Geochemical Variation in the Greenstones of S.W. England

The characteristic rocks of the Upper Palaeozoic greenstonesof S.W. England are intrusive dolerites and extrusive basicpillow lavas with minor intermediate volcanics and ultrabasics(picrites). Pyroclastics are represented by keratophyric andbasic tuffs. The intrusive greenstones show varying degrees of alteration(spilitization) from a primary ilmenite-plagioclase-clinopyroxene?olivineassemblage to a hydrous low-grade spilite (or meta-dolerite)assemblage composed of variable proportions of albite, chlorite,epidote, calcite, and amphibole. Based on the distribution of elements little affected by secondaryprocesses (Ti, P, Y, Nb, and Zn), the intrusive greenstonescontain representatives of both the alkali olivine basalt andtholeiitic basalt magma series. Magmatic differentiation isgenerally minimal with the Devonian alkali basalt greenstonesbeing principally basaltic, while some of the Carboniferousalkali basalt greenstones tend towards mugearitic compositions.No intrusive acid differentiates have yet been reported. Apart from differences of magma type and minor differentiation,low-grade alteration or ‘spilitization’ has alsogoverned the geochemical variation seen in the greenstones.Spilitization caused (a) local redistribution of principallyCa (forming epidote-rich and calcite-rich patches) and Mg (formingchlorite-rich patches), together with their respective coherenttrace elements, and (b) the variable, but often limited, lossof Ca, Sr, K, Rb, and Ba from many bodies, together with a gainin Na and H₂O. Progressive hydration, however, caused a decreasein the oxidation ratio—a feature found to be common inmany spilitic suites and mainly governed by the relative distributionof chlorite versus epidote.     

Microbially mediated re-oxidation of sulfide during dissimilatory sulfate reduction by Desulfobacter latus

Enzymatic reactions during dissimilatory sulfate reduction (DSR) are often treated as unidirectional with respect to dissolved sulfide. However, quantitative models describing kinetic sulfur isotope fractionations during DSR consider the individual enzymatic reactions as reversible (Rees, 1973). Brunner and Bernasconi (2005) extended this line of thought, and suggested that as long as cell external sulfide (CES) concentrations are high enough, CES may diffuse back across the cytoplasmic cell membrane and may subsequently be re-oxidized to sulfate. Here, we test this hypothesis by measuring the time evolution of the δ³⁴S-sulfate signal during DSR in closed system experiments under different levels of sulfide stress (0-20 mM and 0-40 mM total dissolved sulfide). Our results show that the measured δ³⁴S-sulfate signal is markedly different in the latter case and that the observed sulfate S-isotope time-evolution is incompatible with a Rayleigh type fractionation model. In contrast, our results are consistent with a sulfate reduction and fractionation model that allows for a cell internal oxidation of dissolved sulfide by a sulfate reducer.     

Geochemical examination of lake sapropels used as fertilizers and fodder additives,U.S.S.R.

In recent years sapropels have been increasingly used as fertilizers and fodder additives in Byelorussia and in other regions of the Soviet Union. Thorough geochemical investigations are required to elucidate the essential differences in the composition of lake sapropels. At the same time, a rather wide range of element concentrations permits the selection of lakes and deposits with the most valuable proproties for these uses. The agrochemical effectiveness of sapropels is determined by the content of N, P, K, a number of trace elements, the silty fraction, the amount of biologically active substances, and the level of exchange acidity. It is also important to know the content of harmful components, e.g. pesticides, benzopyrine, a number of heavy metals (such as Pb, Hg and Cd) and the presence of pathogenic microorganisms.The content of mobile forms of elements, which the authors investigated by the method of successive extractions and isolation of humic and fulvic acids, is very essential for the utilization of sapropels as fertilizers and fodder additives.Three limno-geochemical provinces, differing in the types of deposits and ion the chamical composition of sapropels, were defined in Byelorussia. This led to more efficient prospecting and identification of the occurrence of sapropels with specific properties.     

Geochemical processes and solute transport at the seawater/freshwater interface of a sandy aquifer

Geochemical processes occurring at a seawater/freshwater interface were studied in a shallow coastal siliclastic aquifer containing minor amounts of calcite. Data were collected from 106 piezometers in a 120-m transect from the coastline and landward. In the first 40 m from the coastline, a wedge of saltwater is intruding below the freshwater aquifer. The aquifer is strongly reduced with mineralization of organic matter by methanogenesis in the freshwater aquifer, and sulfate reduction dominating in the most seaward part of the saline aquifer. The spatial separation of cations in the aquifer indicated a slow freshening process where Ca²⁺ from freshwater displaced the marine cations Na⁺ and Mg²⁺ from the exchanger complex. The resulting loss of Ca²⁺ from solution decreases the saturation state for calcite and possibly causes calcite dissolution. A storm-flooding event was recorded where pulses of dense seawater sank through the fresh aquifer. As a result, the terminal electron accepting process switched from methanogenesis to sulfate reduction. The pulses of sinking seawater also triggered cation exchange reactions where Ca²⁺ was expelled from the exchanger by seawater Na⁺ and Mg²⁺. The released Ca²⁺ is being flushed from the aquifer by groundwater flow, and this export of Ca²⁺ will, in the long term, cause decalcification of the sediment. The water composition in the aquifer is in a transient state as the result of various processes that operate on different timescales. Oxidation of organic matter occurs continuously but at a rate decreasing on a geological time scale. The freshening of the aquifer operates on the timescale of a few years. The episodic flooding and sinking of seawater through the aquifer proceeds in the course of days to weeks, but occurs irregularly with years in between.     

Geochemical evolution of lithospheric mantle beneath S.E. South Australia

The record of mafic magmatism from the Proterozoic to the Holocene in southern Australia reflects episodic incompatible element enrichment of the sub-continental lithospheric mantle (SCLM) recording periodic interaction of asthenosphere and lithosphere. The composition of Jurassic and Cainozoic mantle derived magmas is strongly influenced by the geochemical impact on the SCLM of events which took place during the Neoproterozoic and Cambrian. These events include rifting, passive margin development and orogenesis.Neoproterozoic to Cambrian basalts are widespread in western New South Wales, South Australia and Tasmania and reflect mantle decompression during extension and rifting of the Australian–East Antarctic Craton during the development of the proto-Pacific passive margin. These basalts fall into two regionally extensive and very different suites: (i) a voluminous suite of tholeiites and (ii) a highly undersaturated alkaline (nephelinite–basanite) series.Both Jurassic kimberlite magmas from the Adelaide Fold Belt and highly undersaturated Quaternary analcimites and basanites from the Mt. Gambier district of S.E. South Australia, have geochemical characteristics like those of the Precambrian–Cambrian alkaline suites. They have high concentrations of large ion lithophile (LIL), rare earth (RE) and high field strength (HFS) elements, and high HFSE/LILE and LREE/HREE ratios with T_DM^Nd values of 0.5–0.8 Ga. The Jurassic kimberlites appear to sample lithospheric mantle enrichment zones of Late Neoproterozoic to Early Cambrian age. The Quaternary suites result from mixing of contemporary mantle plume components with this old lithospheric enrichment, which is also identified with the occurrence of metasomatic phlogopite, amphibole and apatite in lherzolite mantle xenoliths from a number of Cainozoic volcanoes in Western Victoria.A very different type of lithospheric mantle enrichment took place during the late stages of the Ross–Delamerian Orogeny. This yielded a crustally contaminated mantle zone that mirrors the Cambro-Ordovician position of that orogen. This zone of contaminated lithospheric mantle interacted with a large plume in the Jurassic to yield the highly anomalous Ferrar–Tasmanian–Kangaroo Island basalts and dolerites.     

Geochemical exploration methods for gold in areas with mountain glaciation in Siberia,U.S.S.R.

In the mountainous areas of Siberia intensive destruction of ore deposits occurs as a result of Pleistocene mountain glaciation and, as a consequence, element dispersion trains form in the eroded material and in the stream sediments. In these areas, cirques and glaciated valleys are incised as much as 250–600 m into ore deposits. Geochemical anomalies in the stream sediments in the glaciated valleys form as water washes through the till and lacustrine sediments. The surface erosion processes result in the removal of fine gold from talus-covered cirque walls from where it is deposited in channels and lakes. Secondary dispersion halos may either be localized entirely within cirques, or they may be found in the drift within the outwash or glaciolacustrine environments downstream of the cirques. Intermittent accumulations of gold are specifically concentrated in glacially-fed stream sediments in those glaciated valleys characterized by smooth, flat bottoms and abundant lakes: gold in such cases tends to be concentrated in the lake muds. After the lakes have silted up, gold will be found in the fluvial deposits. In general, the complete elemental composition of the ore under discussion (Au, Ag, Pb and Zn) is reflected in only short dispersion trains within the fluvial and lacustrine deposits. Gold anomalies, on the other hand, are extensive (up to 6 km) in the stream sediments within the glaciated valleys and will occur sorbed onto hydrous iron oxides and clays, as well as in the form of flattened (thin) gold particles. In the glaciated valleys, the gold geochemical anomalies in moraine, lacustrine and stream sediments properly reflect the mineralization in the drainage basin.     

Geochemical balance of lateritization processes and climatic signatures in weathering profiles overlain by ferricretes in Central Africa

A simple geochemical balance of lateritization processes governing the development of several tens of meters of weathering profiles overlain by ferricretes is estimated on the basis of detailed mineralogical and geochemical data. The lateritic weathering mantle of the “Haut–Mbomou” area in Central Africa is composed of different weathering layers described from the base to the top of vertical profiles as a saprolite, a mottled clay layer, a soft nodular layer, a soft ferricrete, and a ferricrete in which kaolinite, gibbsite, goethite, and hematite occur in various quantities. Incongruent dissolution of kaolinite leads to the formation of gibbsite in the upper saprolite, whereas the hematite does not clearly replace the kaolinite according to an epigene process in the upper ferruginous layers of the profiles. Instead, that kaolinite is also transformed into gibbsite according to an incongruent dissolution under hydrated and reducing conditions induced by a relatively humid climatic pattern. The respective relations of the silica, iron, and aluminum balances and the Al substitution rate of the hematite on the one hand, and of RHG [RHG = 100 (hematite/hematite + goethite)] and the kaolinite on the other hand, to the consumption or the release of protons H⁺ permit differentiation of aggrading ferruginization and degradation processes operating in the different lateritic weathering profiles. The Al substitution rate of the Fe–oxyhydroxides varies according to the nature of lateritization processes, e.g., saprolitic weathering and aggrading ferruginization vs. degradation. The observations and results indicate that the ferruginization process of the weathering materials of parent rocks is not a simple ongoing process as often thought. This suggests that the actual lateritic weathering mantle of the Haut–Mbomou area may result from different stages of weathering and erosion during climatic changes.     

西昆仑塔什库尔干布伦阔勒群的岩石地球化学特征及变质P-T轨迹

西昆仑布伦阔勒群变质岩是西昆仑造山带的重要组成部分,但其成因一直存在争议.在塔什库尔干县的马尔洋地区,布伦阔勒群主要由石榴斜长角闪片麻岩和孔兹岩组成.根据地球化学特征,石榴斜长角闪片麻岩稀土元素配分曲线可以分为两种类型:一种稀土总量较高(∑REE=190.2×10-6 ～ 359.1×10-6),从轻稀土到重稀土逐渐亏损((La/Yb)N =4.28～5.79),与E-MORB类似;另一种稀土总量较低(∑REE=89.28×10-6～113.0×10-6),轻稀土亏损((La/Yb)N=0.59 ～0.84),重稀土曲线平坦((Gd/Yb)N =0.99 ～ 1.07),与N-MORB类似.微量元素蛛网图中石榴斜长角闪片麻岩具有Ba正异常,Sm、Cr、Zr、Hf和Ti的负异常,轻微的Nb、Ta的负异常,显示为岛弧拉斑玄武岩的特征.孔兹岩的原岩判别图解显示其原岩可能为岛弧环境沉积的页岩和硬砂岩.因此,推测塔什库尔干布伦阔勒群的石榴斜长角闪片麻岩和孔兹岩的原岩形成于岛弧环境.根据岩相学观察、矿物化学分析和温压计算,石榴斜长角闪片麻岩经历了三个变质阶段:M1为高压变质阶段,矿物组合为Grt+ Hbl(1)+ Pl1+ Qtz,变质温压条件为850～ 870℃/12.9 ～13.3kb;M2和M3为两期角闪岩相退变质阶段,矿物组合分别为Hbl2+ Pl2+Qtz和Hbl3+ Pl3+ Kfs+ Bt+ Qtz,变质温压条件分别为730 ～ 770℃/7.3～7.8kb和680 ～ 740℃/4.7 ～5.7kb.孔兹岩也经历了三个变质阶段,推测其早期M1阶段变质温压条件可能与石榴斜长角闪片麻岩的峰期变质阶段相同(850～870℃/12.9 ～ 13.3kb);峰期M2和峰期后M3阶段变质矿物组合分别为Grt2+ Pl2+ Bt2+ Sil+ Qtz和Grt3+ Pl3+ Bt3+Sil+ Mus+ Qtz,温压计算结果分别为800～830℃/7.9～9.2kb和670～700℃/5.1～5.6kb.孔兹岩的M1、M2和M3变质阶段对应于石榴斜长角闪片麻岩的M1、M2和M3变质阶段.上述温压计算结果形成顺时针的P-T轨迹,表现为峰期高压变质作用后叠加了由高角闪岩相-中压麻粒岩相到低角闪岩相的退变质作用,反映了西昆仑与碰撞相关的大地构造背景,这可能与海西期古特提斯洋的闭合有关,之后叠加了印支期构造抬升过程中的剪切作用.     

Geochemical exploration for mineralized breccia pipes in northern Arizona,U.S.A.

Thousands of solution-collapse breccia pipe crop out in the canyons and on the plateaus of northern Arizona. Over 80 of these are known to contain U or Cu mineralized rock. The high-grade U ore associated with potentially economic concentrations of Ag, Pb, Zn, Cu, Co and Ni in some of these pipes has continued to stimulate mining and exploration activity in northern Arizona, despite periods of depressed U prices. Large expanses of northern Arizona are comprised of undissected high plateaus; recognition of pipes in these areas is particularly important because mining access to the plateaus is far better than to the canyons. The small size of the pipes, generally less than 600 ft (200 m) in diameter, and limited rock outcrop on the plateaus, compounds the recognition problem. Although the breccia pipes, which bottom in the Mississippian Redwall Limestone, are occasionally exposed on the plateaus as circular features, so are unmineralized near-surface collapse features that bottom in the Permian Kaibab and Toroweap Formations. The distinction between these two classes of circular features is critical during exploration for this unique type of U deposit.Various geochemical and geophysical exploration methods have been tested over these classes of collapse features. Because of the small size of the deposits, and the low-level geochemical signatures in the overlying rock that are rarely dispersed for distances in excess of several hundred feet, most reconnaissance geochemical surveys, such as hydrogeochemistry or stream sediment, will not delineete mineralized pipes.Several types of detailed geochemical surveys made over collapse features, located through examination of aerial photographs and later field mapping, have been successful at delineating collapse features from the surrounding host rock: (1) Rock geochemistry commonly shows low level Ag, As, Ba, Co, Cu, Ni, Pb, Se and Zn anomalies over mineralized breccia pipes; (2) Soil surveys appear to have the greatest potential for distinguishing mineralized breccia pipes from the surrounding terrane. Although the soil anomalies are only twice the background concentrations for most anomalous elements, traverses made over collapse features show consistent enrichment inside of the feature as compared to outside; (3) B. Cereus surveys over a known mineralized pipe show significantly more anomalous samples collected from within the ring fracture than from outside of the breccia pipe; (4) Helium soil-gas surveys were made over 7 collapse features with discouraging results from 5 of the 7 features.Geophysical surveys indicate that scaler audio-magnetotelluric (AMT) and E-field telluric profile data show diagnostic conductivity differences over mineralized pipes as compared to the surrounding terrane. These surveys, coupled with the geochemical surveys conducted as detailed studies over features mapped by field and aerial photograph examination, can be a significant asset in the selection of potential breccia pipes for drilling.     

Geochemical processes in mill tailings deposits: modelling of groundwater composition

A general model is presented for geochemical processes occurring in the unsaturated zone of a carbonate-depleted, pyritic tailings deposit. Quantification of slow geochemical reactions, using published, empirical rate laws from small-scale experiments on monomineralic samples, and geochemical equilibrium reactions successfully reproduced the relative rates of field processes in the case study, Impoundment 1 in Kristineberg. Reproduction of absolute rates was achieved by scaling down all laboratory-derived mineral weathering rates by two orders of magnitude. The sensitivity of the modelled groundwater composition and pH to rates of pH-buffering processes and redox reactions indicated that inclusion and accurate quantification of all dominant geochemical processes on the field scale is necessary for reliable prediction of groundwater composition and pH.     

Accurate Determination of Chlorine,Bromine and Iodine in U.S. Geological Survey Geochemical Reference Materials by Radiochemical Neutron Activation Analysis

Trace amounts of three halogens (chlorine, bromine and iodine) in seventeen U.S. Geological Survey (USGS) geochemical reference materials were determined by radiochemical neutron activation analysis (RNAA). The materials analysed were AGV‐2 (andesite), BCR‐2, BHVO‐2 and BIR‐1a (basalts), CLB‐1 (coal), COQ‐1 (carbonatite), DGPM‐1 (disseminated gold ore), DNC‐1a (dolerite), DTS‐2b (dunite), GSP‐2 (granodiorite), Nod‐A‐1 and Nod‐P‐1 (manganese nodules), QLO‐1a (quartz latite), SBC‐1 (marine shale), SDC‐1 (mica schist), SGR‐1b (shale rock) and W‐2a (diabase). The chlorine, bromine and iodine contents were determined to be 5.64 mg kg^?1 (BIR‐1a) to 4410 mg kg^?1 (Nod‐A‐1), 0.039 mg kg^?1 (BIR‐1a) to 52.1 mg kg^?1 (CLB‐1), and 0.041 mg kg^?1 (BIR‐1a) to 599 mg kg^?1 (CLB‐1), respectively. The RNAA data of the three halogens were compared with the corresponding data in the literature.     

Geochemical controls on sediment reactivity and buffering processes in a heterogeneous aquifer

The injection and recovery of oxic water into deep anoxic aquifers may help to alleviate short- and long-term imbalance between freshwater supply and demand. The extent and structure of physical and geochemical heterogeneity of the aquifer will impact the water quality evolution during injection, storage and recovery. Water–sediment interactions within the most permeable parts of the aquifer, where the bulk of the injectant will penetrate, may dominate, however, water quality may also be impacted by interactions within the finer-grained, less permeable but potentially highly reactive media. In this study, the heterogeneity of the reductive capacity of an aquifer selected for water reuse projects was characterised, the amount, type and reactivity of the sedimentary reductants present determined, and the relationship between reductive capacity and sedimentary lithologies quantified. The average potential reductive capacities (PRC_TOT), based on total organic C and pyrite concentrations of the sediment, were quantified for sands (382 μmol O₂ g⁻¹), clays (1522 μmol O₂ g⁻¹), and silts (1957 μmol O₂ g⁻¹). Twenty-seven samples, spanning the three different lithologies, were then incubated for 50 days and the measured reductive capacities (MRC) determined for the sands (29.2 μmol O₂ g⁻¹), silts (136 μmol O₂ g⁻¹), and clays (143 μmol O₂ g⁻¹). On average, the MRC were 10% of the PRC_TOT. The main consumers of O₂ were pyrite (20–100%), sedimentary organic matter (SOM; 3–56%), siderite (3–28%) and Fe(II)-aluminosilicates (8–55%). The incubation data plus hydrogeochemical modelling, indicated that pH-buffering was controlled firstly by dissolution of trace level carbonates, followed by dissolution of feldspars. Zinc, Co, Ni, Cd and Pb were readily mobilized during incubation.     

Solvation processes in steam: Ab initio calculations of ion-solvent structures and clustering equilibria

Reports of the high ion content of steam and low-density supercritical fluids date back to the work of Carlon [Carlon H. R. (1980) Ion content of air humidified by boiling water.J. Appl.Phys.51, 171-173], who invoked ion and neutral-water clustering as mechanism to explain why ions partition into the low-density aqueous phase. Mass spectrometric, vibrational spectroscopic measurements and quantum chemical calculations have refined this concept by proposing strongly bound ion-solvent aggregates and water clusters such as Eigen- and Zundel-type proton clusters H₃O⁺·(H₂O)_m and the more weakly bound water oligomers (H₂O)_m. The extent to which these clusters affect fluid chemistry is determined by their abundance, however, little is known regarding the stability of such moieties in natural low-density high-temperature fluids. Here we report results from quantum chemical calculations using chemical-accuracy multi-level G3 (Curtiss-Pople) and CBS-Q theory (Peterson) to address this question. In particular, we have investigated the cluster structures and clustering equilibria for the ions and H₃S⁺·(H₂O)_m(H₂S)_n, where m ? 6 and n ? 4, at 300-1000 K and 1 bar as well as under vapor-liquid equilibrium conditions between 300 and 646 K. We find that incremental hydration enthalpies and entropies derived from van’t Hoff analyses for the attachment of H₂O and H₂S onto H₃O⁺, and H₃S⁺ are in excellent agreement with experimental values and that the addition of water to all three ions is energetically more favorable than solvation by H₂S. As clusters grow in size, the energetic trends of cluster hydration begin to reflect those for bulk H₂O liquids, i.e. calculated hydration enthalpies and entropies approach values characteristic of the condensation of bulk water (ΔH^o = −44.0 kJ mol⁻¹, ΔS^o = −118.8 J K mol⁻¹). Water and hydrogen sulfide cluster calculations at higher temperatures indicate that a significant fraction of H₃O⁺, and H₃S⁺ ions exists as solvated moieties.     

Geochemical characteristics of Tertiary oils derived from siliceous sources in Japan, Russia and U.S.A.

Siliceous sourced Tertiary oils from the Circum-Pacific area of Japan, Russia and the U.S.A. have a heavy carbon isotope composition, monomodal n-alkane distributions, and nearly identical regular sterane compositions with a predominance of C₂₇ homologues. These are consistent with open marine depositional environments dominated by diatomaceous organic matter. However, a number of alkane and biomarker parameters such as Pr/Ph, CPI, relative concentration of 28,30-bisnorhopane, and the C₃₅/C₃₄ homohopane ratio indicate more oxic depositional environments for the source rocks of Japan and Russia. In contrast to the California Monterey Formation sourced oils, petroleums with low maturity levels from the North Sakhalin basin, Russia and the Akita basin, Japan have lower concentrations of asphaltenes and sulphur and are characterized by higher API gravities. A correlation of extractable organic matter from source rocks vs the least matured petroleums demonstrates that oil expulsion in siliceous shales of the Akita basin occurs at a maturity level corresponding to R_o≥0.65%, which is in the range of the conventional oil window (R_o = 0.6−1.1%).     

Geochemical evidence for diversity of dust sources in the southwestern United States

Several potential dust sources, including generic sources of sparsely vegetated alluvium, playa deposits, and anthropogenic emissions, as well as the area around Owens Lake, California, affect the composition of modern dust in the southwestern United States. A comparison of geochemical analyses of modern and old (a few thousand years) dust with samples of potential local sources suggests that dusts reflect four primary sources: (1) alluvial sediments (represented by Hf, K, Rb, Zr, and rare-earth elements, (2) playas, most of which produce calcareous dust (Sr, associated with Ca), (3) the area of Owens (dry) Lake, a human-induced playa (As, Ba, Li, Pb, Sb, and Sr), and (4) anthropogenic and/or volcanic emissions (As, Cr, Ni, and Sb). A comparison of dust and source samples with previous analyses shows that Owens (dry) Lake and mining wastes from the adjacent Cerro Gordo mining district are the primary sources of As, Ba, Li, and Pb in dusts from Owens Valley. Decreases in dust contents of As, Ba, and Sb with distance from Owens Valley suggest that dust from southern Owens Valley is being transported at least 400 km to the east. Samples of old dust that accumulated before European settlement are distinctly lower in As, Ba, and Sb abundances relative to modern dust, likely due to modern transport of dust from Owens Valley. Thus, southern Owens Valley appears to be an important, geochemically distinct, point source for regional dust in the southwestern United States.     

Late-Quaternary diminution and abundance of prehistoric bison (Bison sp.) in eastern Washington state, U.S.A.

Bison (Bison spp.) occurred in eastern Washington state during the late Quaternary. This area is considered to be peripheral to the center of this taxon's natural range. Bison in the plains east of the Rocky Mountains, the heart of this range, underwent diminution during the late Quaternary, and apparently also did so in other, peripheral areas. A ratio diagram of measurement data derived from eight zooarchaeological collections of bison remains recovered from eastern Washington, in combination with the presence of both sexes and all age classes of individuals, indicate that local bison may have also undergone diminution there. There are, however, a relative paucity of bison remains during the middle Holocene and an apparent 2000-year absence of bison from eastern Washington at this time. As a result, the hypothesis that bison became smaller elsewhere and then immigrated to eastern Washington cannot be falsified. Both the diminution and the fluctuating abundance of bison appear to be responses to forage quality and quantity.     

Metalliferous sediments from the H.M.S. Challenger voyage (1872-1876)

The legendary cruise of H.M.S. Challenger (1872-1876) around the globe must always occupy an eminent place in the annals of oceanography, as being the first systematic attempt made on a global scale to explore the ocean. This expedition made fundamental discoveries in biology and geology which have not been surpassed by any later scientific cruise. Sediment with high content of metals (later called “metalliferous”) was among the enigmatic findings taken onboard. Although the nature of metalliferous sediments is well known today, the very first sampled sediments of this type have not been studied to date. Motivated by the historical value of Challenger’s metalliferous sediment collection we undertook an investigation addressing two questions: (1) the composition of sediments from seafloor for which we have very limited data; (2) Sr-Nd-Pb-Fe-Zn-isotope signature of these sediments collected before the substantial human impact on the ocean during the 20th century.The SE Pacific metalliferous sediments sampled by the Challenger’s explorers are of 2 types: (1) metalliferous oozes blanketing ridge crests and flanks down to the calcite compensation depth (CCD); and (2) stripped of CaCO₃ metalliferous sediments located beneath the CCD in the deeps near the mid-ocean ridges. The abiogenic part of these sediments is composed mainly of poorly-crystalline to X-ray amorphous Fe-Mn-oxyhydroxides, and an amorphous silicate phase. These sediments have geochemical features similar to those of all the other metalliferous sediments: very high Fe and Mn content (on abiogenic basis), very low Al/(Al + Fe + Mn), and high content (on abiogenic basis) of As, Ba, Be, Bi, Cd, Co, Cu, Mo, Ni, Pb, Sb, Th, Tl, U, V, W, Y, Zn and Zr. Their REE distribution patterns are similar to that of deep seawater and show weak signs of hydrothermal imprint (weak positive or no Eu anomaly).Seawater and/or terrigenous input from South America control the Sr-Nd-Pb-isotope signature of the Challenger metalliferous sediments and have almost completely obliterated any original MORB-derived hydrothermal signal. Zn isotopes are mainly contributed from seawater although other Zn sources (hydrothermal fluid and detrital aluminosilicates, barite and volcanic glass) are necessary to fully explain Zn-isotope ratios. Fe isotopes indicate relatively slow Fe²⁺ to Fe³⁺ oxidation in the non-buoyant plume, thus producing relatively lighter Fe-isotope signature of the FeOOH particles that formed the studied metalliferous sediments.