Transport and retention of suspended particulate matter and bacteria in the Humber-Ouse Estuary, United Kingdom, and their relationship to hypoxia and anoxia

Data are presented on dissolved oxygen (DO) concentrations and their relationship to salinity, suspended particulate matter (SPM), concentrations, and the turbidity maximum in the Humber-Ouse Estuary, United Kingdom, during summer 1995. Measurements in the upper Humber during March 1995 showed DO in the range 82% to 87% of saturation. Suspended particulate matter concentrations were <5000 mg l^?1 and salinity was in the range 0.5 to 12. In contrast, a pronounced DO sag occurred in the upper reaches of the Ouse during medium and spring tide, summer conditions. The DO minimum was essentially an anoxic level and was associated with the location of the turbidity maximum, at salinities between about 0.4 and 1.5. SPM concentrations at 1 m beneath the surface reached 25,000 mg l^?1 in the turbidity maximum, between about 20 km and 40 km from the tidal limit. Suspended particulate matter concentrations were much lower at neap tides, although dense suspensions of SPM (>60,000 mg l^?1) occurred within 1 m of the bed in the turbidity maximum region. A spring-neap record showed a dramatic and tidally controlled decrease in DO at very low salinities as the tides progressed from neaps to springs. An anchor station located down-channel of the turbidity maximum showed that about 95% of the variance in DO, which varied from 28% at low-water slack to 67% at high-water slack, could be explained in terms of salinity variation. At the up-channel margins of the turbidity maximum, DO increased from zero (anoxia) near high water to 60% near low water slack, in contrast to the behavior down-channel of the turbidity maximum. About 82% of the variance in DO could be explained in terms of salinity variations alone. Only 43% of the DO variance could be explained in terms of SPM alone. Up-channel of the turbidity maximum, SPM concentrations were relatively low (<3000 mg l^?1) and DO levels varied from 48% of saturation near high water to 83% near low water slack. About 76% of the variance in DO could be explained in terms of salinity variations alone. Within the turbidity maximum region, DO varied from <2% saturation on the early flood and late ebb and maximized around 7% at high water slack. About 63% of the variance in DO could be explained in terms of salinity variation alone. This increased to 70% when suspended particulate matter was taken into account. Only 29% of the DO variance could be explained in terms of suspended particulate matter alone. Because bacteria were likely to have been the cause of the observed reduction in DO, the numbers of bacteria, both free-living and attached to particles, were measured in the turbidity maximum region. Numbers of free-living bacteria were low and most of the bacteria were attached to sediment particles. There was a linear correlation between total bacterial number and suspended particulate matter concentration, suggesting that the strong DO demand was exerted locally as a result of bacterial activity associated with increased suspended particulate matter concentrations. An order of magnitude analysis of DO consumption within the Ouse’s turbidity maximum, based on the premise that DO depletion was directly related to suspended particulate matter concentrations and that DO addition was due to reaeration, indicates that complete deoxygenation could have occurred with an oxygen depletion rate of ～0.01 mg DO h^?1/g suspended particulate matter during the residence time of waters within the turbidity maximum (～7 d). This rate was sufficiently fast that anoxic to aerobic conditions were able to develop a spring-neap periodicity within the turbidity maximum, but too slow to generate substantial intratidal fluctuations in DO. This is in accordance with the observations, which show that relatively little of the intratidal variance in DO could be explained in terms of suspended particulate matter fluctuations, whereas most of the variance could be explained in terms of salinity, which behaved as a surrogate measure for the proximity of the turbidity maximum.     

Determination of the Rare-Earth Elements and Yttrium In 37 International Silicate Reference Materials By Inductively Coupled Plasma-Atomic Emission Spectrometry

The rare-earth elements (REE) and yttrium have been determined in 37 international rock and mineral reference materials. Samples were prepared using conventional rock-dissolution techniques, and the REE and yttrium were separated from the other constituents using cation-exchange chromatography. The REE (La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb, Lu) and yttrium were determined simultaneously by inductively coupled plasma-atomic emission spectrometry (ICP-AES). Results for four well-characterised USGS standard rocks agree favourably with "recommended" values and with REE determinations made previously by workers using ICP-AES, isotope dilution mass spectrometry, instrumental neutron activaton analysis and X-ray fluorescence spectrometry.
Les éléments de terres rares (TR) et yttrium ont été dosés dans 37 échantillons internationaux de réféence. Les échantillons ont été décomposés par dissolution acide et les TR séparés par résine échangeuse de cations. Les TR (La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb, Lu) et yttrium ont été dosés simultanément par la spectrométrie d'émission-plasma inductif. Les résultats obtenus pour quatre échantillons de référence bien charactérisés de I'USGS se comparent favorablement avec ceux obtenus par la spectrométrie d'émission-plasma, la dilution isotopique, I'activation neutronique et par la spectrométrie d'é fluorescence-X.     

Quaternary volcanism near the Valley of Mexico: implications for subduction zone magmatism and the effects of crustal thickness variations on primitive magma compositions

The Valley of Mexico and surrounding regions of Mexico and Morelos states in central Mexico contain more than 250 Quaternary eruptive vents in addition to the large, composite volcanoes of Popocatépetl, Iztaccíhuatl, and Nevado de Toluca. The eruptive vents include cinder and lava cones, shield volcanoes, and isolated andesitic and dacitic lava flows, and are most numerous in the Sierra Chichináutzin that forms the southern terminus of the Valley of Mexico. The Chichináutzin volcanic field (CVF) is part of the E-W-trending Mexican Volcanic Belt (MVB), a subduction-related volcanic arc that extends across Mexico. The crustal thickness beneath the CVF (∼50 km) is the greatest of any region in the MVB and one of the greatest found in any arc worldwide. Lavas and scoriae erupted from vents in the CVF include alkaline basalts and calc-alkaline basaltic andesites, andesites, and dacites. Both alkaline and calc-alkaline groups contain primitive varieties that have whole rock Mg#, MgO, and Ni contents, and liquidus olivine compositions (≤Fo₉₀) that are close to those expected of partial melts from mantle peridotite. Primitive varieties also show a wide range of incompatible trace element abundances (e.g. Ba 210–1080 ppm; Ce 25–100 ppm; Zr 130–280 ppm). Data for primitive calc-alkaline rocks from both the CVF and other regions of the MVB to the west are consistent with magma generation in an underlying mantle wedge that is depleted in Ti, Zr, and Nb and enriched in large ion lithophile (K, Ba, Rb) and light rare earth (La, Ce) elements. Extents of partial melting estimated from Ti and Zr data are lower for primitive calc-alkaline magmas in the CVF than for those from the regions of the MVB to the west where the crust is thinner. The distinctive major element compositions (low CaO and Al₂O₃, high SiO₂) of the primitive calc-alkaline magmas in the CVF indicate a more refractory mantle source beneath this region of thick crust. In contrast, primitive alkaline magmas from the CVF and other regions of the MVB show compositional similarities to intraplate-type alkali basalts erupted behind the arc in the Mexican Basin and Range province. These similarities are consistent with the hypothesis that slab-induced convection in the mantle wedge beneath the MVB causes advection of asthenospheric mantle from behind the arc to the region of magma generation. Trace element systematics of primitive magmas in the MVB reveal substantial variability in both the extent of mantle wedge enrichment by subduction processes and in the composition of mantle heterogeneities that are related to previous extraction of alkaline to sub-alkaline basaltic melts. Received: 23 June 1998 / Accepted: 23 December 1998     

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

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

The redox states of basic and silicic magmas: a reflection of their source regions?

At present the best estimates of the oxygen fugacity of spinel-lherzolites that could be the source material of basic magmas is about five log units below the Ni–NiO buffer to one above it. However partially glassy basic lavas, ranging from MORBs to minettes, all with olivine on their liquidus, cover a wider range, and may have oxygen fugacities that extend to four log units above NNO. Surprisingly the range of oxygen fugacities observed in silicic lavas and ashflows with quartz phenocrysts is smaller, despite a crustal dominated evolution. The peralkaline silicic lava type pantellerite is the most reduced, equivalent to MORBs, whereas the large volume ashflows with phenocrysts of hornblende and/or sphene are the most oxidised. As the concentration of water in the basic lavas is correlated with increase in their redox state, it would seem that water could be the agent of this increase. That this is unlikely is seen in the behavior of silicic ashflows and lavas, particularly those of Yellowstone. Here the silicic magmas of the last 2Ma contain about 2 wt% FeO_(total), and typically phenocrysts of fayalite, quartz and Fe–Ti oxides. Despite extensive exchange of the ¹⁸O of the magma with meteoric water after caldera collapse (Hildreth et al. 1984), there is no displacement of the redox equilibria. Thus the thermal dissociation of molecular H₂O to H₂, and its subsequent diffusive loss to cause oxidation must have been minimal. This could only be so if the activity of water was small, as it would be if H₂O reacted with the silicate liquid to form OH groups (Stolper 1982). The conclusion is that silicic magmas with small amounts of iron and large amounts of water do not have their redox states reset, which in turn presumably reflect their generation. By analogy basic magmas with large amounts of iron and far less water are even less likely to have their redox equilibria disturbed, so that their oxygen fugacities will also reflect their source regions. The effect of pressure on the ferric-ferrous equilibrium in basic magmas can be calculated from experimental measurements of the partial molar volumes of FeO and Fe₂O₃, and their pressure derivatives V/P, in silicate liquids. The effect of pressure is found to be about the same on the liquid as it is for various solid oxygen buffers. Accordingly there should be mantle source regions covering the same range of oxygen fugacity as that found in basic lavas, but so far samples of spinel-lherzolite of equivalent oxygen fugacity to minettes or other potassic lavas have not been found. Whether or not the redox state of phlogopite-pyroxenites is equivalent to these potassic lavas cannot be established without experiment.     

Seasonality and selectivity in the feeding ecology and reproductive biology of deep-sea bathyal holothurians

Chlorophyll and carotenoid pigments were determined from the gut sediments of five species of bathyal holothurian in the NE Atlantic, sampled shortly after the spring/summer phytoplankton bloom in 2001 and prior to the spring bloom in 2002. Three species, Laetmogone violacea, Paroriza pallens and Bathyplotes natans, sampled within a similar depth range (900–1100 m) in the summer of 2001 showed significant differences in their chlorophyll and carotenoid pigment concentrations. This suggests they may select for slightly different components from the available food resource. Four species sampled in early spring 2002, Laetmogone violacea, Paroriza pallens, Benthogone rosea and Benthothuria funebris, also had significant differences in their pigment concentrations. These species were sampled over a wider depth range (1000–3100 m) showing a bathymetric trend in pigment concentrations. There was a distinct seasonal change in the composition and concentration of the pigments, linked to a reduction in the availability of fresh organic material during autumn and winter periods.Ovarian tissue was also examined. The carotenoid pigments found in the ovary also occurred in the OM ingested by the holothurians. The dominant gonadal carotenoid pigments were β-carotene, echinenone and zeaxanthin. The potential for using these carotenoids to gain a competitive advantage through selectivity of chlorophyll and carotenoid pigment biomarkers are discussed in relation to competition for food resources by deposit-feeders. The results were also compared with selectivity in abyssal species.     

Discussion: “Xenoliths in ultrapotassic volcanic rocks in the Lhasa block: direct evidence for crust–mantle mixing and metamorphism in the deep crust” by Wang et al. 2016 (Contributions to Mineralogy and Petrology) 171:62

Wang et al. (Contrib Mineral Petrol 171:62, 2016a) present data on composition of xenolith from Southern Tibet and conclude that ulrapotassic melts from the region formed by melting mantle, and complex interaction with a crustal component. In this discussion we demonstrate that numerous observations presented by Wang et al. (2016a) can be explained by partial melting of crust followed by interaction between that melt and the mantle. We show that this model can explain the variability of magmas in such suits without evoking occurrence of coincidental, unrelated events. Moreover we demonstrate that our model of a crustal origin of the proto-shoshonite melts is now supported by independent lines of evidence such as geochemistry of restites after high- and ultrahigh- pressure melting and melt inclusion studies.     

A subsidiary fast-diffusing substitution mechanism of Al in forsterite investigated using diffusion experiments under controlled thermodynamic conditions

Diffusion of Al in synthetic forsterite was studied at atmospheric pressure from 1100 to 1500 °C in air along [100] with activities of SiO₂, MgO and Al₂O₃ (a_SiO2, a_MgO and a_Al2O3) buffered. At low a_SiO2, the buffer was forsterite + spinel + periclase (fo + sp + per) at all temperatures, while at high a_SiO2 and subsolidus conditions a variety of three-phase assemblages containing forsterite and two other phases from spinel, cordierite, protoenstatite or sapphirine were used at 1100–1350 °C. Experiments at high a_SiO2 and 1400 °C used forsterite + protoenstatite + melt (fo + en + melt), and at 1500 °C, fo + melt. The resulting diffusion profiles were analysed by LA–ICP–MS in scanning mode. Diffusion profiles in the high a_SiO2 experiments were generally several hundred microns in length, but diffusion at low a_SiO2 was three orders of magnitude slower than in high a_SiO2 experiments carried out at the same temperature, producing short profiles only a few microns in length and close to the spatial resolution of the analytical method. Interface concentrations of Al in the forsterite, obtained by extrapolating the diffusion profiles to the crystal/buffer interface, were only a fraction of those expected at equilibrium, and varied among the differing buffer assemblages according to (a_Al2O3)^1/2 and (a_SiO2)^3/4, pointing to the substitution of Al in forsterite by an octahedral-site, vacancy-coupled (OSVC) component with the stoichiometry Al _4/3 ³⁺ vac_2/3SiO₄, whereas the main substitution expected from previous equilibrium studies would be the coupled substitution of 2 Al for Mg + Si, giving the stoichiometry MgAl₂O₄. It is proposed that this latter substitution is not seen on the length scales of the present experiments because it requires replacement of Si by Al on tetrahedral sites, and is accordingly rate-limited by the slow diffusivity of Si. Instead, diffusion of Al by the OSVC mechanism is relatively fast, and at high a_SiO2, even faster than Fe–Mg interdiffusion.     

Contributions to atmospheric methane by natural seepages on the U.K. continental shelf [Mar. Geol. 137 (1997) 165–189]

Natural gas seepages occur on the United Kingdom's continental shelf and although published reports suggest that they are very rare, the petroleum industry has identified, but not publicly reported, many more. There is also very little data on the flux of gas from seabed seepages, and even less on the contribution of seepages to atmospheric concentrations of gases such as methane.

Potential gas source rocks include Quaternary and Tertiary peats as well as petroliferous source rocks such as the Carboniferous Coal Measures and the Upper Jurassic Kimmeridge Clays. There are also other organic-rich sediments which are potential source rocks. Together these cover a considerable part of the U.K. continental shelf.

Analogue seismic reflection (pinger) profiles acquired during the British Geological Survey's regional mapping programme have been reviewed to identify water column targets including fish and plumes of gas bubbles. The ability to distinguish targets is critical to an assessment of the distribution of gas seepages. Both theoretical predictions of target identity and the habits of shoaling fish have been investigated in order to identify a method of distinction.

Data from seabed seepages and measurements of seepage rates have been used to establish likely ranges of gas flux rates and the sizes of gas bubbles. The likelihood that a rising bubble will survive and escape into the atmosphere is determined primarily by bubble size and water depth; methane, the principal constituent of seepage gas, is relatively unreactive and sparingly soluble.

The studies have enabled a new estimate of the distribution of gas seepages on the U.K. continental shelf, and of the contribution to atmospheric methane levels. The results suggest that natural gas seepages are significantly more important as a source of methane than had hitherto been established. It is estimated that between 120,000 and 3.5 mtonnes of methane per year come from a continental shelf area of about 600,000 km². This represents between 2% and 40% of the total United Kingdom methane emission. It is suggested that similar contributions arise from other continental shelf areas worldwide, and that geological sources of atmospheric methane are more significant than is generally acknowledged.