Contamination of Zn, Pb and Cd in topsoil in Katowice-Szopienice (southern Poland) as a result of 180 years of metal smelting: environmental implications

Based on phase geochemistry and Re-Os isotopic ratios, an exotic (in oceanic setting) K-rich silicate melt, named kimberlite-type, has been claimed as the metasomatising agent interacting with subcontinental lithospheric mantle (SCLM) fragments beneath the Cape Verde Archipelago. On the basis of textural features and major and trace element chemistry, key geochemical indicators able to discriminate percolation at depth of this exotic melt from infiltration of the host magma in Cape Verde mantle xenoliths have been constrained. Cape Verde Type A lherzolites and harzburgites show evidence of dissolution of the primary phases (mainly pyroxenes), the presence of large patches of secondary mineral (and glass) assemblages, and do not show textural evidence of host basalt infiltration. Cape Verde Type A mantle xenoliths frequently contain almost pure K-feldspar (An3.8–8.8, Ab6–24, Or72–89) in the secondary mineral assemblage. They have an anomalously high K content (up to 0.49 wt%), and a K/Na ratio generally >1, with respect to Cape Verde peridotites clearly affected by host basalt infiltration (Type B samples). The dichotomy between Na and K observed in the two textural types suggests that the Na- alkaline host basalt (K/Na<1), which infiltrated at low pressure, was able to modify the whole rock Na content of the xenoliths (Type B samples). In turn, a completely different K-rich alkaline melt, which interacted at depth with the peridotite, imposed its alkali ratio (K/Na>1) to the bulk composition and formed the Type A xenoliths. The kimberlite-type metasomatic agent, which reacted with the Cape Verde peridotite assemblage (manly orthopyroxenes) in those regions where the mantle xenoliths are entrapped in the host basalt (P=17Kb; T=1092°C), reasonably tends towards SiO2-saturated K-rich basic magmas (lamproite-type?) with K-feldspars as the “liquidus” phase. Isotopic data on separate clinopyroxenes, do not contribute to discriminate between metasomatism and infiltration processes, but certainly concur to reinforce the hypothesis that a fragment of SCLM domain has been preserved during the opening of the Atlantic Ocean, forming K-rich undersaturated silicate melts which percolate the peridotite matrix. Whole rock major and trace element and isotopic geochemistry alone would not contribute to the interpretation of the processes occurring in the mantle xenolith. The most reliable tool would be an in situ mineral (and glass) study, which would be valid for Cape Verde mantle xenoliths and others. Small melting degree undersaturated silicate melts percolating at depth are olivine-saturated and may form, by reaction and dissolution of pyroxene, Type A olivine without substantially modifying the original Fe/Mg peridotite ratio. By contrast, at low pressure (< 1.5 GPa)/high temperature regimes, olivine silicate melts infiltrating the mantle xenoliths form Type B olivine, whose Fe/Mg ratios will be controlled by fractionation. Mantle diopsides interact (at depth) with undersaturated silicate melts, re-arranging the most fusible elements in a new diospide composition: Type A cpx. By contrast, diopsides which interact with melts at progressively lower pressure, react and are locally rearranged in a new chemical structure, able to accommodate the high diffusive elements (i.e. Fe and Ti): Type B aegirine-augites. Fe3+ in spinel is a key element to investigate the processes acting on Cape Verde mantle xenoliths. As a metasomatic product, secondary chromian spinel tends towards a Fe3+ buffered compositon, mainly depending on pressure and chemistry of the magma. A decompression system is able to change the percolation regime from porous flow to open conduct. At this stage, the chromian spinel would be the low pressure phase able to accommodate larger amounts of Fe3+. Type A glasses have exceptionally high K2O content and when associated with K-feldspars, they are buffered at ~ 9 K2O wt%, in a silica range of 55.7-66.8 wt%. By contrast, Type B glasses follow a hypothetical major element trend towards the host basanites. In conclusion, the compositional features (in particular major elements) of minerals and glasses in relation to their chemical behaviour in mantle systems, is the most efficient tool to distinguish metasomatism-related (Type A) from infiltration-related (Type B) samples and consequently to place the mantle xenoliths in a correct genetic framework.

Metal tolerance of Rhizobium meliloti isolated from heavy-metal contaminated soils

Effectiveness of thermal treatment on Pb recovery and Cl removal from sintering dust

Since the 12th century in the Silesian-Cracovian area, lead, litharge, and silver have been produced by the pyrometallurgical processing of Pb-Ag-Zn ore. Slags and soils contaminated with heavy metals (Zn, Pb, Cd, Fe, Mn, As) were the subject of this research. Samples were collected during archaeological works in the area of early medieval metallurgical settlement. The main goals of the analyses (Scanning Electron Miscroscopy-Energy Dispersive Spectroscopy (SEM-EDS), Electron Probe Microanalyzer (EPMA), X-ray diffraction (XRD), Atomic Absorption Spectroscopy (AAS)) were the determination of the mineralogical composition of furnace batches and smelting temperatures and conditions. In soils, the anthropogenic phases enriched in Pb, Zn, Fe, Mn, P, and primary minerals like goethite, ferrihydrite, sphalerite, galena, smithsonite, minrecordite, cerussite, gypsum, anglesite, jarosite, and hemimorphite were identified. The soil from former metallurgical settlements contained up to 1106 mg·kg−1 Pb, 782 mg·kg−1 Zn, 4.7 mg·kg−1 Cd in the fine fraction. Much higher heavy metal concentrations were observed in the waste products of ore rinsing, up to 49,282 mg·kg−1 Pb, 64,408 mg·kg−1 Zn, and 287 mg·kg−1 Cd. The medieval smelting industry and Pb-Ag-Zn ore processing are marked by highly anomalous geochemical pollution (Pb, Zn, Cd, Fe, Mn, Ba) in the topsoil. The methods of mineralogical investigation, such as SEM-EDS or EMPA, can be used to identify mineralogical phases formed during metallurgical processes or ore processing. Based on these methods, the characteristic primary assemblage and synthetic phases were identified in the area polluted by medieval metallurgy and mining of Pb-Ag-Zn ores, including MVT (Mississippi Valley Type) deposits. The minerals distinguished in slags and the structural features of metal-bearing aggregates allow us to conclude that batches have included mostly oxidised minerals (PbCO3, ZnCO3, CaZn(CO3)2, FeOOH), sulfides (PbS and ZnS) and quartz (SiO2). The laboratory experiment of high-temperature heating of the examined slags showed that smelting temperatures used in the second half of 13th century were very high and could have reached up to 1550 °C. The results indicate, that geochemical and mineralogical methods can be used to obtain important information from archaeological sites, even after archaeological work has long ceased.

The contribution of the milling, smelting, and refining of sulfide ores to Hg emissions and to Hg byproduction is not adequately quantified in a global context. In this study, we estimate Hg emissions from the pyrometallurgical treatment of Cu, Pb, and Zn sulfide ores. We base our calculations on quantities processed and Hg content in Cu, Pb, and Zn concentrates, derived from unique global databases on smelter feed and production. In 2005, about 275 tons of Hg were emitted globally to the atmosphere from Cu, Pb, and Zn smelters. Nearly one-half was emitted from Zn smelters and the other half equally divided between Cu and Pb smelters. Most Hg was emitted in China, followed by the Russian Federation, India, and South Korea. Global emission factors were 5.81, 15.71, and 12.09 g of Hg ton(-1) of metal for Cu, Pb, and Zn smelters, respectively. Calculations indicate that Hg abatementtechnologies applied to flue gases may have recovered 8.8 tons and 228 tons Hg from Pb and Zn smelters, respectively, most of which was probably sold as a byproduct. In conclusion, Hg emitted from processing copper, lead, and zinc ores has been largely underestimated in Hg emission inventories. Reducing these emissions may be one of the most economical measures to reduce global Hg emissions.

The Tuy River basin, located in north-central Venezuela with an annual average temperature of 27°C and precipitation of 140 cm, was selected to conduct a geochemical study of bottom sediments, with the object of establishing the natural and human influences in the abundance and distribution of Fe, Mn, Cr, Co, Cu, Ni, Pb, Zn and organic carbon. The basin is lithologically divided into two sub-basins, north and south. The north sub-basin drains a iow-grade metasedimentary terrain with a population density of 800 persons km(-2) and approximateiy 600 industrial sites, while the south sub-basin in underlain by metavolcanic and ultramafic rocks, with a population density of less than 10 persons km(-2).Stream bottom sediment samples (150) were collected during the years of 1979-1986 in 16 unpolluted sites and 13 polluted sites. The sediments were air dried at room temperature and sieved through a 120 stainless steel mesh (125 μm). Samples of grain size smaller than 125 μm were analysed, the heavy metals being determined by atomic absorption spectrometry and the organic carbon (Corg) by dry combustion.The higher concentrations of heavy metals and organic carbon found in the pristine areas were in the south sub-basin, especially in those areas with higher annual precipitation and tropical forest. This indicated that the metavolcanic and ultramafic rocks yield higher concentrations of heavy metals than the metasedimentary rocks. It was also noted that the higher concentrations of Cr and Ni are associated with the ultramafic rocks. The results obtained from the sediment samples collected in the polluted sites showed that the elements Pb, Zn and Corg are enriched up to 4 times as a result of ail the human activities taking place in the basin. Organic carbon is an excellent indicator of domestic wastewater, Pb and Zn are good indicators of the automotive traffic and industrial effluents. The concentrations of each heavy metal did not show any significant correlation with grain size fractions; however, the concentration of organic carbon did show a negative correlation with grain size. The lithological, climatic and vegetation influence in the abundance of heavy metals and organic carbon in stream sediments clearly indicates the necessity of establishing background levels for the area under study when carrying out studies in environmental geochemistry.

In many natural and anthropogenically affected environments, alteration of galena produces thermodynamically more stable secondary lead phases. These secondary minerals control the mobility of the toxic heavy metal lead in water. These textural, paragenetic, and stability relations have not been investigated in detail in the literature yet. An extensive petrographic study of 41 thin sections of weathered, zoned galena and adjacent country rock from the Schwarzwald mining area, southwest Germany, is presented. The observed textures were evaluated using PHREEQC fluid path modeling and sequences of stable secondary mineral assemblages were predicted. The most common secondary (supergene) lead minerals of interest here are cerussite, anglesite, and pyromorphite group minerals (PyGM; pyromorphite, mimetite, and vanadinite). These lead phases show a spatially well-ordered zoned texture around the preexisting/relic galena. Cerussite and anglesite commonly occur either as in situ replacement of galena and/or as euhedral crystals in cavities of former, partially dissolved galena. The PyGM are present either as crusts around the margin of the former/relic galena or are common as infiltration products into the host rock/gangue. During progressive weathering anglesite typically disappears first followed by cerussite. Finally, only the highly insoluble PyGM persist as a perimorphose. Hence, a spatially and temporally zoning texture is formed. Thermodynamic models of various fluid evolution paths using PHREEQC show the influence of temperature, pH, variable P CO2 , phosphorous contents and/or different mineral reactions on the sequence of formation and stability of the secondary lead phases. Already small changes in one or more of these parameters can lead to different mineral assemblages or sequences of secondary lead minerals. Over almost the whole relevant pH range, PyGM are the most stable lead phases, precipitating at very low ion activities explaining their textural position. Whether cerussite or anglesite forms, depends mainly on the pH value of the supergene fluids, which is affected by the quite variable fluid pathways. Furthermore a solubility diagram for a typical near-surface fluid was calculated, showing that anglesite is the most soluble phase, followed by cerussite and PyGM. This again reflects the microscopic observations. As a further step, the time span for the formation of a natural millimeter-thick pyromorphite crust was evaluated using subsoil phosphorous fluxes from the literature. The calculation indicates that millimeter-thick pyromorphite crusts can be formed in few tens to about hundred years, which is in agreement with observations in the nature. In this study, a framework for predicting stable secondary lead mineral assemblages and textures by fluid path modeling is given. These models are potentially important for predicting the retention and mobilization of lead in systems around contaminated sites or natural ore deposits.

Secondary sulfate mineralization and basaltic chemistry of craters of the Moon National Monument, Idaho: Potential martian analog

The Apliki mine, a Cyprus-type massive sulphide deposit in Cyprus, was exploited for copper until the mid-1970s. Abandonment of the mine left a deep pit that now hosts a lake fed by surface runoff from the surrounding mineralized zone and hydrothermally altered basalt. Oxidation of the sulphide minerals and factors such as climate and terrain relief control the water–rock interactions that generate acid mine drainage (AMD), which ultimately affects and defines the quality of the lake waters. Pyrite and chalcopyrite constitute an almost inexhaustible sulphide source that leads to the formation of a variety of secondary iron and copper mineral phases. The secondary mineral assemblages in the ore zone are mainly iron, copper, and magnesium sulphates, whereas the lakeshore assemblage is dominated by magnesium-, calcium-, sodium-, and aluminum-bearing sulphate minerals. Near the lakeshore, the highly soluble iron sulphate salts dissolve in the lake water, increasing its iron content. Other less soluble salts are more stable and persist in the lakeshore environment. The precipitation and dissolution of efflorescent salts, and, to a lesser extent, the oxidative weathering of the remaining ore minerals, produce additional AMD. Due to the perpetual cycle of mineral dissolution and precipitation, the lake has a low pH (≈3) and contains high concentrations of some contaminants. The processes that contribute to the formation of the efflorescent mineral assemblages and their environmental impact on pit lake waters, and indeed the complete geochemical system, is a typical example of secondary mineral formation in Cyprus-type Cu-pyrite massive sulphide ore deposits.

Mineralogical and geochemical study of element mobility at the sulfide-rich Excelsior waste rock dump from the polymetallic Zn–Pb–(Ag–Bi–Cu) deposit, Cerro de Pasco, Peru

Detailed, multi-media geochemical mapping has been conducted in the heavily industrialized Silesia–Cracow region in southern Poland. This paper focuses on results for a portion of the region within the Olkusz 1:25 000 scale map sheet as an example. Mapping in the Olkusz area has focused on: topsoils collected from 0–0.3 m; subsoils taken from 0.8–1 m; sediments from streams, ponds, and canals; and surface water. The soils were collected at a sampling density of 16 sites per km 2 . Concentrations of Ag, Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn, Ni, P, Pb, S, Sr, Ti, V and Zn were determined in topsoil, subsoil and sediments following a hot aqua regia digestion. In addition, organic carbon and grain size distribution were determined in topsoil samples; pH was measured in topsoils, subsoils and surface waters; and conductivity was determined in surface water. Constituents of surface water analysed included Ag, Al, As, B, Ba, Ca, Cd, Cl, Co, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, Rb, Sb, SiO 2 , SO 4 , Sr, Ti, Tl, U and Zn. The results revealed that the soils in the Olkusz map sheet are extremely contaminated with As, Cd, Hg, Pb and Zn in the vicinity of Zn-Pb mines and processing facilities, and that these elements show highly anomalous values in areas where soils were developed on outcrops of Zn-Pb ore-bearing Middle Triassic dolomites. The concentrations of the studied elements decrease exponentially with distance from the sources. The sediments of the main watercourses are polluted with Ag, As, Cd, Pb and Zn. In surface waters of high conductivity and nearly neutral pH, high concentrations of heavy metals and Na, K, Li and SO 4 were observed.

Chile is an important producer of copper, and it has serious soil contamination problems, mainly related to mining activities. A typical example is the Aconcagua River basin, which has been the scene of large-scale mining operations throughout history, making it critical to analyze due to the high concentrations of heavy metals in its soils. The objectives of this study are (1) to assess the level of As, Cu, Pb, and Zn contamination in the surface soil ecosystem based on different environmental indexes and (2) to determine the health risks of adults and children located in watersheds of the Aconcagua and Casablanca Rivers. A database of the Aconcagua River and Casablanca River basins is used to achieve the objectives. From the Aconcagua River basin, 20 topsoil samples from agricultural sectors without mining activity and 127 topsoil samples from sectors with mining activity were selected. On the other hand, thirty-five topsoil samples of the Casablanca River basin, without mining activity, were analyzed. The evaluation of soil contamination was done using environmental indexes. Finally, carcinogenic and noncarcinogenic risks to humans were calculated using the USEPA model. The mean concentration of chemical elements in the Aconcagua River basin for samples without mining presence was As 10.55 mg kg−1, Cu 85.75 mg kg−1, Pb 26.65 mg kg−1, and Zn 139.5 mg kg−1. The correlations show that the elements As, Cu, Pb, and Zn come from anthropogenic sources, which are also enhanced by the geogenic origin of Cu and Zn. The spatial distribution of the analyzed elements shows a spatial pattern that extends across industrial areas and emission sources, with higher concentrations of As, Cu, Pb, and Zn identified near mining areas of the Aconcagua River basin. The upper limit of the geogenic values determined by the MAD (median absolute deviation) method for the Aconcagua River basin without mining presence was 14.5 mg kg−1 for As, 94 mg kg−1 for Cu, 37.5 mg kg−1 for Pb, and 194 mg kg−1 for Zn. Finally, the geoaccumulation index, contamination factor, integrated contamination index, and potential ecological risk registered exceptionally high contamination in some soil samples, especially in areas with mining influence. It is essential to highlight that there are non-carcinogenic risks related to As, Cu, and Pb, a hazard quotient (HQ) higher than 1, and acceptable carcinogenic risks between 1.0 × 10−6 and 1.0 × 10−4 to As and Pb in children and adults in the Aconcagua River basin.

Challenging the model for induction of metallothionein gene expression

Introduction: Heavy metals are types of elements naturally present in soil or enter into soil as a result of human activities. The most important route of exposure to heavy metals is daily intake of food. Crops grown in contaminated soil (due to mining activities, industrial operations and agriculture) may contain high concentrations of heavy metals. Also closeness to cities and industrial centers can have a great influence on the accumulation of heavy metals to agricultural products grown in the region. The study aimed to determine the concentration of heavy metals in soil and agricultural products around urban and industrial areas of Zanjan province (North West of Iran) and consumption hazard probability. Materials and Methods: Soil (75 samples of soil from a depth of 0 to 10 cm) and plant (101 samples) samples, in the summer 2011, were randomly taken from industrial areas as follow: tomatoes (Lycopersicum esculentum M), wheat seed (Triticum vulgare), barley seeds (Hordeum vulgare), alfalfa shoots (Medicago sativa L.), potato tubers (Solanumtuberosum L.), apple fruit, vegetables and fruits such as Dill (Aniethum graveolens L.), leek (Allium porrum L.), Gardencress (Barbara verna L.) and basil (Ocimum basilicum L.). Plant samples were then washed with distilled water, oven dried for48 hours at a temperature of 70 ´C until constant weight was attained and then they digested using 2 M hydrochloric acid (HCl) and nitric acid digestion in 5 M. Concentrations of heavy metals in the soil and crops were determined by atomic absorption spectrometry. DTPA extraction of metals by Lindsay and Norvell (1978) method and sequential extraction method by Tessier et al. (1979) were performed. Statistical analysis was accomplished using the software SPSS 16.0 and the comparison of mean values was done using the Duncan test at the 5% level of significance. Results and Discussion: The magnitude of variations for total copper was from 11.5 to 352.5 (average 52.4), zinc was from 96.3 to 1353.8 (average 264.8), lead was between 40.0 and 470.0 (average 105.7), nickel ranged from 12.8 to 77.0 (average 46.7) and chromium varied from 10.0 to 49.5 (average 21.7) mg kg-1. DTPA extracted heavy metals for copper varied from 1.50 to 21.23, averaging 4.47, zinc from 0.57 to 76.50 averaging 23.15, lead from 2.43 to 63.38 averaging 16.81 and nickel from 0.28 to 2.32 averaging 1.20 mg kg-1. Chemical changes in the different fractions were as follows: Cu (residual > bounded to organic matter > bounded to Fe-Mn oxides > bounded to carbonate > exchangeable fraction), Zn and Ni (residual > bounded to Fe-Mn oxides > bounded to carbonate > bounded to organic matter > exchangeable fraction,) and Pb (residual > bounded to Fe-Mn oxides > bounded to organic matter > bounded to carbonate > exchangeable fraction). The concentration of heavy metals in plant parts were high with respect to studied location. The highest amounts of Zn (Gardencress), Pb (Dill), Cu (Leek), Ni (Basil) and Cr (Basil), respectively were found to be 150.25, 41.25, 23.13, 6.46 and 3.47 mg kg-1 and the minimum amounts of the metals studied were found in fruits, wheat and barley grains. The total amount of metals in plants were as follow (Zn >> Pb > Cu > Ni > Cr). Bioaccumulation factor (BAF) of metals in plants were as Zn=Cu > Pb >> Cr > Ni. Hazard probability (HQ) in cancerous diseases for each element (except Pb) in both children and adults was less than unit. HQ content of Pb was much higher than the unit and for children and adults 9.07 and 6.94, respectively showing high contribution of Pb contamination of crops that threatens the consumer health in that location. The total amount of risk (THQ) in children was higher than that in adults. Conclusions: The results obtained in this study indicate that an urgent attention is required for consumer products related to public health, especially vegetables grown in the studied regions. Toxic effects of heavy metals have many deleterious effects which are more pronounced over time. With conventional monitoring of food quality produced in farms and presented in markets, excessive accumulation of heavy metals entering in to the human food chain can be prevented. Also, we can change the risk potential of heavy metals in the region by growing vegetables which accumulate heavy metals. Keywords: Agriculture products, Biological risk, Heavy metals, Soil, Zanjan province

In the year 2016, passive biomonitoring studies were conducted in the forest areas of southern and north-eastern Poland: the Karkonosze Mountains (Kark), the Beskidy Mountains (Beskid), Borecka Forest (P. Bor), Knyszynska Forest (P. Kny), and Białowieza Forest (P. Bia). This study used bark from the tree, Betula pendula Roth. Samples were collected in spring (Sp), summer (Su), and autumn (Au). Concentrations of Mn, Fe, Ni, Cu, Zn, Cd, and Pb were determined for the samples using the atomic absorption spectrometry method with flame excitation (F-AAS). Based on the obtained results, the studied areas were ranked according to level of heavy-metal deposition: forests of southern Poland > forests of north-eastern Poland. Some seasonal changes in the concentrations of metals accumulated in bark were also indicated, which is directly related to their changing concentrations in the air during the calendar year, for instance, the winter heating season produces higher concentrations of heavy metals in the bark samples taken in spring. When deciding to do biomonitoring studies using bark, but also other biological materials, it is necessary to take into account the period in which the conducted research is done and the time when the samples are taken for analysis, because this will have a significant impact on the obtained results.