A New Reference Material for Tritium Organic Molecules in Sediment: Results of an International Intercomparison Exercise

Solid matrix ³H reference materials are challenging to prepare given the volatile nature of ³H and are often unrepresentative of the range of ³H forms that may be encountered during routine analysis. As a result, few ³H reference materials are currently available, undermining verification of analytical techniques for environmental ³H measurement. To address this, an International Working Group on Organically‐Bound Tritium Analysis determined to produce a tritium natural matrix reference material (NMRM). The reference material comprises marine sediment blended with sewage sludge contaminated with ³H‐organic species arising from authorised discharges from a radiopharmaceutical manufacturing site. Previous studies have demonstrated that the ³H species have persisted in the environment over three decades providing valuable supporting data to underpin the characterisation of the NMRM. The preparation and characterisation of the NMRM are described along with the subsequent application of the reference material in an international intercomparison exercise involving nineteen laboratories from nine countries. A reference value of 168 ± 22 Bq kg^?1 was derived from the data arising from the proficiency test.     

The geochemistry and petrogenesis of the Lower Paleozoic granitoids of the Lleyn Peninsula,North Wales

The Lleyn Peninsula of North Wales is penetrated by at least twenty stocks varying from microtonalite through to microgranite and these are closely associated with Caradocian volcanic rocks which include andesitic lavas.Major and trace element analyses show that the sample population may be separated into a peralkaline group and a sub-alkaline group. This latter group may be sub-divided into three compositional series which range from andesite to granite. The andesites are represented by the Caradocian lavas of the Moel y Penmaen district and these plot at one end of major and trace element variation diagrams. Their coherent relationships to the granitoids demonstrate the latter to be Ordovician and therefore ends a longstanding controversy concerning their age. The distinctive geochemistry of the andesites indicates the strong probability that they have evolved from transitional tholeiitic magma by low-pressure crystal fractionation. Apatite fractionation has strongly controlled the rare earth element abundances in the granitoids and for most compositions from andesite through granite their bulk distribution coefficient is greater than unity.The association of peralkaline granites, transitional tholeiites and other geological and geophysical evidence suggests that the area was a region of ensialic crustal tension during the mid-Ordovician.     

A chironomid-based reconstruction of summer temperatures in NW Iceland since AD 1650

Few studies currently exist that aim to validate a proxy chironomid-temperature reconstruction with instrumental temperature measurements. We used a reconstruction from a chironomid percentage abundance data set to produce quantitative summer temperature estimates since AD 1650 for NW Iceland through a transfer function approach, and validated the record against instrumental temperature measurements from Stykkishólmur in western Iceland. The core was dated through Pb-210, Cs-137 and tephra analyses (Hekla 1693) which produced a well-constrained dating model across the whole study period. Little catchment disturbance, as shown through geochemical (Itrax) and loss-on-ignition data, throughout the period further reinforce the premise that the chironomids were responding to temperature and not other catchment or within-lake variables. Particularly cold phases were identified between AD 1683–1710, AD 1765–1780 and AD 1890–1917, with relative drops in summer temperatures in the order of 1.5–2°C. The timing of these cold phases agree well with other evidence of cooler temperatures, notably increased extent of Little Ice Age (LIA) glaciers. Our evidence suggests that the magnitude of summer temperature cooling (1.5–2°C) was enough to force LIA Icelandic glaciers into their maximum Holocene extent, which is in accordance with previous modelling experiments for an Icelandic ice cap (Langjökull).     

新疆阿尔泰克因布拉克铜锌矿床地质特征及成矿作用

克因布拉克中型铜锌矿床赋存于早二叠世花岗岩外接触带的上志留统-下泥盆统康布铁堡组黑云石英片岩、变质石英砂岩中。矿床的形成经历了夕卡岩期、热液期和表生期,铜锌矿主要形成于热液期。矿石中石英和方解石流体包裹体划分为H_2O-NaCl型和H_2O-CO_2(±CH_4/N_2)-NaCl型。成矿温度变化于146～448℃,在170℃、270℃和350℃出现峰值;流体盐度变化于0.2%～46.9%NaCl_(eq),峰值为1.5%NaCl_(eq)和5.5%NaCl_(eq);流体的密度0.55～1.19g/cm~3。硫化物的δ~(34)S集中变化于-8.4‰～1.9‰,峰值为0‰,表明硫来自岩浆。石英和方解石δD_(SMOW)介于-130‰～-79‰,δ~(18)O_(SMOW)值介于8.0‰～11.6‰,δ~(18)O_(H2O)值为-1.7‰～4.43‰,表明成矿流体主要是岩浆水,混合大气降水。方解石中δ~(13)C_(PDB)变化于-5.3‰～-1.1‰,暗示碳来自花岗质岩浆。成矿时代为早中二叠世,成矿作用与花岗质岩浆期后的热液活动有关。     

Sedimentary response of Pagham Harbour, southern England to barrier breaching in AD 1910

This paper examines the evolution of Pagham Harbour, southern England following storm-induced breaching of a protective barrier in AD 1910. Stratigraphic studies of sediments collected from intertidal areas show the presence of a distinct stratigraphic horizon in the northeast of Pagham Harbour at ca. 0 to +1.0 m ordnance datum (OD). Radiometric data indicate that this horizon is a ‘reclamation surface’ formed after land claim in AD 1846. Following marine flooding in AD 1910, sediment has accreted relatively rapidly (at a broadly constant rate of between 4 and 8 mm a⁻¹), wave and/or tidal energy have decreased and extensive marshes have developed. An asymptotic reduction in sediment accretion rate through time, as predicted in various theoretical models of salt marsh accretion, is not observed. Over the entire Pagham Harbour area, the period between AD 1948 and AD 1986 has seen an average marsh loss of 0.0087 km² a⁻¹, which is relatively small in comparison with other more exposed sites in the local area. Historically breached sites such as Pagham Harbour are common around European coasts, and these provide important natural laboratories within which the medium-term (decadal to centennial) coastal response to barrier breaching, and to managed-realignment coastal protection schemes, can be assessed.     

Lead pre-concentration using a novel manganese dioxide resin

A novel manganese dioxide (MnO₂) resin is suitable for the determination and decontamination of lead isotopes (²⁰⁸Pb, ²⁰⁷Pb, ²⁰⁶Pb) in aqueous solutions at trace concentrations. This is desirable due to the toxic nature and high abundance of lead in the environment. Current techniques are both time consuming, expensive and not suitable for low-level lead decontamination. The MnO₂ resin has been demonstrated to pre-concentrate with extraction efficiency above 90% for a range of pH values, and with a mean extraction of 92.5% from fresh waters at a flow rate of 100?ml?min^?1. The lead distribution coefficient is 1.3?×?10⁴ (pH 7) with tolerance to calcium and sodium. Adsorption isotherms have been investigated and the resin shown to follow the Langmuir adsorption isotherm with a saturation point of 41.5?mg per g of MnO₂ resin.     

新疆阿尔泰铁木尔特铅锌矿床流体包裹体研究及地质意义

铁木尔特中型铅锌矿是阿尔泰山南缘克兰盆地内的重要VMS型矿床。矿床赋存于上志留统-下泥盆统康布铁堡组上亚组第二岩性段,容矿岩石为大理岩、绿泥石英片岩、变钙质粉砂岩、夕卡岩。矿体呈似层状和透镜状。矿床的形成经历了喷流沉积期、叠加改造期和表生期。石英、长石、方解石和石榴子石中包裹体类型主要为液体包裹体,在石英中另出现了气体包裹体、纯气体包裹体、含子矿物多相包裹体、含液体CO2的三相包裹体和两相CO2包裹体。喷流沉积期成矿流体均一温度变化于150～330℃,其峰值是165℃和285℃,成矿流体盐度(NaCleq)为4%～16%,流体密度为0.77～0.97g/cm3,流体阳离子主要以Na+为主,次之为K+,阴离子以Cl-为主,其次是SO42-,气相成分主要是H2O和CO2。叠加改造期均一温度范围是150～480℃,峰值为285℃,盐度(NaCleq)为2.2%～17.08%和33.93%～47.2%,流体密度变化于0.61～1.03g/cm3之间,流体阳离子主要以Na+为主,次为K+、Mg2+、Ca2+,阴离子以Cl-为主,其次是SO42-,气相成分主要是H2O和CO2,其次为N2、CH4,含有少量C2H6。     

新疆包古图斑岩铜矿床成矿流体及成矿物质来源——来自硫、氢和氧同位素证据

包古图大型斑岩铜矿位于准噶尔盆地西缘。铜矿化主要呈浸染状、细脉浸染状分布于似斑状(石英)闪长岩、闪长玢岩、隐爆角砾岩和少量花岗闪长岩中。依据矿脉的穿插关系和矿物组合,成矿过程经历了黑云母-钾长石-钠长石阶段、石英-硫化物阶段和石英碳酸盐阶段。矿脉中石英的δDSMOW值介于-107‰～-86‰,δ18OSMOW值变化于11.3‰～16.2‰,δ18OH2O值为4.4‰～9.3‰,表明成矿流体来源为深源的岩浆水。硫化物的δ34S值介于-5.1‰～0.7‰,平均为-1.8‰,表明硫来源于深部岩浆或地幔。结合Ⅱ、Ⅲ和Ⅴ号含矿岩体锆石LA-ICP-MSU-Pb年龄及辉钼矿Re-Os年龄,推断包古图铜矿床成矿作用发生在晚石炭世,与中酸性斑岩体的侵入有密切成因关系。     

Records of radionuclide deposition in two salt marshes in the United Kingdom with contrasting redox and accumulation conditions

Single cores from two salt marshes in the United Kingdom located near different nuclear facilities were investigated to compare chronostratigraphic estimates derived from the natural radionuclide ²¹⁰Pb_excess with estimates from the known times of introduction of artificial radionuclides to the environment. Both cores selected had clear visual indications of redox zonation, and evidence for diagenetic redox perturbation of the radionuclide records was also sought. In the core from Beaulieu Marsh on the south coast of England, the redox zonation was revealed by the profiles of the redox-sensitive elements Mn + I, Fe + P + As, and S, and the records of nuclear discharges were entirely contained within oxidized conditions in the upper 40 cm. The constant flux/constant sedimentation ²¹⁰Pb_excess accumulation estimate was 76% of that derived from the 1963 fallout ¹³⁷Cs level (0.35 vs. 0.46 g cm⁻² yr⁻¹ dry mass), but the constant flux ²¹⁰Pb_excess method indicated that accumulation rates were lower at Beaulieu before ∼1950. On any timescale, ¹³⁷Cs appears earlier in the sediment record than its introduction to the environment, but although downward diffusion of ¹³⁷Cs relative to ²⁴¹Am has clearly occurred, the ¹³⁷Cs peak still appeared in place and there was negligible penetration of ¹³⁷Cs into underlying reduced conditions. This core also contained a peak of the ⁶⁰Co discharges from either or both the Winfrith and La Hague nuclear plants that peaked in 1980 and 1984, respectively. The sediments in the core from Wyre Marsh on the eastern coast of the Irish Sea had accumulated more rapidly than those at Beaulieu, and in this case the redox zonation could be established only from Mn and S profiles. Here, the constant initial activity ²¹⁰Pb_excess accumulation rate estimate was 125% of that derived from the ¹³⁷Cs peak correlated with the 1975 Sellafield discharge maximum (0.79 vs. 0.64 g cm⁻² yr⁻¹). Sellafield discharge ¹³⁷Cs swamps fallout or Chernobyl ¹³⁷Cs signals in this core, but the ¹³⁷Cs and ²⁴¹Am sediment records are well separated and remain consistent with the slightly different discharge patterns over time. This is so despite the fact that the maximum activity levels of both isotopes are now located well into reducing conditions out of which Mn must have migrated. The ²¹⁰Pb profile appeared similarly unaffected by the oxidized/reduced boundary in this case. This core was too short to define the limits of any downward ¹³⁷Cs migration. ²¹⁰Pb_excess accumulation rate estimates for salt marshes should be viewed with some caution because of the steady-state assumptions inherent in all ²¹⁰Pb_excess methods and the potential for fluctuating accumulation conditions and open system behavior in salt marshes.