The silicon isotopic composition of surface waters in the Atlantic and Indian sectors of the Southern Ocean

We report here the silicon isotopic composition (δ³⁰Si) of dissolved silicon (DSi) from 42 surface water samples from the Drake Passage, the Weddell Gyre, other areas south of the Southern Boundary of the Antarctic Circumpolar Current (ACC), and the ACC near the Kerguelen Plateau, taken between the beginning of February and the end of March 2007. From the beginning to end of the cruise (ANTXXIII/9), DSi diminished in the Antarctic by 50 μmol L⁻¹ while concentrations of nitrate + nitrite and phosphate showed no net decline, indicating that the high seasonal Si/N removal ratios well known for the Southern Ocean may be more related to the strength of the silicate pump in the Southern Ocean than to the instantaneous Si/N uptake ratio of diatoms. The δ³⁰Si of DSi in samples containing more than 20 μM DSi were strongly negatively correlated to DSi concentrations, supporting the use of δ³⁰Si as a proxy for DSi removal. The “open system” fractionation observed, ε = −1.2 ± 0.11‰, agrees well with results from previous work in other areas, and the estimate of the initial δ³⁰Si of DSi of +1.4‰ is not far off observations of the δ³⁰Si of DSi in Winter Water (WW) in this area. Results were used to model DSi draw down in the past from the δ³⁰Si of sediment cores, although isotopic fractionation during silica dissolution appeared to influence the δ³⁰Si of some surface water samples, inviting further study of this phenomenon.     

Geochemistry of trace metals and Pb isotopes of sediments from the lowermost Xiangjiang River, Hunan Province (P. R. China): implications on sources of trace metals

This paper reports a geochemical study of trace metals and Pb isotopes of sediments from the lowermost Xiangjiang River, Hunan province (P. R. China). Trace metals Ba, Bi, Sc, V, Cr, Mn, Co, Ni, Cu, Zn, Mo, Cd, Sn, Sb, Pb, Tl, Th, U, Zr, Hf, Nb and Ta were analyzed using ICP-MS, and Pb isotopes of the bulk sediments were measured by MC-ICP-MS. The results show that trace metals Cd, Bi, Sn, Sc, Cr, Mn, Co, Ni, Cu, Zn, Sb, Pb and Tl are enriched in the sediments. Among these metals, Cd, Bi and Sn are extremely highly enriched (EF values >40), metals Zn, Sn, Sb and Pb significantly highly (5 < EF < 20), and metals Sc, Cr, Mn, Co, Ni, Cu and Tl moderately highly (2 < EF < 5) enriched in the river sediments. All these metals, however, are moderately enriched in the lake sediments. Geochemical results of trace metals Th, Sc, Co, Cr, Zr, Hf and La, and Pb isotopes suggest that metals in the river sediments are of multi-sources, including both natural and anthropogenic sources. Metals of the natural sources might be contributed mostly from weathering of the Indosinian granites (GR) and Palaeozoic sandstones (PL), and metals of anthropogenic sources were contributed from Pb–Zn ore deposits distributed in upper river areas. Metals in the lake sediments consist of the anthropogenic proportions, which were contributed from automobile exhausts and coal dusts. Thus, heavy-metal contamination for the river sediments is attributed to the exploitation and utilization (e.g., mining, smelting, and refining) of Pb–Zn ore mineral resources in the upper river areas, and this for the lake sediments was caused by automobile exhausts and coal combustion. Metals Bi, Cd, Pb, Sn and Sb have anthropogenic proportion of higher than 90%, with natural contribution less than 10%. Metals Mn and Zn consist of anthropogenic proportion of 60–85%, with natural proportion higher than 15%. Metals Sc, Cr, Co, Cu, Tl, Th, U and Ta have anthropogenic proportion of 30–70%, with natural contribution higher than 30%. Metals Ba, V and Mo might be contributed mostly from natural process.     

Organic matter in waters of the SW Atlantic sector of the Southern Ocean

The 25th cruise of R/FAkademik Knipovitch conducted in January–April of 1990 comprised investigations of total organic carbon (TOC) at the following sections: through the Polar Frontal Zone (PFZ) along 40° W, made in January and April; from the PFZ to the South Orkney Islands, and on the South Georgia shelf. The measurements made comprised TOC, organic nitrogen, nitrate, nitrite, ammonium nitrogen, phosphate and silicate.The surface waters of the region were characterized by high heat content, which influenced the Antarctic phytosynosis function. The data obtained showed low content of organic matter (OM); high content of TOC, rising up to 3,5 mg m^–3, was recorded at the photic layer and in the layer of OM accumulation, at the upper boundary of the Antarctic Deep Waters and the vertical boundaries of the Antarctic Intermediate Waters. The South Georgia shelf waters showed even distribution of TOC, about 0,2 mg m^–3, being under the influence of the south periphery of the ACC waters.     

Anthropogenic CO2 in Southern Ocean surface waters: evidence from stable organic carbon isotopes

We present an approach for tracing the fate of anthropogenic CO₂, compiling a large data set of stable organic carbon isotope ratios from surface sediments, plankton, and sinking matter in the Atlantic Ocean. The δ¹³C values of sinking matter are generally lower by 0.5–4.6‰ compared to the surface sediments. This difference increases with increasing latitude, which is explained by a stronger modern increase in surface water [CO₂ (aq)] in the Southern Ocean relative to the Tropical/Subtropical Ocean. Preindustrial dissolved CO₂ concentrations in Atlantic surface waters, estimated from the δ¹³C_org of surface sediments, are compared to recently measured surface water [CO₂ (aq)] values taken from literature. We obtain only a slight increase in [CO₂ (aq)] at lower latitudes but a significant change of about 7 ± 2 μ m in high latitudinal surface waters which we attribute to anthropogenic perturbation. Our results suggest that CO₂ released by human activities has been stored in Southern Ocean surface waters.     

Iodine budget in surface waters from Atacama: Natural and anthropogenic iodine sources revealed by halogen geochemistry and iodine-129 isotopes

Iodine enrichment in the Atacama Desert of northern Chile is widespread and varies significantly between reservoirs, including nitrate-rich “caliche” soils, supergene Cu deposits and marine sedimentary rocks. Recent studies have suggested that groundwater has played a key role in the remobilization, transport and deposition of iodine in Atacama over scales of millions-of-years. However, and considering that natural waters are also anomalously enriched in iodine in the region, the relative source contributions of iodine in the waters and its extent of mixing remain unconstrained. In this study we provide new halogen data and isotopic ratios of iodine (¹²⁹I/I) in shallow seawater, rivers, salt lakes, cold and thermal spring water, rainwater and groundwater that help to constrain the relative influence of meteoric, marine and crustal sources in the Atacama waters. Iodine concentrations in surface and ground waters range between 0.35 μM and 26 μM in the Tarapacá region and between 0.25 μM and 48 μM in the Antofagasta region, and show strong enrichment when compared with seawater concentrations (I = ∼0.4 μM). In contrast, no bromine enrichment is detected (1.3–45.7 μM for Tarapacá and 1.7–87.4 μM for Antofagasta) relative to seawater (Br = ∼600 μM). These data, coupled to the high I/Cl and low Br/Cl ratios are indicative of an organic-rich sedimentary source (related with an “initial” fluid) that interacted with meteoric water to produce a mixed fluid, and preclude an exclusively seawater origin for iodine in Atacama natural waters. Iodine isotopic ratios (¹²⁹I/I) are consistent with halogen chemistry and confirm that most of the iodine present in natural waters derives from a deep initial fluid source (i.e., groundwater which has interacted with Jurassic marine basement), with variable influence of at least one atmospheric or meteoric source. Samples with the lowest isotopic ratios (¹²⁹I/I from ∼215 to ∼1000 × 10⁻¹⁵) strongly suggest mixing between the groundwater and iodine storage in organic-rich rocks (with variable influence of volcanic fluids) and pre-anthropogenic meteoric water, while samples with higher values (∼2000–93,700 × 10⁻¹⁵) indicate the input of anthropogenic meteoric fluid. Taking into account the geological, hydrologic and climatic features of the Atacama region, we propose that the mean contribution of anthropogenic ¹²⁹I is associated with ¹²⁹I releases during nuclear weapon tests carried out in the central Pacific Ocean until the mid 1990's (¹²⁹I/I = ∼12,000 × 10⁻¹⁵). This source reflects rapid redistribution of this radioisotope on a global scale. Our results support the notion of a long-lived continental iodine cycle in the hyperarid margin of western South America, which is driven by local hydrological and climate conditions, and confirm that groundwater was a key agent for iodine remobilization and formation of the extensive iodine-rich soils of Atacama.     

Microbial sources of intact polar diacylglycerolipids in the Western North Atlantic Ocean

Intact polar membrane lipids are essential components of microbial membranes and recent work has uncovered a diversity of them occurring in the ocean. While it has long been understood that lipid composition varies across microbial groups, the microbial origins of the intact polar lipids in the surface ocean remain to be fully explained. This study focused on identifying the microbial sources of intact polar diacylglycerolipids (IP-DAGs) in the surface waters of the western North Atlantic Ocean. We used three approaches to define these microbial sources: (i) ¹³C tracing to identify photoautotrophic and heterotrophic production of the major classes of IP-DAGs, (ii) cell sorting flow cytometry of Prochlorococcus, Synechococcus and heterotrophic bacteria to determine IP-DAG composition and (iii) regrowth incubations targeting IP-DAG production by heterotrophic bacteria. Stable isotope tracing indicated that sulfoquinovosyldiacylglycerol (SQDG) and diacylglyceryl-trimethyl-homoserine (DGTS) were produced predominantly by photoautotrophs, while phosphatidylglycerol (PG) production was dominated by heterotrophic bacteria. Of the cells sorted with flow cytometry, Prochlorococcus and Synechococcus were found to have abundant glycolipids, while heterotrophic bacteria were dominated by phospholipids. The regrowth incubations showed that the growth of heterotrophic bacteria correlated with an increase in the concentration of PG, phosphatidylethanolamine (PE) and monoglycosyldiacylglycerol (MGDG). The finding of MGDG in heterotrophic bacteria differs from previous work, which had asserted that the membranes of heterotrophic bacteria in this environment were composed entirely of phospholipids. Overall, our findings indicate that phytoplankton are the primary source of SQDG and DGTS, while heterotrophic bacteria are the dominant source of PG, making these three compounds promising biomarkers for the study of microbes in the surface ocean.     

Spatial distribution of metals in ground/surface waters in the Chandrapur district (Central India) and their plausible sources

This study addresses a framework to evaluate and map environmental hazard with reference to spatial distribution of major and trace metal contamination and its relationship with lithology in Chandrapur district of Maharashtra, India using geospatial, statistical and GIS tools. In all, 208 ground water and 35 surface water samples were collected using global positioning system (GPS) synoptically with satellite imagery IRS P6 LISS III and were analyzed in ICP-AES. Analytical results reflect the presence of major and trace metals in ground water in terms of % as Fe (48%), Mn (12%), Zn (9%), Al (8%), Pb (7%), Cu (6%), Ni (4%), Cd (3%) and Cr (3%) of the total average concentration. The contamination is attributed to weathering of rocks and also to mining activities. Similarly, surface water contribution of major and trace metals was found as Al (47.8%), Fe (42.8%), Mn (5.5%), Zn (2.3%), Pb (0.56%), Ni (0.42%), Cu (0.16%), Cr (0.16%) and Cd (0.10%) of the total average concentration. Ordinary kriging interpolation method was adopted to assess the spatial distribution of different major and trace metals in groundwater samples with their best model fit variogram Classical statistical method like principal component analysis (PCA) was carried out in order to establish correlation between spatial pattern of metal contamination and geology of the area in GIS environment. Various surface and subsurface aspects like landuse/land cover, structural features, hydrogeology, topography etc were also considered to ascertain their impact to supplement the inference of the study.     

The distribution of trace metals in the western North Atlantic off Nova Scotia

The distributions of Fe, Mn, Zn, Cu, Ni, Cd and Co have been determined in a section across the Scotian Shelf into the Atlantic Slope water. Significant differences in concentration exist for most of the trace metals between the four water masses in the section. Depletions of trace metal concentration in the highly productive Atlantic Slope water relative to the underlying Central Atlantic water are thought to be due to biological activity.The distributions of Fe and Mn are strongly related to the distribution of suspended particulate matter. The concentrations of Fe and Mn, extracted from the suspended matter on the Scotian Shelf, are considerably higher than those in the non-detrital fraction of the underlying sediments. This suggests that post-depositional changes cause the loss of both elements from the non-detrital fraction of the particles. Whereas Mn shows major nearshore increases in concentration related to continental runoff, nearshore Fe concentrations are largely controlled by particulate matter distribution. Continental runoff does not appear to have much influence upon the distributions of the other trace metals.     

Contribution of organic complexation to Ni,Co and Cu speciation in surface waters: Implications for hydrogeochemicalsurveys

Organic materials dissolved in surface waters have long been implicated in metal binding and transport. In particular, fulvic and humic acids are considered to have a significant impact on speciation, total metal levels in solution and on the persistence of those metals. This work emphasizes the role played by dissolved organic matter (DOM) on the complexation of nickel, copper and cobalt and on its application to interpretation of surface water hydrogeochemical survey data. Waters from a number of well-known mining districts in Canada have been studied; in particular from Cobalt (Ontario), Sackville (New Brunswick) and Thetford Mines (Quebec). The diafiltration binding technique was used and shows that nickel, copper and cobalt are complexed significantly by DOM in natural waters. The tendency towards complexation was found to be Cu > Ni > Co. The binding functions determined were observed to be highly sensitive to pH and ligand:metal ratios; a gradation of binding site strength is evident.Data from some hydrogeochemical surveys conducted in the Kenora, Algoma and Ottawa districts of Ontario have been reinterpreted in the light of available data on the complexation behaviour of nickel, copper and cobalt. Occurrence of large water-borne anomalies unsupported by lake sediment loadings is most likely for cobalt and nickel and least likely for copper according to both field observations and experimental data. These studies provide good evidence for the formation of strong solution stable metal-organic species; the principal differences in persistence and migration behaviour are probably due to rates of coagulation and adsorption-precipitation processes which preferentially remove copper from solution. It is fair to conclude that these metals can be of use in mineral exploxation surveys using surface waters provided caution is exercised in interpretation of anomalies, especially in the absence of supporting sediment anomalies. Dissolved organic matter concentrations should always be determined when nickel, copper and cobalt are to be employed.     

New constraints on the sources and behavior of neodymium and hafnium in seawater from Pacific Ocean ferromanganese crusts

The behavior of dissolved Hf in the marine environment is not well understood due to the lack of direct seawater measurements of Hf isotopes and the limited number of Hf isotope time-series obtained from ferromanganese crusts. In order to place better constraints on input sources and develop further applications, a combined Nd-Hf isotope time-series study of five Pacific ferromanganese crusts was carried out. The samples cover the past 38 Myr and their locations range from sites at the margin of the ocean to remote areas, sites from previously unstudied North and South Pacific areas, and water depths corresponding to deep and bottom waters.For most of the samples a broad coupling of Nd and Hf isotopes is observed. In the Equatorial Pacific ε_Nd and ε_Hf both decrease with water depth. Similarly, ε_Nd and ε_Hf both increase from the South to the North Pacific. These data indicate that the Hf isotopic composition is, in general terms, a suitable tracer for ocean circulation, since inflow and progressive admixture of bottom water is clearly identifiable.The time-series data indicate that inputs and outputs have been balanced throughout much of the late Cenozoic. A simple box model can constrain the relative importance of potential input sources to the North Pacific. Assuming steady state, the model implies significant contributions of radiogenic Nd and Hf from young circum-Pacific arcs and a subordinate role of dust inputs from the Asian continent for the dissolved Nd and Hf budget of the North Pacific.Some changes in ocean circulation that are clearly recognizable in Nd isotopes do not appear to be reflected by Hf isotopic compositions. At two locations within the Pacific Ocean a decoupling of Nd and Hf isotopes is found, indicating limited potential for Hf isotopes as a stand-alone oceanographic tracer and providing evidence of additional local processes that govern the Hf isotopic composition of deep water masses. In the case of the Southwest Pacific there is evidence that decoupling may have been the result of changes in weathering style related to the buildup of Antarctic glaciation.     

Nutrient inputs to the Choptank River estuary: Implications for watershed management

Degraded water quality due to water column availability of nitrogen and phosphorus to algal species has been identified as the primary cause of the decline of submersed aquatic vegetation in Chesapeake Bay and its subestuaries. Determining the relative impacts of various nutrient delivery pathways on estuarine water quality is critical for developing effective strategies for reducing anthropogenic nutrient inputs to estuarine waters. This study investigated temporal and spatial patterns of nutrient inputs along an 80-km transect in the Choptank River, a coastal plain tributary and subestuary of Chesapeake Bay, from 1986 through 1991. The study period encompassed a wide range in freshwater discharge conditions that resulted in major changes in estuarine water quality. Watershed nitrogen loads to the Choptank River estuary are dominated by diffuse-source inputs, and are highly correlated to freshwater discharge volume. in years of below-average freshwater discharge, reduced nitrogen availability results in improved water quality throughout most of the Choptank River. Diffuse-source inputs are highly enriched in nitrogen relative to phosphorus, but point-source inputs of phosphorus from sewage treatment plants in the upper estuary reduce this imbalance, particularly during summer periods of low freshwater discharge. Diffuse-source nitrogen inputs result primarily from the discharge of groundwater contaminated by nitrate. Contamination is attributable to agricultural practices in the drainage basin where agricultural land use predominates. Groundwater discharge provides base flow to perennial streams in the upper regions of the watershed and seeps directly into tidal waters. Diffuse-source phosphorus inputs are highly episodic, occurring primarily via overland flow during storm events. Major reductions in diffuse-source nitrogen inputs under current landuse conditions will require modification of agricultural practices in the drainage basin to reduce entry rates of nitrate into shallow groundwater. Rates of subsurface nitrate delivery to tidal waters are generally lower from poorly-drained versus well-drained regions of the watershed, suggesting greater potential reductions of diffuse-source nitrogen loads per unit effort in the well-drained region of the watershed. Reductions in diffuse-source phosphorus loads will require long-term management of phosphorus levels in upper soil horizons. *** DIRECT SUPPORT *** A01BY074 00021     

Sulfur and lead isotopes of Guern Halfaya and Bou Grine deposits (Domes zone,northern Tunisia): Implications for sources of metals and timing of mineralization

The Pb–Zn ore deposits in the Guern Halfaya and Bou Grine areas (northern Tunisia) are hosted mainly by dolostones in the contact zone between Triassic and Upper Cretaceous strata and by Upper Cretaceous limestones. The deposits occur as lenticular, stratiform, vein, disseminations and stockwork ore bodies consisting of sphalerite, galena, pyrite, chalcopyrite and sulfosalt (gray copper). Barite and celestite dominate the gangue, with lesser calcite. The δ³⁴S values of barite and celestite (12.7–15.0‰) at the Oum Edeboua mine are consistent with the reduction of sulfates in Triassic evaporites within the study area (12.8 < δ³⁴S < 14.0‰). The δ³⁴S values in base-metal sulfides from both study areas (2.6–9.5‰) and the presence of bacterial relics suggest involvement of bacterially-mediated sulfate reduction in the mineralization. The present Pb isotope data are homogeneous with ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios of 18.723–18.783, 15.667–15.685 and 38.806–38.889, respectively, which suggest a single source reservoir of Pb at depth in the upper crust. The syn-diagenetic mineralization in the Bahloul Formation and the calculated age from the Pb isotopic data suggest an Upper Cretaceous age for the Pb–Zn deposits in the Guern Halfaya and Bou Grine areas. During this period, NE–SW to ENE–WSW trending regional extensional tectonic structures likely favored migration of mineralizing fluids and eventual deposition at Guern Halfaya and Bou Grine.     

Dissolved aluminium in interstitial waters of recent terrigenous marine sediments from the North Atlantic Ocean

The vertical distribution of dissolved Al in interstitial waters of recent marine sediments has been determined using a fluorimetric analytical method adapted for interstitial water analysis. The results suggest that diagenetic reactions occur in the sediment soon after deposition. A narrow depth zone acting as a source of dissolved Al is found in each core. Outside this zone Al appears to be removed from solution and its concentration decreases to values of 1.5 μgAl/l or less, comparable to those of open ocean waters. Dissolved Al and SiO₂ concentrations in interstitial waters close to the sediment-seawater interface are linearly correlated in most cases, suggesting that the geochemistry of Al may be related to the behaviour of biogenic silica in marine sediments.     

Iron and other transition metals in Patagonian riverborne and windborne materials: geochemical control and transport to the southern South Atlantic Ocean

The bulk of particulate transition metals transported by Patagonian rivers shows an upper crustal composition. Riverine particulate 0.5 N HCl leachable trace metal concentrations are mainly controlled by Fe-oxides. Complexation of Fe by dissolved organic carbon (DOC) appears to be an important determinant of the phases transporting trace metals in Patagonian rivers. In contrast, aeolian trace elements have a combined crustal and anthropogenic origin. Aeolian materials have Fe, Mn, and Al contents similar to that found in regional topsoils. However, seasonal concentrations of some metals (e.g., Co, Pb, Cu, and Zn) are much higher than expected from normal crustal weathering and are likely pollutant derived.We estimate that Patagonian sediments are supplied to the South Atlantic shelf in approximately equivalent amounts from the atmosphere (∼30 × 10⁶ T yr⁻¹) and coastal erosion (∼40 × 10⁶ T yr⁻¹) with much less coming from the rivers (∼2.0 × 10⁶ T yr⁻¹). Low trace metal riverine fluxes are linked to the low suspended particulate load of Patagonian rivers, inasmuch most of it is retained in pro-glacial lakes as well as in downstream reservoirs. Based on our estimation of aeolian dust fluxes at the Patagonian coastline, the high nutrient-low chlorophyll sub Antarctic South Atlantic could receive 1.0 to 4.0 mg m⁻² yr⁻¹ of leachable (0.5 N HCl) Fe. Past and present volcanic activity in the southern Andes—through the ejection of tephra—must be highlighted as another important source of Fe to the South Atlantic Ocean. Based on the 1991 Hudson volcano eruption, it appears that volcanic events can contribute several thousand-fold the mass of “leachable” Fe to the ocean as is introduced by annual Patagonian dust fallout.     

冀东平原土壤重金属元素的来源分析

通过对比冀东平原表层和深层土壤样品中8种重金属含量,并利用因子分析提取了7个主因子,结合因子得分图进行重金属来源分析。结果显示Cr的来源具有分异性,一部分源于土壤本底,另一部分来源于矿业污染造成的元素叠加;Hg的来源主要为农业生产,部分地区Hg是由冶金、交通等污染排放所致;唐海县附近Cd主要为河流上游元素搬运成因。局部地区Pb高度富集是由于采矿污染造成。As、Cu、Zn、Ni等元素主要来源于当地自然地质背景。     

Constraints from strontium and neodymium isotopic ratios and trace elements on the sources of the sediments in Lake Huguang Maar

The sediments in Lake Huguang Maar in coastal South China were previously thought to originate mainly from wind-blown dust transported from North China, such that the lake sediments recorded the varying strength of the Asian winter monsoon. An alternative explanation was that the local pyroclastic rocks supplied the lake sediments, but the actual contributions from the different sources remained unclear. Geochemical analyses including ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd and trace elements support the local pyroclastic rock as the dominant source: < 22% of the total Sr in the lake sediments and  17% of the Nd arises from the distant source. Nb/Ta and Zr/Hf for the lake sediments are identical to those for the local rock but differ from the ratios for the wind-blown dust, and chondrite-normalized rare earth element patterns for the lake sediments are similar to those for the local rock and soil, but differ from those for the distant source. The sediments in Lake Huguang Maar are probably input into the lake through runoff and thus controlled by the hydrology of the lake. Wind-blown dust transported by the Asian winter monsoon from arid North China is only a minor contribution to the sediments.     

Geochemistry of highly-undersaturated ocean island basalt suites from the South Atlantic Ocean: Fernando de Noronha and Trindade islands

The volcanic rocks of the South Atlantic Ocean islands of Fernando de Noronha and Trindade comprise a diverse magmatic series ranging from nephelinites and basanites to phonolites and, on Fernando de Noronha, trachytes. All rock types are highly silica undersaturated with the exception of Fernando de Noronha trachytes_, and have high abundances of incompatible trace elements and strongly LREE (light rare earth element)-enriched REE patterns. Crystal fractionation of parental basanitic magmas produced evolved phonolites and trachytes which display severe trace-element fractionation, even among trace elements (Nb, Ta, Zr, Hf) which normally behave highly incompatibly during crystallisation of alkaline magmas. Moderately to highly evolved compositions develop strongly MREE (middle REE)-depleted REE patterns, and become increasingly depleted in elements such as Nb and, in particular, Ta. Ratios of Nb/Ta and Zr/Hf are highly fractionated in phonolites (60–65, 64–77 respectively in Fernando de Noronha phonolites) compared to ratios in basanites (14, 45 respectively). The compatibility of Nb, Ta, and the REE, and the strong fractionation of Nb/Ta and Zr/Hf ratios and the MREE, during crystallisation from basanite to phonolite are attributable to the crystallisation of small amounts (<5%) of sphene. Trace-element behaviour is relatively insensitive to the major phenocryst phases, and is controlled by minor phases in highly undersaturated alkaline suites. Incompatible trace-element ratios (e.g. La/Nb, Th/Ta) in nephelinites and basanites from Fernando de Noronha and Trindade are generally comparable with those in basaltic and hawaiitic OIB (ocean island basalt) lavas from other South Atlantic islands, but are distinct from those of Gough and Tristan da Cunha OIB. The mantle source for the highly undersaturated volcanism on Fernando de Noronha and Trindade is similar in trace-element characteristics to the typical OIB source which produces alkaline lavas with significant relative enrichment in Nb and Ta compared to other trace elements (as expressed by low La/Nb, Ba/Nb and Th/Ta ratios). The highly undersaturated nature of the magmas and the slight fractionation of some incompatible-element ratios (elevated Ba/Nb, Ba/Rb, Ba/Th etc.) is consistent with a smaller degree of melting of a typical OIB source, but with residual phlogopite in the source to account for significant K depletion and LIL-element fractionation.     

Sorption of trace metals on calcite: Applicability of the surface precipitation model

Published Sorption isotherm data of Cd²⁺, Mn²⁺, Zn²⁺, and Co²⁺ on calcite are adequately described by the surface precipitation model which was originally developed by FArley et al. (1985) for the sorption of cations on metal oxides. In addition to monolayer adsorption, the model accounts for the formation of a surface phase with a composition that is described by a solid solution having as end members the sorbent calcium carbonate mineral and a pure carbonate precipitate of the sorbing trace metal. The model thus specifies a continuum between adsorption and precipitation. This feature is supported in the literature by observations on the reaction kinetics and the amount of surface coverage during trace metal sorption on calcite. The apparent adsorption constants of these trace metals, as derived from the model, can be ranked according to the degree to which their ionic radii match the ionic radius of Ca²⁺.     

Distribution and sources of pre-anthropogenic lead isotopes in deep ocean water from FeMn crusts

The lead isotope composition of ocean water is not well constrained due to contamination by anthropogenic lead. Here the global distribution of lead isotopes in deep ocean water is presented as derived from dated (ca. 100 ka) surface layers of hydrogenetic Fe-Mn crusts. The results indicate that the radiogenic lead in North Atlantic deep water is probably supplied from the continents by river particulates, and that lead in Pacific deep water is similar to that characteristic of island and continental volcanic arcs. Despite a short residence time in deep water (80–100 a), the isotopes of lead appear to be exceedingly well mixed in the Pacific basin. There is no evidence for the import of North Atlantic deep water-derived lead into the Pacific ocean, nor into the North Indian Ocean. This implies that the short residence time of lead in deep water prohibits advection over such long distances. Consequently, any climate-induced changes in deep-water flow are not expected to result in major changes in the seawater Pb-isotope record of the Pacific Ocean.