Chemical and physical characterization of lead in three shooting range soils in Florida

Abstract

To better understand the environmental impact of lead (Pb) in shooting range soils, Pb levels in three berm soils were characterized via size distribution, total Pb concentration, water-soluble Pb, sequential extraction and X-ray diffraction (XRD). About 60% of the mid-berm soils of ranges-G and -O existed in grain sizes between 0.5 and 0.25mm (medium sand) while range-L was most abundant in the 0.25–0.106mm (fine sand) size fraction. All three range soils had the most accumulation of lead (60–70%) in the very coarse sand size (2.0–1.0 mm). In ranges-G and -L, the index shows a decreasing Pb enrichment with decreasing particle size, which may be a result of bullet fragmentation and abrasion in shooting range soils. Sequential extractions reveal that ranges-G and -L had the highest proportion of Pb bound to organic matter while range-O was dominated by the carbonate-bound fraction. However, a substantial proportion (one-third) of Pb in soil from the three shooting ranges was associated with carbonates. The XRD result revealed the dominance of carbonates in range-O soil, calcite in range-G soil and metallic lead in ranges-G and -O soil. The conversion of metallic lead to carbonates may be a mechanism for natural attenuation of lead in shooting range soils. Implications for remediation of shooting range soils are further discussed.     

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 field lysimeter study of heavy metal movement down the profile of soils with multiple metal pollution during chelate-enhanced phytoremediation

The agricultural soils near a copper smelter in southeast China were found to be highly contaminated with Cu, Pb, Zn, and Cd. Metal migration from the soil to groundwater presents an environmental risk that depends on the physicochemical properties of the contaminated soils. Soil solution samples were obtained using lysimeters from a loam soil with multiple metal pollutions over a period of about 1 yr. A field lysimeter study was also conducted to examine the potential use of (S, S')-ethylenediamine-N, N'-disuccinic acid trisodium salt (EDDSNa3) in chelate-enhanced phytoremedation and to evaluate the leaching of heavy metals. The average heavy metal concentrations in the soil solution (without the addition of EDDS) were high (e.g., 0.15 mg Pb L(-1) at a 50-cm depth) compared to the upper limit for protection of groundwater in China, but varied during the sampling period. Cu concentrations were not correlated with pH or dissolved organic carbon (DOC), but Zn and Cd concentrations were related to soil solution pH. EDDS enhanced metal solubility in the soil, but plant metal uptake by Elsholtzia splendens Nakai did not increase accordingly. There may be an increasing risk of groundwater pollution by Cu and the EDDS enhanced phytoremediation technique needs to be carefully applied to minimize this side effect.     

城市化对土壤生态环境的影响研究进展

城市土壤是城市生态系统中最重要的组成部分之一,发挥着重要的生态系统服务功能。在全球快速城市化的背景下,城市土壤受到人类活动的强烈干扰,土壤物理、化学性质发生改变,土壤退化与污染日益加重。城市土壤退化导致土壤动物生态特征与行为模式发生变化,城市景观格局与土地利用类型的变化强烈影响了土壤动物的栖息地,为土壤动物的生存与生物多样性带来潜在威胁;另一方面,城市化过程改变了土壤微生物群落组成与功能特征。城市化直接影响了城市土壤维持植物生长、土壤自然消减能力以及碳储存功能等重要的生态系统服务功能。针对城市化过程对土壤生态环境产生的一系列影响,需要采用科学的管理方式,改善土壤理化性质,提高土壤环境质量,保护和恢复土壤生物多样性,从而增强城市土壤的生态系统服务功能。     

工矿区不同类型生物结皮对大气降尘重金属的富集规律及其影响因子

大气降尘是矿区土壤重金属的主要来源,而生物结皮对大气降尘重金属有显著的富集作用。为探究不同类型生物结皮对大气降尘重金属的富集规律及其影响因子,选取宁东典型火电厂周边生物结皮广布区作为试验样地,3类生物结皮作为研究对象,并以临近裸土作为对照,对比分析了生物结皮富集大气降尘过程中土壤理化性质、酶活性及重金属含量的变化,采用相关分析、冗余分析和方差分解方法探讨了不同类型生物结皮的结皮层(A层)和层下土壤(B层)重金属含量与其土壤物理、化学性质及酶活性之间的关系。结果表明：燃煤烟尘是矿区大气降尘重金属污染的主要来源,涉及重金属元素包括Cd、Cr、Hg、Pb、Zn、As。生物结皮对源自大气降尘的重金属元素均具有显著的富集作用,且在不同演替阶段生物结皮间的富集规律完全一致：藓结皮>混生结皮>藻结皮;重金属综合污染指数评价结果显示：生物结皮对重金属具有表层富集效应,表现为A层污染程度高于B层。不同类型生物结皮A、B层综合污染指数存在显著差异,排序为：藓结皮>混生结皮>藻结皮;和对照相比,三类生物结皮均能通过富集大气降尘增加其A、B层养分和细颗粒物含量并改善土壤质地。方差分解结...     

城市土壤碳循环与碳固持研究综述

城市化过程带来的土地利用变化和环境污染是全球变化的重要方面,城市为人们了解人类与自然复合生态系统对全球变化的影响及其对全球变化的响应过程提供一个独特的"天然实验室"。陆地生态系统碳循环是全球变化研究的热点领域之一,然而,人们对城市在全球碳循环中的作用和影响知之甚少,城市土壤碳循环研究处于起步阶段。介绍了城市土壤的主要特性和碳循环特征,指出强烈的人为作用是其最突出的特点;综述了城市土壤碳库、碳通量和碳固持研究方面取得的进展;探讨了城市化过程中土地利用变化、土壤中生物及土壤管护措施、城市小气候、大气污染沉降和土壤污染等对土壤碳循环的影响;提出未来城市碳循环研究需要开展长期系统监测、深化城市土壤碳循环机制研究、创新研究范式和研究方法、并将研究成果与城市景观规划与设计相结合,提升城市土壤碳管理能力。     

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.     

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.     

Concentrations and chemical forms of heavy metals in agricultural soil near the world’s largest and oldest tungsten mine located in China

Abstract

Tungsten (W) mining has taken place in Ganzhou in China for about 100 years. Such long-term W mining may release large amount of metals to soils and waters around these mines. Twenty soil samples were taken from the area around the W mines and 10 soil samples from an area much farther away. These soil samples were analysed for physicochemical properties, heavy metal content and their chemical forms. Results show that long-term W mining significantly increased both total and labile contents of Cd, Cu, Pb and Zn, but did not, or only slightly, increased the total content of Co, Cr and Ni in the soil near the mine. Average enrichment factor (EF) in the agricultural soils was 4.0, 2.4, 2.2, and 2.0 for Cd, Cu, Pb and Zn, respectively. The labile fraction was dominated by the carbonate-bound fraction for Cd (54.5%) and organic matter-bound fraction for Cu (37.9%), while the major labile fractions for Pb and Zn were associated with carbonates (30.2% and 6.4%), oxides (17.9% and 10.6%) and organic matter (9.2% and 18.8%). Consequently, there is a need to be cautious about Cd in the soils contaminated by W mining.     

河北主要土壤中Cd、Pb形态与油菜有效性的关系

当今土壤重金属污染日趋严重而表征土壤污染程度 的指标不够完善、相关性亦较差。为此,采用网室盆栽试验,研究了河北平原主要土壤类型潮土和潮褐土上Cd、Pb的化学形态特征及其与油菜植株干物重、油菜吸收重金属含量的关系。结果表明Cd对油菜的毒害作用大于Pb。总量及各形态Cd、Pb含量与油菜可食部分干物重呈负相关,对油菜干物重影响最大的是交换态Cd、Pb。而对油菜吸收Cd、Pb贡献最大的形态是碳酸盐结合态和铁锰氧化物结合态。深入研究重金属形成与植物有效性间的关系,可为进一步揭示重金属的生物有效性,为更准确评价土壤重金属污染程度提供理论依据,具有重要的理论意义和实际应用价值。     

北京城市公园常见乔木土壤真菌群落特征及影响因素

快速城市化引起的城市环境污染问题日趋严重,由城市中心到城郊往往呈规律性递变趋势。北京城市公园作为城市绿地主体,不仅是城市居民重要的休闲游憩场所,也能在一定程度上反应环境污染,如土壤重金属污染的作用规律。以北京市这一典型大城市为研究区域,根据不同城市公园的建成时间、所处位置和距离市中心的远近选择六个公园作为研究样点,选取公园常见6种乔木下土壤,通过对土壤重金属含量、土壤理化性质以及土壤真菌群落测定和测序,旨在探讨城市公园植被下土壤真菌群落特征（多样性和群落结构组成）以及影响因素。研究结果表明：北京城市公园乔木下的土壤真菌群落多样性、群落组成以及优势类群受到土壤pH值、土壤养分和水分以及重金属铅的调控。其中公园土壤重金属铅含量增加会降低土壤真菌多样性、显著影响优势类群子囊真菌（占真菌群落73%）以及土壤真菌功能类群病原真菌群落组成。研究揭示了北京城市公园土壤真菌群落特征及调控因素,特别是重金属铅对土壤真菌群落的影响,这对提高城市公园科学管理和环境健康具有积极的应用价值。     

Various Applications of Soil Contaminant Database Developed for the Central Artery/Tunnel Project

One of the largest environmental assessment programs in the United States was initiated in the early 1990s to determine the chemical characteristics of soil located within the planned alignment for the Central Artery (I-93) / Tunnel (I-90) (CA/T) Project in Boston, Massachusetts. The primary purpose of the program was to support management of the handling and disposal of over 17 million cubic yards of soil to be excavated during construction of the CA/T Project. As part of this work, more than 8,000 soil samples were collected from more than 2,600 soil borings and analyzed for a range of chemical contaminants, including volatile organic compounds, acid/base neutral compounds, total petroleum hydrocarbons, polychlorinated biphenyls, and heavy metals. The soils encountered during the investigations exhibited properties influenced by numerous anthropogenic activities. These activities, such as vehicular emissions, historic industrial/manufacturing operations, and waterfront filling with both building rubble and dredge spoils from Boston Harbor, resulted in soils primarily contaminated with petroleum hydrocarbons and metals. As a result of this program, an extensive database of the chemical constituents present in urban soils in downtown Boston was developed. These results were primarily used to delineate the limits of contaminated areas affecting the planned construction. In addition, the database has been used by the Project to support various soil management activities, as well as by the regulatory community in developing guidelines and criteria governing the management of contaminated soils in Massachusetts. This paper focuses on the various applications of this database throughout the course of the Project, and with the additional aim of stimulating potential future applications by both the regulatory and scientific communities.     

The Influence of Soil Properties on the Mobility of Metals Following a Single Application of Polluted Sewage Sludge to Seventy Agricultural Topsoils: A Laboratory Column Study

The main aim of this study was to examine the influence of soil properties on the leaching of Cd, Cr, Cu, Ni, Pb, and Zn following the application of polluted sewage sludge to contrasting topsoils. Seventy agricultural soil samples from different parts of Spain were amended with a single dose of sewage sludge (equivalent to 50 t dry weight ha^?1) and a column study was performed under controlled conditions. After two, four, and six months of incubation, 283 ml of distilled water (equivalent to a rainfall event of 25 l m^?2) was applied. The leachates were then collected and analyzed for metals. For all of the soils considered, the pH was the most important parameter for the control of mobility metals (except for Cu, determined by the sand and soil organic carbon and only to a lesser extent by the soil pH r² = 0.604, p < 0.001) and was negatively related to all of the studied metals. For Pb and Zn, soil pH was the single soil property explaining their mobility (r² = 0.411, p < 0.001 for Pb; r² = 0.713, p < 0.001 for Zn) while for Cd, Cr and Ni, EC, sand and silt also appeared in the statistical models (r² = 0.753, p < 0.001 for Cd; r² = 0.366, p < 0.001 for Cr; r² = 0.784, p < 0.001 for Ni). In the basic soils, soil texture was the most important soil property controlling the mobility of metals (except for that of Pb, which it only weakly predicted). For the acidic-neutral soils, the soil pH was the most important soil property controlling metal mobility (except for that of Cr, which was mainly determined by the pseudo-total Cr content).     

Geochemical baseline determination and pollution assessment of heavy metals in urban soils of Karachi,Pakistan

Karachi is one of the most populated urban agglomerations in the world. No categorical study has yet discussed the geochemical baseline concentrations of metals in the urban soil of Karachi. The main objectives of this study were to establish geochemical baseline values and to assess the pollution status of different heavy metals. Geochemical baseline concentrations of heavy metals were estimated using the cumulative frequency distribution (CDF) curves. The estimated baseline concentrations of Pb, Cr, Cu, Zn and Fe were 56.23, 12.9, 36.31, 123.03 and 11,776 mg kg⁻¹, respectively. The pollution status of heavy metals in urban soils was evaluated using different quantitative indices (enrichment factor–EF, Geo-accumulation Index–I_geo, and pollution index–PI). Enrichments factors of the selected heavy metals determined by using Fe as a normalizer showed that metal contamination was the product of anthropogenic activities. The urban soils of Karachi were found to have a moderate to moderately severe enrichment with Pb, whereas Cr and Cu has moderate and Zn has minor enrichment. I_geo results indicated moderate soil contamination by Pb at some of the sampling locations. PI for Pb, Cr, Cu and Zn was found in the range of 0.04–3.42, 0.19–1.55, 0.27–2.45 and 0.32–1.57, respectively. Large variations in PI values of Pb revealed that soil in those areas of the city which are influenced by intensive anthropogenic activities have exceptionally high concentrations of Pb. The findings of this study would contribute to the environmental database of the soil of the region and would also facilitate both at the local and the international scales, in a more accurate global environmental monitoring, which will eventually facilitate the development of management and remediation strategies for heavy metal contaminated urban soil.     

Integrated Field Lysimetry and Porewater Sampling for Evaluation of Chemical Mobility in Soils and Established Vegetation

Potentially toxic chemicals are routinely applied to land to meet growing demands on waste management and food production, but the fate of these chemicals is often not well understood. Here we demonstrate an integrated field lysimetry and porewater sampling method for evaluating the mobility of chemicals applied to soils and established vegetation. Lysimeters, open columns made of metal or plastic, are driven into bareground or vegetated soils. Porewater samplers, which are commercially available and use vacuum to collect percolating soil water, are installed at predetermined depths within the lysimeters. At prearranged times following chemical application to experimental plots, porewater is collected, and lysimeters, containing soil and vegetation, are exhumed. By analyzing chemical concentrations in the lysimeter soil, vegetation, and porewater, downward leaching rates, soil retention capacities, and plant uptake for the chemical of interest may be quantified. Because field lysimetry and porewater sampling are conducted under natural environmental conditions and with minimal soil disturbance, derived results project real-case scenarios and provide valuable information for chemical management. As chemicals are increasingly applied to land worldwide, the described techniques may be utilized to determine whether applied chemicals pose adverse effects to human health or the environment.     

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.     

Pollution characteristics and risk assessment of heavy metals in the soil of a construction waste landfill site

Heavy metals found in construction waste can enter soil and water bodies through surface runoff and leachate, where they represent an environmental hazard. In this study, we investigate the pollution characteristics and ecological risks of eight heavy metals (Cd, Cr, Cu, Mn, Ni, Pb, Zn, and As) in the soils of an unofficial construction waste landfill site in Beijing, China. The results indicate that long-term disposal of construction waste in the dry riverbed can reduce the pH value of the soil, increase the soil organic carbon content, and affect the total amount and distribution of heavy metals. Moreover, the landfill site pollutes the external soil environment, with Cd, Zn, Pb, and Cu as the characteristic pollutants. According to the Nemerow comprehensive pollution index and potential ecological risk assessment, heavy metal pollution decreases in the following order: internal soil > bottom soil > boundary soil. Cd, Zn, Pb, and Cu pollution is higher in the internal region, with single heavy-metal pollution indexes (Pi) of 1.41, 1.65, 1.26, and 1.28, respectively. Conversely, the Pi for Cr is higher in boundary and bottom soils (1.91 and 1.94, respectively). Risk assessment codes indicate that Cd and Mn pose the greatest environmental risk (31.9% and 17.8%, respectively) as they have the highest effective content, bioavailability, and mobility. Thus, environmental monitoring is a necessity for these metals.     

Humus status of different soils affected by pollution with fluorides from aluminum production in the Baikal region

The effect of pollution by fluorides from aluminum production on the humus status in different types of arable soils was studied in field experiments. They included modeling of a high pollution level by addition of NaF prevailing in industrial air emissions. The negative effect of fluorides on the humus status, related to an increase in the mobility of humic substances, was more pronounced in gray forest soil than in sod-meadow soil. This depended on the soil physicochemical properties determining the buffer capacity toward NaF and the content of water-soluble fluorides.     

Manure Application and Cannabis Cultivation Influence on Speciation of Lead and Cadmium by Selective Sequential Extraction

The contamination of agricultural soils by heavy metals is a worldwide problem. Degradation of organic matter (OM) from organic amendments used in the remediation of metal-contaminated soils leads to changes in soil chemical properties shortly after their addition, which may affect the soil metal distribution. The effects of four differing organic amendments on chemical forms of Pb and Cd in a contaminated soil were investigated in a pot experiment of control unamended soil and soils amended with dry cow and poultry manures (20 g CM or PM kg^?1 soil), and cow and poultry manure extracts (2 g CME or PME kg^?1 soil) cultured with cannabis sativa. After eight weeks, a sequential extraction scheme was used to fractionate soil Pb and Cd into soluble-exchangeable (Sol-Exch), organic matter associated (AOM), and carbonates associated (ACar) forms. The addition of animal manures and their extracts increased the DTPA-extractable Pb and Cd in soil significantly. Soil Pb and Cd in Sol-Exch fraction were increased by manure applications. Both Pb and Cd in AOM fraction were increased by application of manures and their extracts. This increase was more obvious for Pb in application of cow and poultry manure extracts. The ACar chemical forms of Pb and Cd were also increased by application of manures and their extracts. The increases of Pb and Cd in Acar fraction was noticeable in soils treated with cow manure. Soil cultivation with cannabis sativa increased available, Sol-Exch, and AOM chemical forms of Pb in soil significantly compared to control soil. However, soil Pb and Cd in ACar fraction were decreased significantly by cannabis cultivation. The effect of cannabis cultivation on all of the Cd chemical forms (except on Sol-Exch) was similar to the results of Pb chemical forms. Plant cultivation had no significant effect on Cd in Sol-Exch chemical form.     

新疆焉耆盆地辣椒地土壤重金属污染及生态风险预警

从新疆加工辣椒主产地(焉耆盆地)采集105个辣椒地典型土壤样品,测定其中As、Cd、Cr、Cu、Mn、Ni、Pb和Zn等8种重金属元素的含量。采用污染负荷指数(Pollution load index,PLI)、潜在生态风险指数(Potential ecological risk index,RI)和生态风险预警指数(Ecological risk warning index,I_(ER))对辣椒地土壤重金属污染及生态风险进行评价。结果表明:(1)焉耆盆地辣椒地土壤Cd、Cr、Ni、Pb和Zn含量的平均值分别超出新疆灌耕土背景值的1.65、1.40、1.32、3.21、6.42倍。辣椒地土壤Pb和Zn呈现重度污染,Cd、Cr和Ni轻度污染,As、Mn和Cu无污染。(2)土壤PLI平均值为1.40,呈现轻度污染。各重金属元素单项生态风险指数从大到小依次为:Cd、Ni、As、Cu、Pb、Cr、Zn。土壤RI平均值为18.40,属于轻微生态风险态势,IER平均值为-4.78,属于无警态势;博湖县辣椒地污染水平、潜在生态风险程度与生态风险预警等级最高,焉耆县污染水平、潜在生态风险程度与生态风险预警等级最低。(3)辣椒地土壤As、Cd、Pb与Zn主要受到人类活动的影响,Cr、Cu、Mn和Ni主要受到土壤地球化学作用的控制。Cd是焉耆盆地辣椒地生态风险等级最高的重金属元素,研究区农业生产过程中要防范Cd的污染风险。