Acid mine drainage at Cerro Rico de Potosí I: unabated high-strength discharges reflect a five century legacy of mining

Intensive mining and processing of Ag, Sn, Pb and Zn ores have occurred in various locations within and around the city of Potosí, Bolivia since 1545. Surface and subsurface waters, stream sediments and soils are contaminated with various ecotoxic metals in the headwaters of the economically vital, yet highly impacted, upper Rio Pilcomayo watershed. Previous studies have documented downstream trace metal contamination, however, not addressed specific sources. The AMD discharges identified in this study help link downstream pollution to primary origins. The majority of AMD would be considered high-strength due to metal concentrations and acidity orders of magnitude greater than typical AMD. Discharges from both operating and abandoned portals as well as tailings-related deposits displayed a high degree of heterogeneity with total metal concentrations ranging from 0.11 to 7480, <0.022 to 889, <0.0006 to 65.3, <0.001 to 310, 0.12 to 72,100, 0.3 to 402, <0.012 to 34.8, and 0.24 to 19,600 mg/L of Al, As, Cd, Cu, Fe, Mn, Pb and Zn, respectively. Net acidity and pH ranged from −10 to 246,000 mg/L as CaCO₃ equivalent and 0.90–6.94 standard units, respectively. Data were gathered during two sampling events centered around the most extreme periods of the dry and wet seasons of one water-year. Loadings to local streams were marginally greater for most metals in the wet season. If observed loadings are historically representative, Cerro Rico AMD has contributed thousands of tonnes of ecotoxic metals to the upper Rio Pilcomayo over the last five centuries. Metal and hydrogen ion concentrations in the majority of AMD sampled were several orders of magnitude above discharge limits set by the Bolivian government, yet no action has historically or contemporarily been taken.     

Anthropogenic relief changes in a long-lasting lignite mining area (‘Ville’, Germany) derived from historic maps and digital elevation models

Humans constitute one of the main geomorphological agents in modern times. As an example, post-mining regions represent a typical landscape of the Anthropocene. Strong relief modifications are particularly obvious with open pit mining. However, many existing mining areas are lacking detailed pre-mining information for the quantification of anthropogenic relief changes, which is a considerable challenge in regions with historic mining activities. Here, the Ville (Rhenish lignite district, Germany) is used to quantify surface mining induced relief changes in one of the oldest and currently largest lignite districts in Europe. Historical maps from first geodetic mapping in 1893 enabled construction of a historic digital elevation model to quantify the relief changes in comparison to elevation data from 2000 and 2015. The vertical accuracy of the historic data is remarkably high, with relief differences < 2 m in areas not affected by mining. In total, 49.2% of the investigated area (184 km²) shows a relief deficit and 14.5% has positive relief differences. Absolute changes account for more than 80 m heightening (dumpsites of overburden) and lowering of the natural relief (pits). Besides these altitudinal changes, overall steeper slopes are significant for the new topography, but levelling exists likewise. The spatial variabilities are discussed in the context of the regional geology and the mining techniques. Undoubtedly, such large-scale anthropogenic relief changes persist for a very long time and will last as a human legacy far into the future. Only the detailed reconstruction of the pre-mining relief offers the ability to clarify the dimension of humans as geomorphological agents and to understand landscape perception. Due to the fact that the impact of open pit mining has such a large vertical and horizontal extension, their consideration as part of anthropogeomorphology can significantly contribute to support future Critical Zone research in the Anthropocene.     

Occurrence and Distribution of Organic Contaminants in the Aquatic System in Berlin.Part II: Substituted Phenols in Berlin Surface Water

In a surface water screening, 30 representative surface water samples collected from rivers, canals, and lakes in Berlin were investigated for the presence of 22 substituted phenols. The phenols selected include the 11 phenols considered as “priority pollutants” by the US Environmental Protection Agency (US-EPA). Surface water samples were extracted applying solid-phase extraction with styrenedivinylbenzene adsorbent. The recoveries, determined in spiking experiments, were between 80 % and 103 %. After derivatization with N-(tert-butyldimethylsilyl)-N-methyl-trifluoroacetamide (MTBSTFA) the samples were analyzed by capillary gas chromatography-mass spectrometry (GC-MS). Phenol, cresols, 2-ethylphenol, 2-chlorophenol, 4-chloro-3-methylphenol, pentachlorophenol, 2-nitrophenol, and 4-nitrophenol were detected in the surface water samples at concentrations between 0.02 μg/L and 7.8 μg/L, respectively. The distribution of these residues in the Berlin surface waters showed that the phenolic residues, with the exception of pentachlorophenol and 2-ethylphenol, do not originate primarily from municipal sewage treatment plants discharges. Some of the phenols are formed naturally or occur as ubiquitous anthropogenic contaminants in the aquatic system.     

Diffusive equilibrium in thin films provides evidence of suppression of hyporheic exchange and large‐scale nitrate transformation in a groundwater‐fed river

The hyporheic zone of riverbed sediments has the potential to attenuate nitrate from upwelling, polluted groundwater. However, the coarse‐scale (5–10 cm) measurement of nitrogen biogeochemistry in the hyporheic zone can often mask fine‐scale (<1 cm) biogeochemical patterns, especially in near‐surface sediments, leading to incomplete or inaccurate representation of the capacity of the hyporheic zone to transform upwelling NO₃^?. In this study, we utilised diffusive equilibrium in thin‐films samplers to capture high resolution (cm‐scale) vertical concentration profiles of NO₃^?, SO₄^2?, Fe and Mn in the upper 15 cm of armoured and permeable riverbed sediments. The goal was to test whether nitrate attenuation was occurring in a sub‐reach characterised by strong vertical (upwelling) water fluxes. The vertical concentration profiles obtained from diffusive equilibrium in thin‐films samplers indicate considerable cm‐scale variability in NO₃^? (4.4 ± 2.9 mg N/L), SO₄^2? (9.9 ± 3.1 mg/l) and dissolved Fe (1.6 ± 2.1 mg/l) and Mn (0.2 ± 0.2 mg/l). However, the overall trend suggests the absence of substantial net chemical transformations and surface‐subsurface water mixing in the shallow sediments of our sub‐reach under baseflow conditions. The significance of this is that upwelling NO₃^?‐rich groundwater does not appear to be attenuated in the riverbed sediments at <15 cm depth as might occur where hyporheic exchange flows deliver organic matter to the sediments for metabolic processes. It would appear that the chemical patterns observed in the shallow sediments of our sub‐reach are not controlled exclusively by redox processes and/or hyporheic exchange flows. Deeper‐seated groundwater fluxes and hydro‐stratigraphy may be additional important drivers of chemical patterns in the shallow sediments of our study sub‐reach. © 2015 The Authors. Hydrological Processes Published by John Wiley & Sons Ltd.     

Deep inside a neoproterozoic intra-oceanic arc: growth,differentiation and exhumation of the Amalaoulaou complex (Gourma,Mali)

We show here that the Amalaoulaou complex, in the Pan-African belt of West Africa (Gourma, Mali), corresponds to the lower and middle sections of a Neoproterozoic intra-oceanic arc. This complex records a 90–130-Ma-long evolution of magmatic inputs and differentiation above a subducting oceanic slab. Early c. 793 Ma-old metagabbros crystallised at lower crustal or uppermost mantle depths (25–30 km) and have geochemical characteristic of high-alumina basalts extracted from a depleted mantle source slightly enriched by slab-derived sedimentary components ((La/Sm)_N < 1; ε_Nd: +5.4–6.2; ⁸⁷Sr/⁸⁶Sr: 0.7027–0.7029). In response to crustal thickening, these mafic rocks were recrystallised into garnet-granulites (850–1,000°C; 10–12 kbar) and subject to local dehydration–melting reactions, forming trondhjemititic leucosomes with garnet–clinopyroxene–rutile residues. Slightly after the granulitic event, the arc root was subject to strong HT shearing during partial exhumation (detachment faults/rifting or thrusting), coeval with the emplacement of spinel- and garnet-pyroxenite dykes crystallised from a high-Mg andesitic parental magma. Quartz and hornblende-gabbros (700–660 Ma) with composition typical of hydrous volcanic rocks from mature arcs ((La/Sm)_N: 0.9–1.8; ε_Nd: +4.6 to +5.2; ⁸⁷Sr/⁸⁶Sr: 0.7028–0.7031) were subsequently emplaced at mid-arc crust levels (~15 km). Trace element and isotopic data indicate that magmas tapped a depleted mantle source significantly more enriched in oceanic sedimentary components (0.2%). Exhumation occurred either in two stages (700–660 and 623 Ma) or in one stage (623 Ma) with a final exhumation of the arc root along cold P-T path (550°C, 6–9 kbar; epidote–amphibolite and greenschist facies conditions) during the main Pan-African collision event (620–580 Ma). The composition of magmas forming the Cryogenian Amalaoulaou arc and the processes leading to intra-arc differentiation are strikingly comparable to those observed in the deep section of exposed Mezosoic oceanic arcs, namely the Kohistan and Talkeetna complex. This evolution of the Amalaoulaou oceanic arc and its accretion towards the West African craton belong to the life and closure of the Pharusian Ocean that eventually led to the formation of the Greater Gondwana supercontinent, a similar story having occurred on the other side of the Sahara with the Mozambique Ocean.     

Temperature dependence of the cation distribution in nickel aluminate (NiAl2O4) spinel: a powder XRD study

NiAl₂O₄ is a largely inverse spinel, which in detail shows increasing randomisation with temperature of Ni and Al between the octahedral and tetrahedral cation sites of the spinel structure. We have used powder XRD to determine this cation distribution in various samples of NiAl₂O₄ quenched after annealing between 700 and 1400° C. The inversion parameter (x) can be measured with a precision of ± 0.004 (one standard deviation), and a comparison of different methods of synthesis, X-ray diffraction and refinement techniques, suggests a probable accuracy of better than 0.01. The results are supported by some preliminary single crystal refinements on flux-grown samples.Below 800° C the rate of cation ordering becomes very slow, and, despite reaching an apparently steady state, it is doubtful if our samples attained complete internal equilibrium. Above 1250° C the cation redistribution becomes so fast that the quenching method becomes unreliable. Between 800 and 1250° C inclusive, the degree of inversion changes smoothly from 0.87 at 800° C to 0.79 at 1250° C, and is accompanied by linear changes in u, the oxygen parameter, from 0.2555 to 0.2563 (±0.0002), and a₀, the lattice parameter, from 8.0462 to 8.0522 Å (±0.0002 Å).     

Fractional Crystallization and Liquid Immiscibility Processes in the Alkaline-Carbonatite Complex of Juqui (So Paulo, Brazil)

The Juqui circular intrusion, which is Cretaceous in age (130–135Ma), crops out in the Precambrian gneissic basement in Brazilover an area of 14 km2. It consists of olivine clinopyroxen-itecumulates (with minor olivine gabbros) in the northeastern sector(74 vol.%), whereas ijolites-melteigites-urtites (4%) and nephelinesyenites with minor essexites and syenodiorites (21%) outlinesubannular concentric patterns with an Mg-carbonatite core (1%), in the southwestern part of the complex. Petrographical, bulk rock, and mineral compositional trendsindicate that the origin of the complex can be largely accountedfor by shallow-level fractional crystallization of a carbonatedbasanitic parental magma. Such a magma was generated deep inthe subcontinental lithosphere by low-degree partial meltingof a garnet-phlogopite peridotite source. Mass-balance calculations in agreement with field volume estimatespermit definition of several fractionation stages of the magmaticevolution under nearly closed-system conditions, with inwarddevelopment of zonally arranged side-wall cumulates. These stagesinvolved: (1) fractionation from basanite to essexite magma(liquid fraction F = 33–5%) by crystallization of olivineclinopyroxenite plus minor olivine alkali gabbro cumulates;(2) derivation of the least differentiated mafic nepheline syenite(F = 5–5 %) from essexitic magma by subtraction of a syenodioriteassemblage; (3) exsolution of a carbonatite liquid (5%) froma CO₂-enriched mafic nepheline syenite magma, which also underwentcontinuous fractionation giving rise to ijolite-melteigite-urtitecumulates. The proportion of cumulus clinopyroxene and biotiteand intercumulus nepheline and alkali feldspar in these lastrocks, as well as the absence of alkalis in carbonatite, maybe attributed, at least in part, to loss of alkali-rich hydrousfluids released during and after the unmixing formation of thetwo conjugate liquids. The KD values determined for Mg-carbonatite/nepheline syeniteare lower (1–4–2–9) for light rare earth elements(LREE) than for REE from Eu to Yb (4–6–7–8),in contrast to recent experimental results (Hamilton et al.,1989). A possible explanation is that Juquia Mg-carbonatiterepresents an alreadydifferentiated magma, which underwent extensivefractionation of LREE-enriched calcite. In this way, the highvariability of K₀ REE patterns observed in several alkaline-carbonatitecomplexes can also be accounted for. The remarkably constant initial ⁸⁷Sr/⁸⁶Sr ratios (mostly between0–7052 and 0–7057) support the interpretation ofthe intrusion as having been generated by fractrional crystallizationand liquid immiscibility from a common parental magma. Iligherisotopic ratios (0–7060–0–7078), found mainlyin dykes and in the border facies of the intrusion, may be dueto contamination by the gecissic basement.     

Westward moving dynamic substorm features observed with the IMAGE magnetometer network and other ground-based instruments

We present the ground signatures of dynamic substorm features with particular emphasis on the event interpretation capabilities provided by the IMAGE magnetometer network. This array covers the high latitudes from the sub-auroral to the cusp/cleft region. An isolated substorm on 11 Oct. 1993 during the late evening hours exhibited many of well-known features such as the Harang discontinuity, westward travelling surge and poleward leap, but also discrete auroral forms, known as auroral streamers, appeared propagating westward along the centre of the electrojet. Besides the magnetic field measurements, there were auroral observations and plasma flow and conductivity measurements obtained by EISCAT. The data of all three sets of instruments are consistent with the notion of upward field-aligned currents associated with the moving auroral patches. A detailed analysis of the electro-dynamic parameters in the ionosphere, however, reveals that they do not agree with the expectations resulting from commonly used simplifying approximations. For example, the westward moving auroral streamers which are associated with field-aligned current filaments, are not collocated with the centres of equivalent current vortices. Furthermore, there is a clear discrepancy between the measured plasma flow direction and the obtained equivalent current direction. All this suggests that steep conductivity gradients are associated with the transient auroral forms. Also self-induction effects in the ionosphere may play a role for the orientation of the plasma flows. This study stresses the importance of multi-instrument observation for a reliable interpretation of dynamic auroral processes.