Suzanne A. McEnroe

Lamellar magnetism in the haematite–ilmenite series as an explanation for strong remanent magnetization

Magnetic anomalies associated with slowly cooled igneous and metamorphic rocks are commonly attributed to the presence of the mineral magnetite. Although the intermediate members of the ilmenite–haematite mineral series can also carry a strong ferrimagnetic remanence, it is preserved only in rapidly cooled volcanic rocks, where formation of intergrowths of weakly magnetic haematite and paramagnetic ilmenite is suppressed. But the occurrence of unusually large and stable magnetic remanence in rocks containing such intergrowths has been known for decades, and has recently been the subject of intense investigation. These unmixed oxide phases have been shown to contain pervasive exsolution lamellae with thickness from 100 µm down to about 1 nm (one unit cell). These rocks, many of which contain only a few per cent of such oxides, show natural remanent magnetizations up to 30 A m-1—too strong to be explained even by pure haematite in an unsaturated state. Here we propose a new ferrimagnetic substructure created by ferrous–ferric ‘contact layers’ that reduce charge imbalance along lamellar contacts between antiferromagnetic haematite and paramagnetic ilmenite. We estimate that such a lamellar magnetic material can have a saturation magnetization up to 55 kA m-1—22 times stronger than pure haematite—while retaining the high coercivity and thermal properties of single-domain haematite.

Magnetization of exsolution intergrowths of hematite and ilmenite: Mineral chemistry, phase relations, and magnetic properties of hemo‐ilmenite ores with micron‐ to nanometer‐scale lamellae from Allard Lake, Quebec

Hemo-ilmenite ores from Allard Lake, Quebec, were first studied over 50 years ago. Interest was renewed in these coarsely exsolved oxides, based on the theory of lamellar magnetism as an explanation for the high and stable natural remanent magnetizations (NRMs), 32 to 120 A/m, reported here. To understand the magnetism and evolution of the exsolution lamellae, the microstructures and nanostructures were studied using scanning electron microscopy and transmission electron microscopy (TEM), phase chemistry, and relations between mineral chemistry and the hematite-ilmenite phase diagram. Cycles of exsolution during slow cooling resulted in lamellae down to 1-2 nm thick. Combined electron microprobe, TEM, and X-ray diffraction (XRD) results indicate that hematite hosts reached a composition approximately ilmenite (Ilm) 14.4, and ilmenite hosts ∼Ilm 98. The bulk of the very stable NRM, which shows thermal unblocking ∼595-620°C, was acquired during final exsolution in the two-phase region canted antiferromagnetic R3c hematite + R3 ilmenite. Hysteresis measurements show a very strong anisotropy, with a stronger coercivity normal to, than parallel to, the basal plane orientation of the lamellae. Magnetic saturation (M s ) values are up to 914 A/m, compared to 564 A/m predicted for a modally equivalent spin-canted hematite corrected for ∼15% R 2+ TiO 3 substitution. Low-temperature hysteresis, AC-susceptibility measurements, and Mossbauer results indicate a Neel temperature (T N ) of the geikielite-substituted ilmenite at ∼43 K. The low-temperature hysteresis and AC-susceptibility measurements also show a cluster-spin-glass-like transition near 20 K. Below T N of ilmenite an exchange bias occurs with a 40 mT shift at 10 K.

Aeromagnetic anomalies, magnetic petrology, and rock magnetism of hemo-ilmenite- and magnetite-rich cumulate rocks from the Sokndal Region, South Rogaland, Norway

Abstract Aeromagnetic maps of the Egersund Mid-Proterozoic igneous province show a spectacular range of positive and negative magnetic anomalies with a contrast up to 15 600 nT. The positive magnetic anomalies are over magnetite norites and overlying mangerites and quartz mangerites of the Bjerkreim- Sokndal layered intrusion. These rocks are dominated by multi-domain (MD) magnetite. The negative magnetic anomalies are over ilmenite-rich norites of the Bjerkreim-Sokndal layered intrusion, the Tellnes ilmenite norite ore deposit, and massif anorthosites. These rocks are dominated by hemoilmenite and/or by silicates containing fine-grained oxide exsolution lamellae. Electron microprobe analyzes of coexisting Fe-Ti oxides in the layered intrusion confirm earlier observations that oxides in early magmatic rocks are dominated by hemo-ilmenite with minor end-member magnetite, followed by more reduced oxides dominated by titanomagnetite with minor near end-member ilmenite. What is not fully understood is the property of ilmenite with hematite exsolution lamellae, or, even more striking, hematite with ilmenite lamellae, to produce strong remanent magnetization of high coercivity and with a Néel temperature equal to or above the Curie temperature of magnetite. This property makes the rhombohedral oxides an important candidate to explain some high-amplitude deep-crustal anomalies on earth, or strong remanent magnetization on other planets. A remarkable feature in the Egersund province is that primitive magmas produced rocks rich in hemo-ilmenite causing negative magnetic anomalies related to magnetic remanence, and more evolved magmas produced rocks rich in magnetite related to positive induced magnetic anomalies, all in the course of crystallization-differentiation.

Nature and origin of lamellar magnetism in the hematite-ilmenite series

Abstract Grains consisting of finely exsolved members of the hematite-ilmenite solid-solution series, such as are present in some slowly cooled middle Proterozoic igneous and metamorphic rocks, impart unusually strong and stable remanent magnetization. TEM analysis shows multiple generations of ilmenite and hematite exsolution lamellae, with lamellar widths ranging from millimeters to nanometers. Rock-magnetic experiments suggest remanence is thermally locked to the antiferromagnetism of the hematite component of the intergrowths, yet is stronger than can be explained by canted antiferromagnetic (CAF) hematite or coexisting paramagnetic (PM) Fe-Ti-ordered (R3̅) ilmenite alone. In alternating field demagnetization to 100 mT, many samples lose little remanence, indicating that the NRM is stable over billions of years. This feature has implications for understanding magnetism of deep rocks on Earth, or on planets like Mars that no longer have a magnetic field. Atomic-scale simulations of an R3̅ ilmenite lamella in a CAF hematite host, based on empirical cation-cation and spin-spin pair interaction parameters, show that contacts of the lamella are occupied by “contact layers” with a hybrid composition of Fe ions intermediate between Fe2+-rich layers in ilmenite and Fe3+-rich layers in hematite. Structural configurations dictate that each lamella has two contact layers magnetically in phase with each other, and out of phase with the magnetic moment of an odd non-self-canceling Fe3+-rich layer in the hematite host. The two contact layers and the odd hematite layer form a magnetic substructure with opposite but unequal magnetic moments: a lamellar “ferrimagnetism” made possible by the exsolution. Because it is confined to magnetic interaction involving the moments of just three ionic layers associated with each individual exsolution lamella, lamellar magnetism is unique and quite distinct from conventional ferrimagnetism. Simulation cells indicate that the magnetic moments of contact layers are locked to the magnetic moments of adjacent AF hematite layers and are parallel to the basal plane (001). Thus, lamellar magnetism is created at the temperature of chemical exsolution, and is a chemical remanent, rather than thermal remanent, magnetization. However, in thermal demagnetization experiments, too short for lamellar resorption, demagnetization temperatures are those of the CAF hematite, considerably higher than temperatures of original lamellae formation. Internal crystal structure cannot dictate that the contact layers of different lamellae will form magnetically in phase with each other to give the highest net magnetic moment, but magnetic moments of lamellae can be made to form in phase by the external force of the magnetizing field at the time of exsolution. A thesis of this paper is that an external magnetic field can dictate the magnetic moments and hence the chemical location of ilmenite lamellae in a hematite host, and that once in place, neither the location nor the magnetic moment will be easily disturbed. In an ilmenite host, the external magnetic field cannot control the chemical location of a hematite lamella, which is dictated by the enclosing ilmenite, but once lamellae have formed, the field can dictate their magnetic moments. These moments, however, are not locked chemically to the host, resulting in lower coercivity. The effectiveness of the external force in single crystals is dictated by their orientation with respect to the magnetizing field. In grains with (001) oriented parallel to the field, it would be effective in producing in-phase magnetic moments and very strong remanence. In grains with (001) normal to the field, the field would be less effective in producing in-phase magnetic moments, hence producing weak remanence. The most intense lamellar magnetism per formula unit occurs with in-phase magnetization, high lamellar yields, and the largest number of lamellae per unit volume (i.e., smallest lamellar size). Compared to the magnetic moment per formula unit (Mpfu) and magnetic moment per unit volume (MV) of end-member magnetite (Mpfu = 4 μB, MV = 480 kA/m) and hematite (Mpfu = 0.0115 μB, MV = 2.1 kA/m), results for some atomic models reasonably tied to natural conditions are Mpfu = 0.46-1.36 μB and MV = 84-250 kA/m

Effect of fine-scale microstructures in titanohematite on the acquisition and stability of natural remanent magnetization in granulite facies metamorphic rocks, southwest Sweden: Implications for crustal magnetism

Mid-Proterozoic granulites in SW Sweden, having opaque minerals hematiteilmenite with minor magnetite, and occurring in an area with negative aeromagnetic anomalies, have strong and stable reversed natural remanent magnetization ∼9.2 A/m, with 100% remaining after demagnetization to 100 mT. Samples were characterized by optical microscopy, electron microprobe (EMP), transmission electron microscopy (TEM), and rock-magnetic measurements. Earliest oxide equilibrium was between grains of titanohematite and ferri-ilmenite at 650°–600°C. Initial contacts were modified by many exsolution cycles. Hematite and ilmenite (Ilm) hosts and lamellae by EMP are Ilm 24–25, ILm 88–93, like titanohematite, and ilmenite above 520°C on Burtons diagram [1991]. Finer hosts and lamellae by TEM are Ilm16 ±3 and Ilm 88±4, like coexisting antiferromagnetically ordered (AF) hematite and ilmenite below 520°C on Burtons diagram. This may be the first example of analytical identification, in one sample, of former hematite, now finely exsolved, and AF hematite. TEM microstructures consist of gently curving semicoherent ilmenite lamellae within hematite, flanked by precipitate-free zones and abundant ilmenite disks down to unit cell scale (1–2 nm). Strain contrast of disks suggests full coherence with the host, and probable formation at the reaction titanohematite ---> AF hematite + ilmenite at 520°C. Magnetic properties are a consequence of chemical and magnetic evolution of hematite and ilmenite with bulk compositions ilmenite-richer than Ilm 28, that apparently exsolved without becoming magnetized, down to 520°C where hematite broke down to AF hematite plus ilmenite, producing abundant AF hematite below its Neel temperature. Intensity of magnetization is greater than possible with hematite alone, and TEM work suggests that ultrafine ilmenite disks in AF hematite are associated with a ferrimagnetic moment due to local imbalance of up and down spins at coherent interfaces.

A closer look at remanence-dominated aeromagnetic anomalies: Rock magnetic properties and magnetic mineralogy of the Russell Belt microcline-sillimanite gneiss, northwest Adirondack Mountains, New York

A large, distinct negative aeromagnetic anomaly of over 2000 nT associated with microcline-sillimanite-quartz gneisses in the Russell area, northwest Adirondack Mountains, was previously shown to be remanence-dominated, although the carriers of remanence were not well documented. Russell Belt gneisses have a strong natural remanent magnetization with steep remanence directions, D = 263°, I = −58°, an average intensity of 3.6 A/m, and typical susceptibilities of 10−4 SI. The remanence is thermochemical in origin, acquired during cooling from peak metamorphic conditions of 650°–750°C during the Ottawan Orogen (1050–1080 Ma). The reversed polarity of remanence reflects a reversed paleofield, rather than self-reversed, contrary to earlier suggestions. The gneisses contain up to 3% oxide, predominantly metamorphic titanohematite, which accounts for the low susceptibility values and highly stable remanence. Optical observations show titanohematite grains with multiple generations of ilmenite, pyrophanite, rutile, and spinel exsolution lamellae. Microprobe analyses confirm titanohematite compositions ranging from 72 to 97% Fe2O3 with hematite83 being most typical. In rare samples, inclusions of magnetite were identified. The ubiquitous presence of titanohematite, and the rare occurrence of magnetite, is supported by thermal and alternating field demagnetization studies, saturation magnetization measurements, hysteresis properties, temperature-hysteresis studies, and low-temperature remanence measurements. Numerous crustal granulites have titanohematite as part of the oxide assemblage, and this may contribute a strong remanent component to what have previously been considered to be solely induced anomalies.

A low-temperature phase diagram for ilmenite-rich compositions in the system Fe2O3-FeTiO3

Abstract An approximate low-temperature, metastable phase diagram is drawn for the system (1 - X) Fe2O3-(X)FeTiO3. It is based on published and new magnetic data from nine synthetic samples with bulk compositions in the range 0.6 < X < 1.0. Fields are plotted for (1) the paramagnetic phase (PM); the Fe2O3-rich ferrimagnetic phase (FM); (2) the FeTiO3-rich antiferromagnetic phase (AF); and (3) a re-entrant spin-glass phase (RSG). In addition, two subfields are plotted: (1) FM′, a subfield of the FM-phase, which occurs below a characteristic temperature TK, at which the magnetic susceptibility drops sharply on cooling, and (2) PM′, a subfield of the PM-phase (traditionally called superparamagnetic) forms below a sharp rise in susceptibility at TS, and exhibits measurable dispersion in the magnetic susceptibility at T < TS. The diagram is drawn with a bicritical point, Tλλ′, at X ≈ 0.87, T ≈ 39 K, which is the intersection of second-order magnetic phase boundaries for the paramagnetic → ferrimagnetic [PM(PM′) → FM] transition, TC(X), and the PM(PM′) → AF transition, TN(X). In addition, the RSG phase is plotted as one of four stable phases at Tλλ′, a construction that is not required by the phase rule, but is strongly favored by the physics of competition between the incompatible magnetically ordered structures of the FM- and AF-phases. These phase relations are at such low temperature as to be of little consequence for terrestrial magnetism, however, they may well be essential for interpreting the magnetism of the Moon, Mars, and other cold planets. These phase relations are also essential for the characterization of fine natural and synthetic intergrowths, and for understanding magnetic materials for low-temperature technological applications.

Magnetic properties and potential field modeling of the Peculiar Knob metamorphosed iron formation, South Australia: An analog for the source of the intense Martian magnetic anomalies?

an extremely intense (� 120 A m � 1 ) remanence, directed steeply upward. This ancient remanence reinforces the local Earth’s field (inclination � 63). A simple geological model, constrained by drilling and physical property measurements, explains both the observed magnetic and gravity anomalies, consistent with the Poisson theorem. Koenigsberger ratios (Qs) of 10 and greater, as found here, are rare in nature. We postulate that acquisition of a thermoremanent magnetization (TRM) by the ore during

Magnetic properties of terrestrial moss (Hylocomium splendens) along a north-south profile crossing the city of Oslo, Norway.

Magnetic measurements are routinely used in geophysics and environmental sciences to obtain detailed information about concentrations and quality of iron minerals. Here, magnetic properties of 38 terrestrial moss samples (Hylocomium splendens) from a ~120km south-north transect through Oslo are studied to gain better insight into the nature and origin of their Fe fraction. The concentration-dependent quantities, magnetic susceptibility k, and isothermal remanent magnetization IRM(700mT) after weight normalization have significantly higher values in urban regions, and parallel the previously found concentration signals of 16 out of 29 chemical elements (Ag, Al, Au, Bi, Cd, Co, Cr, Cu, Fe, Mo, Ni, Pb, Pt, Sb, Ti, and Zn). Because there is no evidence that Hylocomium splendens produces biogenic magnetic remanence carriers, the increase in IRM is attributed to adsorption of dust containing iron oxide minerals. This agrees with previous observations that Ti concentrations, related to local mineral dust, have a peak in Oslo, and at sites close to known dust sources. Scanning electron microscopy images also showed an increased density of minerogenic particles on the moss surfaces in the urban samples, which qualitatively supports the dust based interpretation. The concentration-independent ratios k/Fe and IRM(700mT)/Fe also have extreme values in the urban parts of the transect. This indicates that more of the total iron occurs in magnetically ordered form and in remanence carriers, interpreted as adsorbed dust. In addition, purely magnetic ratios displayed differences in urban and rural areas, indicating that their magnetic dust particles are inherently of different types. Therefore, it is likely that anthropogenic dust sources contribute considerably to the magnetic signal. Urban dust enhancement is not exclusively due to increased erosion, leading to higher loads of geogenic dust in the atmosphere, but also to specific anthropogenic sources from combustion, corrosion, or other synthetic emitters.

Fe2+/Fe3+ charge ordering in contact layers of lamellar magnetism: Bond valence arguments

Abstract Fe2+/Fe3+ charge orderingin the contact layers of lamellar magnetism in the hematite-ilmenite series is not a postulate of the lamellar magnetism hypothesis. Such ordering is possible, however, and a model was suggested earlier in which contact layer Fe2+ octahedra share faces with ilmenite layer Ti4+ octahedra, and contact layer Fe3+ octahedra share faces with hematite layer Fe3+ octahedra, thus copying the shared-face configurations of ilmenite and hematite, respectively. This model and related charge-balance matters could be explored using bond-valence theory, a simplified picture of complex bonding which takes into account the relationship between bond strength and bond distance, but ignores magnetism. This has now been done, and shows that local oxygen charge satisfaction is strongly favored by a different charge-ordering scheme, in which contact layer Fe3+ octahedra share faces with ilmenite layer Ti4+ octahedra, and contact layer Fe2+ octahedra share faces with hematite layer Fe3+ octahedra. A new, more sophisticated, Monte Carlo simulation of the interface, including electrostatic and magnetic interaction parameters of cations, reported in detail elsewhere, independently shows the same charge-ordering scheme. For the cation ordered metastable ilmenite 50 composition, bond-valence theory indicates that, unlike the contact layers, the favored charge ordering scheme in Fe layers would have the same shared-face configurations as ilmenite and hematite.