Isotopic Record of Lead Contamination in Alluvial Soils and Tree Rings on Recent Floodplains (Southern Québec, Canada)

Current and past industrial pollution leaves many traces in the environment, in particular along rivers in industrial and urban areas. The isotopic analysis of the lead found in soils and tree rings offers a kind of environmental archive for presenting a portrait of the pollutant distribution in the environment in both spatial and temporal terms. This study is an attempt to identify and compare the source of contamination found in soils and tree rings located along two rivers affected by pollution over several years. Specifically, the focus is on the pattern of lead concentrations and lead isotopic signatures (206Pb/207Pb, 208Pb/206Pb, and 206Pb/204Pb) detected in soils and tree rings located on polluted floodplains. The concentration of Pb in overbank sediments does not rise with the increasing distance downstream from the point source (mining area), suggesting that significant fluvial transport of the pollutant particles over 80 km is involved. For the soil profiles, Pb concentration levels range between 12.32 and 149.13 mg/kg, with the highest concentrations found at the base of the profiles (>1 m). For the lead isotope ratios in the soil profiles, the values obtained range from 0.851 to 0.872 (206Pb/207Pb), 2.081 to 2.111 (208Pb/206Pb), and 0.547 to 0.562 (206Pb/204Pb). The tree ring analysis of red ash (Fraxinus pennsylvanica Marsh.) shows average lead concentrations of 0.63 μg/g, and the lead values of all the tree specimens range between 0.03 and 11.38 μg/g. Pb concentrations varied greatly between the specimens in selected sites and lead isotope ratios in the tree rings showed a strong variability in the time series, particularly from 1945 to 1970. The greater number of variations in the lead concentration rates and isotopic ratios suggest that many more events associated with pollution and contamination have in fact occurred in this area. The study demonstrates the utility of combining stable isotope analyses (soils and tree rings) to examine the source and dispersion of contaminant Pb in fluvial systems by providing reliable and robust indicators for the detection of environmental changes on a local and regional scale.     

The Isotopic Composition of Anthropogenic Pb in Soil Profiles of Northern Germany: Evidence for Pollutant Pb from a Continent-wide Mixing System

Seventy-five samples of six soil profiles from forests on different substrates plus one next to a motorway were analyzed for the variation of Pb concentration and isotopic composition with depth. A substantial fraction of the anthropogenic Pb (peak concentrations between 74 and 300 ppm) is still stored in the organic top soil, and seldom penetrates deeper than 20–30 cm. In (²⁰⁸Pb/²⁰⁶Pb) vs. (²⁰⁷Pb/²⁰⁶Pb)-diagrams the Pb in the uppermost layers of the profiles plots on an excellent correlation line (R = 0.99) indicating essentially a two-component mixing system. Values for the dust on Scottish plants, Norwegian and Swiss bogs as well as for aerosols collected over the North Atlantic (data from the literature) plot on the same correlation line showing that the Pb was deposited from a continent-wide mixing system with two apparent end members: The radiogenic one is similar to geogenic Pb and could consist of contributions from certain European ore deposits and from different soil components (e.g. silicates and Fe-oxides), power plants and cement factories. The less radiogenic component must contain or consist of Pb from Proterozoic or even Archaic ore deposits. However, the sources of this Pb remain somewhat elusive. In any case, this isotopic pattern is so consistent all over Europe that the correlation line may serve as a line of reference for quasi normal or European Standard Lead Pollution (ESLP). The gasoline derived Pb in the soils is swamped by Pb of other provenances.     

Lead Concentrations,Isotope Ratios,and Source Apportionment in Road Deposited Sediments,Honolulu, Oahu,Hawaii

Anthropogenic contributions of lead to the urban environment havebeen dominated by combustion of leaded gasoline. A number of studies have used lead concentrations in road deposited sediments(RDSs) to infer automobile contributions. However, few studies have combined concentration data, enrichment ratios, and lead isotope ratio data into a comprehensive picture of lead contamination of road sediments. An urban, non-industrialized basin, in Oahu, Hawaii, was selected for investigation. Twenty RDSsamples were collected throughout the 11 km² system, with anundisturbed soil profile sampled to a depth of 30 cm to documentbackground lead levels.Median lead concentrations from a weak (cold) HCl digestion and a hot nitric acid digestion were 3 and 7 mg kg^-1 for thebackground soil, and 256 and 303 mg kg^-1 for RDSs. The median Pb enrichment ratio (HCl digestion) for RDSs was 129, witha range from 24 to 883. All the data collected point to a highlycontaminated environment.Lead isotope ratios from potential sources were examined relativeto those observed for RDSs in the system. Host geological rocks,paint, and long-range aerosol transport were ruled-out as significant sources based on an examination of isotope ratios andpotential loadings to road sediments. Leaded gasoline wasidentified as the major contributor to present-day road sedimentsbased on their radiogenic nature, with mean ²⁰⁶Pb/²⁰⁴Pb = 18.787 ± 0.096 (95% confidence interval), ²⁰⁷Pb/²⁰⁴Pb = 15.847± 0.074, ²⁰⁸Pb/²⁰⁴Pb= 38.836 ± 0.221, and ²⁰⁶Pb/²⁰⁷Pb = 1.184 ± 0.009. The contribution of gasoline additives to RDS for two periods, pre-1968 and post-1968, were estimated using ²⁰⁶Pb/²⁰⁷Pb ratios. The average contribution of post-1968 lead to RDSs was 59%, with a range from 32 to 81%. To explain the mixed age of lead in the RDSs, we suggest that erosional processes have mobilized sediment from roadside reservoirs in the basin that have accumulated automobile emissions primarily since the 1930s. The significant shift in useof radiogenic (J-type) ores, mostly from Missouri, USA, have allowed us to fingerprint and apportion lead in RDSs of thissystem.     

Investigation of Past and Present Multi-metal Input along Two Highways of British Columbia, Canada, Using Lead Isotopic Signatures

A multi-media monitoring field investigation, which included atmospheric, road sediment and soil samples, was carried out at two highway study sites to identify past and present Pb sources. Past Pb anthropogenic sources such as paint and leaded gasoline were linked to significant Pb accumulation in roadside soils at both sites through Pb isotopic analyses. This was achieved by identifying the distinct Pb isotopic composition in older versus newer Pb accumulation at different depths across the soil profile. Older Pb accumulations exhibited lower ²⁰⁶Pb/²⁰⁷Pb isotopic ratios, consistent with Canadian Pb-bearing ores, whereas newer Pb accumulations reflected a mixture of the ²⁰⁶Pb/²⁰⁷Pb ratios of road sediment samples, with the Pb isotopic signature of uncontaminated soil. Isotopic analyses were also helpful in identifying road sediment as an important current source of Pb in roadside soils, by comparing the isotopic signatures derived from road sediment and atmospheric dustfall. The known association of Pb with anthropogenic sources was used to indirectly relate other metals (Cu, Mn, Zn) to the same source by the Enrichment Ratio method. Significant positive correlations at the 90–95% confidence level were found between Cu, Zn and Pb Enrichment Ratios in roadside and dust deposition samples. Weaker correlations were found between Mn and Pb, at the highway study site with the least amount of traffic. However, correlations between these two metals were significant at the 90% confidence level for the busier highway site highlighting Mn potential anthropogenic source. An isotopic tracer study is suggested to further investigate the process of Mn redistribution in the environment due to exhaust fuel emissions. More research is needed regarding the potential impact from using a Mn-based fuel additive.     

Lead Isotopic and Metallic Pollution Record in Tree Rings from the Copperbelt Mining�CSmelting Area, Zambia

The composition of tree rings and soils was studied at several locations affected by smelting and transportation in the vicinity of Kitwe (Copperbelt, Zambia). The contents of cobalt (Co), copper (Cu), manganese (Mn), and lead (Pb) and the ²⁰⁶Pb/²⁰⁷Pb isotope ratios in the tree rings were interpreted in relation to potential sources of contamination such as smelter production, acidification of the environment, soil composition, raw material processing, and atmospheric suspended particulate matter (SPM). The highest Co contents in the tree rings correspond to maximum ore production in the mid-1970s. Acidification through SO₂ emissions is documented in the increased Mn contents from the mid-1980s. The isotopic composition of the tree rings of the studied tree species varies in the interval 1.16?C1.34 and the youngest parts of all the studied trees exhibit a low ²⁰⁶Pb/²⁰⁷Pb ratio (<1.17). The soil isotope composition varies in the range ²⁰⁶Pb/²⁰⁷Pb?=?1.18?C1.35. The Pb isotope composition in the soils and tree rings was formed by a combination of lithogenic Pb (²⁰⁶Pb/²⁰⁷Pb????1.3), Pb in processed ores (²⁰⁶Pb/²⁰⁷Pb????1.2), and SPM (automobile) Pb (²⁰⁶Pb/²⁰⁷Pb??1.1). As the soils in the distant region have high ²⁰⁶Pb/²⁰⁷Pb ratios (>1.3) in the whole profile and simultaneously the youngest parts of the tree rings of tree species growing in this soil have a low ²⁰⁶Pb/²⁰⁷Pb ratio (<1.17), it can be assumed that the Pb in the youngest parts of the tree species is derived from absorption of SPM Pb through the bark rather than root uptake. The absence of Pb with a low ²⁰⁶Pb/²⁰⁷Pb ratio in soils in the distant area is probably affected by fires in the herbaceous and bush undergrowth and plant litter, which prevents Pb from biomass from entering the soil and mobilize it back into the atmosphere.     

Fractional-Isotopic Composition of Lead Compounds in Soils of the Kologrivskii Forest Reserve

Isotopic composition of lead is a very sensitive indicator allowing us to determine even very low contamination of soils by this element, which is not noticeable from the change in its concentration against the background of the natural variability. Isotopic composition of loosely bound lead fractions (exchangeable and specifically sorbed) changes in soils of the Kologrivskii Forest State Natural Reserve under the impact of global or regional atmospheric transport and deposition of contaminants, though these soils are not subjected to the local technogenic pollution. The maximum portion of lead bound with the soil organic matter in the upper organic horizons reaches 75% of the total lead content. The portion of lead bound with iron and manganese (hydr)oxides increases down the soil profile. The portion of the residual fraction of lead also increases significantly down the soil profile. The most pronounced changes are observed for the ²⁰⁶Pb/²⁰⁷Pb ratio, which decreases from 1.20–1.24 to 1.15–1.18 under the impact of global pollution. The technogenic compounds of lead migrate down the soil profile. In the gray-humus gley alluvial soil (Fluvic Gleysol), low values of the ²⁰⁶Pb/²⁰⁷Pb ratio are observed for the exchangeable and specifically sorbed lead fractions in the entire soil profile, which is explained by the worse conditions for lead fixation in the profile of this soil in comparison with those in the podzolic soils.     

Quantification of anthropogenic lead in Slovak forest and arable soils along a deposition gradient with stable lead isotope ratios

Isotope ratios of Pb may provide the opportunity to determine the contribution of Pb from a point source to Pb concentrations in soil. Our objective was to quantify the contribution of anthropogenic Pb to total Pb and chemical Pb fractions in contaminated soil profiles with the help of ²⁰⁶Pb/²⁰⁷Pb isotope ratios. We sampled 5 forest and 5 arable Cambisols along a transect from a Cu smelter and determined Pb concentrations and ²⁰⁶Pb/²⁰⁷Pb isotope ratios in total digests of all horizons and in 7 chemical fractions of the A horizons. In the organic layer under forest, Pb concentrations decreased from 2155 mg kg^—1 at 1.1 km distance from the smelter to 402 mg kg^—1 at 8 km distance; in the Ap horizons, it decreased from 126 to 72 mg kg^—1. In the total digests, ²⁰⁶Pb/²⁰⁷Pb isotope ratios could be explained by simple mixing of smelter‐ and background‐Pb as indicated by the correlation between the inverse of the Pb concentration and the ²⁰⁶Pb/²⁰⁷Pb ratio (r = 0.93). The mean proportion of smelter‐Pb in soil horizons decreased with depth from 87% (Oi) to 21% (C) under forest and from 64% (A) to 30% (B) in the arable soils. The smelter‐Pb proportions in the B horizons ranged from 6 to 66% and were independent of the distance from the smelter indicating variable leaching rates. The ²⁰⁶Pb/²⁰⁷Pb ratios in the chemical fractions could not be explained by a simple mixing model. Thus, the ²⁰⁶Pb/²⁰⁷Pb ratios may be used to determine the contribution of anthropogenic Pb in total digests but not in chemical Pb fractions.     

A Comparison of Tree Rings and Peat Deposit Geochemical Archives in the Vicinity of a Lead Smelter

The content of Pb, Cd, Mn, K, Ca, Mg and ²⁰⁶Pb/²⁰⁷Pb isotope ratios in spruce tree rings (Picea abies) and peat cores from the Brdy Hills area (10 km W of the Pb smelter) were compared with those in spruce tree rings in the vicinity of the Pb smelter. Maximum Pb content in tree rings (up to 60 mg kg^?1 Pb) corresponds to a peak of metallurgical production in the mid 1970s and highest smelter emissions in the early 1970s. The Pb concentration curves obtained from peat deposit profiles closely correlate with the Pb concentrations in tree rings at both sampling sites. The small differences between the individual tree cores, with the identical general trend, may be attributed to the difference in distance from the smelter and the altitude of each sampling site. Similar behaviour to Pb can be observed for Cd and Ca. Lead isotope composition in tree rings (²⁰⁶Pb/²⁰⁷Pb ~1.143–1.174) is controlled mainly by the smelter emissions (²⁰⁶Pb/²⁰⁷Pb ~1.16–1.17), with the exception of the youngest segments from the more distant locality from the smelter, which yield isotopic signatures corresponding to car-emission Pb (²⁰⁶Pb/²⁰⁷Pb ~1.143–1.150). Higher content of Mn, Mg and Ca in tree rings corresponding to the 1970s and 1980s may be related to soil chemistry changes caused by acid deposition. In addition, an increase in K, Mg (and in some cases also Mn) in the youngest part of wood cores corresponds to the physiological processes in sapwood, and may be influenced by a decrease in Pb in organic soil horizons, which limited the cycling of basic inorganic nutrients.     

Lichens Used as Monitors of Atmospheric Pollution Around Agadir (Southwestern Morocco)—A Case Study Predating Lead-Free Gasoline

More than 30 epiphytic lichens, collected in Agadir (Morroco) and along a 150-km transect from the Atlantic Ocean eastward, were analyzed for their metal content and lead isotopic composition. This dataset was used to evaluate atmospheric metal contamination and the impact of the city on the surrounding area. The concentrations of Cu, Pb, and Zn (average ± 1 SD) were 20.9 ± 15.2 μg g⁻¹, 13.8 ± 9.0 μg g⁻¹, and 56.6 ± 26.6 μg g⁻¹, respectively, with the highest values observed in lichens collected within the urban area. The ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁷Pb ratios in the lichens varied from 1.146 to 1.186 and from 2.423 to 2.460, respectively. Alkyllead-gasoline sold in Morocco by the major petrol companies gave isotopic ratios of ²⁰⁶Pb/²⁰⁷Pb = 1.076–1.081 and ²⁰⁸Pb/²⁰⁷Pb = 2.348–2.360. These new, homogeneous values for gasoline-derived lead improve and update the scarce isotopic database of potential lead sources in Morocco, and may be of great value to future environmental surveys on the presence of lead in natural reservoirs, where it persists over time (e.g., soils and sediments). The interest of normalizing metal concentrations in lichens to concentrations of a lithogenic element is demonstrated by the consistency of the results thus obtained with lead isotopic ratios. Leaded gasoline contributed less than 50% of the total amount of lead accumulated in lichens, even in areas subject to high vehicular traffic. This strongly suggests that the recent banishment of leaded gasoline in Morocco will not trigger a drastic improvement in air quality, at least in Agadir.     

Trace metals in sediments and aquatic plants from the Xiangjiang River, China

Purpose

The metal concentrations and Pb isotopic composition in sediments and plants from the Xiangjiang River, China, were investigated to understand the contamination and potential toxicity of metals in sediments; to determine the accumulation and distribution of metals in plant tissues; and to trace the possible pollution source of Pb in sediments and plants.

Materials and methods

Sediments and plants were collected from 43 sampling sites in the study region. After sediments were air-dried and passed through a 63-??m sieve, they were acid-digested and DTPA-extracted for determination of total and bioavailable metals. The plants were separated into roots, leaves, and stems; dried; cut into pieces; and digested with HNO₃?CH₂O₂. Metals (As, Cd, Cr, Cu, Ni, Pb, and Zn) and Pb isotopic composition were analyzed by inductively coupled plasma-mass spectrometry.

Results and discussion

Maximum As, Cd, Cr, Cu, Ni, Pb, and Zn concentrations in sediments were 47.18, 55.81, 129.5, 161.6, 160.4, 430.7, and 1,098.8?mg?kg^?1, respectively. The bioavailable fractions of As, Cd, Cu, Pb, and Zn had significant linear relationship with their corresponding total contents in sediments while no significant relationship was observed between bioavailable and total contents of Cr and Ni. In general, plant tissues showed higher As, Cd, Cu, Pb, and Zn concentrations and lower Cr and Ni concentrations compared with sediments. The ²⁰⁶Pb/²⁰⁷Pb ratios decreased in the order of total > bioavailable > stems ?? leaves > roots. A strong linear correlation was observed between the ²⁰⁸Pb/²⁰⁶Pb and ²⁰⁶Pb/²⁰⁷Pb ratios of the plant tissues, sediments, and the possible pollution sources of Pb in the Xiangjiang River.

Conclusions

As, Cd, Cu, Pb, and Zn demonstrated higher contamination levels in sediments and plants compared with Cr and Ni. Cd had highest potential ecological risk. The Pb from anthropogenic sources with low ²⁰⁶Pb/²⁰⁷Pb ratios was preferentially associated with the bioavailable fractions in sediments and accumulated in roots. The Pb in plant tissues is mainly derived from the Pb in sediment and is taken up through the sediment-to-root pathway.     

Using isotopic tracers in lake sediments to assess atmospheric transport of lead in Eastern Canada

The isotopic composition of lead pollution in the environment provides information as to the source of emission. The ²⁰⁶Pb/²⁰⁷Pb ratio for Canadian industrial emissions (1.153±0.005) is significantly less than U.S. industrial emissions (1.213±0.008) making it possible to determine the relative contributions of emissions from both countries within Eastern North America by means of a simple isotopic mixing model. Profundal sediments in lakes chronicle contaminant inputs and are therefore useful monitors of environmental pollution. Surface sediment from 32 sediment cores across Quebec and Ontario, Canada were analyzed for ²⁰⁶Pb^/207Pb to ascertain the relative proportions of Pb emission from Canada and the U.S.A. Data show that U.S. contributions to the total lead burden in surficial sediments across much of southern Quebec and Ontario are often in excess of 50%. Local sources were particularly important in the Eastern Township region of Quebec which lies 200 km south east of the city of Montreal. The results are discussed in relation to the major sources of industrial lead emissions in North America.     

The assessment of point and diffuse metal pollution of soils from an urban geochemical survey of Sheffield, England

Abstract. A model of soil variability as a continuous background process with superimposed point contamination was applied to 569 measurements of metal concentrations (Cr, Ni and Pb) in the topsoils of Sheffield, England. Robust estimators of the variogram were shown to be required to describe spatial variation of the metal concentrations at most sampled locations. This is diagnostic of the presence of a contaminant process. Values of the standardized kriging error from the cross‐validation of each datum were used to identify spatial outliers for each metal. The ordinary kriged estimates of Cr, Ni and Pb were mapped after removing the outliers to estimate the background variation. Each of the 35 spatial outliers that occured in gardens have concentrations exceeding their Soil Guideline Value for residential land use with plant uptake, highlighting a potentially significant exposure pathway. The frequent observation of coal and furnace waste at these sites suggests that their dispersal, following domestic use and industrial processes, respectively, represents a significant point contaminant process. There was no evidence for spatial clustering of the point process. However, the spatial outliers of Cr and Ni showed a significant association with disturbed sites identified from historical land use maps, in part due to their prevalence in areas of historical steel manufacture. The magnitude of diffuse pollution for each metal in the urban soil was estimated by removing the spatial outliers and comparing robust measures of location with those from a survey of soils developed over the same parent materials in adjacent rural and peri‐urban environments. The Winsorized mean Pb concentrations in urban topsoil (203 mg kg^?1) were twice the value in the rural environment (101 mg kg^?1), highlighting a very substantial diffuse Pb load to urban soils. The equivalent estimated diffuse components in urban soils for Cr and Ni were, respectively, 25% and 14% higher than the rural soils.     

Contributions of different parent materials in soils developed from periglacial cover‐beds

Soils frequently develop from mixtures of different parent materials. We quantified the contributions of different parent materials to the substrate for recent soil development using trace metal concentrations and Pb isotope ratios as input data for end‐member mixing analyses (EMMAs). We examined six transects (320–775 m) at two sites in the Rhenish Slate Mountains. Soil types ranged from acid Cambisols to stagnic Luvisols developed from periglacial cover‐beds. Sixteen O, 11 A, 120 B and 10 C horizons were analysed for total trace metal concentrations and partly also ²⁰⁶Pb:²⁰⁷Pb ratios. Most metal concentrations in the B horizons were in the background range, except for Pb, which partly had elevated concentrations of up to 135 mg kg⁻¹. The depth distribution of metal concentrations and ²⁰⁶Pb:²⁰⁷Pb ratios suggested that metals deposited from the atmosphere had hardly reached the B horizons. A principal component analysis (PCA) of the trace element concentrations in the 120 B horizons identified four main metal sources of the B horizons, which we interpreted as bedrock (slate), loess, Laacher See tephra (LST) resulting from the last volcanic eruption in the Eifel mountains and ore veins. The slate was characterized by Cr and Zn, the loess by Zr, the LST by Nb and the ore veins by Pb. Based on EMMAs with four end‐members using two different sets of tracers (Set 1: concentration ratios of Zr:Cr, Nb:Cr, Pb:Cr, Set 2: Zr:Zn, Nb:Zn, and Pb:Zn), slate, loess and LST contributed, on average, 39–40, 22–24 and 37–38%, respectively, at Site 1 and 19–21, 53–63 and 18–26%, respectively, at Site 2. In contrast, the ore contribution was consistently estimated at 0%. An additional EMMA with two end‐members based on the ²⁰⁶Pb:²⁰⁷Pb ratios estimated the contribution of the ore at 0.02%. We conclude that EMMAs based on trace element concentrations and isotope ratios provide a tool for determining the contribution of different parent materials to the substrate from which soils develop, at least at a small regional scale and if an appropriate tracer that distinguishes all the considered substrates is found.     

Contamination of highly weathered urban soils in Uberlândia,Brazil

We determined heavy metal, polycyclic aromatic hydrocarbon (PAH), and polychlorinated biphenyl (PCB) concentrations in 18 topsoils of Uberlândia (420,000 inhabitants, Brazil) and in 3 rural topsoils. Concentrations of Al (11—124 g kg^—1) and Fe (13—109 g kg^—1) are large because of desilification. Concentrations of Cd (0.1—0.5 mg kg^—1), Cr (13—72), Cu (6—154), Mn (28—974), Ni (4—29), Pb (3—26), Zn (4—107), the sum of 20 PAHs (=Σ20PAHs:7—390 μg kg^—1), and the sum of 14 PCBs (=Σ14PCBs:0.05—1.25) are comparable to or below background concentrations in temperate soils except for Cu at two sites. More than 67% of the metals are strongly bound in Fe oxides and silicates; metals are more bioavailable in the urban than in the rural soils. The most abundant PAHs in the urban soils, on average, are naphthalene (19.0 ± 13.4% of Σ20PAHs) and the benzo(b+j+k)fluoranthenes (11.4 ± 6.7%); the most abundant PCBs are nos. 138 (23.3 ± 11.0% of Σ14PCBs) and 153 (14.3 ± 6.4%). The rural soils contain larger percentages of low molecular PAHs and up to tetra‒chlorinated PCBs than the urban soils. The different pollutant concentrations and patterns in the studied tropical compared with many temperate soils indicate different sources and fate.     

Tracing Pb Pollution Penetration in Temperate Podzols

We combine high‐resolution soil sampling with lead (Pb) analyses (concentrations and stable isotopes) in two temperate podzols, together with previous data obtained with selective Al and Fe dissolution techniques. We aim to assess how atmospheric Pb is incorporated into the soils during pedogenesis. Partial least squares modelling for Pb concentrations shows that the podzolization process has the largest effect on Pb concentration (80·3% of the variance). The proportion of inorganic secondary compounds, the input of fresh organic matter from the soil surface and the relative abundance of Fe versus Al are responsible for a small part of the Pb concentration variance. Lead isotopic composition (²⁰⁶Pb/²⁰⁷Pb ratios) depends on soil organic matter content either fresh/poorly humified (57·3% of the variance) or humified (24·7% of the variance). The Pb linked to inorganic compounds and the overall podzolization process play a minor role in isotopic signature (5·3 and 3·7% of the variance respectively). Soil pH appears to be the controlling variable of the different transport and retention mechanisms. The relatively low isotopic ratios observed in spodic horizons result from geogenic Pb released through the preferential dissolution of the isotopically distinct most weatherable minerals of the parent material in the eluvial horizons, which undergoes downward mobilization. An accurate knowledge of soil reactive components and formation mechanisms is essential to a correct diagnose of the scope of Pb pollution and a more effective design of remediation strategies. Copyright © 2017 John Wiley & Sons, Ltd.     

Historical change of soil Pb content and Pb isotope signatures of the cultural layers in urban Nanjing

Soils in urban areas are often artificially formed and preserved as cultural layers in which soil materials are mixed with artifacts. The vertical change of soil properties denotes the historical change of human activities, and therefore, urban soil can be considered as a record of history of urban development. We studied a deep profile of urban soil (600 cm) in Nanjing, China, by intensively sampling at every 5 cm. Soil samples were analyzed for lead content. Charcoal from several layers was found and was dated using ¹⁴C to recognize archaeological cultural layers that might be formed in different Chinese dynasties. Pb isotope ratios were determined by thermal ionization mass spectrometry (TIMS) technology. The study found that artificial deposition, i.e., the formation of cultural layer started about 1700 years ago and lasted until recently. All cultural layers above the original loess were heavily contaminated by Pb with total content varying from 100 mg kg^− 1 to more than 2000 mg kg^− 1. There were several historical periods in which Pb content peaked, indicating significant contamination by human activities, such as ancient ore smelting for various purposes and use of Pb-containing materials for handicraft manufacture. Various Pb isotope ratios of the cultural layers differed substantially from that of the original undisturbed loess in the deepest position. ²⁰⁶Pb/²⁰⁷Pb value decreased gradually from the bottom layer to top layer, although with occasional exceptions, indicating a long-lasting mixing of extraneous sources of Pb during the entire history since ca. 300 A.D. In comparison with the isotope ratios of lead ores of different sources and that of aerosols, it was illustrated that the source of Pb in cultural layers might come from lead ores of southern China in the earlier dynasties, while Pb from north China might have contributed to the Pb source in the more recent years, suggested by the lowering of ²⁰⁶Pb/²⁰⁷Pb ratio in the near-surface cultural layers. However, the impact of petrol burning on cultural layers was basically excluded, considering the relatively short history of petroleum use in this area.     

Assessment of soil contamination by potentially toxic elements in the aljustrel mining area in order to implement soil reclamation strategies

Land pollution due to past mining activities is a major environmental issue in many European countries. The Aljustrel mine (SW Portugal), located in the western sector of the Iberian Pyrite Belt (IBP) presents a negative visual and environmental impact as a consequence of the mining activity that has developed since the Roman era. Its impacts are also a restraint on the life quality of the population. The exposure of pyrite and other sulphides to air are responsible for the pollution observed in soils, surface water and stream sediments. This paper investigates the pollution load of potential toxic elements in soil samples collected around the Aljustrel mining area. The aim is to assess the levels of soil contamination with respect to average concentrations of toxic elements in the region and to understand the partitioning and availability of pollutants in the area. The results showed severe soil contamination (mainly As, Cd, Cu, Pb and Zn). The concentrations of As (up to 3936 mg kg⁻¹) and certain heavy metals (up to 5414 mg kg⁻¹ Cu, 61·6 mg kg⁻¹ Cd, 20 000 mg kg⁻¹ Pb and 20 000 mg kg⁻¹ Zn) are two orders of magnitude above the regional South Portuguese Zone (SPZ) background values. The median concentrations of As, Cd, Cu, Pb and Zn exceed the values established for world soils, the European Union, Portugal and Andalusia. The results suggest that the distribution patterns of Co, Cr and Ni element concentrations in the Aljustrel area are primarily influenced by the lithology and geochemistry nature of bedrock. The soil background of this geological domain is characterized by relatively high heavy metal contents, essentially derived from the parent rocks. Copyright © 2010 John Wiley & Sons, Ltd.     

河北板蓝根产地土壤-植物中镉铅汞砷含量特征及其污染评价

采用野外调查和室内分析相结合的方法,研究了河北省安国市和蔚县板蓝根产地土壤-植物中Cd、Pb、Hg、As含量特征及其在菘蓝中的累积特性,并对板蓝根产地土壤和草药中Cd、Pb、Hg、As污染状况进行了评价,为该地区安全、合理地发展中草药生产提供数据支撑和科学依据。结果表明,安国市和蔚县板蓝根产地土壤中重金属Cd、Pb、Hg、As含量差异不大,土壤重金属含量的变异系数在11.70%~97.65%。以《土壤环境质量标准》(GB 15618—1995)一级标准值进行评价,综合污染指数评价结果显示45%板蓝根种植区土壤Cd、Pb、Hg、As污染等级为警戒限,其他处于清洁水平;而以《土壤环境质量标准》二级标准值进行评价,种植区单项污染指数及综合污染指数结果均0.7,土壤环境清洁。此外,菘蓝地上部(大青叶)Cd、Pb、Hg、As平均含量分别为0.22 mg·kg~(-1)、0.89 mg·kg~(-1)、0.04 mg·kg~(-1)、0.25 mg·kg~(-1),对重金属的富集能力表现为CdHgPbAs;菘蓝地下部(板蓝根)Cd、Pb、Hg、As含量均值分别为0.14 mg·kg~(-1)、0.57 mg·kg~(-1)、0.04 mg·kg~(-1)、0.26 mg·kg~(-1),对重金属的富集能力表现为CdHgAsPb。所有菘蓝样品中Pb、Hg、As含量均未超出《药用植物及制剂进口绿色行业标准》(WM2—2001),大青叶9.09%样品中Cd超标,且Cd平均污染指数0.7,属警戒限污染等级。因此,在中药材GAP(良好的农业规范)产地环境质量评价时,除板蓝根产地土壤完全符合土壤环境质量二级标准外,也不应忽视板蓝根和大青叶吸收和累积重金属的自身特性。     

Distribution of anthropogenic lead estimated by Pb isotopic composition in the upper layers of soil from a mixed forest at Dinghushan, southern China

Purpose

The heavy metal lead (Pb) is toxic to living organisms. Forest soils are important sinks for heavy metals generated by human activities. The forest at Dinghushan of southern China has experienced long-term exposure to atmospheric pollutants from the Pearl River Delta (PRD). The objectives of this research were (a) to determine the vertical and temporal distribution of Pb in the forest soil at Dinghushan, (b) to determine whether dilute acid extraction could be used to identify anthropogenic sources of Pb in forest soil, and (c) to determine the main anthropogenic contributors to soil Pb.

Materials and methods

Lead concentrations and isotopes were measured in two sets of forest soil samples. One set consisted of archived samples from 0 to 20 cm depth collected annually from 1997 to 2010. The other set was collected throughout three profiles sampled at 5-cm intervals to the bedrock (85 cm depth) in 2011. The soil samples were air-dried, ground, and passed through a 100-mesh polyethylene sieve. Lead in the samples was digested with concentrated acid (HNO₃?+?HClO₄, 4:1?v/v) or extracted with dilute acid (1 M HCl with a soil/solution ratio of 1:10) and was measured with an inductively coupled plasma mass spectrometer.

Results and discussion

Concentrations of Pb obtained both by total digestion and dilute acid extraction decreased with soil depth in the profile samples and increased over time in the archived ones. Soils at 0–20 cm depth had Pb concentrations of more than twice of the local soil background value. In all soil samples, the ^206/207Pb ratios was lower and the ^206/204Pb, ^207/204Pb, and ^208/204Pb ratios were higher with the dilute acid extraction than with the strong-acid digestion, indicating that dilute acid extraction could be used to distinguish between anthropogenic and geogenic Pb. Comparison of the Pb isotope ratios in the samples with those in the main pollutants from the PRD indicated that coal combustion and industrial emission were the main contributors to the forest soil Pb at Dinghushan.

Conclusions

The forest soil (0–20 cm depth) at Dinghushan was contaminated by Pb. Dilute acid extraction could be used to identify anthropogenic Pb sources. From 1997 to 2010, the main contributors of anthropogenic Pb to the forest soil at Dinghushan were coal combustion and industrial emission. Measures that control Pb emission from coal combustion and industrial activity, changes in coal consumption, and re-adjustments of industry development in the PRD should reduce Pb contamination of forest soil.