Multi-stage mixing in subduction zones: Application to Merapi volcano (Java island, Sunda arc)

Many studies have argued for the contribution of at least three components, namely the mantle wedge, the subducted oceanic crust, and its sediment cover, to describe the geochemistry of island arc volcanics. However, isotope correlations reflecting a simple binary mixing can be observed at the scale of a single arc island or volcano. Here we investigate the possibility that these trends reflect pseudo-binary mixing relationships in a three-component system. We present a simplified, two-stage model for the systematic isotope modelling of a cogenetic suite of arc lavas. This includes metasomatism of portions of the mantle wedge by hydrous phases released from the down-going oceanic crust, and sediments, followed by progressive mixing and melting. A consequence of this model is that it leads to a two end-member mixing process from the mantle wedge, oceanic crust, and sediment components. To solve the model we reduce it to a step-by-step procedure combined with a Monte-Carlo simulation. The procedure consists of: (i) producing a large number of random values on each variable of the model; (ii) using the computed values to calculate the isotopic compositions of lavas; and (iii) comparing the obtained isotopic compositions with measured data. Applied to a new set of Sr, Nd, and Pb isotope data for volcanics (basalts, basaltic andesites, trachybasalts, and basaltic trachyandesites) from Merapi volcano (Java island, Sunda arc), the model successfully reproduces the binary mixing relationships previously documented for the medium-K and high-K lava series from this volcano, thus giving further support to the hypothesis that this distinction is inherited from the primary magmas and primarily reflects a property of the mantle source. The results allow identification of a set of numerical values for bulk partition coefficients (solid/hydrous fluid, and solid/H₂O-rich melt) and variables (e.g., the mass ratio between the metasomatizing phase and the mantle wedge), which can be used for quantitative arc-lava petrogenetic calculations. They also require a direct relationship between dehydration of the slab and melting of the metasomatized mantle wedge. Finally, our evaluation shows that for isotope modelling of the Merapi lavas, the two-stage procedure is controlled more by the considered source components (mantle wedge, oceanic crust, sediments, and their derivatives) than by the various processes involved (dehydration, melting, and mixing).     

GGR Biennial Critical Review: Analytical Developments Since 2014

This GGR biennial critical review covers developments and innovations in key analytical methods published since January 2014, relevant to the chemical, isotopic and crystallographic characterisation of geological and environmental materials. In nine selected analytical fields, publications considered to be of wide significance are summarised, background information is provided and their importance evaluated. In addition to instrumental technologies, this review also presents a summary of new developments in the preparation and characterisation of rock, microanalytical and isotopic reference materials, including a précis of recent changes and revisions to ISO guidelines for reference material characterisation and reporting. Selected reports are provided of isotope ratio determinations by both solution nebulisation MC‐ICP‐MS and laser ablation‐ICP‐MS, as well as of radioactive isotope geochronology by LA‐ICP‐MS. Most of the analytical techniques elaborated continue to provide new applications for geochemical analysis; however, it is noted that instrumental neutron activation analysis has become less popular in recent years, mostly due to the reduced availability of nuclear reactors to act as a neutron source. Many of the newer applications reported here provide analysis at increasingly finer resolution. Examples include atom probe tomography, a very sensitive method providing atomic scale information, nanoscale SIMS, for isotopic imaging of geological and biological samples, and micro‐XRF, which has a spatial resolution many orders of magnitude smaller than conventional XRF.     

Is the invasion of the common reed,Phragmites australis,into tidal marshes of the eastern US an ecological disaster?

Studies of effects of the invasive brackish marsh plant Phragmites australis (common reed) on estuarine biota are reviewed. With few exceptions, most field studies indicate that these P. australis-dominated marshes have diverse and abundant benthic biota, and are utilized by nekton, comparable to Spartina alterniflora marshes. However, larval mummichogs, Fundulus heteroclitus, appear to be reduced in P. australis marshes compared with S. alterniflora marshes. Small epifauna living on plant stems also appear to be denser on S. alterniflora than P. australis stems. Other studies indicate that the detritus produced by decaying P. australis litter provides food value comparable to that of S. alterniflora and that its production enters estuarine food webs. Therefore, the general assumption that these marshes are ecologically "useless" is untrue. This information should be considered by marsh managers when making decisions about restoration projects.     

Mercury uptake by the estuarine species Palaemonetes pugio and Fundulus heteroclitus compared with their parasites,Probopyrus pandalicola and Eustrongylides sp

When exposed to methylmercury in the laboratory, grass shrimp, Palaemonetes pugio, parasitized by the isopod Probopyrus pandalicola, accumulated lower concentrations of mercury than their unparasitized counterparts. The parasitic isopod accumulated far less mercury than the grass shrimp. When exposed to mercury in a contaminated field site, mummichogs, Fundulus heteroclitus, parasitized with the nematode Eustrongylides, similarly accumulated lower concentrations of mercury than unparasitized fish, and the parasite similarly accumulated less than the host. The lower uptake by the parasites compared to their hosts is counter to the general view of biomagnification of methylmercury, since parasites are a trophic level above their hosts. The mechanism whereby parasitized animals accumulate less toxicant than unparasitized ones is unknown, but may be partially due to lower metabolic rate.     

Effect of zinc on regeneration in the fiddler crab Uca pugilator and its interactions with methylmercury and cadmium

After multiple autotomy (one chela and six walking legs) fiddler crabs (Uca pugilator) were exposed to zinc chloride, cadmium chloride, methylmercuric chloride or combinations of these metals. Zinc at 1, 3 and 5 ppm had a retarding effect on limb regeneration, which was amplified in water of reduced salinity. Methylmercury at 0·5 ppm and cadmium at 1·0 ppm have previously been found to retard regeneration. When crabs were exposed to meHg and Zn the effects were additive, both in sea water (30% salinity) and in water of reduced salinity (7–8%). However, when crabs were exposed to combinations of Zn and Cd the effects were antagonistic and the rate of regeneration was almost that of controls. In water of 7–8% salinity the Cd effect was greatly intensified and growth was almost totally prevented. The presence of Zn counteracted this and allowed growth and ecdysis to occur.     

Geochemical constraints on the origin of the late Jurassic proto-Caribbean oceanic crust in Hispaniola

The nature of the oceanic crust produced through rifting and oceanic spreading between North and South America during the Late Jurassic is a key element for the Caribbean plate tectonic model reconstruction. Located in the Cordillera Central of Hispaniola, the Loma La Monja volcano-plutonic assemblage (LMA) is composed of gabbros, dolerites, basalts, and oceanic sediments, as well as metamorphic equivalents, which represent a dismembered fragment of this proto-Caribbean oceanic crust. Petrologic and geochemical data show that the LMA have a relatively broad diversity in composition, which represent the crystallization products of a typical low-pressure tholeiitic fractionation of mid-ocean ridge basalts (MORB)-type parental magmas, ranging from N- to E-MORB. Three geochemical groups have been distinguished in the volcanic sequence: LREE-flat to slightly LREE-enriched basalts of groups II and III occur interlayered in the lower stratigraphic levels; and LREE-depleted basalts of group I in the upper levels. Mantle melt modeling suggests that group III magmas are consistent by mixing within a mantle melt column of low-degree (<1%) melts of a deep garnet lherzolite source and high-degree (>15%) melts of a shallow spinel source, and groups II and I magmas are explained with moderate to high (14–18%) and very high (>20%) fractional melting degrees of a shallower spinel mantle source, respectively. Thus, upward in the volcanic sequence of the LMA, the magmas represent progressively more extensive melting of shallower sources, in a plume-influenced spreading ridge of the proto-Caribbean oceanic crust. Nb/Y versus Zr/Y systematics combined with recent plate tectonic model reconstructions reveal that Caribbean Colombian oceanic plateau fragments in Hispaniola formed through melting of heterogeneous mantle source regions related with distinct plumes during at least from Aptian–Albian (>96 Ma) to Late Campanian.     

A Common Reference Material for Cadmium Isotope Studies – NIST SRM 3108

Research into natural mass‐dependent stable isotope fractionation of cadmium has rapidly expanded in the past few years. Methodologies are diverse with MC‐ICP‐MS favoured by all but one laboratory, which uses thermal ionisation mass spectrometry (TIMS). To quantify the isotope fractionation and correct for instrumental mass bias, double‐spike techniques, sample‐calibrator bracketing or element doping has been used. However, easy comparison between data sets has been hampered by the multitude of in‐house Cd solutions used as zero‐delta reference in different laboratories. The lack of a suitable isotopic reference material for Cd is detrimental for progress in the long term. We have conducted a comprehensive round‐robin assay of NIST SRM 3108 and the Cd isotope offsets to commonly used in‐house reference materials. Here, we advocate NIST SRM 3108 both as an isotope standard and the isotopic reference point for Cd and encourage its use as ‘zero‐delta’ in future studies. The purity of NIST SRM 3108 was evaluated regarding isobaric and polyatomic molecular interferences, and the levels of Zn, Pd and Sn found were not significant. The isotope ratio ¹¹⁴Cd/¹¹⁰Cd for NIST SRM 3108 lies within ～ 10 ppm Da^?1 of best estimates for the Bulk Silicate Earth and is validated for all measurement technologies currently in use.