Martin R. Palmer

Atmospheric carbon dioxide concentrations over the past 60 million years

Knowledge of the evolution of atmospheric carbon dioxide concentrations throughout the Earths history is important for a reconstruction of the links between climate and radiative forcing of the Earths surface temperatures. Although atmospheric carbon dioxide concentrations in the early Cenozoic era (about 60 Myr ago) are widely believed to have been higher than at present, there is disagreement regarding the exact carbon dioxide levels, the timing of the decline and the mechanisms that are most important for the control of CO2 concentrations over geological timescales. Here we use the boron-isotope ratios of ancient planktonic foraminifer shells to estimate the pH of surface-layer sea water throughout the past 60 million years, which can be used to reconstruct atmospheric CO2 concentrations. We estimate CO2 concentrations of more than 2,000 p.p.m. for the late Palaeocene and earliest Eocene periods (from about 60 to 52 Myr ago), and find an erratic decline between 55 and 40 Myr ago that may have been caused by reduced CO2 outgassing from ocean ridges, volcanoes and metamorphic belts and increased carbon burial. Since the early Miocene (about 24 Myr ago), atmospheric CO2 concentrations appear to have remained below 500 p.p.m. and were more stable than before, although transient intervals of CO2 reduction may have occurred during periods of rapid cooling approximately 15 and 3 Myr ago.

Uranium in the oceans: Where it goes and why

Abstract Uranium is removed from the oceans by diffusion across the sediment-water interface of organic-rich sediments. This pathway is the largest single sink in the global budget of this element. Dissolved uranium is drawn into suboxic sediments along a concentration gradient established by the precipitation of an insoluble phase which forms when U(VI) is reduced to U(IV). This transformation occurs relatively late in the diagenetic sequence, after the microbially mediated dissolution of manganese and iron oxides, and may be induced by the onset of sulfate reduction. Metallo-organics play an important role in the diagenetic behavior of this element as some uranium is released into solution when labile organics are consumed at the sediment-water interface. In contrast, the diagenesis of authigenic Fe- and Mn-oxides exerts negligible influence on the uranium diagenetic cycle. Variations in the uranium concentration of sediment with time are controlled directly by the uranium content of the source material settling from the water column, and indirectly, by the organic content of this material and the sedimentation rate. Since diffusion from seawater influences dramatically the short-term burial rate of uranium, downcore distributions of dissolved and solid uranium can provide an estimate of recent sedimentation rates in rapidly accumulating sediments.

Controls over the strontium isotope composition of river water

Abstract Strontium concentrations and isotope ratios have been measured in river and ground waters from the Ganges, Orinoco, and Amazon river basins. When compared with major element concentrations, the data set has allowed a detailed examination of the controls over the strontium isotope systematics of riverine input to the oceans in the following environments: 1. (1) “typical” drainage basins containing limestones, evaporites, shales, and alumino-silicate metamorphic and igneous rocks; 2. (2) shield terrains containing no chemical or biogenic sediments; and 3. (3) the floodplains that constitute the largest areas of many large rivers. The strontium concentration and isotope composition of river waters are largely defined by mixing of strontium derived from limestones and evaporites with strontium derived from silicate rocks. The strontium isotope composition of the limestone endmember generally lies within the Phanerozoic seawater range, which buffers the 87 Sr 86 Sr ratios of major rivers. A major exception is provided by the rivers draining the Himalayas, where widescale regional metamorphism appears to have led to an enrichment in limestones of radiogenic strontium derived from coexisting silicate rocks. The strontium isotope systematics of rivers draining shield areas are controlled by the intense, transportlimited, nature of the weathering reactions, and thereby limits variations in the strontium flux from these terrains. Floodplains are only a minor source of dissolved strontium to river waters, and precipitation of soil salts in some floodplains can reduce the riverine flux of dissolved strontium to the oceans. The most effective mechanisms for altering the isotope ratio and flux of riverine strontium to the oceans are increased glaciation and large-scale regional metamorphism of the type produced during continental collision. Both mechanisms provide a means for increasing the 87 Sr 86 Sr ratio of the global riverine flux.

Widespread dissemination of metal debris from implants

In a post-mortem study, we compared subjects with metal implants with and without visible wear with an age-matched control group to determine the extent and effects of dissemination of wear debris. In subjects with stainless-steel and cobalt-chrome prostheses metal was found in local and distant lymph nodes, bone marrow, liver and spleen. The levels were highest in subjects with loose, worn joint prostheses and the main source of the debris was the matt coating. Metal levels were also raised in subjects with implants without visible wear and, to a less extent, in those with dynamic hip screws. Necrosis of lymph nodes was seen in those cases with the most wear, and potential damage to more distant organs such as the bone marrow, liver and spleen in the long term cannot be discounted. The consequences for the immune system and the role of metal dissemination in the possible induction of neoplasia are discussed.

Uranium in river water

The concentration of dissolved uranium has been determined in over 250 river waters from the Orinoco, Amazon, and Ganges basins. Uranium concentrations are largely determined by dissolution of limestones, although weathering of black shales represents an important additional source in some basins. In shield terrains the level of dissolved U is transport limited. Data from the Amazon indicate that floodplains do not represent a significant source of U in river waters. In addition, we have determined dissolved U levels in forty rivers from around the world and coupled these data with previous measurements to obtain an estimate for the global flux of dissolved U to the oceans. The average concentration of U in river waters is 1.3 nmol/kg, but this value is biased by very high levels observed in the Ganges-Brahmaputra and Yellow rivers. When these river systems are excluded from the budget, the global average falls to 0.78 nmol/kg. The global riverine U flux lies in the range of 3–6 × 107 mol/yr. The major uncertainty that restricts the accuracy of this estimate (and that of all other dissolved riverine fluxes) is the difficulty in obtaining representative samples from rivers which show large seasonal and annual variations in runoff and dissolved load.

The lithium isotope composition of international rock standards

We present the results of analysis of the Li isotope composition of open ocean seawater, nine international rock standards and a C1 chondrite. In addition, we suggest some modifications of the chemical preparation techniques for analysis of lithium isotopes in low concentration samples that give precise isotope ratios by thermal ionisation mass spectrometry (TIMS). The aim of this study is to provide a benchmark for ensuring the reliability of Li isotope data between different laboratories by TIMS and other isotope ratio techniques, including multi collector-inductively coupled plasma-mass spectrometry and ion probe.

The chemistry of hydrothermal fluids from the Broken Spur site, 29°N Mid-Atlantic ridge

Abstract Hydrothermal fluids have been collected from three high temperature (360–364°C) vents from Broken Spur (29°10.08′N, 43°10.46′W; water depth ∼ 3100 m). This is only the fourth site on a slow spreading ridge from which such fluids have been collected. Compared to other vent sites, the hydrothermal fluids are enriched in Li (1035 μM) and have lower dissolved Mn (∼250 μM) and Sr (43 μM) concentrations. The boron isotope systematics indicate that substantial removal (>50%) of seawater B has occurred in the low-temperature portion of the hydrothermal convection cell. In addition, low temperature removal of seawater Sr is ∼10% greater at Broken Spur compared to similar vent sites in the Pacific where spreading rates are faster. A low Eu anomaly (11 ± 3) and a Cs Rb ratio (10.8) intermediate between pristine and weathered basalt suggest that the vent fluids have interacted with a component of basalt that has previously undergone low-temperature weathering. the fluids are 14% depleted in Cl relative to seawater. Supercritical phase separation appears to be the only reasonable process that may account for the fluid depletion.

The rare earth element geochemistry of acid-sulphate and acid-sulphate-chloride geothermal systems from Yellowstone National Park, Wyoming, USA

Rare earth element (REE) concentrations have been determined by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) in acid-sulphate and acid-sulphate-chloride waters and the associated sinters and volcanic rocks from the Yellowstone National Park (YNP), Wyoming, USA, geothermal system. REE concentrations in the volcanic rocks range from 222 to 347 ppm; their chondite-normalised REE patterns are typical of upper continental crust, with LREE > HREE and negative Eu anomalies. Total REE concentrations in the fluids range from 3 to 1133 nmol kg−1 (≥ 162 ppm), and ΣREE concentrations in sinter are ≥ 181 ppm. REE abundances and patterns in drill core material from YNP indicate some REE mobility. Normalisation of REE concentrations in altered Lava Creek Tuff (LCT) from Y-12 drill core to REE concentrations in fresh LCT indicate that the REE overall have been depleted with the exception of Eu, which has been decoupled from the REE series and concentrated in the altered rocks. Relative to the host rocks the REE patterns of the fluids are variably depleted in HREEs and LREEs, and usually have a pronounced positive Eu anomaly. This decoupling of Eu from the REE suite suggests that (1) Eu has been preferentially removed either from the host rock glass or from the host rock minerals, or (2) the waters are from a high temperature or reducing environment where Eu2+ is more soluble than the trivalent REEs. Since the latter is inconsistent with production of acid-sulphate springs in a low temperature, oxidising near-surface environment, we suggest that the positive Eu anomalies in the fluids result from preferential dissolution of a Eu-rich phase in the host rock. Spatial and temporal variations in major element chemistry and pH of the springs sampled from Norris Geyser Basin and Crater Hills accompany variations in REE concentrations and patterns of individual geothermal springs. These are possibly related to changes in subsurface plumbing, which results in variations in mixing and dilution of the geothermal fluids and may have lead to changes in the extent and nature of REE complexing.

The influence of symbiont photosynthesis on the boron isotopic composition of foraminifera shells

Culture experiments were carried out with the planktonic foraminifer Orbulina universa under high and low light levels in order to determine the influence of symbiont photosynthetic activity on the boron isotopic composition of shell calcite. Under low light (reduced photosynthetic rates) the boron isotopic composition of the tests is 1.5‰ lower compared to shells grown under high light (elevated photosynthetic rates). In terms of inferred pH, the lower boron isotope values correspond to a reduction in pH of approximately 0.2 units. The boron isotopic composition of Orbulina universa from plankton tows is similar to that of shells grown under low light conditions in the laboratory. These data are consistent with reduced symbiont concentrations in recently secreted shells. In addition to laboratory and field grown O. universa, we present the first data for a symbiont-barren foraminifer, Globigerina bulloides. Data obtained for G. bulloides fall ∼1.4‰ below those of the field grown O. universa. Although the plankton tow results are preliminary, they support the hypothesis that respiration and photosynthesis are the key physiological parameters responsible for species-specific vital effects.

Preliminary observations on possible premalignant changes in bone marrow adjacent to worn total hip arthroplasty implants

Previous epidemiologic studies have suggested that there may be a risk of malignancy, especially lymphoma and leukemia, after joint replacement, but the followup has been relatively short. This is a preliminary study to see if there is any biologic basis for such a risk. Blood and bone marrow samples from 71 patients at revision arthroplasty of a loose or worn prosthesis and 30 control patients at primary arthroplasty were analyzed with cytogenetic techniques and molecular biology. There was a higher chromosomal aberration rate in cells adjacent to the prosthesis at revision surgery compared with iliac crest marrow from the same patients or with femoral bone marrow at primary arthroplasty. Clonal expansion of lymphocytes without a serum paraprotein was seen in 2 of 21 patients at revision arthroplasty performed more than 10 years after primary arthroplasty. The results of this preliminary study suggest that future epidemiologic studies should concentrate on patients with longer postoperative intervals to see if there is any risk that would be pertinent to a young patient at primary arthroplasty.