Whole-rock geochemical analyses of serpentinized harzburgites from ODP Site 209-1270

Small-scale shear zones are present in drillcore samples of abyssal peridotites from the Mid-Atlantic ridge at 15°20'N (Ocean Drilling Program Leg 209). The shear zones act as pathways for both evolved melts and hydrothermal fluids. We examined serpentinites directly adjacent to such zones to evaluate chemical changes resulting from melt-rock and fluid-rock interaction and their influence on the mineralogy. Compared to fresh harzburgite and melt-unaffected serpentinites, serpentinites adjacent to melt-bearing veins show a marked enrichment in rare earth elements (REE), strontium and high field strength elements (HFSE) zirconium and niobium. From comparison with published chemical data of variably serpentinized and melt-unaffected harzburgites, one possible interpretation is that interaction with the adjacent melt veins caused the enrichment in HFSE, whereas the REE contents might also be enriched due to hydrothermal processes. Enrichment in alumina during serpentinization is corroborated by reaction path models for interaction of seawater with harzburgite-plagiogranite mixtures. These models explain both increased amounts of alumina in the serpentinizing fluid for increasing amounts of plagiogranitic material mixed with harzburgite, and the absence of brucite from the secondary mineralogy due to elevated silica activity. By destabilizing brucite, nearby melt veins might fundamentally influence the low-temperature alteration behaviour of serpentinites. Although observations and model results are in general agreement, due to absence of any unaltered protolith a quantification of element transport during serpentinization is not straightforward.

Composition of Holocene lithificates at the slopes of the Untersee Mountain Valley, East Antarctica

It was found out that the lower parts of slopes of the Untersee mountain valley (East Antarctica) were locally covered with lithificates (both carbonate-free and carbonate-poor). They occur in three modes: crusts, films, and impregnates. All of them cover Late Pleistocene moraine material and consist of mixture of lacustrine sedimentary material and filling material of moraines. A mechanism of their genesis is offered.

Geochemistry at DSDP Leg 73 Holes

In the South Atlantic, at Sites 519 to 523, the dissolution of calcareous oozes ended in the formation of red clays rich in iron and manganese. The early authigenesis of manganese oxides and clays is described in Miocene marly calcareous oozes. The mineralogical and geochemical influences of basaltic basement weathering are shown by the occurrence of palagonite, authigenic clays, and oxides in the basal sediments. The development of red clay facies can be inhibited by local topographic and paleoceanographic changes, as at Site 520.

Chemical composition of Fe-Mn nodules and crusts from the Pacific Ocean

The book is devoted to study of diagenetic changes of organic matter and mineral part of sediments and interstitial waters of the Pacific Ocean due to physical-chemical and microbiological processes. Microbiological studies deal with different groups of bacteria. Regularities of quantitative distribution and the role of microorganisms in geochemical processes are under consideration. Geochemical studies highlight redox processes of the early stages of sediment diagenesis, alterations of interstitial waters, regularities of variations in chemical composition of iron-manganese nodules.

Major element chemistr yof fallout tephra from ODP Hole 125-782A

New and published analyses of major element oxides (SiO2, TiO2, Al2O3, FeO*, MnO, MgO, CaO, K2O, Na2O and P2O5) from the central Izu Bonin and Mariana arcs (IBM) were compiled in order to investigate the evolution of the IBM in terms of major elements since arc inception at ~49 million years ago. The database comprises ?3500 volcanic glasses of distal tephra fallout and ?500 lava samples, ranging from the Quaternary to mid-Eocene in age. The data were corrected to 4 wt% MgO in order to display the highly resolved temporal trends. These trends show that the IBM major elements have always been "arc-like" and clearly distinct from N-MORB. Significant temporal variations of some major element oxides are apparent. The largest variations are displayed by K4.0. The data support a model wherein the K2O variability is caused by the addition of slab component with strongly differing K2O contents to a fairly depleted subarc mantle; variable extents of melting, or mantle heterogeneity, appear to play a negligible role. The other major element oxides are controlled by the composition and processes of the subarc mantle wedge. The transition from the boninitic and tholeiitic magmatism of the Eocene and Oligocene to the exclusively tholeiitic magmatism of the Neogene IBM is proposed to reflect a change in the composition of the subarc mantle wedge. The early boninitic magmas originate from an ultra-depleted subarc mantle, that is residual to either the melting of E-MORB mantle, or of subcontinental lithospheric mantle. During the Eocene and Oligocene, this residual mantle is gradually replaced by Indian MORB mantle advected from the backarc regions. The Indian MORB mantle is more radiogenic in Nd isotope ratios but also more fertile with respect to major and trace elements. Therefore the Neogene tholeiites have higher Al2O3 and TiO2 contents and lower mg# numbers at given SiO2 content. After the subarc mantle replacement was complete in the late Oligocene or early Miocene, the Neogene IBM entered a "steady state" that is characterized by the continuous advection of Indian MORB mantle from the reararc, which is fluxed by fluids and melt components from slab. The thickness of the IBM crust must have grown with time, but any effects of crustal thickening on the major element chemistry of the IBM magmas appear to be minor relative to the compositional changes that are related to source composition. Therefore next to the processes of melting, the composition of the mantle sources must play a major role in creating substantiative heterogeneities in the major element chemistry of the arc crust.

Chemical, isotopic and mineral compositions of basal metalliferous sediments from DSDP Legs 5 and 7

Sediments from near the basement of a number of Deep Sea Drilling Project (DSDP) sites, from the Bauer Deep, and from the East Pacific Rise have unusually high transition metal-to-aluminum ratios. Similarities in the chemical, isotopic, and mineralogical compositions of these deposits point to a common origin. All the sediments studied have rare-earth-element (REE) patterns strongly resembling the pattern of sea water, implying either that the REE's were coprecipitated with ferromanganese hydroxyoxides (hydroxyoxides denote a mixture of unspecified hydrated oxides and hydroxides), or that they are incorporated in small concentrations of phosphatic fish debris found in all samples. Oxygen isotopic data indicate that the metalliferous sediments are in isotopic equilibrium with sea water and are composed of varying mixtures of two end-member phases with different oxygen isotopic compositions: an iron-manganese hydroxyoxide and an iron-rich montmorillonite. A low-temperature origin for the sediments is supported by mineralogical analyses by x-ray diffraction which show that goethite, iron-rich montmorillonite, and various manganese hydroxyoxides are the dominant phases present. Sr87/Sr86 ratios for the DSDP sediments are indistinguishable from the Sr87/Sr86 ratio in modern sea water. Since these sediments were formed 30 to 90 m.y. ago, when sea water had a lower Sr87/Sr86 value, the strontium in the poorly crystalline hydroxyoxides must be exchanging with interstitial water in open contact with sea water. In contrast, uranium isotopic data indicate that the metalliferous sediments have formed a closed system for this element. The sulfur isotopic compositions suggest that sea-water sulfur dominates these sediments with little or no contribution of magmatic or bacteriologically reduced sulfur. In contrast, ratios of lead isotopes in the metalliferous deposits resemble values for oceanic tholeiite basalt, but are quite different from ratios found in authigenic marine manganese nodules. Thus, lead in the metalliferous sediments appears to be of magmatic origin. The combined mineralogical, isotopic, and chemical data for these sediments suggest that they formed from hydrothermal solutions generated by the interaction of sea water with newly formed basalt crust at mid-ocean ridges. The crystallization of solid phases took place at low temperatures and was strongly influenced by sea water, which was the source for some of the elements found in the sediments.

Annotated record and spectrochemical analyses of Mn nodules from Georgia Strait, British Columbia obtained during CNAV Laymore in 1970

A study of the distribution, dispersal and composition of surficial sediments in the Strait of Georgia, B.C., has resulted in the understanding of basic sedimentologic conditions within this area. The Strait of Georgia is: a long, narrow, semi-enclosed basin with a restricted circulation and a single, main, sediment source. The Fraser. River supplies practically all the sediment now being deposited in the Strait of Georgia, the bulk of it during the spring and summer freshet. This river is building a delta into the Strait from the east side near the south end. Ridges of Pleistocene deposits within the Strait and Pleistocene material around the margins, like bedrock exposures, provide local sources of sediment of only minor importance. Rivers and streams other than the Fraser contribute insignificant quantities of sediment to the Strait. Sandy sediments are concentrated in the vicinity of the delta, and in the area to the south and southeast. Mean grain size decreases from the delta toward the northwest along the axis of the Strait, and basinwards from the margins. Silts and clays are deposited in deep water west and north of the delta front, and in deep basins northwest of the delta. Poorly sorted sediments containing a gravel component are located near tidal passes, on the Vancouver Island shelf area, on ridge tops within the Strait, and with sandy sediments at the southeastern end of the study area. The Pleistocene ridges are areas of non-deposition, having at most a thin veneer of modern mud on their crests and upper flanks. The southeastern end of the study area contains a thick wedge of shandy sediment which appears to be part of an earlier delta of the Fraser River. Evidence suggests that it is now a site of active submarine erosion. Sediments throughout the Strait are compositionally extremely similar, with-Pleistocene deposits of the Fraser River drainage basin providing the principal, heterogeneous source. Gravels and coarse sands are composed primarily of lithic fragments, dominantly of dioritic to granodloritlc composition. Sand fractions exhibit increasing simplicity of mineralogy with decreasing grain-size. Quartz, felspar, amphibole and fine-grained lithic fragments are the dominant constituents of the finer sand grades. Coarse and medium silt fractions have compositions similar to the fine sands. Fine silts show an increase in abundance of phyllosilicate material, a feature even more evident in the clay-size fractions on Montmorillonite, illite, chlorite, quartz and feldspar are the main minerals in the coarse clay fraction, with minor mixed-layer clays and kaolinite. The fine clay fraction is dominated by montmorillonite, with lesser amounts of illite and chlorite. The sediments have high base-exchange capacities, related to a considerable content of montmorillonite. Magnesium is present in exchange positions in greater quantity in Georgia Strait sediments than in sediments from the Fraser River, indicating a preferential uptake of this element in the marine environment. Manganese nodules collected from two localities in the Strait imply slow sediment accumulation rates at these sites. Sedimentation rates on and close to the delta, and in the deep basins to the northwest, are high.

The relationship between soil geochemistry and the bioaccessibility of trace elements in playground soil

A total of 32 samples of surficial soil were collected from 16 playground areas in Madrid (Spain), in order to investigate the importance of the geochemistry of the soil on subsequent bioaccessibility of trace elements. The in vitro bioaccessibility of As, Co, Cr, Cu, Ni, Pb and Zn was evaluated by means of two extraction processes that simulate the gastric environment and one that reproduces a gastric + intestinal digestion sequence. The results of the in vitro bioaccessibility were compared against aqua regia extractions (“total” concentration), and it was found that total concentrations of As, Cu, Pb and Zn were double those of bioaccessible values, whilst that of Cr was ten times higher. Whereas the results of the gastric + intestinal extraction were affected by a high uncertainty, both gastric methods offered very similar and consistent results, with bioaccessibilities following the order: As = Cu = Pb = Zn > Co > Ni > Cr, and ranging from 63 to 7 %. Selected soil properties including pH, organic matter, Fe and CaCO3 content were determined to assess their influence on trace element bioaccessibility, and it was found that Cu, Pb and Zn were predominantly bound to organic matter and, to a lesser extent, Fe oxides. The former fraction was readily accessible in the gastric solution, whereas Fe oxides seemed to recapture negatively charged chloride complexes of these elements in the gastric solution, lowering their bioaccessibility. The homogeneous pH of the playground soils included in the study does not influence trace element bioaccessibility to any significant extent except for Cr, where the very low gastric accessibility seems to be related to the strongly pH-dependent formation of complexes with organic matter. The results for As, which have been previously described and discussed in detail in Mingot et al. (Chemosphere 84: 1386–1391, 2011), indicate a high gastric bioaccessibility for this element as a consequence of its strong association with calcium carbonate and the ease with which these bonds are broken in the gastric solution. The calculation of risk assessments are therefore dependant on the methodology used and the specific environment they address. This has impacts on management strategies formulated to ensure that the most vulnerable of society, children, can live and play without adverse consequences to their health.

Origin and patterns of distribution of trace elements in street dust. Unleaded petrol and urban lead

The elemental composition, patterns of distribution and possible sources of street dust are not common to all urban environments, but vary according to the peculiarities of each city. The common features and dissimilarities in the origin and nature of street dust were investigated through a series of studies in two widely different cities, Madrid (Spain) and Oslo (Norway), between 1990 and 1994. The most comprehensive sampling campaign was carried out in the Norwegian capital during the summer of 1994. An area of 14 km2, covering most of downtown Oslo and some residential districts to the north of the city, was divided into 1 km2 mapping units, and 16 sampling increments of approximately 150 g were collected from streets and roads in each of them. The fraction below 100 μm was acid-digested and analysed by ICP-MS. Statistical analyses of the results suggest that chemical elements in street dust can be classified into three groups: “urban” elements (Ba, Cd, Co, Cu, Mg, Pb, Sb, Ti, Zn), “natural” elements (Al, Ga, La, Mn, Na, Sr, Th, Y) and elements of a mixed origin or which have undergone geochemical changes from their original sources (Ca, Cs, Fe, Mo, Ni, Rb, Sr, U). Soil resuspension and/or mobilisation appears to be the most important source of “natural” elements, while “urban” elements originate primarily from traffic and from the weathering and corrosion of building materials. The data for Pb seem to prove that the gradual shift from leaded to unleaded petrol as fuel for automobiles has resulted in an almost proportional reduction in the concentration of Pb in dust particles under 100 μm. This fact and the spatial distribution of Pb in the city strongly suggest that lead sources other than traffic (i.e. lead accumulated in urban soil over the years) may contribute as much lead, if not more, to urban street dust.