Comparison of different methods for assessing heavy metal contamination in street dust of Xianyang City, NW China

Street dust is one of the important indicators that reflect the status of urban environmental pollution. There are many studies of heavy metals contamination of street dust in capital cities; however, little attention has been paid to this kind of study in medium cities, including China. The dust samples were collected in the district of traffic crossroads in Xianyang city, Shaanxi Province. Pb, Cd, Cu, Ni, Zn, Cr and Mn concentrations were determined using atomic absorption spectrometry (AAS). The results indicate that the concentrations of heavy metals are higher than the background values of soils in Shaanxi Province. The contamination level of heavy metals is assessed by potential ecological risk index (E _r), geoaccumulation index (I _geo), enrichment factor (EF) and pollution index (Pi). The low I _geo, EF, E _r, Pi and PI_n (integrated pollution index) for Mn in street dusts indicate an absence of distinct Mn pollution. The high EF, Pi and PI_n of Cu and Zn indicate that there is considerable Cu and Zn pollution. It is suggested that more attention should be paid to heavy metals contamination of Cu and Zn. The assessment results of Pi and PI_n suggest that Pb, Ni and Cr present strong pollution; however, their EFs indicate that they cause moderate pollution and their I _geo indicates that they are unpolluted to moderately polluted. The contamination class value with different assessing methods is of the order: Pi ≈ PI_n > EF > I _geo > E _r.     

Contamination assessment and health risk of heavy metals in dust from Changqing industrial park of Baoji,NW China

The contents of Co, Cr, Cu, Mn, Ni, Pb and Zn in the dust samples collected from Changqing industrial park of Baoji city, NW China, were measured by XRF, while As and Hg in the dust samples were analyzed by AFS. Geo-accumulation index (I _geo), pollution index (PI) and integrated pollution index (IPI) were calculated to evaluate the heavy metal contamination level of dust. The health risk due to exposure to heavy metals in dust was analyzed by the Health Risk Assessment Model of US EPA. The results show that the arithmetic means of As, Co, Cr, Cu, Hg, Mn, Ni, Pb and Zn are 23.3, 16.4, 1591.8, 178.2, 0.243, 346.5, 40.2, 1,586.2 and 1,918.8 mg kg^?1, respectively, which are higher than the background values of Shaanxi soil, especially for Cr, Cu, Hg, Pb, and Zn. The mean values of I _geo reveal the order of Pb > Zn > Cr > Hg > Cu > As > Co > Ni > Mn. The high I _geo of Cr, Cu, Hg, Pb and Zn in dust indicates that there is considerable pollution from Cr, Cu, Hg, Pb and Zn, while the low I _geo of As, Co, Mn and Ni presents no pollution in dust. The assessment results of PI support the results of I _geo, and IPI indicates heavy metals in dust polluted seriously. The health risk assessment shows that ingestion of dust particles is the route for exposure to heavy metals from dust, followed by dermal adsorption. Exposure to As, Cr and Pb from dust may pose a potential health threat to children and adults. The risk of cancer from As, Co, Cr and Ni due to dust exposure is low.     

Contamination and ecological risk assessment of heavy metals in street dust of Tehran,Iran

Heavy metals are introduced in human tissue through breathing air, food chain and human skin. They can cause damage to the nervous system and internal organs. In the present study, sixty street dust samples were collected from the central area of Tehran and were digested in the laboratory to determine the content of Zn, Ni, Cd, Cr, Cu and Pb, using inductively coupled plasma optical emission spectrometry (ICP-OES). The level of contamination with the analyzed metals was determined according to the following indices: geo-accumulation index (I _geo), enrichment factor (EF), pollution index (PI), integrated pollution index (IPI) and potential ecological risk index (RI). The average concentration of heavy metals found was in the order of Zn > Cu > Pb > Ni > Cr > Cd. The average I _geo values for Cd, Cr, Cu, Ni, Pb and Zn were 1.53, ?1.88, 2.68, ?0.67, 1.62 and 2.70, respectively. Among the investigated heavy metals, zinc and copper had the maximum average EF values and were placed into the “very severe enrichment” class. Potential ecological risk factor (E _r) also indicated that Cd had the highest risk, and it was classified as of considerable potential ecological risk. Therefore, it is necessary to pay more attention to the appearance of Cd in the human environment. The calculated potential ecological risk index values also illustrated that the street dust samples presented a “moderate ecological risk.” The calculated IPI values showed that the pollution levels of the street dust samples ranged from high to extremely high.     

Assessment of trace metal and rare earth elements contamination in rivers around abandoned and active mine areas. The case of Lubumbashi River and Tshamilemba Canal,Katanga, Democratic Republic of the Congo

Active and abandoned mine activities constitute the sources of deterioration of water and soil quality in many parts of the world, particularly in the African Copperbelt regions. The accumulation in soils and the release of toxic substances into the aquatic ecosystem can lead to water resources pollution and may place aquatic organisms and human health at risk. In this study, the impact of past mining activity (i.e., abandoned mine) on aquatic ecosystems has been studied using ICP-MS analysis for trace metals and Rare Earth Elements (REE) in sediment samples from Lubumbashi River (RL) and Tshamilemba Canal (CT), Katanga, Democratic Republic of the Congo (DRC). Soil samples from surrounding CT were collected to evaluate trace metal and REE concentrations and their spatial distribution. The extent of trace metal contamination compared to the background area was assessed by Enrichment Factor (EF) and Geoaccumulation Index (I_geo). Additionally, the trace metal concentrations probable effect levels (PELs) for their potential environmental impact was achieved by comparing the trace metal concentrations in the sediment/soil samples with the Sediment Quality Guidelines (SQGs). Spearman's Rank-order correlation was used to identify the source and origin of contaminants. The results highlighted high concentrations of trace metals in surface sediments of CT reaching the values of 40152, 15586, 610, 10322, 60704 and 15152 mg kg⁻¹ for Cu, Co, Zn, Pb, Fe and Mn, respectively. In the RL, the concentrations reached the values of 24093, 2046, 5463, 3340, 68290 and 769 mg kg⁻¹ for Cu, Co, Zn, Pb, Fe and Mn, respectively. The ΣREE varied from 66 to 218 and 142–331 mg kg⁻¹ for CT and RL, respectively. The soil samples are characterized by variable levels of trace metals. The EF analysis showed “extremely severe enrichment” for Cu and Co. However, no enrichment was observed for REE. Except for Mo, Th, U, Eu, Mo, Ho and Tm for which Igeo is classified as “moderately polluted and/or unpolluted”, all elements in different sites are classified in the class 6, “extremely polluted”. The trace metal concentrations in all sampling sites largely exceeded the SQGs and the PELs for the Protection of Aquatic Life recommendation. Cu and Co had positive correlation coefficient values (r = 0.741, P < 0.05, n = 14). This research presents useful tools for the evaluation of water contamination in abandoned and active mining areas.     

Metal contamination and solid phase partitioning of metals in the stream and bottom sediments in a reservoir receiving mine drainage

This study was conducted to assess the anthropogenic impact on metal concentrations in the bottom sediments of the Juam reservoir, Korea, and in stream sediments in its catchment, and to estimate the potential mobility of selected metals (Fe, Mn, Cu, Ni, Pb and Zn) using sequential extraction. A comparison of the metal concentrations in the stream sediments with mean background values in sediments collected from first- or second-order creeks shows that Pb, Cu and Ni are the most affected by anthropogenic inputs. The ²⁰⁶Pb/²⁰⁷Pb ratios of the bottom and core sediments (means: 1.2320 ± 0.0502 and 1.2212 ± 0.0040, respectively) suggest that Pb contamination is mainly due to the waste discharge of abandoned coal and metal mines rather than industrial and airborne sources. Considering the proportion of metals bound to the exchangeable, carbonate and reducible fractions, the comparative mobility of metals is suggested to decrease in the order Mn > Pb > Zn > Ni > Fe ≫ Cu.     

Assessment of heavy metal contamination levels of street dust in the city of Lublin,E Poland

Heavy metals are constantly emitted into the environment and pose a major threat to human health, particularly in urban areas. The threat is linked to the presence of Cd, Cr, Cu, Ni, Pb, and Zn in street dust, which consists of mineral and organic particles originating from the soil, industrial emitters, motor vehicles, and fuel consumption. The study objective was to determine the level of street dust contamination with trace metals in Lublin and to indicate their potential sources of origin. The analyses were carried out with an energy-dispersive X-ray fluorescence spectrometer. The sampling sites (49) were located within the city streets characterised by varying intensity of motor traffic. The following mean content values and their variation (SD) were determined: Cd: 5.1?±?1.7 mg kg^?1, Cr: 86.4?±?23.3 mg kg^?1, Cu: 81.6?±?69.2 mg kg^?1, Ni: 16.5?±?3.9 mg kg^?1, Pb: 44.1?±?16.4 mg kg^?1, and Zn: 241.1?±?94.6 mg kg^?1. The level of pollution was assessed with several widely used geochemical indices (geoaccumulation index, enrichment factor, pollution index, index of ecological risk, and potential ecological risk index). For most of the indices, the mean (median) values are arranged in the following manner: Zn?>?Cu(or Cd)?>?Pb?>?Ni?>?Cr. In general, street dust in Lublin does not show pollution with Cr, Ni, and Pb. I_geo and EF indices show moderate levels for Cu, Cd, and Zn; their presence in street dust is linked with anthropogenic factors (motor traffic). A significant threat is posed by Cd, and more than half of the samples show considerable pollution with cadmium (median for the index of ecological risk: 151). The spatial pattern of indices and the results of statistical analyses (CA, PCA) indicate three groups of elements: (1) Cr and Ni: natural origin; (2) Pb: mixed origin; and (3) Cd, Cu, and Zn: anthropogenic origin (mainly motor vehicle traffic). Higher content values for metals of anthropogenic origin in street dust indicate that it is a source of pollution of soil and air in the city.     

Correlations between metals in tree-rings of Prosopis julifora as indicators of sources of heavy metal contamination

Heavy-metals (Cu, Pb and Zn) in tree-ring sequences of Prosopis juliflora, a tree species native to arid environments, were analyzed by ICP-MS. The tree-ring sequences were obtained from three specimens growing in an urban area previously reported as contaminated by the activity of a Cu smelter facility. The metal found in highest concentration in the wood was Zn, with concentrations up to 120 mg/kg and an enrichment factor up to 26; followed by Cu (up to 9.6 mg/kg, enrichment factor up to 8.6) and Pb (up to 1.4 mg/kg, enrichment factor up to 3). By assessing the correlation between different metal concentration trends, it was possible to infer two main pollution sources: vehicle traffic and Cu smelter emissions. Vehicle traffic is indicated by a correlation between Pb and Zn over time within individual trees, whereas contamination from the Cu-smelting facility is indicated by a correlation of Cu over time between trees. In tree A there was a significant within-tree correlation between Pb and Zn concentration trends (r = 0.856, P < 0.001), whereas Cu showed no correlation with the other metals. For tree B, there were no within-tree correlations between these metals, but when comparing the concentration–time trends between trees A and B, there was a significant correlation for Cu (r = 0.768, P < 0.01). The tree-ring sequence from tree C showed significant within-tree correlation for Cu:Zn (r = 0.430, P < 0.01) and for Pb:Zn (r = 0.753, P < 0.001). The highest enrichment values were found in tree A, located along the path of the growing-season dominant wind direction from the smelter facility, and not in the tree growing closer to the smelter (tree C), suggesting that the smelter’s emissions are dispersed to longer distances through the tall chimneys, attenuating the impact to the area directly closest to the smelter facility. It is concluded that Prosopis juliflora appears as a good bioindicator based on its metal accumulation capacity and lack of metal mobility among tree rings, thus providing information on the chronology and sources of heavy-metal pollution in urban and industrial areas.     

Metal speciation in coastal marine sediments from Singapore using a modified BCR-sequential extraction procedure

The chemical speciation of heavy metals (Cd, Cr, Cu, Ni, Pb and Zn) in marine sediments from two coastal regions of Singapore (Kranji in the NW, and Pulau Tekong in the NE) was determined using the latest version of the 3-step sequential extraction procedure, as described by the European Community Bureau of Reference (1999). To obtain a mass balance, a fourth step, i.e., digestion and analysis of the residue was undertaken using a microwave-assisted acid digestion procedure. The total content of all metals except for Pb in sediments was greater in Kranji than in Pulau Tekong. All metals, except Cd were more mobile and bio-available in Kranji, where metals were present at higher percentages in the acid-soluble fractions (the most labile fraction). In sediments from Kranji, the mobility order of the heavy metals studied was Cd > Ni > Zn > Cu > Pb > Cr, whereas sediments from Pulau Tekong showed the same order for Cd, Ni, Pb and Cr, but had a reverse order for Cu and Zn (Cu > Zn). The highest percentages of Cr, Ni and Pb were found in the residual fractions in both Kranji (78.9%, 54.7%, 55.9%, respectively) and Pulau Tekong (82.8%, 77.3%, 62.2%, respectively), meaning that these metals were strongly bound to the sediments. Results are consistent with findings from Barcelona, Spain where similar results for Cr and Ni have also been reported for marine sediments. The sum of the 4 steps (acid-soluble + reducible + oxidizable + residual) was in good agreement with the total content, which implies that the accuracy of the microwave extraction procedure in conjunction with the GFAAS analytical method is assured.     

Contamination assessment of copper,lead, zinc and chromium in dust fall of Jinan,NE China

To assess the pollution of heavy metal in dust fall, nine dust fall samples were collected during the heating period and non-heating period from Jinan, a city in northeastern China. The samples were analyzed for Cu, Pb, Zn and Cr and the contamination level of heavy metals was assessed on the basis of the geo-accumulation index (I _geo). The results indicated that all of the four investigated metals accumulated significantly in the dust fall of Jinan, and the metal concentrations were much higher than background values. During the heating period, the mean values for Cu, Pb, Zn and Cr in the dust fall were 354.9, 688.5, 2,585.5 and 478.6 mg kg⁻¹. During the non-heating period, the mean values for Cu, Pb, Zn and Cr in the dust fall were 228.2, 518.2, 1,933.9 and 96.3 mg kg⁻¹, respectively. The I _geo values calculated based on background values revealed that the contamination level of heavy metal in the dust fall ranges from moderately contaminated to heavily contaminated, and it mainly originates from traffic and industry. In this work, the dust fall residue compared to the standard reference was also chosen as the background value to calculate the I _geo value. This method is useful for situations in which the background value is difficult to obtain.     

Assessment of heavy metals contamination in deposited street dusts in different urbanized areas in the city of Ma’an, Jordan

190 Street dust samples were collected from nine different localities including high traffic (desert highway), moderate traffic (city center), light traffic (minor streets), residential streets, school gardens, hospital and health centers, industrial sites, parks and background sites (control) of Ma’an area. The concentrations of Fe, Zn, Ni, Pb, Mn, Cu and Cd were analyzed by flame atomic absorption spectrophotometer to assess and to compare road dust contamination levels of metals among the different types of urban environment. The results showed that dust samples from the urban and industrial site contained significant levels of the metals studied compared to the values obtained from the background site. The variation in concentration of the heavy metals determined from different locations was in the decreasing order as: industrial > high traffic > parks > moderate traffic > hospital and health centers > school gardens > light traffic > background sites. The mean concentrations of the metals were in the order of C _Fe > C _Zn > C _Ni > C _Pb > C _Mn > C _Cu > C _Cd where C is the concentration of these metals in solution. Enrichment factor calculations indicated that Cd, Pb, Zn and Ni were highly enriched. Fossil fuel combustion, wear of brake lining materials, traffic emissions and several industrial processes are considered the main sources of these metals. Assessment of the contamination level in dust sample was estimated based on the geoaccumulation index (I _geo), the pollution index, and integrated pollution index (IPI). The values of IPI are in the following order: Pb > Zn > Cu > Ni > Cd > Mn. All the indices for the metals under consideration were either low or corresponded to middle level of contamination. The use of factor analysis showed that anthropogenic activities seem to be the responsible source of contamination for metals in dust samples.     

Partitioning and mobility of trace metals in the Blesbokspruit: Impact assessment of dewatering of mine waters in the East Rand,South Africa

A suite of trace metals was analyzed in water and sediment samples from the Blesbokspruit, a Ramsar certified riparian wetland, to assess the impact of mining on the sediment quality and the fate of trace metals in the environment. Limited mobility of trace metals was observed primarily because of their high partition coefficient in alkaline waters. Nickel was most mobile with a mean K_d of 10^3.28 L kg⁻¹ whereas Zr was least mobile with a mean K_d of 10^5.47 L kg⁻¹. The overall trace metal mobility sequence, derived for the Blesbokspruit, in increasing order, is: Zr < Cr < Pb < Ba < V < Cu < Zn < Sr < Mn < U < Mo < Co < Ni. Once removed from the solution, most trace metals were preferentially associated with the carbonate and Fe–Mn oxide fraction followed by the exchangeable fraction of the sediments. Organic C played a limited role in trace metal uptake. Only Cu was primarily associated with the organic fraction whereas Ti and Zr were mostly found in the residual fraction. Compared to their regional background, Au and Ag were most enriched, at times by a factor of 20–400, in the sediments. Significant enrichment of U, Hg, V, Cr, Co, Cu and Zn was also observed in the sediments.The calculated geoaccumulation indices suggest that the sediments are very lightly to lightly polluted with respect to most trace metals and highly polluted with respect to Au and Ag. The metal pollution index (MPI) for the 20 sampled sites varied between 2.9 and 45.7. The highest MPI values were found at sites that were close to tailings dams. Sediment eco-toxicity was quantified by calculating the sediment quality guideline index (SQG-I). The calculated SQG-I values (0.09–0.69) suggest that the sediments at the study area have low to moderate potential for eco-toxicity.     

Geology,geochemistry, and geochronology of the Wangjiazhuang porphyry–breccia Cu(–Mo) deposit in the Zouping volcanic basin,eastern North China Block

The Wangjiazhuang porphyry–breccia Cu(–Mo) deposit is located in the Zouping volcanic basin, western Shandong Province. Seven molybdenite samples yield a Re–Os weighted mean age of 127.8 ± 0.7 Ma (2σ), which is identical within error to the zircon weighted mean ²⁰⁶Pb/²³⁸U age of 128.3 ± 1.3 Ma (2σ) determined for quartz monzonite samples. The host rock is characterized by high concentrations of K₂O (4.26–4.53 wt.%), Na₂O (4.97–5.76 wt.%), LILEs and LREEs, and high Mg# (> 40), and low concentrations of HFSEs and HREEs, with K₂O/Na₂O ratios of 0.76–0.88. The quartz monzonite also has high Sr/Y (69.9–112.5) and (La/Yb)_N (22.0–30.0) ratios, similar to adakitic rocks worldwide. Relatively low initial ⁸⁷Sr/⁸⁶Sr ratios (0.70549–0.70556), high ε_Nd(t) values (2.58–3.06), high radiogenic Pb [(²⁰⁶Pb/²⁰⁴Pb)i = 18.3424–18.4606, (²⁰⁷Pb/²⁰⁴Pb)_i = 15.5692–15.5985, (²⁰⁸Pb/²⁰⁴Pb)_i = 38.1714–38.2734] and high zircon ε_Hf(t) values (− 2.1 to + 4.3) indicate that the magma was likely derived from the partial melting of subducted oceanic crust which then reacted with the peridotitic mantle wedge. Both the breccia and porphyry ores have a narrow range of δ³⁴S (− 4.8 to + 2.1‰) and Pb isotopic compositions (²⁰⁶Pb/²⁰⁴Pb = 18.295–18.402, ²⁰⁷Pb/²⁰⁴Pb = 15.551–15.573, and ²⁰⁸Pb/²⁰⁴Pb = 38.215–38.331), suggesting that the ore metals were extracted primarily from the quartz monzonite or similar source. Subduction of the Paleo-Pacific slab during the Early Cretaceous resulted in the formation of the Wangjiazhuang quartz monzonite and associated Cu(–Mo) deposit in western Shandong Province.     

Net alkalinity and net acidity 2: Practical considerations

The pH, alkalinity, and acidity of mine drainage and associated waters can be misinterpreted because of the chemical instability of samples and possible misunderstandings of standard analytical method results. Synthetic and field samples of mine drainage having various initial pH values and concentrations of dissolved metals and alkalinity were titrated by several methods, and the results were compared to alkalinity and acidity calculated based on dissolved solutes. The pH, alkalinity, and acidity were compared between fresh, unoxidized and aged, oxidized samples.Data for Pennsylvania coal mine drainage indicates that the pH of fresh samples was predominantly acidic (pH 2.5–4) or near neutral (pH 6–7); ≈ 25% of the samples had pH values between 5 and 6. Following oxidation, no samples had pH values between 5 and 6.The Standard Method Alkalinity titration is constrained to yield values >0. Most calculated and measured alkalinities for samples with positive alkalinities were in close agreement. However, for low-pH samples, the calculated alkalinity can be negative due to negative contributions by dissolved metals that may oxidize and hydrolyze.The Standard Method hot peroxide treatment titration for acidity determination (Hot Acidity) accurately indicates the potential for pH to decrease to acidic values after complete degassing of CO₂ and oxidation of Fe and Mn, and it indicates either the excess alkalinity or that required for neutralization of the sample. The Hot Acidity directly measures net acidity (= −net alkalinity). Samples that had near-neutral pH after oxidation had negative Hot Acidity; samples that had pH < 6.3 after oxidation had positive Hot Acidity. Samples with similar pH values before oxidation had dissimilar Hot Acidities due to variations in their alkalinities and dissolved Fe, Mn, and Al concentrations. Hot Acidity was approximately equal to net acidity calculated based on initial pH and dissolved concentrations of Fe, Mn, and Al minus the initial alkalinity. Acidity calculated from the pH and dissolved metals concentrations, assuming equivalents of 2 per mole of Fe and Mn and 3 per mole of Al, was equivalent to that calculated based on complete aqueous speciation of Fe^II/Fe^III. Despite changes in the pH, alkalinity, and metals concentrations, the Hot Acidities were comparable for fresh and most aged samples.A meaningful “net” acidity can be determined from a measured Hot Acidity or by calculation from the pH, alkalinity, and dissolved metals concentrations. The use of net alkalinity = (Alkalinity_measured − Hot Acidity_measured) to design mine drainage treatment can lead to systems with insufficient Alkalinity to neutralize metal and H⁺ acidity and is not recommended. The use of net alkalinity = −Hot Acidity titration is recommended for the planning of mine drainage treatment. The use of net alkalinity = (Alkalinity_measured − Acidity_calculated) is recommended with some cautions.     

Using cocrystallization coefficients of isomorphous admixtures for determination of element concentrations in ore-forming solutions (by the example of Mn/Fe ratio in magnetite)

The cocrystallization coefficient of Mn and Fe (D_Mn/Fe) in magnetite crystals is determined in hydrothermal-growth experiments with internal sampling at 450 and 500 °C and 100 MPa (1 kbar). It is weakly dependent on temperature in the studied PT-region and is constant over a wide range of Mn/Fe values. This permits using the magnetite composition as an indicator of Mn/Fe in the fluid under equilibrium: (Mn/Fe)_aq ≈ 100 (Mn/Fe)_mt. Since Mn is often a macrocomponent of the fluid and a microcomponent of magnetite, local analysis of fluid inclusions for Mn might help to determine Fe even in iron minerals. This will permit evaluation of the contents of other ore metals if the D_Me/Fe values are known. For fine crystals (< 0.1–0.2 mm) with low contents of Mn (< 0.01–0.02%), it is necessary to take into account the fractionation of Mn into the surficial nonautonomous phase, in which its content can reach several percent. Comparison of these data with earlier data on the distribution of Mn in the system magnetite–pyrite–pyrrhotite–greenockite–hydrothermal solution shows that D_Mn/Fe remains constant in the presence of sulfur and sulfides. Precipitation of magnetite, in which Mn is a compatible admixture, cannot affect radically Mn/Fe in the solution because of the low D_Mn/Fe value. This effect is still more unlikely for pyrrhotite and pyrite, in which Mn is an incompatible admixture. The most probable mechanism of Mn fractionation into the solid phase is crystallization of FeOOH at lower temperatures. This is indirectly supported by the strong fractionation of Mn into the nonautonomous oxyhydroxide phase on the surface of magnetite crystals. The necessity of a more rigorous validation of “the new Fe/Mn geothermometer for hydrothermal systems” is substantiated.     

S,Pb, and Sr isotope geochemistry and genesis of Pb–Zn mineralization in the Huangshaping polymetallic ore deposit of southern Hunan Province,China

The Huangshaping Pb–Zn–W–Mo polymetallic deposit, located in southern Hunan Province, China, is one of the largest deposits in the region and is unique for its metals combination of Pb–Zn–W–Mo and the occurrence of significant reserves of all these metals. The deposit contains disseminated scheelite and molybdenite within a skarn zone located between Jurassic granitoids and Carboniferous sedimentary carbonate, and sulfide ores located within distal carbonate-hosted stratiform orebodies. The metals and fluids that formed the W–Mo mineralization were derived from granitoids, as indicated by their close spatial and temporal relationships. However, the source of the Pb–Zn mineralization in this deposit remains controversial.Here, we present new sulfur, lead, and strontium isotope data of sulfide minerals (pyrrhotite, sphalerite, galena, and pyrite) from the Pb–Zn mineralization within the deposit, and these data are compared with those of granitoids and sedimentary carbonate in the Huangshaping deposit, thereby providing insights into the genesis of the Pb–Zn mineralization. These data indicate that the sulfide ores from deep levels in the Huangshaping deposit have lower and more consistent δ³⁴S values (− 96 m level: + 4.4‰ to + 6.6‰, n = 13) than sulfides within the shallow part of the deposit (20 m level: + 8.3‰ to + 16.3‰, n = 19). The δ³⁴S values of deep sulfides are compositionally similar to those of magmatic sulfur within southern Hunan Province, whereas the shallower sulfides most likely contain reduced sulfur derived from evaporite sediments. The sulfide ores in the Huangshaping deposit have initial ⁸⁷Sr/⁸⁶Sr ratios (0.707662–0.709846) that lie between the values of granitoids (0.709654–0.718271) and sedimentary carbonate (0.707484–0.708034) in the Huangshaping deposit, but the ratios decreased with time, indicating that the ore-forming fluids were a combination of magmatic and formation-derived fluids, with the influence of the latter increasing over time. The lead isotopic compositions of sulfide ores do not correlate with sulfide type and define a linear trend in a ²⁰⁷Pb/²⁰⁴Pb vs. ²⁰⁶Pb/²⁰⁴Pb diagram that is distinct from the composition of the disseminated pyrite within sedimentary carbonates and granitoids in the Huangshaping deposit, but is similar to the lead isotopic composition of sulfides within coeval skarn Pb–Zn deposits in southern Hunan Province. In addition, the sulfide ores have old signatures with relative high ²⁰⁷Pb/²⁰⁶Pb ratios, suggesting that the underlying Paleoproterozoic basement within southern Hunan Province may be the source of metals within the Huangshaping deposit.The isotope geochemistry of sulfide ores in the Huangshaping deposit shows a remarkable mixed source of sulfur and ore-forming fluids, and the metals were derived from the basement. These features are not found in representative skarn-type Pb–Zn mineralization located elsewhere. The ore-forming elements (S, Pb, and Zn) from the granitoids made an insignificant contribution to sulfide precipitation in this deposit. However, the emplacement of granitoids did provide large amounts of heat and fluids to the hydrothermal system in this area and extracted metals from the basement rocks, indicating that the Jurassic magmatism associated with the Huangshaping deposit was crucial to the Pb–Zn mineralization.     

Contemporary lead concentration and stable lead isotope ratio distribution in forest moss across the Czech Republic

Lead concentrations and stable lead isotopes (²⁰⁴Pb, ²⁰⁶Pb, ²⁰⁷Pb, ²⁰⁸Pb) were measured in forest moss samples (Pleurozium schreberi or Scleropodium purum) collected at 273 sites across the Czech Republic during 2010. Continuously decreasing median Pb concentrations in moss were documented over the last two decades: 1995: 11 mg/kg, 2000: 5.66 mg/kg, 2005: 4.94 mg/kg and 2010: 2.85 mg/kg. Several local anomalies have decreased in scale, the overall regional distribution patterns remained, however, the same. The regional Pb isotope ratio distributions show that the ratios show little variation for a large central part of the country and provide the large-scale background isotope ratios for the Czech Republic of about ²⁰⁴Pb/²⁰⁶Pb = 0.0550, ²⁰⁶Pb/²⁰⁷Pb = 1.167, ²⁰⁶Pb/²⁰⁸Pb = 0.478 and ²⁰⁷Pb/²⁰⁸Pb = 0.409 for 2010. This background Pb isotope ratio signal in moss has been locally (900–7500 km²) modified by specific Pb isotopic ratio signals caused by deposition of Pb emissions from known local anthropogenic Pb emission sources, such as industrial combustion of local coal, and a variety of industrial enterprises (metallurgical, engineering and glass works). At some sites where mining of uranium and polymetallic ores took place the moss samples show also a locally specific Pb isotope signal. The in terms of area affected largest deviations in the Pb-isotope ratios, e.g., in the Bohemian Massif, may be due to the input of geogenic dust.     

Contamination and potential mobility assessment of heavy metals in urban soils of Hangzhou,China: relationship with different land uses

Concentration and distribution of heavy metals (Cd, Cu, Pb and Zn) in urban soils of Hangzhou, China, were measured based on different land uses. The contamination degree of heavy metals was assessed on the basis of pollution index (PI), integrated pollution index (IPI) and geoaccumulation index (I _geo). The 0.1 mol l⁻¹ HCl extraction procedure and gastric juice simulation test (GJST) were used to evaluate the potential mobility and environmental risk of heavy metals in urban soils. The average concentration of Cd, Cu, Pb and Zn in urban soils was measured at 1.2 (with a range of 0.7–4.6), 52.0 (7.4–177.3), 88.2 (15.0–492.1) and 206.9 (19.3–1,249.2) mg kg⁻¹, respectively. The degree of contamination increased in the order of industrial area (IA) > roadside (RS) > residential and commercial areas (RC) > public park and green areas (PG). The PIs for heavy metals indicated that there is a considerable Cd, Cu, Pb and Zn pollution, which originate from traffic and industrial activities. The IPI of these four metals ranged from 1.6 to 11.8 with a mean of 3.5, with the highest IPI in the industrial area. The assessment results of I _geo also supported that urban soil were moderately contaminated with Cd and to a lesser extent also with Cu, Pb and Zn. The IP and I _geo values reveal the pollution degree of heavy metal was the order of Cd > Pb > Zn ≈ Cu. It was shown that mobility and bioavailability of the heavy metals in urban soils increased in the order of Cd > Cu > Zn ≈ Pb. Owing to high mobility of Cd and Cu in the urban soils, further investigations are needed to understand their effect on the urban environment and human health. It is concluded that industrial activities and emissions from vehicles may be the major source of heavy metals in urban contamination. Results of this study present a rough guide about the distribution and potential environmental and health risk of heavy metals in the urban soils.     

Constraints of C–O–S–Pb isotope compositions and Rb–Sr isotopic age on the origin of the Tianqiao carbonate-hosted Pb–Zn deposit,SW China

The Tianqiao Pb–Zn deposit in the western Yangtze Block, southwest China, is part of the Sichuan–Yunnan–Guizhou (SYG) Pb–Zn metallogenic province. Ore bodies are hosted in Devonian and Carboniferous carbonate rocks, structurally controlled by a thrust fault and anticline, and carried about 0.38 million tons Pb and Zn metals grading > 15% Pb + Zn. Both massive and disseminated Pb–Zn ores occur either as veinlets or disseminations in dolomitic rocks. They are composed of ore minerals, pyrite, sphalerite and galena, and gangue minerals, calcite and dolomite. δ³⁴S values of sulfide minerals range from + 8.4 to + 14.4‰ and display a decreasing trend from pyrite, sphalerite to galena (δ³⁴S_pyrite > δ³⁴S_sphalerite > δ³⁴S_galena). We interpret that reduced sulfur derived from sedimentary sulfate (gypsum and barite) of the host Devonian to Carboniferous carbonate rocks by thermal–chemical sulfate reduction (TSR). δ¹³C_PDB and δ¹⁸O_SMOW values of hydrothermal calcite range from –5.3 to –3.4‰ and + 14.9 to + 19.6‰, respectively, and fall in the field between mantle and marine carbonate rocks. They display a negative correlation, suggesting that CO₂ in the hydrothermal fluid was a mixture origin of mantle, marine carbonate rocks and sedimentary organic matter. Sulfide minerals have homogeneous and low radiogenic Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb = 18.378 to 18.601, ²⁰⁷Pb/²⁰⁴Pb = 15.519 to 15.811 and ²⁰⁸Pb/²⁰⁴Pb = 38.666 to 39.571) that are plotted in the upper crust Pb evolution curve and overlap with that of Devonian to Carboniferous carbonate rocks and Proterozoic basement rocks in the SYG province. Pb isotope compositions suggest derivation of Pb metal from mixed sources. Sulfide minerals have ⁸⁷Sr/⁸⁶Sr ratios ranging from 0.7125 to 0.7167, higher than Sinian to Permian sedimentary rocks and Permian Emeishan flood basalts, but lower than basement rocks. Again, Sr isotope compositions are supportive of a mixture origin of Sr. They have an Rb–Sr isotopic age of 191.9 ± 6.9Ma, possibly reflecting the timing of Pb–Zn mineralization. C–O–S–Pb–Sr isotope compositions of the Tianqiao Pb–Zn deposit indicate a mixed origin of ore-forming fluids, which have Pb–Sr isotope homogenized before the mineralization. The Permian flood basalts acted as an impermeable layer for the Pb–Zn mineralization hosted in the Devonian–Carboniferous carbonate rocks.     

Heavy metal contamination in dust from kindergartens and elementary schools in Xi’an,China

Concentrations of As, Ba, Co, Cr, Cu, Mn, Ni, Pb, V, and Zn in campus dust from kindergartens and elementary schools in Xi’an, China, were analyzed using X-ray fluorescence spectrometry and heavy metal contamination levels were assessed based on the geoaccumulation index (I _geo), enrichment factor (EF) and numero synthesis pollution index (NSPI). The results indicate that, in comparison with Shaanxi soil, dust samples have elevated metal concentrations as a whole, except for V, Mn, Ni, and As. The assessment results of I _geo and EF indicate that V, Mn, Ni, and As in campus dust are uncontaminated, while Ba and Cr are uncontaminated to moderately contaminated, and Co, Cu, Pb, and Zn are moderately to strongly contaminated. The NSPI results show that most dust samples presented heavily contaminated by heavy metals. More attention should be paid to heavy metal contamination of campus dust from kindergartens and elementary schools of Xi’an.     

Geochronology and geochemistry of Mesozoic mafic–ultramafic complexes in the southern Liaoning and southern Jilin provinces,NE China: Constraints on the spatial extent of destruction of the North China Craton

LA–ICP–MS zircon U–Pb ages, geochemical and Sr–Nd–Pb isotope data are presented for mafic–ultramafic complexes from the southern Liaoning–southern Jilin area with the aim of determining the nature of the Mesozoic lithospheric mantle and to further constrain the spatial extent of destruction of the North China Craton (NCC). The complexes consist of olivine-websterite, gabbro, dolerite, and gabbro-diorite. Zircons from the complexes show typical zoning absorption, are euhedral–subhedral in shape, and yield high Th/U ratios (1.23–2.87), indicating a magmatic origin. Zircon U–Pb age data indicate that they formed in the Early Cretaceous (129–137 Ma). Geochemically, they have SiO₂ = 44.3–49.8%, MgO = 6.8–26.5%, Cr = 102–3578 ppm, and Ni = 31–1308 ppm, and are characterized by enrichment in large ion lithophile elements (LILEs) and light rare earth elements (LREEs), and depletion in high field strength elements (HFSEs) and heavy rare earth elements (HREEs), as well as a wide range of Sr–Nd–Pb isotopic compositions [(⁸⁷Sr/⁸⁶Sr)i = 0.70557–0.71119; ε_Nd (t) = ?5.4 to ?20.1; (²⁰⁶Pb/²⁰⁴Pb)i = 15.13–17.85; Δ7/4 = ?11.49 to 16.00; Δ8/4 = 102.64–203.48]. Compared with the southern Liaoning mafic–ultramafic rocks, the southern Jilin mafic–ultramafic rocks have high TiO₂ and Al₂O₃ contents, high ε_Nd (t) values, low (La/Yb)_N values, low initial ⁸⁷Sr/⁸⁶Sr ratios, and low radiogenic Pb isotopic compositions. These findings indicate that the primary magmas of the southern Jilin complexes were derived from lithospheric mantle that was previously metasomatized by a melt derived from the delaminated ancient lower crust, whereas the primary magmas of the southern Liaoning complexes originated from partial melting of a lithospheric mantle source that was previously modified by melt derived from the broken-off Yangtze slab. Therefore, the lateral extent of the NCC destruction should include the southern Liaoning–southern Jilin area.