesticides, domestic garbage dumps, and shooting ranges. While Pb is typically considered relatively insoluble in the soil environment, some fungi may potentially contribute to mobilization of heavy metal cations by means of secretion of low-molecular-weight organic acids (LMWOAs). We sought to better understand the potential for metal mobilization within an indigenous fungal community at an abandoned shooting range in Oak Ridge, TN, where soil Pb contamination levels ranged from 24 to >2,700 mg Pb kg dry soil(-1). We utilized culture-based assays to determine organic acid secretion and Pb-carbonate dissolution of a diverse collection of soil fungal isolates derived from the site and verified isolate distribution patterns within the community by 28S rRNA gene analysis of whole soils. The fungal isolates examined included both ascomycetes and basidiomycetes that excreted high levels (up to 27 mM) of a mixture of LMWOAs, including oxalic and citric acids, and several isolates demonstrated a marked ability to dissolve Pb-carbonate at high concentrations up to 10.5 g liter(-1) (18.5 mM) in laboratory assays. Fungi within the indigenous community of these highly Pb-contaminated soils are capable of LMWOA secretion at levels greater than those of well-studied model organisms, such as Aspergillus niger. Additionally, these organisms were found in high relative abundance (>1%) in some of the most heavily contaminated soils. Our data highlight the need to understand more about autochthonous fungal communities at Pb-contaminated sites and how they may impact Pb biogeochemistry, solubility, and bioavailability, thus consequently potentially impacting human and ecosystem health.     

Lead Distribution and Mobility in a Soil Embankment Used as a Bullet Stop at a Shooting Range

The distribution of lead in and below a soil embankment used as a stop butt for lead bullets at a sport shooting range for more than 30 years was investigated. A vertical profile, just behind the shooting target, was mapped by 54 soil samples characterized by contents of lead bullets, soil lead, and easily leachable lead as measured in a leaching test (L/S 2). At the target, the soil contained up to 40% metallic lead and 5 to 10% lead associated with the soil particles (<2?mm). The leaching test showed concentrations of dissolved lead in the range 5 to 20?mg/l. However, in the bottom of the stop butt (about 1?m lower than the target) soil lead was only slightly elevated, and no increase in lead was found below the stop butt in the original soil profile. In the lower part of the stop butt, pH was around 5, which is considered to favor lead migration, but in the soil samples with lead bullets present pH was between 6 and 7. The elevated pH values, probably caused by the corrosion of lead bullets, may have been a significant factor in limiting the migration of lead in the stop butt. The investigation showed that the lead in the stop butt did not affect the surroundings, but that the high lead content of the soil would require that this be treated as waste if the facility was abandoned.     

退耕植茶地土壤团聚体及其无机磷组分分布特征

为了揭示土壤团聚体及其无机磷组分对退耕植茶的响应特征,以雅安市名山区中峰乡退耕植茶地(2～3年、9～10年、16～17年)为研究对象,选取邻近耕地为对照,采用野外调查与室内分析相结合的方法开展退耕植茶地土壤团聚体及其无机磷组分分布特征的研究.结果表明: 耕地及退耕植茶地土壤团聚体均以粒径>2 mm团聚体为主.随着退耕植茶年限的延长,各退耕植茶地粒径>5 mm的团聚体含量逐渐增加,粒径<5 mm的团聚体含量却逐渐降低.退耕植茶初期,退耕植茶地土壤团聚体平均质量直径(MWD)和几何平均直径(GMD)值与对照差异不明显,退耕植茶9～10年和退耕植茶16～17年显著高于对照,且随着退耕植茶年限的延长逐渐增大.退耕植茶地与耕地相比,其有效性较高的Al-P、Fe-P含量增加,有效性较低的O-P含量降低,随着退耕植茶年限的延长,各粒径团聚体中有效性较低的O-P逐渐降低,有效性较高的Al-P、Fe-P逐渐增加.耕地及退耕植茶地中Al-P、Ca-P含量随粒径的减小而增加,在<0.25 mm粒径中的含量最高;Fe-P在<0.25 mm粒径团聚体中的含量最多,其次是2～5 mm和0.25～0.5 mm粒径团聚体;退耕植茶后,O-P逐渐向较小粒径中富集,在<2 mm粒径中含量较高.     

东北黑土水稳性团聚体及其结合碳分布特征

以东北黑土区32对自然和耕作黑土为研究对象,对比研究了两种土壤水稳性团聚体及其结合碳的分布特征.结果表明：自然土壤0～30 cm水稳性大团聚体（>0.25 mm）质量分数及其结合碳均高于微团聚体;随着土层深度的增加,大团聚体及其结合碳逐渐降低,而微团聚体（<0.25 mm）及其结合碳显著增加（P<0.01）.耕作土壤团聚体分布特征与自然土壤相反,与自然土壤相比,耕作土壤大团聚体数量及其结合碳急剧降低,且>1 mm的大团聚体降低幅度远大于其他粒级团聚体.自然土壤大团聚体质量分数与土壤有机碳（SOC）存在明显的正相关关系（P<0.01）,尤其是>1 mm大团聚体;耕作土壤>1 mm大团聚体质量分数与土壤总SOC相关不显著;自然与耕作土壤总SOC与各级团聚体结合碳呈极显著正相关（P<0.01）.与自然土壤相比,耕作土壤大团聚体结合碳明显降低,而微团聚体结合碳增加了37.1%,总SOC含量下降了29.5%,表明大团聚体在总SOC变化中起主要作用.水稳性大团聚体对管理措施响应迅速,可以作为评价农业管理措施转变对土壤肥力和土壤质量影响的指标.     

Speciation and Vertical Distribution of Lead and Lead Shot in Soil at a Recreational Firing Range

In this study, the speciation, vertical distribution and soil particle size fractions of lead in soil samples at a recreational firing range was determined. This study was performed to gain a better understanding of how lead shot breaks down at ranges. Both the chemical form of lead and the types of soil particles with which lead is associated are important for understanding not only the mobility and persistence, but also the human and ecological impact of lead at these ranges. Lead as shot gun pellets was found to be the dominant form of lead in soil samples. The highest levels were measured in surface samples located in the “fall zone” of the range. Results indicate shot to be relatively absent below surficial samples. Lead concentrations in soil decreased markedly across a 0–6″ depth profile. Lead carbonates were the dominant non-shot form of lead present at all depths. Water-soluble lead species made up a minor fraction of the non-shot lead present in the samples. Based on soil particle sizes measured, highest concentrations of lead were measured in soil particles passing a 0.075 mm sieve.     

Rapid Method of Determining Factors Limiting Bacterial Growth in Soil

A technique to determine which nutrients limit bacterial growth in soil was developed. The method was based on measuring the thymidine incorporation rate of bacteria after the addition of C, N, and P in different combinations to soil samples. First, the thymidine incorporation method was tested in two different soils: an agricultural soil and a forest humus soil. Carbon (as glucose) was found to be the limiting substance for bacterial growth in both of these soils. The effect of adding different amounts of nutrients was studied, and tests were performed to determine whether the additions affected the soil pH and subsequent bacterial activity. The incubation time required to detect bacterial growth after adding substrate to the soil was also evaluated. Second, the method was used in experiments in which three different size fractions of straw (1 to 2, 0.25 to 1, and <0.25 mm) were mixed into the agricultural soil in order to induce N limitation for bacterial growth. When the straw fraction was small enough (<0.25 mm), N became the limiting nutrient for bacterial growth after about 3 weeks. After the addition of the larger straw fractions (1 to 2 and 0.25 to 1 mm), the soil bacteria were C limited throughout the incubation period (10 weeks), although an increase in the thymidine incorporation rate after the addition of C and N together compared with adding them separately was seen in the sample containing the size fraction from 0.25 to 1 mm. Third, soils from high-pH, limestone-rich areas were examined. P limitation was observed in one of these soils, while tendencies toward P limitation were seen in some of the other soils.     

Lead Retention by Soils at Field Moisture Contents

The majority of studies pertaining to lead retention by clays and soils have examined the mechanisms, kinetics, and adsorption isotherms using the batch experiment technique that employs solid: water extracts of 1:10 and 1:20. Field soil deposits generally have much lower gravimetric water content ranging between 9 and 45%. Given the wide disparity in the solids: water ratio employed in the batch experiment technique and that prevailing in field deposits, this paper examines the lead retention characteristics of soils at field moisture contents (6%, 13%, and 25%) using artificially lead-contaminated soil specimens. A residually derived (i.e., formed by in-situ weathering of parent rock) red soil was used to prepare the artificially contaminated soil specimens. The impact of variations in clay content on lead retention was examined by diluting the residual soil with various amounts (0 to 60%) of river sand. Soil specimens remolded at 6 and 13% moisture contents produced very stiff to hard soils on compaction, while specimens remolded at 25% moisture content existed in the slurry state. The soil specimens were contaminated with low (30 mg/kg) to high (2500 mg/kg) concentrations of lead ions by remolding them with 160 ppm to 10,000 ppm ionic lead solutions. Lead retention by soils at field moisture contents was determined by extracting the lead from the soil using a water leach test. Experimental results showed that the bulk (71 to 99%) of the added lead was retained by the soil in insoluble form at the field moisture content. Correlations between the amount of lead retained and soil/solution parameters indicated that the amounts of Pb retained at field moisture content is a function of the initial Pb addition, total sand content, effective clay porosity, and soil pH.     

Lead fractionation and bioaccessibility in contaminated soils with variable chemical properties

Abstract

The hazard imposed by trace elements within soils is dependent on soil properties and the relative distribution of metal species. Hence, a greenhouse column study was conducted to investigate the geochemical speciation and bioaccessibility of lead (Pb) as a function of soil properties. Four different soil types (Immokalee, Belle Glade, Tobosa and Millhopper series) varying in physico-chemical properties were selected and amended with Pb as Pb(NO₃) at 400, 800, and 1,200 mg kg^?1. A sequential extraction was employed to define the reactive metal pool, which was correlated with Pb bio-accessibility as determined by the physiologically based extraction test. Results show that Pb was mainly distributed in soluble+exchangeable phase in Immokallee (82%) and Millhopper (45%) series, and carbonate and Fe+Mn oxide fractions in Belle Glade (14–74%) and Tobosa (31–64%) series at time zero. With soil aging, Pb underwent chemical transformations in the soils and the majority of added Pb was associated with Fe+Mn oxide fraction (64–81%). Also, Pb bioaccessibility varied widely as a function of soil type and soil aging. Gastric phase (IVG-S) extracted 34–81% and 29–75% and the absorbed intestinal phase (IVG-AI) extracted 12–79% and 12–45% of amended Pb in all the soils at time zero and 6 months, respectively. Among soil types, Tobosa and Belle Glade showed reduced bioaccessibility relative to Immokalee and Millhopper. Statistical analysis revealed that the IVG-S Pb decreases as soil organic matter and cation exchange capacity (CEC) increases and total P decreases. While the Mehlich extractable P and Ca+Mg, total Fe+Al and organic matter predicted the Pb in an intestinal system.     

Assessment of lead availability in soils contaminated by mine spoil

The uptake of lead by two contrasting plant species, radish and red fescue, grown in soils contaminated by mine spoil was investigated. Uptake was found to be poorly correlated either with pH or total Pb concentration in the soils. By contrast, a good correlation was obtained, particularly for red fescue, between Pb uptake and Pb concentration in the solution of equilibrated soil suspensions over a wide range of soil pH, total soil Pb and soil solution Pb concentration.Calculations suggested a similar order of magnitude in the total amounts of Pb taken up by the plants and Pb in the soil solution of the root zone, justifying the latter as a good index of Pb-availability. ei]Section editor: A C Borstlap     

长期植稻年限序列水稻土团聚体有机碳分布特征

通过开展有机质物理分组试验,研究了杭州湾南岸不同植稻年限序列水稻土有机碳含量的粒级分布变化特征.结果表明: 各植稻年限耕层水稻土中,土壤团聚体主要分布在微团聚体(<0.25 mm)中,其中大微团聚体(0.053～0.25 mm)随着植稻年限的增加而减少;在微团聚体(0.053~0.25 mm,<0.053 mm)中,有机碳含量随着植稻年限的增加而增加,在0.053～2 mm粒径范围内,各粒级有机碳占总有机碳比例随着粒级的减小而增加,有机碳主要集中在大微团聚体(0.053～0.25 mm)中;随着种植年限的增加,颗粒有机碳含量减少.栽培年限长的水稻土比栽培年限短的水稻土碳封存量大,早期开垦的水稻土仍有很大的固碳潜力.     

Lead transformation to pyromorphite by fungi

Lead (Pb) is a serious environmental pollutant in all its chemical forms [1]. Attempts have been made to immobilize lead in soil as the mineral pyromorphite using phosphate amendments (e.g., rock phosphate, phosphoric acid, and apatite [2-5]), although our work has demonstrated that soil fungi are able to transform pyromorphite into lead oxalate [6, 7]. Lead metal, an important structural and industrial material, is subject to weathering, and soil contamination also occurs through hunting and shooting [8, 9]. Although fungi are increasingly appreciated as geologic agents [10-12], there is a distinct lack of knowledge about their involvement in lead geochemistry. We examined the influence of fungal activity on lead metal and discovered that metallic lead can be transformed into chloropyromorphite, the most stable lead mineral that exists. This is of geochemical significance, not only regarding lead fate and cycling in the environment but also in relation to the phosphate cycle and linked with microbial transformations of inorganic and organic phosphorus. This paper provides the first report of mycogenic chloropyromorphite formation from metallic lead and highlights the significance of this phenomenon as a biotic component of lead biogeochemistry, with additional consequences for microbial survival in lead-contaminated environments and bioremedial treatments for Pb-contaminated land.     

长期施肥对水稻土有机碳分布及化学结合形态的影响

采用湖南省4个23年连续施肥的稻田长期定位试验,研究了施肥对湖南省水稻土有机碳分布及化学键合形态的影响。试验设不施肥(CK)、化肥(NPK)、中量有机肥(MOM)和高量有机肥(HOM)4个处理。结果表明:在所有施肥处理中,水稳性团聚体均以0.25～1mm和2～5mm粒径含量最高,分别达全土总量的18%～43%和13%～48%。中、高量有机肥处理显著增加了>1mm大团聚体含量以及有机碳在大团聚体中的分配,其中0.25～1mm和1～2mm粒径团聚体中有机碳含量均略高于其余粒径组。与不施肥比较,钙结合态有机碳(Ca-SOC)占总有机碳的比例在2%～4%左右且随有机肥施用呈下降趋势,而铁铝结合态有机碳Fe(Al)-SOC占总有机碳的18%～33%呈上升趋势。有机肥施用条件下,有机碳在大团聚体中的分布的增加、Fe(Al)-SOC的提升以及Ca-SOC的降低意味着土壤有机碳物理和化学保护作用的增强,有利于稻田土壤有机碳的积累,是有机肥施用条件下保持稻田土壤较高固碳速率的重要原因。     

Influence of groundwater and wastewater irrigation on lead accumulation in soil and vegetables: Implications for health risk assessment and phytoremediation

The current study evaluated the effect of groundwater and wastewater irrigation on lead (Pb) accumulation in soil and vegetables, and its associated health implications. A pot experiment was conducted in which spinach (Spinacia oleracea), radish (Raphanus sativus), and cauliflower (Brassica oleracea) were irrigated with groundwater and wastewaters containing varying concentrations of Pb. Lead contents were measured in wastewaters, soils and root and shoot of vegetables. We also measured health risk index (HRI) associated with the use of vegetables irrigated by wastewaters. Results revealed that Pb contents in groundwater and wastewater samples (range: 0.18–0.31 mg/L) were below the permissible limits (0.5 mg/L) set by the Food and Agriculture Organization (FAO). Application of Pb-containing groundwater and wastewater increased Pb concentration in soil and vegetables. Lead concentrations in all soils ranged from 10 to 31 mg/kg and were below the permissible limits of 300 mg/kg set by the European Union. Significant Pb enrichment was observed in the soils whereby all types of vegetables were grown and assessed for Pb risk. Our data showed that Pb contents, in all three vegetables (21–28 mg/kg DW), were higher than the permissible Pb limit of FAO (5 mg/kg Dry Weight (DW)). The HRI values were > 1.0 for radish and cauliflower. It is proposed that Vehari city wastewater/groundwater must be treated prior to its use for irrigation to avoid vegetable contamination by Pb, and as such for reducing Pb-induced human health risk.     

基于大麦根伸长测定土壤Pb毒性阈值、淋洗因子及其预测模型

选取了我国10个典型的不同性质农田土壤,外源添加8个不同Pb浓度,分别进行淋洗与非淋洗处理,根据ISO 11269-1根伸长毒性测试方法,测定了土壤外源Pb对大麦根伸长的毒性阈值(EC₁₀、EC₅₀)及Pb毒性的淋洗因子,同时建立了基于不同土壤性质的Pb毒性阈值预测模型. 结果表明: 不同性质土壤中Pb对大麦根伸长的毒性阈值有显著差异(P<0.01),EC₅₀ 值在300～4130 mg·kg^-1,EC₁₀ 值在55～633 mg·kg^-1. 淋洗处理明显降低了土壤中外源Pb的毒性,基于EC₅₀和EC₁₀测定的不同土壤淋洗因子(LF_ECx)的变化范围分别为0.96～1.96(LF_EC50)和1.03～1.81(LF_EC10). 相比而言,在酸性(pH<6.81)土壤中,淋洗处理对降低土壤外源Pb的毒性作用更为明显. 基于主控因子(pH、有机碳含量OC、阳离子交换量CEC)的淋洗与非淋洗土壤中Pb的大麦根伸长毒性(EC_x,_x=10,50)预测模型表明,除了江西红壤外,淋洗与非淋洗土壤中Pb的EC₅₀实测值均落在模型预测值±2倍标准误差范围之内,说明基于上述土壤主要性质可以较好预测不同性质土壤中Pb的毒性阈值.