The release of zinc and lead from mine tailings

Mining and processing of metal ores are important causes of soil and groundwater contamination in many regions worldwide. Metal contaminations are a serious risk for the environment and human health. The assessment of metal contaminations in the soil is therefore an important task. A common approach to assess the environmental risk emanating from inorganic contaminations to soil and groundwater is the use of batch or column leaching tests. In this regard, the suitability of leaching tests is a controversial issue. In the first part of this work the applicability and comparability of common leaching tests in the scope of groundwater risk assessment of inorganic contamination is reviewed and critically discussed. Soil water sampling methods (the suction cup method and centrifugation) are addressed as an alternative to leaching tests. Reasons for limitations of the comparability of leaching test results are exposed and recommendations are given for the expedient application of leaching tests for groundwater risk assessment. Leaching tests are usually carried out in open contact with the atmosphere disregarding possible changes of redox conditions. This can affect the original metal speciation and distribution, particularly when anoxic samples are investigated. The influence of sample storage on leaching test results of sulfide bearing anoxic material from a former flotation dump is investigated in a long-term study. Since the oxidation of the sulfide-bearing samples leads to a significant overestimation of metal release, a feasible modification for the conduction of common leaching tests for anoxic material is proposed, where oxidation is prevented efficiently. A comparison of leaching test results to soil water analyzes have shown that the modified saturation soil extraction (SSE) is found to be the only of the tested leaching procedures, which can be recommended for the assessment of current soil water concentrations at anoxic sites if direct investigation of the soil water is impossible due to technical reasons. The vertical distribution and speciation of Zn and Pb in the flotation residues as well as metal concentrations in soil water and plants were investigated to evaluate the environmental risk arising from this site due to the release of metals. The variations in pH and inorganic C content show an acidification of the topsoil with pH values down to 5.5 in the soil and a soil water pH of 6 in 1 m depth. This is due to the oxidation of sulfides and depletion in carbonates. In the anoxic subsoil pH conditions are still neutral and soil water collected with suction cups is in equilibrium with carbonate minerals. Results from extended x-ray absorption fine-structure (EXAFS) spectroscopy confirm that Zn is mainly bound in sphalerite in the subsoil and weathering reactions lead to a redistribution of Zn in the topsoil. A loss of 35% Zn and S from the topsoil compared to the parent material with 10 g/kg Zn has been observed. 13% of total Zn in the topsoil can be regarded as mobile or easily mobilizable according to sequential chemical extractions (SCE). Zn concentrations of 10 mg/L were found in the soil water, where pH is acidic. Electron supply and the buffer capacity of the soil were identified as main factors controlling Zn mobility and release to the groundwater. Variable Pb concentrations up to 30 µg/L were observed in the soil water. In contrast to Zn, Pb is enriched in the mobile fraction of the oxidized topsoil by a factor of 2 compared to the subsoil with 2 g/kg Pb. 80% of the cation exchange capacity in the topsoil is occupied by Pb. Therefore, plant uptake and bioavailability are of major concern. If the site is not prevented from proceeding acidification in the future, a significant release of Zn, S, and Pb to the groundwater has to be expected. Results from this study show that the assessment of metal release especially from sulfide bearing anoxic material requires an extensive comprehension of leaching mechanisms on the one hand and on weathering processes, which influence the speciation and the mobility of metals, on the other hand. Processes, which may change redox and pH conditions in the future, have to be addressed to enable sound decisions for soil and groundwater protection and remediation.

Observation of Associated Near-Side and Away-Side Long-Range Correlations in √sNN=5.02 TeV Proton-Lead Collisions with the ATLAS Detector

Two-particle correlations in relative azimuthal angle (Delta phi) and pseudorapidity (Delta eta) are measured in root S-NN = 5.02 TeV p + Pb collisions using the ATLAS detector at the LHC. The measurements are performed using approximately 1 mu b(-1) of data as a function of transverse momentum (p(T)) and the transverse energy (Sigma E-T(Pb)) summed over 3.1 < eta < 4.9 in the direction of the Pb beam. The correlation function, constructed from charged particles, exhibits a long-range (2 < vertical bar Delta eta vertical bar < 5) "near-side" (Delta phi similar to 0) correlation that grows rapidly with increasing Sigma E-T(Pb). A long-range "away-side" (Delta phi similar to pi) correlation, obtained by subtracting the expected contributions from recoiling dijets and other sources estimated using events with small Sigma E-T(Pb), is found to match the near-side correlation in magnitude, shape (in Delta eta and Delta phi) and Sigma E-T(Pb) dependence. The resultant Delta phi correlation is approximately symmetric about pi/2, and is consistent with a dominant cos2 Delta phi modulation for all Sigma E-T(Pb) ranges and particle p(T).

The Yanque prospect (Peru): from polymetallic Zn-Pb mineralization to a nonsulfide deposit

The Yanque nonsulfide Pb-Zn deposit (inferred resources 12.5 Mt @ 3.7% Pb and @ 3.5% Zn) is located in the Andahuaylas-Yauri ore province (Cuzco, southern Peru). The deposit occurs within a base metal mineralized district, centered on the medium-sized Dolores porphyry copper. A thorough geological, mineralogical and geochemical study has carried out in order to define: the relationships between the Dolores Cu-porphyry ore and the Yanque Zn-Pb polymetallic mineralization, and the characteristics of the economic nonsulfide concentrations. Both sedimentary and igneous rocks constitute the backbone of the Yanque-Dolores area. The sedimentary lithologies belong to the Soraya, Mara and Ferrobamba Fms. (upper Jurassic-middle Cretaceous). The Yanque orebody is hosted by the Mara Fm., which prevailingly consists of a siliciclastic sedimentary breccia. The original sulfide mineralization consisted of galena, pyrite and sphalerite. The host rock has been affected by a strong hydrothermal alteration, characterized by prevailing sericite/illite, as in the typical porphyry-related phyllic-argillic alteration stage, and by minor kaolinite, dolomite and quartz. Minor element geochemistry, characterized by Sb, As, Mn, Ag and locally also by Cu, points to magmatic-hydrothermal related mineralizing fluids. The Pb isotopic compositions from Dolores and Yanque sulfides are similar, and are typical of the Tertiary magmatically-derived ores in this part of Peru. The hydrothermally altered rocks at Yanque have the same Pb isotopic compositions as the sulfides, thus confirming the hypothesis that the Yanque primary Zn-Pb mineralization may have been produced by hydrothermal circulation related to the emplacement of the Dolores Cu-porphyry, as it is the case of other porphyry Cu systems associated with polymetallic mineralization elsewhere. However, no simple genetic model for the mineralization involving just one fluid circulation episode is able to explain the data. The Yanque economic nonsulfide ore association consists of sauconite, hemimorphite, smithsonite and cerussite, which result from the weathering and alteration of the original sulfide mineralization. Zinc is allocated mainly in sauconite (Zn-smectite), rather than in carbonates: a factor strictly related to the prevailing siliciclastic character of the host rock. Distinctive features of the Yanque orebody are the comparable ore grades for both Pb and Zn (3.5% Zn and 3.7% Pb), and the inverse supergene chemical zoning. In fact, contrary to other supergene ores of this type, zinc prevails in the top zone of the Yanque deposit, whereas lead content increases with depth. Considering the different mobility of the two metals in solution, it may be assumed that most of the primary zinc that was the source for the Yanque nonsulfides was originally located far from the position occupied by the galena mineralization, whose remnants have been observed on site. Zinc sulfides may have been originally contained in the eroded rock volumes that surrounded the actual deposit: the zinc-rich solutions have possibly migrated through the siliciclastic Mara Fm. and precipitated the nonsulfide minerals by porosity filling and replacement processes. In this sense, the Yanque secondary Zn-Pb deposit could be considered as a special type of “Exotic” mineralization.

Elemental and Lead Isotopic Data of Copper Finds from the Singen Cemetery, Germany – a Methodological Approach to Investigate Early Bronze Age Trade Networks

We report a trace element - Pb isotope analytical (LIA) database on the "Singen Copper", a peculiar type of copper found in the North Alpine realm, from its type locality, the Early Bronze Age Singen Cemetery (Germany). What distinguishes “Singen Copper” from other coeval copper types? (i) is it a discrete metal lot with a uniform provenance (if so, can its provenance be constrained)? (ii) was it manufactured by a special, unique metallurgical process that can be discriminated from others? Trace element concentrations can give clues on the ore types that were mined, but they can be modified (more or less intentionally) by metallurgical operations. A more robust indicator are the ratios of chemically similar elements (e.g. Co/Ni, Bi/Sb, etc.), since they should remain nearly constant during metallurgical operations, and are expected to behave homogeneously in each mineral of a given mining area, but their partition amongst the different mineral species is known to cause strong inter-element fractionations. We tested the trace element ratio pattern predicted by geochemical arguments on the Brixlegg mining area. Brixlegg itself is not compatible with the Singen Copper objects, and we only report it because it is a rare instance of a mining area for which sufficient trace element analyses are available in the literature. We observe that As/Sb in fahlerz varies by a factor 1.8 above/below median; As/Sb in enargite varies by a factor of 2.5 with a 10 times higher median. Most of the 102 analyzed metal objects from Singen are Sb-Ni-rich, corresponding to “antimony-nickel copper” of the literature. Other trace element concentrations vary by > 100 times, ratios by factors > 50. Pb isotopic compositions are all significantly different from each other. They do not form a single linear array and require > 3 ore batches that certainly do not derive from one single mining area. Our data suggest a heterogeneous provenance of “Singen copper”. Archaeological information limits the scope to Central European sources. LIA requires a diverse supply network from many mining localities, including possibly Brittany. Trace element ratios show more heterogeneity than LIA; this can be explained either by deliberate selection of one particular ore mineral (from very many sources) or by processing of assorted ore minerals from a smaller number of sources, with the unintentional effect that the quality of the copper would not be constant, as the metallurgical properties of alloys would vary with trace element concentrations.

Measurement of the distributions of event-by-event flow harmonics in lead-lead collisions at = 2.76 TeV with the ATLAS detector at the LHC

The distributions of event-by-event harmonic flow coefficients v_n for n=2-4 are measured in sqrt(s_NN)=2.76 TeV Pb+Pb collisions using the ATLAS detector at the LHC. The measurements are performed using charged particles with transverse momentum pT> 0.5 GeV and in the pseudorapidity range |eta|<2.5 in a dataset of approximately 7 ub^-1 recorded in 2010. The shapes of the v_n distributions are described by a two-dimensional Gaussian function for the underlying flow vector in central collisions for v_2 and over most of the measured centrality range for v_3 and v_4. Significant deviations from this function are observed for v_2 in mid-central and peripheral collisions, and a small deviation is observed for v_3 in mid-central collisions. It is shown that the commonly used multi-particle cumulants are insensitive to the deviations for v_2. The v_n distributions are also measured independently for charged particles with 0.51 GeV. When these distributions are rescaled to the same mean values, the adjusted shapes are found to be nearly the same for these two pT ranges. The v_n distributions are compared with the eccentricity distributions from two models for the initial collision geometry: a Glauber model and a model that includes corrections to the initial geometry due to gluon saturation effects. Both models fail to describe the experimental data consistently over most of the measured centrality range.

Measurement of long-range pseudorapidity correlations and azimuthal harmonics in √s_NN=5.02 TeV proton-lead collisions with the ATLAS detector

Measurements of two-particle correlation functions and the first five azimuthal harmonics, v 1 to v 5 , are presented, using 28 nb −1 of p+Pb collisions at a nucleon-nucleon center-of-mass energy of √s NN=5.02 TeV measured with the ATLAS detector at the LHC. Significant long-range “ridgelike” correlations are observed for pairs with small relative azimuthal angle (|Δϕ|<π/3 ) and back-to-back pairs (|Δϕ|>2π/3 ) over the transverse momentum range 0.4

Pb-fragmentation side. The azimuthal structure of such long-range correlations is Fourier decomposed to obtain the harmonics v n as a function of p T and event activity. The extracted v n values for n=2 to 5 decrease with n . The v 2 and v 3 values are found to be positive in the measured p T range. The v 1 is also measured as a function of p T and is observed to change sign around p T ≈1.5 –2.0 GeV and then increase to about 0.1 for p T >4 GeV. The v 2 (p T ) , v 3 (p T ) , and v 4 (p T ) are compared to the v n coefficients in Pb+Pb collisions at √s NN=2.76 TeV with similar event multiplicities. Reasonable agreement is observed after accounting for the difference in the average p T of particles produced in the two collision systems.

Measurement of the centrality and pseudorapidity dependence of the integrated elliptic flow in lead-lead collisions at √sNN=2.76 TeV with the ATLAS detector

The integrated elliptic flow of charged particles produced in Pb+Pb collisions at √sNN = 2.76 TeV has been measured with the ATLAS detector using data collected at the Large Hadron Collider. The anisotropy parameter, v2, was measured in the pseudorapidity range |η| ≤ 2.5 with the event-plane method. In order to include tracks with very low transverse momentum pT, thus reducing the uncertainty in v2 integrated over pT, a 1 μb−1 data sample recorded without a magnetic field in the tracking detectors is used. The centrality dependence of the integrated v2 is compared to other measurements obtained with higher pT thresholds. The integrated elliptic flow is weakly decreasing with |η|. The integrated v2 transformed to the rest frame of one of the colliding nuclei is compared to the lower-energy RHIC data.

Measurement of event-plane correlations in √s_NN=2.76 TeV lead-lead collisions with the ATLAS detector

A measurement of event-plane correlations involving two or three event planes of different order is presented as a function of centrality for 7 μb −1 Pb+Pb collision data at √s NN =2.76 TeV, recorded by the ATLAS experiment at the Large Hadron Collider. Fourteen correlators are measured using a standard event-plane method and a scalar-product method, and the latter method is found to give a systematically larger correlation signal. Several different trends in the centrality dependence of these correlators are observed. These trends are not reproduced by predictions based on the Glauber model, which includes only the correlations from the collision geometry in the initial state. Calculations that include the final-state collective dynamics are able to describe qualitatively, and in some cases also quantitatively, the centrality dependence of the measured correlators. These observations suggest that both the fluctuations in the initial geometry and the nonlinear mixing between different harmonics in the final state are important for creating these correlations in momentum space.

APPLICATION OF THE BRAINSTEM EVOKED RESPONSE (BER) TO NEUROTOXICITY EVALUATION OF THE AUDITORY SYSTEM: ASSESSMENT OF INORGANIC LEAD-INDUCED OTOTOXICITY

An experimental procedure was developed using the Brainstem Evoked Response (BER) electrophysiological technique to assess the effect of neurotoxic substances on the auditory system. The procedure utilizes Sprague-Dawley albino rats who have had dural electrodes implanted in their skulls, allowing neuroelectric evoked potentials to be recorded from their brainstems. Latency and amplitude parameters derived from the evoked potentials help assess the neuroanatomical integrity of the auditory pathway in the brainstem. Moreover, since frequency-specific auditory stimuli are used to evoke the neural responses, additional audiometric information is obtainable. An investigation on non-exposed control animals shows the BER threshold curve obtained by tests at various frequencies very closely approximates that obtained by behavioral audibility tests. Thus, the BER appears to be a valid measure of both functional and neuroanatomical integrity of the afferent auditory neural pathway.^ To determine the usefulness of the BER technique in neurobehavioral toxicology research, a known neurotoxic agent, Pb, was studied. Female Sprague-Dawley rats were dosed for 45 days with low levels of Pb acetate in their drinking water, after which BER recordings were obtained. The Pb dosages were determined from the findings of an earlier pilot study. One group of 6 rats received normal tap water, one group of 7 rats received a solution of 0.1% Pb, and another group of 7 rats received a solution of 0.2% Pb. After 45 days, the three groups exhibited blood Pb levels of 4.5 (+OR-) 0.43 (mu)g/100 ml, 37.8 (+OR-) 4.8 (mu)g/100 ml and 47.3 (+OR-) 2.7 (mu)g/100 ml, respectively.^ The results of the BER recording indicated evoked response waveform latency abnormalities in both the Pb-treated groups when midrange frequency (8 kHz to 32 kHz) stimuli were used. For the most part, waveform amplitudes did not vary significantly from control values. BER recordings obtained after a 30-day recovery period indicated the effects seen in the 0.1% Pb group had disappeared. However, those anomalies exhibited by the 0.2% Pb group either remained or increased in number. This outcome indicates a longer lasting or possibly irreversible effect on the auditory system from the higher dose of Pb. The auditory pathway effect appears to be in the periphery, at the level of the cochlea or the auditory (VIII) nerve. The results of this research indicate the BER technique is a valuable and sensitive indicator of low-level toxic effects on the auditory system.^

(Table 1) Sr, Nd, and Pb isotopic composition of ODP Leg 129 basalts

Basaltic rocks recovered from three drill sites in the western Pacific during Ocean Drilling Program Leg 129 have fairly distinct Sr, Nd, and Pb isotopic compositions. The Cretaceous alkali olivine dolerites from Site 800 in the northern part of Pigafetta Basin have fairly low 87Sr/86Sri (0.70292-0.70320) and 143Nd/144Ndi (0.51277-0.51281) and high present-day Pb isotopic ratios (206Pb/204Pb = 20.53-21.45; 207Pb/204Pb = 15.70-15.77; 208Pb/204Pb = 40.02-40.68). The Middle Jurassic tholeiites from Site 801 in the southern part of the basin have low 87Sr/86Sri (0.70237-0.70248), high 143Nd/144Ndi (0.51298-0.51322), and moderate present-day Pb isotopic ratios (206Pb/204Pb = 18.20-19.12; 207Pb/204Pb = 15.47-15.60; 208Pb/204Pb = 37.56-38.18); isotopic compositions of the alkali olivine basalts overlying the tholeiites fall between those of the tholeiites and Site 800 dolerites. The Cretaceous tholeiites from Site 802 in the East Mariana Basin have high 87Sr/86Sri (0.70360-0.70372), fairly low 143Nd/144Ndi (0.51277-0.51280), and fairly low and homogeneous present-day Pb isotopic ratios (206Pb/204Pb = 18.37-18.39; 207Pb/204Pb = 15.49-15.51; 208Pb/204Pb = 38.34-38.39). Isotopic compositions of Site 801 tholeiites are indistinguishable from those of modern mid-ocean ridge basalts, consistent with the proposal that these tholeiites are a part of the oldest Pacific crust. The diverse isotopic compositions of the younger basalts appear to be the result of Jurassic Pacific plate migration over the geologically anomalous south-central Pacific region, wherein they acquired their distinct isotopic compositions. The anomalous region was volcanically more active during the Cretaceous than at present.