Implications from concentrations and isotopic data for Pb partitioning processes in soils

Lead concentrations and stable isotopic measurements were examined in the different chemical fractions of Czech forest soils to investigate the mechanisms of Pb partitioning. A method of selective sequential dissolution (SSD) was employed that distinguished between five different fractions: exchangeable, surface bound, organic matter, Fe-oxides, and silicates (non-labile).From an analysis of the concentrations and isotopic compositions associated with the different fractions, it is apparent that Pb in the deep Czech mineral soils is of predominantly natural origin and is primarily associated with silicates (69-81%) and Fe-oxides (11-19%). Natural Pb associated with surface bound and organic matter fractions in mineral soils accounts for only 7 to 15%. Anthropogenic Pb in the Czech soils is concentrated primarily in the organic horizons and is strongly associated with the surface-bound and organic matter fractions in which the proportion of total Pb is 33 to 50% and 23 to 47%, respectively.At high and low levels of contamination, Pb isotopic signatures within the labile fractions of the same soil samples are generally homogenous, although a degree of heterogeneity among these fractions is noted in samples of intermediate degrees of contamination. Such heterogeneity probably reflects different levels of natural and anthropogenic Pb mixing.Determination of the mass-normalized affinity of Pb to the primary components using solid-solution distribution coefficients suggests that in Czech forest soils, the order of affinity may be summarized as Fe-oxides > organic matter > silicates. A similar treatment of the data reported for semiarid Mediterranean soils indicates the prevailing order to be Fe-oxides > carbonates > organic matter > silicates. The general similarity of the behaviour of Pb with respect to the different soil components in both temperate and semiarid soils suggests that these orders of affinity may have wider significance for a variety of other soil types.     

Using atmospheric fallout to date organic horizon layers and quantify metal dynamics during decomposition

High concentrations of metals in organic matter can inhibit decomposition and limit nutrient availability in ecosystems, but the long-term fate of metals bound to forest litter is poorly understood. Controlled experiments indicate that during the first few years of litter decay, Al, Fe, Pb, and other metals that form stable complexes with organic matter are naturally enriched by several hundred percent as carbon is oxidized. The transformation of fresh litter to humus takes decades, however, such that current datasets describing the accumulation and release of metals in decomposing organic matter are timescale limited. Here we use atmospheric ²¹⁰Pb to quantify the fate of metals in canopy-derived litter during burial and decay in coniferous forests in New England and Norway where decomposition rates are slow and physical soil mixing is minimal. We measure ²¹⁰Pb inventories in the O horizon and mineral soil and calculate a 60-630 year timescale for the production of mobile organo-metallic colloids from the decomposition of fresh forest detritus. This production rate is slowest at our highest elevation (∼1000 m) and highest latitude sites (>63°N) where decomposition rates are expected to be low.We calculate soil layer ages by assuming a constant supply of atmospheric ²¹⁰Pb and find that they are consistent with the distribution of geochemical tracers from weapons fallout, air pollution, and a direct ²⁰⁷Pb application at one site. By quantifying a gradient of organic matter ages with depth in the O horizon, we describe the accumulation and loss of metals in the soil profile as organic matter transforms from fresh litter to humus. While decomposition experiments predict that Al and Fe concentrations increase during the initial few years of decay, we show here that these metals continue to accumulate in humus for decades, and that enrichment occurs at a rate higher than can be explained by quantitative retention during decomposition alone. Acid extractable Al and Fe concentrations are higher in the humus layer of the O horizon than in the mineral soil immediately beneath this layer: it is therefore unlikely that physical soil mixing introduces significant Al and Fe to humus. This continuous enrichment of Al and Fe over time may best be explained by the recent suggestion that metals are mined from deeper horizons and brought into the O horizon via mycorrhizal plants. In sharp contrast to Al and Fe, we find that Mn concentrations in decomposing litter layers decrease exponentially with age, presumably because of leaching or rapid uptake, which may explain the low levels of acid extractable Mn in the mineral soil. This study quantifies how metals are enriched and lost in decomposing organic matter over a longer timescale than previous studies have been able to characterize. We also put new limits on the rate at which metals in litter become mobile organo-metallic complexes that can migrate to deeper soil horizons or surface waters.     

Discussion on Tunis Soft Soil Sensitivity

In Tunis City, the sensitivity of the marine deposits at shallow depth (z = 0–20 m) varies significantly. The influence of the process of the leaching out of Tunis soft soil on its geotechnical parameters is a focal point in this research. This process leads finally to moderate levels of sensitivity for Tunis clays since it appears to happen in a two steps with increasing sensitivity. The “hard water” leaching out and the dispersive action of organic matter (humus) lead unexpectedly to higher but still moderate level of sensitivity as measured on many Tunis sites. These sensitivity variations result from the combination of leaching out with hard ground water and high content of organic matter. This sensitivity attracted our attention and remains of high interest for the study of the behaviour of the Tunis soft clay.     

The development of a multi-surface soil speciation model for Cd (II) and Pb (II): Comparison of two approaches for metal adsorption to clay fractions

The mobility of toxic metals in soils or sediments is of great concern to scientists and environmentalists since it directly affects the bioavailability of metals and their movement to surface and ground waters. In this study, a multi-surface soil speciation model for Cd (II) and Pb (II) was developed to predict the partition of metals on various soil solid components (e.g. soil organic matter (SOM), oxide mineral, and clay mineral). In previous study, the sorption of metal cations on SOM and oxide minerals has been evaluated by thermodynamically based surface complexation model. However, metal binding to soil clay fractions was normally treated in a simplistic manner: only cation exchange reactions were considered and exchange coefficient was assumed unity. In this study, the binding of metals onto clays was described by a two-site surface sorption model (a basal surface site and an edge site). The model was checked by predicting the adsorption behavior of Cd (II) and Pb (II) onto three selected Chinese soils as a function of pH and ionic strengths. Results showed that the proposed model more accurately predicted the metal adsorption on soils under studied condition, especially in low ionic strength condition, suggesting that adsorption of metals to soil clay fractions need to be considered more carefully when modeling the partition of trace elements in soils. The developed soil speciation model will be useful when evaluating the movement and bioavailability of toxic metals in soil environment.     

Distribution and origin of major and trace elements (particularly REE,U and Th) into labile and residual phases in an acid soil profile (Vosges Mountains,France)

A 7 step sequential extraction procedure has been conducted on a podzolic soil profile from the Vosges Mountains in order to determine the ability of several elements to be released to the environment. Very little Si, K and Al were extractable (<10% of the total soil concentration) but larger proportions (> 10% of the total soil concentration) of Ca, P, metals (Fe, Pb), REE and actinides (Th, U) could be leached. For each element, preferential binding sites can be recognized. High recovery of P and Ca in the acid soluble fraction (AS) suggests that phosphate minerals are highly involved in this step of the extraction. Organic matter appears to control the adsorption of Ca, Fe, Th, U and REE, even at depths in the soil profile where organic matter content is particularly low (0.5%). Weak acid leaching experiments (with HCl and acetic acid 0.001 N) were also performed in order to characterize the origin of the insoluble material in this soil profile. The leachable REE distributions indicate that a large part of the labile REE in the surface horizon has an atmospheric origin whereas at greater depth phosphate mineral (apatite) alteration is the main factor controlling REE release in the leachate. The study further suggests that adsorbed material holding actinides and REE are not strictly the same. So, caution should be taken when using REE as analogues for actinides in soils systems.     

Anthropogenic Pb accumulation in forest soils from Lake Clair watershed: Duchesnay experimental forest (Québec, Canada)

Mineral soil horizons (Ae, Bhf1, Bhf2, Bf, BC and C) were carefully collected from two podzolic soil profiles in the Lake Clair watershed (Québec) in order to assess anthropogenic trace metal accumulation. Petrographic and selective analyses were performed to establish the soil mineralogy and properties. Furthermore, a complete sequential extraction procedure has been applied to help understanding the complex chemical speciation of Pb in forest soils. Chemical speciation of Pb showed a strong vertical gradient: 85% of this metal is mainly partitioned in refractory minerals in the C-horizon whereas in the upper Bhf1 and Ae-horizons, less than 50% of Pb is associated with this fraction. In the Ae-horizon, for example, 35%, 30% and 12% of total Pb, respectively, is associated with the exchangeable, labile organic matter and amorphous Fe-Mn oxides fractions. The distribution of Pb and Cr in the studied forest soils mainly reflects progressive contamination of the watershed by anthropogenic atmospheric sources. The anthropogenic source is indicated by elevated Cr and Pb concentrations in the topsoil (Bhf and Ae) horizons and by strong negative correlation between ²⁰⁶Pb/²⁰⁷Pb ratios and total Pb concentrations. According to these isotopic values, penetration of anthropogenic Pb does not exceed 10 cm in both soil profiles. Below this depth, both Pb concentrations and isotopic ratios remain nearly constant and similar to values observed in pre-anthropogenic sediments from Lake Clair. These values are interpreted as the natural geochemical backgrounds of the watershed. Based on that behaviour, calculated anthropogenic Pb net inputs amounted to between 1.24 and 1.8 g/m².     

The use of 210Pb as a heavy metal tracer in the Susquehanna River system

Analysis of soil profiles and shallow ground water in the Susquehanna River basin, northeastern U.S.A., indicates that the atmospheric flux of ²¹⁰Pb is efficiently scavenged by the organic-rich horizons of the soils. This atmospherically supplied ²¹⁰Pb in soil profiles can only be lost from the system by soil erosion. Based on the annual sediment yield of the Susquehanna River and the excess ²¹⁰Pb concentration in particulate matter, a mean residence time of 2000 yr is calculated for metals similar to Pb in soil profiles.The West Branch of the Susquehanna River (WBSR) is strongly affected by acid mine drainage and is low in pH and high in dissolved ( <0.4 μm) ²¹⁰Pb, Fe and Mn. Along its course iron hydroxide is precipitating at a pH of between 4 and 4.5 and the ²¹⁰Pb supplied by the acid mine water is diminished by about 25% as a result of dilution. As the WBSR enters the Valley and Ridge Province of the Appalachians it has a ²¹⁰Pb concentration of ~ 0.2 dpm/l. At this juncture it receives a considerable influx of alkalinity from tributaries draining carbonate terranes, resulting in neutralization of the sulfuric acid and increase of the river pH to around 6.5–7. This pH adjustment is accompanied by the precipitation of Fe and Mn. Due to the slow rate of Mn removal from solution, the Mn precipitation extends a considerable distance down river from the point of acid neutralization. Analyses for ²¹⁰Pb in the river at points in or below the region of Mn precipitation show that ²¹⁰Pb is rapidly scavenged from solution onto suspended particles. From the data it is possible to calculate the removal rate of Pb from water in the presence of Fe and Mn hydroxides and other particles. At a pH of 4–4.5 Pb removal is nonexistent relative to the river flow rate, but at a pH of 6.5–7 the ²¹⁰Pb data indicate a residence time of <0.7 day for dissolved Pb.     

The form,distribution and mobility of arsenic in soils contaminated by arsenic trioxide,at sites in southeast USA

Soils from many industrial sites in southeastern USA are contaminated with As because of the application of herbicide containing As₂O₃. Among those contaminated sites, two industrial sites, FW and BH, which are currently active and of most serious environmental concerns, were selected to characterize the occurrence of As in the contaminated soils and to evaluate its environmental leachability. The soils are both sandy loams with varying mineralogical and organic matter contents. Microwave-assisted acid digestion (EPA method 3051) of the contaminated soils indicated As levels of up to 325 mg/kg and 900 mg/kg (dry weight basis) for FW and BH soils, respectively. However, bulk X-ray powder diffraction (XRD) analysis failed to find any detectable As-bearing phases in either of the studied soil samples. Most of the soil As was observed by scanning electron microscopy, coupled with energy dispersive X-ray spectroscopy (SEM/EDX), to be disseminated on the surfaces of fine-grained soil particles in close association with Al and Fe. A few As-bearing particles were detected in BH soil using electron microprobe analysis (EMPA). Synchrotron micro-XRD and X-ray absorption near-edge structure (XANES) analyses indicated that these As-rich particles were possibly phaunouxite, a mineral similar to calcium arsenate, which could have been formed by natural weathering after the application of As₂O₃. However, the scarcity of those particles eliminated them from playing any important role in As sequestration.     

Accumulation and distribution of Hg and 210Pb in superficial sediments from a coastal lagoon in the SE Gulf of California associated with urban-industrial and port activities

The Estero de Urías Lagoon (EUL) is an inner shelf barrier coastal lagoon, located in the Mexican Pacific Coast (SE Gulf of California). It is surrounded by Mazatlán City, one of the most important international tourist areas of Mexico. To provide a comprehensive reassessment of the concentration levels and spatial variability of Hg and ²¹⁰Pb in the EUL, 40 surface sediment samples were analyzed for several geochemical variables (e.g. grain size distribution, organic matter and reference element concentrations) that could explain the observed variability of Hg and ²¹⁰Pb. The Hg concentrations ranged from 23 to 214 ng g^?1, whereas ²¹⁰Pb activities varied from 20 to 56 Bq kg^?1. No defined distribution pattern was observed for Hg and ²¹⁰Pb concentrations in the lagoon and no evidence of a common atmospheric delivery route was observed. The sediments from EUL were found contaminated by Hg, and according to international guidelines 48 % of the sampling sites have concentrations that could be harmful to biota.     

Pollution of south of Tehran ground waters with heavy metals

The reuse of nutrients and organic matter in wastewater sludge via on agricultural lands application is a desirable goal. However, trace or heavy metals present in sludge pose the risk of human or phytotoxicity from land application. The aim of this research is possibility of ground water pollution of south of Tehran because of ten years irrigation with Ni, Cd and Pb borne waste water. For this purpose, 6 soil samples from southern parts of Tehran city and 2 ones from Zanjan city without lime and organic matter were selected. The soils differed in their texture from sandy to clayey. Each soil sample in duplicate and uniformly packed into PVC columns. Soil samples were irrigated with Cd, Pb and Ni-added wastewater. After irrigating, the columns were cut and the soils separated from sectioned pieces and their heavy metal concentrations (Pb, Cd and Ni) were measured by atomic absorption spectrophotometer by use of HNO₃ 4N solution. Because of high sorption capacity of these elements by soils, these metals were accumulated in surface layer of the soils. Movement in the soils without lime and organic matter were as low as other samples. Ni has had the most accumulation or the least vertical movement, and Pb the opposite ones.     

河北平原农田土壤重金属元素Pb、Hg地球化学行为的影响因素

土壤重金属元素地球化学行为是目前国内外研究的热点。研究显示重金属元素地球化学行为与土壤理化性质有密切关系。本文选择河北平原农田为研究区,采集了325个根系土样品,测定了Pb、Hg有效态含量,并探讨了影响其地球化学行为的主要因素。研究表明:(1)Pb、Hg水溶态和离子交换态与土壤p H值呈显著负相关关系,土壤酸化使Pb、Hg有效性增加,直接导致农作物中Pb、Hg含量增加,保持土壤p H值在弱酸性至弱碱性范围,防止土壤酸化,可以降低重金属危害。(2)土壤中有机质含量与Pb、Hg全量呈显著的正相关性,但与水溶态和离子交换态呈负相关。所以土壤中有机质的增加可以降低Pb、Hg元素水溶态和离子交换态含量。(3)随着土壤黏粒的增加,Pb、Hg水溶态和离子交换态含量降低,说明黏粒可以吸附一定量的重金属离子,与重金属元素Pb、Hg地球化学行为存在一定关系。土壤p H值、有机质、黏粒是控制重金属元素Pb、Hg地球化学行为的重要因素。     

天津市西郊富硒土壤地球化学特征和成因分析

为了查明天津市西郊富硒土壤的地球化学特征和成因,开展针对土壤-大气-水体-作物的调查研究工作。结果显示:研究区土壤Se元素平均值为0.66 mg/kg,是天津市土壤背景值的2.87倍,有83%为富硒土壤。土壤Se元素被颗粒状有机物质大量固定和吸附,富集于耕层土壤。耕层土壤Se元素与粗砂粒、细砂粒、Pb、Zn、Cd、Cu、Hg、N、P等指标显著正相关,与黏粒、粉粒、Na、K、Mg、As、CEC、pH等指标显著负相关。农民大量持续使用富含Se的有机肥是土壤Se元素显著富集的主要原因,占输入总通量的86.55%;大气沉降是次要原因,占13.35%。研究区土壤Se元素的年增加量为0.019 mg/kg,按2.77%的速度逐年增长。     

Metal ion binding to colloids from database to field systems

Nowadays, environmental problems related to soil pollution with heavy metals are numerous, therefore, it is important to understand metals behaviour in aquatic sediments and soils and to estimate their transfer. The fate of metals in the environment is closely related to their interactions with the major reactive compartments (organic matter, iron and manganese oxides, clays). The objective of this work is to develop an approach based on the combination of several models to study metal ion speciation in different environmental systems. Models used to describe the interactions of metals with the main reactive phases in the soil are CD-MUSIC (amorphous and crystallized iron oxides), NICA-Donnan (organic matter and manganese oxides) and cationic ion exchange model (clays). First, this work implies the definition of generic parameters to describe the interactions of the studied metals with iron and manganese oxides and part of this information is missing in the literature. Then, after a validation of the approach by comparison with analytical results, this multi-surface model is applied to test sites corresponding to one soil and two riverine environments.These new models give good predictions of the behaviour of major and trace metal ions even in heterogeneous systems characteristic of natural environment. The measured free metal concentrations in the solution are in agreement with those obtained from model calculations. In the case of the soil test site, the soil solution composition and speciation are predicted using the soil major constituents characteristics.     

Study of Carbon‐Bearing Particles in Ascending Geogas Flows in the Dongshengmiao Polymetallic Pyrite Deposit,Inner Mongolia,China

Samples of ascending geogas flow particles were collected on to SiN grids directly in the Quaternary sediments overlying the Dongshengmiao polymetallic pyrite deposit, China. Corresponding soil samples were collected in the surface of Dongshengmiao district at the same time. After pretreatment, these SiN grid samples were analyzed by transmission electron microscopy. The tests focused on the characteristics of particles including size, shape, chemical composition, structure and association. The results show that there are numerous carbon‐bearing particles in particulate samples of the ascending geogas flow. The particles contain organic matter, carbonate or carbonate mixed with other minerals. These carbon‐bearing particles generally contain metallic elements like Fe/Zn/Au/Cu/Pb. However, all of the soil particles do not contain elemental C and only consist of common elements (O, Na, Mg, Al, Si, Ca, Ti) just like the composition of earth crust. Through a comparison between the particles from different sources, the carbon‐bearing particles were found to come only from the deep earth and carried useful information about concealed deposits as they pass through the deep‐seated orebodies. Given the influences of organic matter on mineralization, the carbon‐bearing particle may provide information on the deposit genesis. Combining the use of geogas particle for prospecting with characteristics of large depth, and the carbon‐bearing materials' close spatial and genetic relationship with orebodies, we propose a new prospecting method based on the characteristics of carbon‐bearing particles, including morphology, size, chemical component and ultra‐microstructure. This approach could be applied to the exploration of deposits deep in the earth and abundant in carbon‐bearing matter. This approach can provide efficient and effective deposit exploration.     

A surface complexation and ion exchange model of Pb and Cd competitive sorption on natural soils

The bioavailability and fate of heavy metals in the environment are often controlled by sorption reactions on the reactive surfaces of soil minerals. We have developed a non-electrostatic equilibrium model (NEM) with both surface complexation and ion exchange reactions to describe the sorption of Pb and Cd in single- and binary-metal systems over a range of pH and metal concentration. Mineralogical and exchange properties of three different acidic soils were used to constrain surface reactions in the model and to estimate surface densities for sorption sites, rather than treating them as adjustable parameters. Soil heterogeneity was modeled with >FeOH and >SOH functional groups, representing Fe- and Al-oxyhydroxide minerals and phyllosilicate clay mineral edge sites, and two ion exchange sites (X⁻ and Y⁻), representing clay mineral exchange. An optimization process was carried out using the entire experimental sorption data set to determine the binding constants for Pb and Cd surface complexation and ion exchange reactions.Modeling results showed that the adsorption of Pb and Cd was distributed between ion exchange sites at low pH values and specific adsorption sites at higher pH values, mainly associated with >FeOH sites. Modeling results confirmed the greater tendency of Cd to be retained on exchange sites compared to Pb, which had a higher affinity than Cd for specific adsorption on >FeOH sites. Lead retention on >FeOH occurred at lower pH than for Cd, suggesting that Pb sorbs to surface hydroxyl groups at pH values at which Cd interacts only with exchange sites. The results from the binary system (both Pb and Cd present) showed that Cd retained in >FeOH sites decreased significantly in the presence of Pb, while the occupancy of Pb in these sites did not change in the presence of Cd. As a consequence of this competition, Cd was shifted to ion exchange sites, where it competes with Pb and possibly Ca (from the background electrolyte). Sorption on >SOH functional groups increased with increasing pH but was small compared to >FeOH sites, with little difference between single- and binary-metal systems. Model reactions and conditional sorption constants for Pb and Cd sorption were tested on a fourth soil that was not used for model optimization. The same reactions and constants were used successfully without adjustment by estimating surface site concentrations from soil mineralogy. The model formulation developed in this study is applicable to acidic mineral soils with low organic matter content. Extension of the model to soils of different composition may require selection of surface reactions that account for differences in clay and oxide mineral composition and organic matter content.     

Crystalline gold in soil and the problem of supergene nugget formation: Freezing and exclusion as genetic mechanisms

Many of the world's richest gold placer deposits now occur in cold regions despite differences in their climatic history. It therefore seems possible that there may be some fundamental connection between freezing climates and the local chemical behavior of gold in the weathering cycle. This hypothesis, along with the problematical occurrence of gold as euhedral crystals in arctic gravel and soil placers, has led me to review low temperature phenomena that may bear on the geochemistry of gold.Several effects which may influence the weathering of natural gold-bearing rocks, the chemical complexation of gold, and its subsequent mobility and deposition appear to be strongly connected with freeze action. The exclusion of dissolved solutes, solute gases, and particles from ice, subjects rock and soil minerals to increased corrosion from thin, unfrozen, adsorbed water films which remain at particle surfaces throughout the freezing of rocks and soils. The preferential exclusion of cations (over anions) from growing ice crystals creates charge separations and measurable current flow across waterice phase boundaries in freezing soil — a phenomenon which leads to troublesome seasonal electrolytic corrosion of pipelines buried in soil; this phenomenon may also favor the dissolution of normally insoluble metals such as gold during geologic time periods. The ice-induced accumulation of clays, organic acids, bacteria, and other organic matter at mineral surfaces may also speed chemical attack by providing a nearby sink of alternate cation-binding sites and hence rapid removal of liberated cations from solution. The latter mechanism may be operative in both the dissolution and redeposition of gold.These physical, chemical, and electrical effects are favorable to the dissolution of rocks (in addition to frost shattering) and to the dissolution, mobilization, and redeposition of gold and other noble metals and must therefore contribute significantly to the behavior of gold at low temperatures. The occurrence of large numbers of gold placer deposits in northern Canada, Alaska, and Siberia may thus be due in part to the low temperatures common to these regions.     

Mineralization of organic material and bacterial dynamics in Mississippi River plume water

Net remineralization rates of organic matter and bacterial growth rates were observed in dark-bottle incubation experiments conducted in July–August and February with water samples collected from sites in the Mississippi River plume of the Gulf of Mexico. Our objectives were to measure site-specific degradation rates of labile dissolved and particulate organic matter, quantify the potential importance of bacteria in these processes, and examine the kinetics of degradation over time. Unfiltered samples, and samples treated to remove (or dilute out) particles larger than bacteria, were enclosed in 9-1 bottles and incubated in the dark for 3–5 d. Respiration rates and inorganic compound accumulation rates were higher in summer than in winter and were highest in unfiltered surface samples at sites of intermediate salinities where phytoplankton were most abundant. The ratio of ammonium accumulation to oxygen removal in summer experiments suggested that the mineralized organic material resembled “Redfield” stoichiometry. Chemical fluxes were greater in bottles containing large (>1–3 μm) particles than in the bottles with these particles removed, but bacterial activities were generally similar in both treatments. These results suggest that particle consumers were an important component of total organic matter degradation. However, these experiments may have underestimated natural bacterial degradation rates because the absence of light could affect the production of labile organic substrates by phytoplankton. In agreement, with this hypothesis, bacterial growth rates tended to decrease over time in summer in surface plume waters where phytoplankton were abundant. In conjunction with other data, our results indicate that heterotrophic processes in the water column are spatially and temporally dependent on phytoplankton production.     

Uptake and recycling of lead by boreal forest plants: Quantitative estimates from a site in northern Sweden

As a consequence of deposition of atmospheric pollution, the lead concentration in the mor layer (the organic horizon) of remote boreal forest soils in Sweden is raised far above natural levels. How the mor will respond to decreased atmospheric pollution is not well known and is dependent on future deposition rates, downward migration losses and upward fluxes in the soil profile. Plants may contribute to the upward flux of lead by ‘pumping’ lead back to the mor surface through root uptake and subsequent litter fall. We use lead concentration and stable isotope (²⁰⁶Pb, ²⁰⁷Pb and ²⁰⁸Pb) measurements of forest vegetation to quantify plant uptake rates from the soil and direct from the atmosphere at two sites in northern Sweden; an undisturbed mature forest and a disturbed site with Scots pine (Pinus sylvestris) growing on a recently exposed mineral soil (C-horizon) containing a minimum of atmospherically derived pollution lead. Analyses of forest mosses from a herbarium collection (spanning the last ∼100 yr) and soil matrix samples suggest that the atmospheric lead deposited on plants and soil has an average ²⁰⁶Pb/²⁰⁷Pb ratio of 1.15, while lead derived from local soil minerals has an average ratio of ∼1.47. Since the biomass of trees and field layer shrubs has an average ²⁰⁶Pb/²⁰⁷Pb ratio of ∼1.25, this indicates that 70% ± 10% of the inventory of 1 ± 0.8 mg Pb m⁻² stored in plants in the mature forest originates from pollution. Needles, bark and apical stemwood of the pine growing on the disturbed soil, show lower ²⁰⁶Pb/²⁰⁷Pb ratios (as low as 1.21) than the roots and basal stemwood (having ratios > 1.36), which indicate that plants are able to incorporate lead directly from the atmosphere (∼50% of the total tree uptake). By partitioning the total uptake of lead into uptake from the atmosphere and different soil layers using an isotopic mixing model, we estimate that ∼0.03 ± 0.01, 0.02 ± 0.01 and 0.05 ± 0.01 mg Pb m⁻² yr⁻¹ (mean ± SD), is taken up from the mor layer, the mineral soil and the atmosphere, respectively, by plants in the undisturbed mature forest. These small fluxes, which are at least a magnitude lower than reported downward migration losses, suggest that plant uptake will not strongly prolong the self-cleaning rate of the mor layer.     

水稻土中重金属元素Cd、Pb的竞争吸附 ——以长株潭地区水稻土为例

对中国南方的3个水稻土样品进行了Cd、Pb单一离子和混合离子吸附特点的研究。结果表明,3个水稻土样品中Cd、Pb的吸附特点都相似,Langmuir等温方程可很好地描述Cd、Pb的吸附等温线。3个土壤样品中,有较高pH值和较低有机物、CEC浓度、粘土含量、高岭石含量的2个土壤样品对Cd、Pb有较大的吸附量,且其等温吸附拟合的最大吸附量(B)也较大。在两组分混合溶液中,尽管共存离子的存在影响了土壤对单一离子的吸附,同时土壤对Cd的吸附在一定程度上受影响的程度大,但3个土壤样品都表现出对Pb有强的吸附能力。在3个土壤样品中,Langmuir等温方程中Pb的健合能常数(K)都大于Cd的健合能常数(K),混合溶液中的K值高于单一溶液的K值,表明2种金属离子对吸附位点的竞争提高了特定吸附位点的保持力,使金属离子在土壤中特定位点的吸附更加坚固。     

Is there a chronological record of atmospheric mercury and lead deposition preserved in the mor layer (O-horizon) of boreal forest soils?

The organic horizon (the mor layer) of podzolized boreal forest soils has accumulated atmospheric fallout of mercury and lead over centuries, resulting in current concentrations close to levels where negative effects on soil biota are thought to occur. To what extent the pollution history is preserved in the stratigraphy of this horizon is not well known. In this study we asses whether the chronology of a large historic pulse of atmospheric pollution emitted from the Rönnskär smelter in northern Sweden, particularly between 1950 and 1980, is preserved within the stratigraphy of the mor layer, which is typically 5-cm thick. Vertical sub-sampling (?5 mm) of five mor profiles sampled along a 100-km pollution gradient away from the smelter are analyzed for mercury and lead concentrations, spheroidal carbonaceous particles from fossil fuel combustion (SCPs) and stable lead isotopes (²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁷Pb). Their vertical distribution is compared with the temporal variations in atmospheric inputs reconstructed for the last ∼100 years from analyses of an ombrotrophic peat core and a varved lake sediment core sampled within a distance of 50 km of the smelter. The mor profiles situated ?12 km from the smelter record the pollution history of the smelter. There is a 20 to 40-times enrichment of Hg, Pb and SCP at the transition in the O-horizon from the F- to H-layer compared to the basal part and a distinct peak in the ²⁰⁶Pb/²⁰⁷Pb ratio (∼1.22) in the F-layer. The mor profiles situated outside the historical contamination range of the smelter (80 and 100 km away) record no obvious influence from the Rönnskär smelter, instead their vertical ²⁰⁶Pb/²⁰⁷Pb profiles follow the general regional pollution history in northern Sweden. We conclude that the mor layer preserves a record of atmospheric Hg, Pb and SCP inputs and due to low leaching rates this organic horizon serves as a semi-archive of atmospheric Hg and Pb pollution. We stress the need of including this property in the existing ‘black-box’ models predicting the fate of Hg and Pb within contaminated boreal forest soils.