Zinc,Copper, and Lead Geochemistry of Oceanic Igneous Rocks—Ridges,Islands, and Arcs

Variations in the abundances of Zn, Cu, and Pb are found to be useful in identifying tectonic regimes and separating oceanisland basalts into enriched- and depleted-source categories. The average Zn, Cu, and Pb contents of normal mid-ocean ridge basalts (N-MORB) are 84, 70, and 0.35 ppm, respectively. Differences in average Zn contents for various ridges reflect more the varying degrees of differentiation than variations of Zn content in the source rocks. At a Mg# of 70, or Mg#₇₀, which is taken to represent primitive MORB, many MORB sequences converge at a Zn content of 58 ± 6 ppm, which is close to the value for primitive mantle (50 ppm) and ordinary chondrites (～55 ppm). Values of 0.1 to 0.15 ppm Pb in MORB at Mg#₇₀, best defined at the superfast-spreading Southern East Pacific Rise, are similar to estimates of Pb in the primitive mantle (0.12 to 0.18 ppm). They also are near the lower end of the range for ordinary chondrites. The very slow spreading Southwest Indian Ocean Ridge has a sequence with higher Pb contents, in addition to a more normal sequence, which has a visual best value of 0.4 ppm Pb at Mg#₇₀. With the exception of the Walvis Ridge, Zn and Cu appear to be little affected by proximity to hotspots (i.e., E-MORB); however, Pb contents are higher and average about 0.6 ppm.

Both Zn and Pb in MORB are incompatible elements (i.e., favor the melt), but Cu is a compatible element. At Mg#₇₀, there is the suggestion of a value of 100 ppm for Cu, with lower values possibly representing partial removal of sulfides and their associated Cu from the source. Nonetheless, Cu contents of primitive MORB tend to be much higher than even high estimates for the primitive mantle (28 ppm), and are closer to ordinary chondrites (～90 ppm). Therefore, Zn, Cu, and Pb all approximate chondritic values in the primitive MORB melt.

Average contents of Zn, Cu, and Pb in oceanic island basalts (OIB) are 115, 62, and 3.2 ppm, respectively. At Mg#₇₀, values of Zn and Cu are similar to the respective averages for OIB, with Zn higher and Cu lower than MORB. At a Mg# of ～40, however, OIB and MORB tend to have similar Zn contents. With further differentiation, OIB trachytes can contain >200 ppm Zn. Unlike MORB, OIB can differentiate to high Cu contents of 200 ppm at Mg#s of 40 to 60. In contrast to Zn and Cu, Pb regresses to a value of 0.83 ppm at Mg#₇₀ for Hawaiian and Reunion volcanics, which is much less than the average value for Pb in OIB volcanics, but higher than for MORB.

Average Zn, Cu, and Pb contents of magmatic-arc basalts are 77, 108, and 1.9 ppm, respectively. In basalts, Zn tends to be incompatible, but a dual incompatible and compatible behavior can occur at high SiO₂ contents. Dacites may average near 55 ppm Zn, but peralkalic rhyolite can contain >300 ppm Zn. A dual compatible and incompatible nature occurs for Cu. Most common, particularly in submarine volcanics, is a compatible trend, with a Cu content of around 80 ppm at a Mg# of 60, which decreases to less than 40 ppm at a Mg# of 30. The incompatible trend of increasing Cu can achieve >200 ppm at a Mg# of 30, leaving a gap approaching 100 ppm at that Mg#. The gap is less obvious on a plot of Cu vs. SiO₂, but is still there. The compatible trend is proposed to result from sulfur-saturated magmas, whereas the incompatible trend is believed to result from sulfur-deficient magmas. Support for this hypothesis is found in sparse sulfur-isotope data. Zn and Cu both can be incompatible over an extended range of Mg#s or silica content. When Zn and Cu are both compatible, Cu decreases more than twice as rapidly as Zn.

Primitive magmas at Mg#₇₀ average about 50 ppm Zn for submarine Mariana arc basalts and 58 ppm for forearc boninites, contents close to MORB values. Mariana arc basalts have a Zn content of ～45 ppm estimated at Mg#₇₀. Cu varies more widely than Zn in primitive magmas, being about 50 ppm Cu for Mariana Islands volcanics and 120 ppm for Kermadec Islands volcanics, a range broadly around MORB values. Average Pb contents are 1.9 ppm for island-arc tholeiites, 5.6 ppm for high-Al basalt, and 3.2 ppm for alkali basalt with average boninite of approximately 1.8 ppm. Back-arc-basin basalts in the deepest parts of the Mariana trough have Pb contents of 0.45 ppm, but more shallow parts may exceed 1.0 ppm Pb. Although the lower contents are similar to MORB values, the ²⁰⁸Pb/²⁰⁴Pb values are greater than Pacific Ocean MORB. At Mg#₇₀ for rocks from the Tonga and Kermadec island arcs, the Pb content is about 0.1 ppm, similar to MORB.     

Heterogeneous mantle melting and magmatic processes at the East Pacific Rise (2.6–3.1°S): Evidence from mid-ocean ridge basalt geochemistry and Sr–Nd–Pb isotopes

ABSTRACT

We present the major and trace elements and Sr, Nd, and Pb isotopes in mid-ocean ridge basalts (MORB) from the East Pacific Rise (EPR) at 2.6–3.1°S. These samples are low-K tholeiites and show significant variation in their major element compositions (e.g. 4.60–8.18 wt% MgO, 8.34–12.12 wt% CaO, 9.78–14.25 wt% Fe₂O₃, and 0.06–0.34 K₂O wt%). Trace element abundances of the 2.6–3.1°S MORB are variably depleted (e.g. (La/Sm), _N = 0.51–0.78, Zr/Y = 2.35–3.42, Th/La = 0.035–0.056, and Ce/Yb = 2.38–3.96) but closely resemble the average N-MORB. In the compatible elements (Ni and Cr) against incompatible element Zr plots, the 2.6–3.1°S MORB show well-defined negative correlations, together with a liquid line of descent (LLD) modelling and petrographic observations, implying a significant role of olivine, plagioclase and clinopyroxene fractionation during magma evolution. When compared to global MORB and peridotites, the 2.6–3.1°S MORB and most of the other axial lavas from the South EPR show similar Zn/Fe, Zn/Mn, and Fe/Mn ratios, attesting to a peridotite-dominated mantle lithology. However, the relationships between incompatible trace element ratios, such as Zr/Rb and Nb/Sm, and the negative correlation between Zr/Nb and ⁸⁷Sr/⁸⁶Sr indicate a geochemically heterogeneous mantle source. The mantle beneath the South EPR likely consists of two components, with the enriched component residing as physically distinct domains (e.g. veins or dikes) in the depleted peridotite matrix. In the Sr–Nd–Pb isotope space, the South EPR MORB lie along the mixing lines between the depleted MORB mantle (DMM) and the ‘C’-like Pukapuka endmember. We infer that low-F melts derived from these enriched materials may cause localized mantle heterogeneity (veins or dikes) via an infiltration process. Subsequent melting of the refertilized mantle may impart an isotopically distinct characteristic to South EPR MORB.     

XRF AND INAA DETERMINATIONS OF MAJOR AND TRACE ELEMENTS IN GEOLOGICAL SURVEY OF JAPAN IGNEOUS AND SEDIMENTARY ROCK STANDARDS

Major and trace element analyses have been obtained by wavelength dispersive X-ray fluorescence for the Geological Survey of Japan Igneous rock series and selected samples from the Sedimentary rock series reference samples. Additional trace element data for the Igneous rock series were obtained by instrumental neutron activation analysis. Samples were analyzed multiple times for 10 major elements (with loss-on-ignition) and the following trace elements; As, Ba, Ce, Co, Cr, Cs, Cu, Eu, Ga, Hf, La, Lu, Nb, Nd, Ni, Pb, Rb, Sb, Sc, Sm, Sr, Ta, Tb, Th, U, V, W, Y, Yb, Zn and Zr.     

Volcanism in nascent back-arc basins behind the Shichito Ridge and adjacent areas in the Izu-Ogasawara arc,northwest Pacific: evidence for mixing between E-type MORB and island arc magmas at the initiation of back-arc rifting

Mineral chemistry, major and trace elements, and ⁸⁷Sr/⁸⁶Sr ratios are presented for 29 igneous rocks dredged from the northern portion of the Izu-Ogasawara arc. These rocks are compositionally bimodal. Basement gabbro and trondhjemite from the arc are extremely poor in K₂O (0.05–0.19%) and Rb (0.48–0.62 ppm), and their REE patterns and Sr isotope ratios indicate that there are island arc tholeiites. Quaternary volcanic rocks from the present volcanic front (Shichito Ridge; active arc), back-arc seamounts (east side; inactive arc) and Torishima knoll between the two back-arc depressions (incipient back-arc basins) behind the active arc have the same geochemical characteristics as the above plutonic rocks though they are not as depleted in K and Rb. Rhyolite pumice from the backarc depression is also the depleted island arc tholeiite, whereas basalts from the depression have compositions that are transitional between MORB and island arc tholeiites in trace element (Ti, Ni, Cr, V, Y and Zr) and mineral chemistries. The back-arc depression basalts have relatively high Ba_N/Ce_N(0.66–1.24), Ce_n/Yb_N(1.1–1.9) and K/Ba(45–105) and low ⁸⁷Sr/⁸⁶Sr (0.70302–0.70332) and Ba/Sr (0.1–0.2), which are similar to other back-arc basin basalts and E-type MORB, but are quite unlike the depleted island arc tholeiites. The diverse trace element and Sr isotope compositions of basalt-andesite from the back-arc depressions imply the interplay between E-type MORB and island arc tholeiite. These chemical characteristics and the relationships of (Ce/Yb)_N vs (Ba/Ce)_N and (Ce/Yb)_N vs ⁸⁷Sr/⁸⁶Sr suggest that the back-arc depression magmas are generated by mixing of E-type MORB and depleted island arc tholeiite magmas. Geochemical characters of the associated rhyolite from the depression are compatible with partial melting of lower crust.     

Pedo-geochemical baseline content levels and soil quality reference values of trace elements in soils from the Mediterranean (Castilla La Mancha, Spain)

To evaluate trace element soil contamination, geochemical baseline contents and reference values need to be established. Pedo-geochemical baseline levels of trace elements in 72 soil samples of 24 soil profiles from the Mediterranean, Castilla La Mancha, are assessed and soil quality reference values are calculated. Reference value contents (in mg kg^?1) were: Sc 50.8; V 123.2; Cr 113.4; Co 20.8; Ni 42.6; Cu 27.0; Zn 86.5; Ga 26.7; Ge 1.3; As 16.7; Se 1.4; Br 20.1; Rb 234.7; Sr 1868.4; Y 38.3; Zr 413.1; Nb 18.7; Mo 2.0; Ag 7.8; Cd 4.4; Sn 8.7; Sb 5.7; I 25.4; Cs 14.2; Ba 1049.3; La 348.4; Ce 97.9; Nd 40.1; Sm 10.7; Yb 4.2; Hf 10.0; Ta 4.0; W 5.5; Tl 2.3; Pb 44.2; Bi 2.2; Th 21.6; U 10.3. The contents obtained for some elements are below or close to the detection limit: Co, Ge, Se, Mo, Ag, Cd, Sb, Yb, Hf, Ta, W, Tl and Bi. The element content ranges (the maximum value minus the minimum value) are: Sc 55.0, V 196.0, Cr 346.0, Co 64.4, Ni 188.7, Cu 49.5, Zn 102.3, Ga 28.7, Ge 1.5, As 26.4, Se 0.9, Br 33.0 Rb 432.7, Sr 3372.6, Y 39.8, Zr 523.2, Nb 59.7, Mo 3.9, Ag 10.1, Cd 1.8, Sn 75.2, Sb 9.9, I 68.0, Cs 17.6, Ba 1394.9, La 51.3, Ce 93.5, Nd 52.5, Sm 11.2, Yb 4.2, Hf 11.3, Ta 6.3, W 5.2, Tl 2.1, Pb 96.4, Bi 3.0, Th 24.4, U 16.4 (in mg kg^?1). The spatial distribution of the elements was affected mainly by the nature of the bedrock and by pedological processes. The upper limit of expected background variation for each trace element in the soil is documented, as is its range as a criterion for evaluating which sites may require decontamination.     

Approaches to equilibrium in the distribution of trace elements among the principal minerals in a high-grade metamorphic terrane

X-ray fluorescence, instrumental neutron activation, and particle-induced X-ray emission methods were used to determine the distribution of numerous trace elements among garnet (Grt), Ca-pyroxene (Cpx), hornblende (Hbl), biotite (Bt), plagioclase (Pl) and K-feldspar (Kf) in a high-grade metamorphic terrane within the Grenville Province of the Canadian Shield. Results are presented as distribution formulae, e.g. Sr: Kf 1.1 Pl 16 Hbl 2.2 Cpx 1.0 Bt 1.2 Grt Sc: Hbl 1.1 Cpx 1.0 Grt 7.8 Bt 22 Pl 2.6 Kf V: Hbl 1.15 Bt 2.07 Cpx 6.0 Grt (1.4% CaO)>1 (Pl, Kf) Zn: Bt 1.6 Hbl 1.62 Cpx 2.9 Grt 10 Pl Ga: Bt 1.2 Hbl 1.2 Pl 2.5 Cpx 1.3 Grt where numbers are distribution ratios, e.g. ppm Sr in Hbl/ppm Sr in Cpx=2.2. Examples of inter-element similarities and differences are (a) both Rb and Cs are concentrated in biotite relative to K-feldspar, but for Rb the ratio is 2.3 and for Cs it is 16, (b) the distribution formulae for seven lanthanides are similar except for the position of garnet, e.g. Ce: Hbl 2.7 Cpx 2.8 Pl 1.1 Bt 11 Kf 16 Grt Yb: Grt 2.8 Hbl 2.7 Cpx 9 Pl 1.0 Bt 7 Kf and (c) all of Sr, eight lanthanides, Zr, V and Cr are concentrated in hornblende relative to Ca-pyroxene by a factor that lies in the narrow range of 2.2–3.1. There is a larger variation (departure from the mean) in some distribution ratios than in others. Thus the mean ratios (Hbl/Cpx) for each of six elements and in parentheses the percentage relative standard deviation are Zn 1.62 (8.6), V 2.38 (12), Cr 2.42 (18), Sr 2.7 (28), Ba 2.9 (36) and Ni 1.66 (38). We suggest that variation of this kind is the result of differences from place to place in the magnitude of deformation and recrystallization (which facilitated the rearrangement of atoms), combined with rates of lattice and crystal-boundary diffusion that are unique for the various elements, thus permitting some trace elements to approach equilibrium more closely than others.     

REE-HFSE distribution/partitioning between garnetiferous restites and TTG from Nademavinapura area,Western Dharwar craton

The major part of the Peninsular Gneiss in Dharwar craton is made up of Trondjhemite-Tonalite-Granodiorite (TTG) emplaced at different periods ranging from 3.60 to 2.50 Ga. The sodic-silicic magma precursors of these rocks have geochemical features characteristic of partial melting of hydrated basalt. In these TTGs, enclaves of amphibolites (± garnet) are abundant. These restites are considered to be the residue of a basaltic crust after its partial melting. A detailed study of these (residue) enclaves reveals textures formed due to the process of partial melting. Major, trace and REE analysis of these residue enclaves and the melt TTGs and microprobe analysis of the coexisting minerals show partitioning of REE and HFSE between the precursor melt of TTGs and the upper amphibolite facies residues. Formation of garnetiferous amphibolites with biotite, Cpx and plagioclase consequent to melting, has squeezed the original MORB type of basaltic crust and given rise to the TTGs, depleted in Y, Yb, K₂O, MgO, FeO, TiO₂ and enriched in La, Th, U, Zr and Hf. Coevally during the process of melting, the hydrated basalt was depleted in Na₂O, Al₂O₃, LREE, Th, U and enriched in K₂O, MgO, Nb, Ti, Yb, Y, Sc, Ni, Cr and Co. Mineral chemistry of co-existing garnet-biotite and amphibole-plagioclase in these amphibolitic (restite) enclaves indicates an average temperature of 700 ± 50° C and pressure of 5 ± 1 Kbar. These data are inferred to indicate that during the garnet stability field metamorphism, effective fractionation of HREE and HFSE has taken place between the restites having Fe-Mg silicates, ilmenites and the extracted melt generated from the MORB type of hydrated basalt. These results are strongly substantiated by the reported melting experiments on hydrated basalts.     

LA-ICP-MS study of apatite- and K feldspar-hosted primary carbonatite melt inclusions in clinopyroxenite xenoliths from lamprophyres, Hungary: Implications for significance of carbonatite melts in the Earth’s mantle

We report the results of LA-ICP-MS analyses of rock forming minerals in clinopyroxene-apatite-K feldspar-phlogopite (CAKP) metasomatic xenoliths and primary carbonatite melt inclusions (CMI) hosted in apatite (Ap) and K feldspar (Kfs). The xenoliths are from the Cretaceous lamprophyre dikes of the Transdanubian Central Range, Hungary. The CMI in Ap have phosphorus dolomitic composition as opposed to CMI in Kfs, which display dolomitic alkali-aluminosiliceous character. The melts found in CMI in Ap and in Kfs likely formed by liquid-liquid separation from an originally carbonate- and phosphorous-rich melt. Primitive mantle (PM) normalized trace element distributions of both Ap- and Kfs-hosted CMI (n = 60 and 20, respectively) reveal a strong negative Ti-anomaly, and an extreme enrichment in incompatible elements (U, Th, LILE and LREE) relative to HREE, Sc, V, Ni and Cr. Rarely, apatites contain unique CMI, which show major- and trace-element signature transitional to K feldspar-hosted CMI. This is due to heterogeneous entrapment of an immiscible phosphorous-bearing carbonatite melt and a carbonate-bearing alkali aluminosiliceous melt, which is a further evidence for their co-existence. CMI reveal that U, Th, Pb, Nb, Ta, P, Sr, Y and REE partitioned into the phosphorous-bearing carbonatite melt, whereas Cs, Rb, Na, K, B, Al, Zr and Hf preferred the silicate-bearing liquid.PM normalized REE pattern (high LREE/HREE), elevated Zr and Hf contents and negative Ti anomaly of clinopyroxene (Cpx) indicate that its formation is genetically linked to carbonatite metasomatism attested by CMI. Trace element partitioning between the studied Cpx and CMI is in accordance with experimentally determined trace element distributions between Cpx and carbonatite melt. Cpx, which occur in samples with high modal proportion of apatite represent mantle section, which interacted with a higher amount of “initial” carbonatite melt than Cpx from apatite-poor xenoliths. This is confirmed by higher Cr, Ni, V, Sc, Ti and lower Zr, as well as Hf concentration in Cpx from xenoliths with low modal abundance of Ap. CMI reveal that Ti, V, Ni and Cr were in lower concentration in the “initial” carbonatite melt than in PM. Contrarily, Zr and Hf were more abundant in this melt than in PM. Consequently, a continuously migrating “initial” carbonatite melt, increased Zr and Hf concentration, and decreased Ti, Sc, V, Ni and especially Cr in the clinopyroxenes. Our findings suggest that the studied CAKP rocks were formed by carbonatite melt metasomatism, which occurred in an open system in the upper mantle.     

Origin of coexisting minette and ultramafic breccia,Navajo volcanic field

Trace element evidence indicates that at the Buell Park diatreme, Navajo volcanic field, the felsic minette can be best explained by crystal fractionation from a potassic magma similar in composition to the mafic minettes. Compatible trace element (Cr, Ni, Sc) abundances decrease while concentrations of most incompatible elements (Ce, Yb, Rb, Ba, Sr) remain constant or increase from mafic to felsic minette. In particular, the nearly constant Ce/Yb ratio of the minettes combined with the decrease in Cr, Ni, and Sc abundances from mafic to felsic minette is inconsistent with a model of varying amounts of partial melting as the process to explain minette compositions. The uniformity of rare earth element (REE) abundances in all the minettes requires that an accessory mineral, apatite, dominated the geochemistry of the REE during fractionation. A decrease in P₂O₅ from mafic to felsic minette and the presence of apatite in cognate inclusions are also consistent with apatite fractionation. Higher initial⁸⁷Sr/⁸⁶Sr ratios in the felsic minettes relative to the proposed parental mafic minettes, however, is inconsistent with a simple fractionation model. Also, a separated phlogopite has a higher initial⁸⁷Sr/⁸⁶Sr ratio than host minette. These anomalous isotopic features probably reflect interaction of minette magma with crust.The associated ultramafic breccia at Buell Park is one of the Navajo kimberlites, but REE concentrations of the matrix do not support the kimberlite classification. Although the matrix of the breccia is enriched in the light REE relative to chondrites, and has high La, Rb, Ba, and Sr concentrations relative to peridotites, the concentrations of these elements are significantly lower than in South African kimberlites. A high initial⁸⁷Sr/⁸⁶Sr ratio combined with petrographic evidence of ubiquitous crustal xenoliths in the Navajo kimberlites suggests that the relatively high incompatible element concentrations are due to a crustal component. Apparently, Navajo kimberlites are most likely a mixture of comminuted mantle wall rock and crustal material; there is no evidence for an incompatible element-rich magma which is characteristic of South African kimberlites.If the mafic minettes are primary magmas derived from a garnet peridotite source with chondritic REE abundances, then REE geochemistry requires very small (less than 1%) degrees of melting to explain the minettes. Alternatively, the minettes could have formed by a larger degree of melting of a metasomatized, relatively light REE-enriched garnet peridotite. The important role of phlogopite and apatite in the differentiation of the minettes supports this latter hypothesis.     

Eclogite trace in evolution of Late Cenozoic alkaline basalt volcanism on the southwestern flank of the Baikal Rift Zone: Geochemical features and geodynamic consequences

Eclogitized material from the oceanic lithosphere are the most likely source of alkaline basalt magmas in the formation of Late Cenozoic volcanic areas on the southwestern flank of the Baikal Rift Zone. Basaltic trachyandesites of the early stage of volcanism (Pg₃² ~ 28–23 Ma) are rich in high field strength elements (HFSE), P₂O₅, F, Zn, Ga, Sr, Sn, and light rare earth elements (LREE); they are characterized by high values of the following ratios: Fe/Mn = 72–77, Sm/Yb = 7.7–8.5, Sr/Y = 57–63, and Ga/Sc = 2.1–2.3. At this stage, magmas are formed under conditions with a 2–8% degree of partial melting of the mantle substrate enriched with the material of the eclogite source (50–70%) (Cpx/Grt = 1.5–1.7). Basaltoid magmas of the final stage of volcanism (N₁³–N₂¹ ~ 6–4 Ma) are formed from melting (1.5–4%) of a less fertilized mantle (Cpx/Grt = 2.1–3.1, Fe/Mn = 62–71, Sm/Yb = 3.5–4.6, Sr/Y = 29–44, Ga/Sc = 1.0–1.4). The directed variations of the compositions of the successive basaltoid magmas, which were formed in the Late Cenozoic, create an “eclogite trace” in this area.     

Experimental cpx/melt partitioning of 24 trace elements

Cpx/melt partition coefficients have been determined by ion probe for 24 trace elements at natural levels in an alkali basalt experimentally equilibrated at 1,380°C and 3 GPa. One goal was to intercompare Ds for both high-field-strength elements and rare earth elements (REE) in a single experiment. Relative to the REE spidergram, Hf and Ti show virtually no anomaly, whereas Zr exhibits a major negative anomaly. Other incompatible elements (Ba, K, Nb) fall in the range of published values, as do elements such as Sr, Y, Sc, Cr and V. Pb shows a value intermediate between La and Ce. Values for Be, Li and Ga are reported for the first time, and show that Be is as incompatible as the light REEs whereas Li and Ga are somewhat more compatible than the heavy REE.     

Concentration and distribution of elements in Late Permian coals from western Guizhou Province,China

With the aim of better understanding geochemistry of coal, 71 Late Permian whole-seam coal channel samples from western Guizhou Province, Southwest China were studied and 57 elements in them were determined. The contents of Al, Ca, Co, Cr, Cu, Fe, Ga, Hf, K, Li, Mn, Mo, Nb, Ni, Sn, Ta, Ti, Th, U, V, Zr, and REEs in the Late Permian coals from western Guizhou Province are higher than the arithmetic means for the corresponding elements in the US coals, whereas As, Ba, Br, F, Hg, P, Se, and Tl are lower. Compared to common Chinese coals, the contents of Co, Cr, Cu, Ga, Hf, Li, Mn, Mo, Ni, Sc, Sn, Ti, U, V, Zn, and Zr in western Guizhou coals are higher, and As, F, Hg, Rb, Sb, Tl, and W are lower. Five groups of elements may be classified according to their mode of occurrence in coal: The first two, Group A, Tm–Yb–Lu–Y–Er–Ho–Dy–Tb–Ce–La–Nd–Pr–Gd–Sm, and Group B, As–Sr–K–Rb–Ba–F–Ash–Si–Sn–Ga–Hf–Al–Ta–Zr–Be–Th–Na, have high positive correlation coefficients with ash yield and they show mainly inorganic affinity. Some elements from Group B, such as Ba, Be, Ga, Hf, and Th, are also characterized by significant aluminosilicate affinity. In addition, arsenic also exhibits high sulfide affinity (r_S–Fe>0.5). The elements, which have negative or lower positive correlation coefficients with ash yield (with exceptions of Bi, Cs, Nb, Mn, Se, and Ti), are grouped in other four associations: Group C, Cr–V–Mo–U–Cd–Tl; Group D, Hg–Li–Sc–Ti–Eu–Nb–Cs–W; Group E, Bi–Sb; and Group F, Co–Ni–Cu–Pb–Zn–Mg–Se–Ca–Mn–S–Fe. The correlation coefficients of some elements, including Co, Cr, Cu, Fe, Hg, Li, Mo, Ni, P, S, Sc, U, V, and Zn, with ash yield are below the statistically significant value. Only Cr and Cu are negatively correlated to ash yield (−0.07 and −0.01, respectively), showing intermediate (organic and inorganic) affinity. Manganese and Fe are characterized by carbonate affinity probably due to high content of epigenetic veined ankerite in some coals. Phosphorus has low correlation coefficients with any other elements and is not included in these six associations. There are five possible genetic types of enrichment of elements in coal from western Guizhou Province: source rock, volcanic ash, low-temperature hydrothermal fluid, groundwater, and magmatic hydrothermal inputs.     

Clinopyroxene/liquid trace element partitioning in natural trachyte–trachyphonolite systems: insights from Campi Flegrei (southern Italy)

Trace element partition coefficients between clinopyroxenes and associated glassy matrix (^Cpx/L D) have been determined for 13 REE, HFSE^4+,5+, U, Th, Sr, Pb, Sc and V from combined LA-ICP-MS/EMP analyses in selected trachytes and trachyphonolites from Campi Flegrei. Composition of clinopyroxene and glass is pretty homogeneous in the trachyphonolites, pointing to an overall attainment of the equilibrium conditions. In trachytes, conversely, phases show some compositional heterogeneity (due to the presence of clinopyroxene xenocrysts) that requested a more careful petrographic and geochemical inspection of the samples to assess the equilibrium clinopyroxene composition. In the trachyte clinopyroxenes, REE are compatible from Nd to Lu (^Cpx/L D up to 2.9), like Y, Ti, Sc and V. The ^Cpx/L D for Eu is lower than those of the adjacent REE, highlighting Eu²⁺ contribution. High D values are also shown by U, Th, Pb, Zr, Hf, Nb and Ta relatively to basaltic and andesitic systems, whereas the D _Sr is roughly similar to that found for less evolved magmas. Trachyphonolites are characterized by an overall decrease of the ^Cpx/L D for highly-charged cations (with the exception of V), and by a slight increase of D _Sr. REE are still compatible from Nd to Lu (^Cpx/L D up to 2.1), like Ti, Y, Sc and V. This variation is also predicted for REE and Y by models based on the elastic strain theory, being consistent with the slightly lower polymerization degree estimated for the trachyphonolites. However, the observed ^Cpx/L D _(REE,Y) are matched by the modelled ones only considering very low T (≤825°C), which are believed unlikely. This mismatch cannot be attributed to effects induced by the water-rich composition of the trachyte–trachyphonolite suite, since they would lower the observed ^Cpx/L D _(REE,Y). Moreover, the anomalous inflections of measured ^Cpx/L D for HREE suggests some crystal-chemical control, such as the entrance of these elements in a site distinct from M2. It is concluded that the large ^Cpx/L D determined for trachytes and trachyphonolites are likely induced by hitherto unconstrained changes of the Z³⁺ activities related to the composition of melt and/or solid. All these considerations strongly highlight the importance of a direct characterization of trace element partitioning in natural samples from magmatic systems poorly characterized by experimental studies. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

MORB‐like rocks in a Palaeozoic convergent margin setting,northeast New South Wales

The Devonian mafic rocks from the Folly Basalt, northeast New South Wales, were emplaced in the forearc section of the Devonian‐Carboniferous magmatic arc preserved in the western part of the New England Fold Belt. Trace‐element abundances in fractionated metadolerites (maximum concentration of Ni = 85 ppm) from the Folly Basalt outcropping near Nundle demonstrate that these rocks have MORB affinity. Chondrite‐normalised rare‐earth element patterns are smooth and quasi‐horizontal; Ce/Yb ratios are 3.34–7.98; (La/Yb)_N ratios range from 0.69 to 2.23; (La/Sm)_N ratios of the rocks range from 0.63 to 1.55. The data are compatible with an origin of the melts from large degrees (>15%) of partial melting of mantle peridotite. A plausible mechanism for the production and emplacement of depleted magmas in the forearc zone of the Middle Palaeozoic eastern Australian magmatic arc involves the subduction of a hot oceanic spreading centre, which could cause the presence of a region of asthenospheric temperatures below the upper plate. It is also suggested that sustained high‐temperature conditions may have prevailed in the eastern Australian mantle for at least the last 400 million years.     

Geochemistry and Origin of Layers in Single Manganese Nodule from the Philippine Sea and Manganese Nodules from Offshore Minami-Torishima,Western Pacific

Layers from one manganese nodule dredged from the Philippine Sea(16°56'N, 129°48'E; water depth, 5700 m) and 45 bulk nodules from offshore Minami-Torishima Island, Japan(23°3'N, 153°22'E; water depth, 1200 m) were analyzed chemically and their origin is discussed based on geochemical constraints. In general, Cu, Ni, Zn and Mo tend to increase with increasing Mn content, while Co, Pb, Ba, V, Sc, Th, and the rare earth elements(REEs) show less variation with increasing Mn content. Nodule 42 H from the Philippine Sea has an average Mn/Fe ratio close to 1 and shows a positive Ce anomaly, suggesting a predominant hydrogenous origin. Profiles of 230Th230 ex and Thex/232 Th ratios in the outer ~0.3 mm of nodule 42 H indicate a steady growth rate of ~1.7 mm/Myr. Nodule E30 from offshore Minami-Torishima is characterized by lower Mn, Fe, Mn/Fe(0.53) and Mo/V(0.2) ratios but higher P and Cu/Ni(0.31) ratio relative to other nodules from that area. The Ce content of E30 is unusually low(82 ppm) when compared with other nodules from the area and it is the only nodule analyzed with a negative Ce anomaly(-0.64). Based on the geochemical data we suggest that most nodules from offshore Minami-Torishima are primarily of hydrogenous origin except E30, which is dominated by hydrothermal input, and E45, which has about a 35% hydrothermal contribution.     

Taxonomical and Biogeochemical Investigation of Elements in Holocene Mollusk Shells in the South and Southwestern Marmara Basin,Turkey

Concentrations of some heavy metals and trace elements such as Cr, Ga, Ni, Zn, Mo, Cu, Pb, Yb, Y, Nb, Ti, Sr, Ba, Mn, Sc, Co, V, Zr, Fe, Al, W, Se, Bi, Sb, As, Cd in recent mollusk shells and factors affecting their distribution and deposits collected from various depths in the southern and southwestern parts of the Marmara Sea are investigated. The distribution of the elements in the shells is categorized into four groups. Of these, concentrations of 12 elements （As, Bi, Cd, Co, Ga, Mo, Nb, Sb, Se, Sc, W and Yb） are below zero [（0.053-0.79）×10^-6]; concentrations of seven elements （Cr, Ni, Pb, V, Y, Zr and Cu） are （1.0-6.0）×10^-6; concentrations of four elements （Ti, Mn, Ba and Zn） are 10- 20×10^-6; and concentrations of five elements （Si, Al, Fe, Mg and Sr） are （47.44-268.11）×10^-6. The taxonomic characteristics of the 29 elements were studied separately in mollusk shells such as Chamalea gallina （Linn6）, Pitar rudis （Poli）, Nassarius reticulatus （Linn6）, Venerupis senescens （Coocconi）, Mytilus galloprovincialis （Lamarck）, Mytilaster lineatus （Gemelin in Linne） and Chlamys glabra. It was found that, in mollusk taxonomy, the elements have unique values. In other words, element concentrations in various mollusk shells depend mainly on the taxonomic characteristics of mollusks. In various bionomic environments different element distributions of the same species are attributed to the different geochemical characters of the each environment. Data obtained in this study indicate that the organisms are the most active and deterministic factors of the environment.     

Dynamic melting of the Precambrian mantle: evidence from rare earth elements of the amphibolites from the Nellore–Khammam Schist Belt, South India

The Nellore–Khammam Schist Belt (NKSB) in South India is a Precambrian greenstone belt sited between the Eastern Ghats Mobile Belt (EGMB) to the east and the Cratonic region to the west. The belt contains amphibolites, granite gneisses and metasediments including banded iron formations. Amphibolites occurring as dykes, sills and lenses—in and around an Archaean layered complex—form the focus of the present study. The amphibolites are tholeiitic in composition and are compositionally similar to Fe-rich mafic rocks of greenstone belts elsewhere. The NKSB tholeiites show highly variable incompatible trace element abundances for similar Mg#s, relatively constant compatible element concentrations, and uniform incompatible element ratios. Chondrite-normalized REE patterns of the tholeiites range from strongly LREE depleted ((La/Yb) _N = 0.19) to LREE enriched ((La/Yb) _N = 6.95). Constant (La/Ce) _N ratios but variable (La/Yb) _N values are characteristic geochemical traits of the tholeiites; the latter has resulted in crossing REE patterns especially at the HREE segment. Even for the most LREE depleted samples, the (La/Ce) _N ratios are > 1 and are similar to those of the LREE enriched samples. There is a systematic decrease in FeO^t, K₂O and P₂O₅, as well as Ce and other incompatible elements from the LREE enriched to the depleted samples without any variation in the incompatible element ratios and Mg#s. Neither batch and fractional melting, nor magma chamber processes can account for the non-correlation between the LREE enrichment and HREE concentrations. We suggest that dynamic melting of the upper mantle is responsible for these geochemical peculiarities of the NKSB tholeiites. Polybaric dynamic melting within a single mantle column with variable mineralogy is the likely mechanism for the derivation of NKSB tholeiitic melts. It is possible that the NKSB tholeiites are derived from a source with higher FeO/MgO than that of present day ridge basalts.     

Geochemical Characteristics and LA-ICP-MS Zircon U-Pb Dating of Amphibolites in the Songshugou Ophiolite in the Eastern Qinling

Geochemical studies on the arnphibolites in the Songshugou ophiolite from Shangnan County, Shaanxi Province demonstrate that the protolith of the amphibolites is tholeiitic. The arnphibolites can be classified into two groups according to their REE patterns and trace element features. Rocks of the first group are depleted in LREE while rocks of the second group are slightly depleted in LREE or flat from LREE to HREE without significant Eu anomaly. The first group of rocks have (La/Yb)N=0.33-0.55, (La/Sm)N= 0.45-0.65, and their La/Nb, Ce/Zr, Zr/Nb, Zr/Y and Ti/Y ratios are averaged at 1.20, 0.12, 31.02, 2.92 and 198, respectively, close to those of typical N-MORB. The second group of rocks have (La/Yb)N=0.63-0.95, (La/ Sm)N = 0.69--0.90, and their average La/Nb, Ce/Zr, Zr/Nb, Zr/Y and Ti/Y ratios are 0.82, 0.83, 1.15, 0.16, 19.00, 2.58 and 225, respectively, which lie between those of typical N-MORB and E-MORB but closer to the former. The two groups of rocks both exhibit flat patterns from Th to Yb in th     

Immiscible separation of metalliferous Fe/ Ti-oxide melts from fractionating alkali basalt: P-T-f O2 conditions and two-liquid elemental partitioning

Globules of iron-dominated (59–69 wt% FeO_tot) and titanium-dominated (43.5 wt% TiO₂) oxide melts have been detected in igneous xenoliths from Pliocene-to-Pleistocene alkali basalts of the Western Carpathians. Fluid inclusion and mineral composition data indicate immiscible separation of the high-iron-oxide melt (HIM) at magmatic temperatures. The HIM separation occurred during clinopyroxene (augite) accumulation in an alkali trachybasalt and continued during crystallization of amphibole (kaersutite) and K-feldspar (anorthoclase), the latter coexisting with trachyte and alkalic rhyolite residual melts. Some HIM was also expelled from sub-alkalic rhyolite (70–77% SiO₂), coexisting with An_27–45 plagioclase and quartz in granitic (tonalite-trondhjemite) xenoliths. Oxygen fugacities during HIM separation range from −1.4 to +0.6 log units around the QFM buffer. A close genetic relationship between HIM-hosted xenoliths and mantle-derived basaltic magma is documented by mineral ¹⁸O values ranging from 4.9 to 5.9‰ V-SMOW. δD values of gabbroic kaersutite between −61 and −86‰ V-SMOW are in agreement with a presumed primary magmatic water source. Most trace elements, except Li, Rb and Cs, have preferentially partitioned into the HIM. The HIM/Si-melt partition coefficients for transition elements (Sc, V, Cr, Co, Ni) and base metals (Zn, Cu, Mo) are between 2–160, resulting in extreme enrichment in the HIM. La and Ce also concentrate in the silicic melt, whereas Tb-Tm in the HIM. Hence, the immiscible separation causes REE fractionation and produces residual silicic melt enriched in LREE and depleted in HREE. The weak fractionation among Tb-Tm and Yb, Lu can be attributed to recurrent extraction of the HIM from the magmatic system, while flat HREE chondrite-normalized patterns are interpreted to indicate no or little loss of the HIM. Received: 30 September 1997 / Accepted: 23 March 1998     

汇聚板块边缘岩浆中金属和氯的地球化学性质研究

总结了铜(Cu)、金(Au)、铼(Re)和氯(Cl)在汇聚板块边缘岩浆中的性质。在岛弧型的火山岩岩浆演化的早期,Cu、Au和Re均表现为中度不相容元素,含量随SiO2含量的增加而增加。在SiO2质量分数为58%时,多数岛弧型火山岩中Au、Cu的含量会突然大幅度下降。这一变化与铁和钛的变化是耦合的,铁和钛均由不相容元素变为相容元素,显示钛磁铁矿开始结晶了。进一步的研究表明,钛磁铁矿的结晶使硫酸根被还原为氢硫酸根,后者与Au、Cu形成氢硫酸根络合物,被萃取到流体相中,从而形成成矿流体。这一过程可以很好地解释Au、Cu矿床广泛分布于汇聚板块边缘的现象。与Au、Cu相反,Re的含量在SiO2质量分数为60%时才开始下降,而且是缓慢下降。这是因为Re通常比Au、Cu更亲石。此外,Re还具有强烈的挥发性。氯在东Manus岩浆中表现为高度不相容的特点。氯的性质主要受压力、初始水含量和岩浆演化分异程度的控制。计算结果显示,由于MORB和OIB含水量低,分异演化程度低,氯在上述岩浆中表现为高度不相容的特点。相比之下,氯在岛弧岩浆中的性质就复杂得多。随着水含量和岩浆房深度的不同,氯的性质可以从相容变到高度不相容。