Domain structure of small synthetic titanomagnetite particles and experiments with IRM and TRM

Stoichiometric titanomagnetites Fe_3?xTi_xO₄ with compositions between x = 0 (magnetite) and x = 0.72 (a titanomagnetite having a Curie temperature of 60°C) have been synthesised using the double-sintering technique in controlled atmospheres. The quality of these materials was tested by various mineralogical and magnetic measurements. Isolated small multidomain (MD) and pseudo-single-domain (PSD) particles within pores of the bulk material were investigated with respect to their domain structures, and threshold sizes for the transition from the PSD to the SD stage determined for titanomagnetites of various compositions by extrapolation from the domain state of small MD grains. The threshold size was found to be 0.7 and 0.5 μm, respectively, for TM72 (x = 0.72) and TM62 (x = 0.62). The threshold size decreases slightly for smaller x values; however, the experimental data obtained to date are not sufficiently reliable to yield precise results.Preliminary experiments concerning hysteresis loops and TRM generation are also reported.     

Magnetic hysteresis as a function of low temperature for deep-sea basalts containing large titanomagnetite grains-inference of domain state and controls on coercivity

Hysteresis loops to 1200 oersteds (9.55×10⁴ A m^?1) are measured between 295 K and 105 K for two deep-sea basalts (DSDP, Leg 34 and 37) containing large (～200 μm) unexsolved titanomagnetite grains. The Curie points, electron microprobe analyses and saturation magnetizations of the magnetic grains are the same as for unoxidized synthetic titanomagnetite (xFe₂TiO₄·(l ? x)Fe₃O₄) with x=0.6.As temperature is lowered from 295 to 190 K, coercive force H_c slowly rises from ～40 Oe to ～95 Oe approximately in proportion to the rise in the magnetostriction constant λ. Presumably, H_c is controlled by λ through internal stresses impeding domain wall motion. As expected of multidomain grains, the ratio of saturation remanence to saturation magnetization (in 1200 oersted cycles) j_R/j_S rises approximately in proportion to H_c, with a constant of proportionality consistent with titanomagnetite (x=0.6).As temperature is lowered from 190 to 120 K, H_c rises rapidly to ～400 Oe as a roughly linear function of the magnetocrystalline anisotropy constant K₁. Perhaps H_c is now controlled by K₁ through non-magnetic inclusions impeding domain wall motion.As temperature is lowered from 120 to 105 K, H_c rises even more rapidly to ～600 Oe. The control over H_c seems to have changed again, though most of the titanomagnetite is in grains large enough to still contain a few domains. The ratio j_R/j_S reaches 0.7 by 105 K and appears to be saturating towards the theoretical limit of 0.83.     

Thermal equation of state of magnesiowüstite (Mg0.6Fe0.4)O

Volume measurements for magnesiowüstite (Mg_0.6Fe_0.4)O, were carried out up to pressures of 10.1 GPa in the temperature range 300–1273 K, using energy-dispersive synchrotron X-ray diffraction. These data allow reliable determination of the temperature dependence of the bulk modulus and good constraint on the thermal expansitivity at ambient pressure which was previously not known for magnesiowüstite. From these data, thermal and elastic parameters were derived from various approaches based on the Birch–Murnaghan equation of state (EOS) and on the relevant thermodynamic relations. The results from three different equations of state are remarkably consistent. With (∂K_T/∂P)_T fixed at 4, we obtained K₀=158(2) GPa, (∂K_T/∂T)_P=−0.029(3) GPa K⁻¹, (∂K_T/∂T)_V=−3.9(±2.3)×10⁻³ GPa K⁻¹, and α_T=3.45(18)×10⁻⁵+1.14(28)×10⁻⁸T. The K₀, (∂K_T/∂T)_P, and (∂K_T/∂T)_V values are in agreement with those of Fei et al. (1992) and are similar to previously determined values for MgO. The zero pressure thermal expansitivity of (Mg_0.6Fe_0.4)O is found to be similar to that for MgO (Suzuki, 1975). These results indicate that, for the compositional range x=0–0.4 in (Mg_1−xFe_x)O, the thermal and elastic properties of magnesiowüstite exhibit a dependence on the iron content that is negligibly small, within uncertainties of the experiments. They are consequently insensitive to the Fe–Mg partitioning between (Mg, Fe)SiO₃ perovskite and magnesiowüstite when applied to compositional models of the lower mantle. With the assumption that (Mg_0.6Fe_0.4)O is a Debye-like solid, a modified equation of heat capacity at constant pressure is proposed and thermodynamic properties of geophysically importance are calculated and tabulated at high temperatures.     

An investigation of ulvospinel composition and cation migration during maghemitization in DSDP,Leg 61, titanomagnetites

Titanomagnetites of basalts and diorites from an off-axis volcanic episode in the Pacific Ocean (Leg 61, DSDP) were studied for their ulvospinel composition and for changes in the iron-titanium ratio with progressive low-temperature oxidation. Thermomagnetic analysis and microscopy indicate that these Fe/Ti spinels show relatively little low-temperature oxidation, despite their Cretaceous age. Microprobe investigation shows that the Fe/Ti spinels have a wide range of ulvospinel content directly reflecting the range of parent rock chemistries. This is an important demonstration that ulvospinel contents are not constant but vary within a restricted range of compositions, namely at least x =0.5 to x=0.75 (Fe_2?xTi_xO₄). Recognition of this fact is important in attempting to elucidate changes in cation ratio as a result of progressive low-temperature oxidation.Examination of samples of different oxidation states for cation ratio changes as a result of low-temperature oxidation revealed lower titanium in the more oxidized samples and Ti enrichment in the less oxidized ones. This is probably a reflection of changing x values with progressive crystallization of individual sills, and thus unrelated to cation ratio changes with oxidation.In more than 100 grains analyzed, no evidence was found for a more oxidized shell on the exteriors of grains, suggesting that the oxidation process did not proceed uniformly with respect to grain geometry.     

Magnetic properties of synthetic titanomagnetites

Magnetic properties and crystal structure parameters of synthetic solid solutions Fe₃O₄Fe₃TiO₄, Fe₂O₄MgFe₂O₄ and Fe₃O₄Mg₂TiO₄ have been studied. Basic regularities in the behaviour of saturation magnetisation (I_s), Curie temperature (T_C) and cubic lattice parameter a during the substitution of Ti and Mg ions for Fe ions have been found. As the concentration of Ti ions increases, I_s reduces from 70 Gs·cm³ g^?1 to 0, T_C changes from 580 to 130°C and a from 8.391 to 8.520 Å. Growth of the Mg concentration leads to changes in I_s to 19.8 Gs·cm³, g^?1, T_C, to 440°C and a, to 8.360 Å. The full Fe ions substitution gives $\text{“a”=8.440}\text{A}\text{?}$.Chemical compositions of the samples, in which the valency variation of Fe ions at oxidation leads to an increase in susceptibility and T_C, have been determined.     

Magnetic properties of monodomain aluminium-substituted titanomagnetite

A suite of synthetic titanomagnetites were prepared with compositions Fe_2.6?δTi_0.4Al_δO₄ and Fe_2.4?δTi_0.6Al_δO₄ (δ = 0, 0.1, 0.2 in both cases). Ball-milling of the synthesized samples produced material in the magnetic monodomain state as indicated by hysteresis loops and the Lowrie-Fuller test. The coercive force of the specimens depends on the Al concentration and lies in the range 1–2 kOe. The TRM induced in the samples is correspondingly “hard”. The low-field (0–1 Oe) TRM acquisition curve is linear. The higher field TRM-H curve is not in agreement with either monodomain or two-domain theoretical models.     

Synthesis of γ-Mg2SiO4

Magnesium orthosilicate with spinel structure (γ-Mg₂SiO₄) was synthesized at about 250 kbar and 1000°C. Unit cell dimension was established to be 8.076 ± 0.001Å. X-ray powder diffraction pattern revealed a significant difference between γ-Mg₂SiO₄ and other γ-M₂SiO₄ spinels (M = Fe, Co, and Ni) in the intensities of (111) and (331) reflections, both of which are virtually absent in the Mg₂SiO₄ spinel. This feature could be thoroughly understood by the calculation of the intensities for several silicate spinels.     

Spinel disproportionation at high pressure: calorimetric determination of enthalpy of formation of Mg2SnO4 and Co2SnO4 and some implications for silicates

The enthalpies of formation from the oxides of Mg₂SnO₄ and Co₂SnO₄ were found by oxide melt solution calorimetry to be +1.13 ± 0.48 kcal/mol and ?2.31 ± 0.28 kcal/mol, respectively. Using these data, the slopes, ?P/?T, for disproportionation of these spinels to the component oxides at high pressure were calculated to be +30.4 ± 4.2 bar/K for Mg₂SnO₄ and ?10.3 ± 2.4 bar/K for Co₂SnO₄, in general agreement with the data of Jackson et al. (1974a,b). Using thermochemical data for the formation of olivines, for olivine-spinel transitions and for the transformation of quartz to stishovite, we calculate pressures for the disproportionation of silicate spinels to be in the range 150–200 kbar. Calculated slopes ?P/?T for the disproportionation reactions are ?10.7, ?24.9, ?11.2, and +7.6 bar/K for Mg₂SiO₄, Fe₂SiO₄, Co₂SiO₄, and Ni₂SiO₄. The large negative slope calculated for Fe₂SiO₄ results from a surprisingly large positive slope reported for the olivine-spinel transition in that compound (Akimoto et al., 1969). Further consideration of the systematic trends in the thermodynamics of spinel formation from the oxides suggests that the silicate spinels should have entropies of formation close to zero, resulting in values of ?P/?T which are zero or at most only slightly negative. This confirms the conclusion of Jackson, Liebermann, and Ringwood that values of ?P/?T for spinel disproportionation are unlikely to be more negative than ?10 bar/K and may well be slightly positive. Reaction of spinels to form other post-spinel phases, particularly ilmenite and perovskite, are discussed in terms of available thermochemical data.     

A new high-pressure phase of spinel

A new phase which is much denser than the component oxides of spinel (MgAl₂O₄) was synthesised at loading pressures greater than 250 kbar and at about 1000°C in a diamond-anvil press coupled with laser heating. The new phase (ε-MgAl₂O₄) was indexed on the basis of an orthorhombic cell with a = 8.507 ± 0.004, b = 2.740 ± 0.003, c = 9.407 ± 0.005Å, and Z = 4 at room temperature and 1 bar pressure. Thus the molar volume for ε-MgAl₂O₄ at the above conditions was calculated to be 33.01 ± 0.07 cm³, which is 10.3% less than that of the mixture corundum plus periclase. The dense phase of spinel found in shock-wave experiments can be reasonably interpreted as ε-MgAl₂O₄, and this may be a potentially important mineral component of the earth's lower mantle. The new structure may also provide a possible candidate for the dense phases of Fe₃O₄ and Mg₂SiO₄ which were found by shock experiments.     

Iron ions Fe<Superscript>2+</Superscript> and Fe<Superscript>3+</Superscript> in a magnetic model of the sedimentary medium

The concentration of rock-forming elements, the static magnetic susceptibility κ, spectra of electron paramagnetic resonance, and their relative intensities I are studied in samples from a borehole drilled in Cenozoic sedimentary deposits of southern Western Siberia. All measured values experience appreciable irregular variations with depth. A linear dependence exists between κ and I within the range of their medium and large values; κ and I have maximum values in the same sample, and κ_max = 1920 × 10^?6SI, κ_min = 210 × 10^?6 SI, and κ_av = 630 × 10^?6 SI. The magnetic properties of the samples are controlled by Fe²⁺ ions present in clastic material and by microphases (clusters) with Fe³⁺ ions of the goethite and lepidocrocite type present in the cement. The theoretically possible magnetic susceptibility of the Fe²⁺ ion system (provided that all iron exists in this form) is quite comparable with κ_min but, even with very high concentrations of Fe²⁺, does not reach half of κ_av: (154 < κ(Fe²⁺) < 254) × 10^?6 SI. Anomalously high values of κ are due to a large number of clusters with Fe³⁺ ions if structural units FeOOH do not dissociate and the interaction of the clusters with hydroxides of aluminum and precipitation medium impedes the process of their coagulation. Otherwise, the cluster sizes gradually increase, an antiferromagnetic structure develops in clusters, and the magnetic susceptibility decreases.     

Ab initio study of the composition dependence of the pressure-induced spin crossover in perovskite (Mg1 − x,Fex)SiO3

We present ab initio calculations of the zero-temperature iron high- to low-spin crossover in (Mg_1 ? xFe_x)SiO₃ perovskite at pressures relevant to Earth's lower mantle. Equations of state are fit for a range of compositions and used to predict the Fe spin transition pressure and associated changes in volume and bulk modulus. We predict a dramatic decrease in transition pressure as Fe concentration increases. This trend is contrary to that seen in ferropericlase, and suggests the energetics for spin crossover is highly dependent on the structural environment of Fe. Both Local Density Approximation (LDA) and Generalized Gradient Approximation (GGA) exchange-correlation methods are used, and both methods reproduce the same compositional trends. However, GGA gives a significantly higher transition pressure than LDA. The spin transition is made easier by the decreasing spin-flip energy with pressure but is also driven by the change in volume from high to low spin. Volume trends show that high-spin Fe²⁺ is larger than Mg²⁺ even under pressure, but low-spin Fe²⁺ is smaller at ambient conditions and approximately the same size as Mg²⁺ under high pressure, indicating that low-spin Fe²⁺ is less compressible than high-spin Fe²⁺. We find large changes between high- and low-spin in the slope of volume with Fe concentration. Although these changes are small in absolute magnitude for small Fe content, they are still important when measured per Fe and could be relevant for calculating partitioning coefficients in the lower mantle.     

The Blithfield meteorite and the origin of sulfide-rich,metal-poor clasts and inclusions in brecciated enstatite chondrites

Blithfield (EL6) is one of five known enstatite chondrite breccias. It consists of troilite-rich clasts (35 ± 5vol.%) embedded in an extremely metallic Fe,Ni-rich matrix (65 ± 5 vol.%) that contains metal nodules up to 17 mm in size. Clasts and matrix agglomerated independently in the solar nebula under conditions of high and lowpS₂/pO₂ ratios, respectively. The matrix accreted to an EL chondrite planetesimal and was metamorphosed to～ 1000°C, above the FeNiS eutectic; chondrule textures were obliterated. The S-rich eutectic melt was lost from the matrix. The matrix material was buried to a depth of at least 3 km; accreting troilite-rich material was incorporated into the matrix as clasts. The breccia cooled through～ 500°C at 1000–10,000°C/Myr. After cooling below～ 500°C, Blithfield was quenched, possibly by impact excavation from depth and deposition onto the surface.Clasts or inclusions that are enriched in sulfide and depleted in metallic Fe,Ni are common in brecciated enstatite chondrites. Variations in thepS₂/pO₂ ratio in the nebular regions where these materials formed may explain many of their petrologic properties. The silica-rich clasts in Adhi Kot (EH4) formed at very highpS₂/pO₂ratios(> 10²⁷); niningerite, free silica and troilite were produced from the sulfurization of enstatite and metallic Fe. The troilite-rich clasts in Blithfield and Atlanta (EL6) as well as the troilite-rich regions of the Hvittis (EL6) matrix formed at somewhat lowerpS₂/pO₂ ratios where sulfurization of metalic Fe produced troilite. The Ni content of the residual metal increased, forming some metal of martensitic composition. The dark inclusions in Abee (EH 4), which contain up to 9 wt.% oldhamite, formed at highpS₂/pO₂ ratios in the presence of an additional Ca-rich component.     

The effect of ferromagnetism on the equation of state of Fe3C studied by first-principles calculations

First-principles calculations have been used to determine the equation of state of Fe₃C in both its low-pressure magnetically ordered and high-pressure non-magnetically ordered states; at 0 K the ferromagnetic transition was found to occur at about 60 GPa. In the high pressure, non-magnetically ordered regime at 0 K the material may be described by a Birch-Murnaghan third-order equation of state with V₀=8.968(7) ų per atom, K₀=316.62(2) GPa and K′=4.30(2). At atmospheric pressure the ferromagnetic phase transition in Fe₃C occurs at ∼483 K; preliminary measurements of the thermal expansion by powder neutron diffraction show that this transition produces a large effect on thermoelastic properties. The volumetric thermal expansion coefficient in the paramagnetic phase was found to be 4.34×10⁻⁵ K⁻¹ at T∼550 K. By applying a thermal expansion correction to the calculated equation of state at 0 K, predicted values for the density and adiabatic incompressibility of this material at core pressures and temperatures were obtained. These results appear to be sufficiently different from seismological data so as to preclude Fe₃C as the major inner core-forming phase.     

Ni2SiO4-enthalphy of the olivine-spinel transition by solution calorimetry at 713°C

The high pressure spinel polymorph of Ni₂SiO₄ persists metastably at 713°C and atmospheric pressure. The enthalpy of the olivine-spinel transition was obtained by measuring the heats of solution of both polymorphs in a molten oxide solvent, 2PbO · B₂O₃, at that temperature. For Ni₂SiO₄(ol)→Ni₂SiO₄, ΔH₉₈₆⁰ = +1.4 ± 0.7kcal/mol. The heat content increments, H₉₈₆ ? H₂₉₇, were found to be: olivine, 25.73 ± 0.42kcal/mol, and spinel, 25.39 ± 0.20kcal/mol. The measured enthalpy of the transformation is consistent with the low slope of the phase boundary, ?P/?T = ～ 12b/deg, observed by Akimoto and others. The entropy of the olivine-spinel transition in Ni₂SiO₄ is accordingly about a factor of three smaller in magnitude (ΔS = ～ ?1cal/deg mol) than that for Co₂SiO₄,Fe₂SiO₄,Mg₂SiO₄or Mg₂GeO₄ (ΔS = ?3to?3.5cal/deg mol).     

Internal flow structures in columnar jointed basalt from Hrepphólar, Iceland: II. Magnetic anisotropy and rock magnetic properties

The anisotropy of magnetic susceptibility (AMS) and rock magnetic properties were measured on specimens from a basalt plate that was cut from a vertical section of a basalt column from Hrepphólar, Iceland. Macroscopic structures are clearly distinguishable in the plate, including banding inferred to represent viscous fingering parallel to the vertical axis of the column. Rock magnetic experiments indicate that the dominant ferromagnetic (sensu lato) mineral is titanomagnetite, Fe _3?x Ti _x O₄, with a Ti-composition of x?=?~0.6. Magnetic properties are related to the position within the plate and reveal a dominant volume fraction of single domain titanomagnetite in the center of the basalt column, with multidomain titanomagnetite away from the center. The AMS determined by low-field measurements shows an inconclusive relationship with the visual structures, which arises from variation of the grain size (i.e., single domain versus multidomain) across the column. In contrast, the AMS measured with a high-field torsion magnetometer avoids the complication of magnetic domain state, as is demonstrated in this contribution, and additionally allows for the separation of ferrimagnetic from paramagnetic sub-fabrics. Both sub-fabrics display a clear relationship with the macroscopic structures and support the hypothesis that vertical flow of melt took place during development of the Hrepphólar columnar basalt. Maximum susceptibility axes of the ferrimagnetic sub-fabric are grouped near the vertical axis of the column. The paramagnetic sub-fabric varies systematically across the column in coincidence with internal structure. The shape of the magnetic susceptibility ellipsoid varies across the basalt column, showing an increasingly prolate fabric toward its center.     

Co2+ as a chemical analogue for Fe2+ in high-temperature experiments in basaltic systems

High-temperature experiments on ferromagnesian compositions have been hampered by the rapid absorption of up to 95% of the original iron by platinum and 40% by silver-palladium capsules. Molybdenum or iron capsule materials can decrease or alleviate iron loss, but restrict oxygen fugacities to values near the iron-wustite buffer. Because Co²⁺ is stable at f_O2 =HM and because the solubility of Co in platinum in this range of f_O2 is ～0.05% at temperatures to 1350°C, its use as an analogue for Fe²⁺ is possible. In addition, experiments simulating various Fe²⁺ ratios can be easily performed by choosing appropriate Co²⁺/Fe³⁺ ratios. The cobalt phases produced possess brilliant and distinctive colors which are valuable aids in optical identification of minute phases. The cobalt analogue hypothesis was tested with atmospheric pressure experiments in air on the cobalt analogue of the 1921 Kilauea basalt at three simulated Fe²⁺/Fe³⁺ ratios. The results were compared with those of R.E.T. Hill (1969) for the natural 1921 basalt. The phase relations were the same, with the cobalt system stability fields systematically shifted by about +50°C. Microprobe analysis of olivines and the coexisting glasses indicate that the distribution of Co²⁺ between olivine and melt is independent of temperature and liquid composition. Although the analogue liquid composition differs from the equilibrium composition of the natural system, it may be corrected be employing distribution coefficients (K_D = 0.61 for the Co system; K_D = 0.33 for the Fe system) to closely approximate what the natural system would yield if iron loss did not occur.     

The crystal structure and thermal history of orthopyroxene from lunar anorthosite 15415

A single crystal of untwinned orthopyroxene from lunar anorthosite sample 15415, with composition (Mg_1.14Fe_0.80Mn_0.02Ca_0.04)(Si_1.97Al_0.03)O₆, has a unit cell in space groupPbca witha = 18.310(15)Å,b = 8.904(10)Å,c = 5.214(7)Å, containing 2 formula units. A set of 742 counter-measured intensity data made with MoK_α radiation has been used to refine the crystal structure in isotropic thermal mode toR = 0.116. Anisotropic refinement led toR = 0.092, but thermal parameters are distorted by non-random errors resulting from poor crystal texture. The resulting structure is in close agreement with that obtained by Ghose [9] for a hypersthene from Greenland. A parameterq, which gives (Mg_qFe_1?q) for cation siteM(1) and (Mg_1.14?qFe_q?0.18Ca_0.04) for siteM(2), was included in the least-squares analysis, yieldingq = 0.90(1).This orthopyroxene has the high degree of cation order expected of pyroxenes subjected to Apollonian metamorphism at lower than 500–600°C. No evidence exists for a subsequent thermal event of sufficient intensity to disorder the pyroxene. On the basis of previous laboratory studies of argon-release patterns of lunar plagioclase and order-disorder kinetics of terrestrial pyroxenes, we attribute the reported isotopic age (3.9–4.1 AE) to cessation of metamorphism, perhaps caused by impact excavation.     

Comment on “The July 9 and 23, 1905, Mongolian earthquakes,a surface-wave investigation” by Emile Okal

K-Ar ages have been determined for sulfide minerals for the first time. The occurrence of adequate amounts of potassium-bearing sulfides with ideal compositions K₃Fe₁₀S₁₄ (～10 wt.% K) and KFe₂S₃ (～16 wt.% K) in samples from a mafic alkalic diatreme at Coyote Peak, California, prompted an attempt to date these materials. K₃Fe₁₀S₁₄, a massive mineral with conchoidal fracture, gives an age of 29.4 ± 0.5m.y.(⁴⁰Ar/³⁹Ar), indistinguishable from the 28.3 ± 0.4m.y.(⁴⁰Ar/³⁹Ar) and 30.2 ± 1.0m.y.8 (conventional K-Ar) ages obtained for associated phlogopite (8.7 wt.% K). KFe₂S₃, a bladed, fibrous sulfide, gives a younger age, 26.5 ± 0.5m.y.(⁴⁰Ar/³⁹Ar), presumably owing to Ar loss.     

Thermomagnetic analysis of meteorites, 2. C2 chondrites

Samples of all eighteen of the known C2 chondrites have been analyzed thermomagnetically. For eleven of these, initial Fe₃O₄ content is low (generally <1%) and theJ_s-T curves are irreversible. The heating curves show variable greater (up to 10 times) than it is initially. This behavior is attributed to the production of magnetite from a thermally unstable phase — apparently FeS. Four of the remaining seven C2 chondrites contain Fe₃O₄ as the only significant magnetic phase: initial magnetite contents range from 4 to 13%. The remaining three C2 chondrites contain iron or nickel-iron in addition to Fe₃O₄. These seven C2 chondrites show little evidence of the breakdown of a thermally unstable phase.     

Benthic respiration and stoichiometry of regenerated nutrients in lake sediments with Dreissena polymorpha

The effect of patchy colonies of the invasive zebra mussel (Dreissena polymorpha) on sedimentary processes was investigated in a mesotrophic lake (Plateliai Lake, Lithuania). Benthic fluxes of O₂, TCO₂, CH₄, Mn²⁺, Fe²⁺, N₂, the inorganic forms of N, Si and P and dissolved organic C and N were quantified by dark incubations of sediments cores, with and without D. polymorpha. Individual mussels also were incubated for metabolic measurements. Sediments with D. polymorpha had significantly higher O₂ and TCO₂ fluxes and displayed higher rates of denitrification. The presence of mussels also resulted in higher regeneration of P and N (mostly as ammonium) while the effect on Si was not significant. However, likely due to the low zebra mussel biomass (57.2 ± 25.3 g_SFDW m^?2), biodeposition has not changed the ratio between anaerobic and total respiration. Methane and reduced metals fluxes were in fact similar in the presence and absence of D. polymorpha. Incubations of mussels without sediments confirmed that bivalve metabolism was the main driver of benthic respiration and nutrient recycling. Nitrate production suggested the presence of nitrifiers associated with the molluscs. The main outcome of this study was that zebra mussels alter the quantity and the stoichiometry of nutrients regenerated by the benthic compartment. The enhancement of nitrogen loss via denitrification, by a factor of 1.5, was much less pronounced than the increase in ammonium recycling rate, stimulated by a factor of 33. Negligible PO₄ ^3? fluxes in bare sediments (?3.4 ± 6.8 μmol m^?2 h^?1) increased in the presence of mussels and considerable amounts of this nutrient (69.6 ± 29.4 μmol m^?2 h^?1) were mobilized to the water column. Further research should address other nutrient sources to the lake to verify whether altered rates and stoichiometry of benthic regeneration can affect primary producer community composition and activity.