The effects of chemical reduction of structural Fe3+ in nontronite SWa-1 (ferruginous smectite) on intervalence electron transfer (IT) and magnetic exchange were investigated. Visible absorption spectra in the region 800-400 nm of a chemical reduction series of the SWa-1 nontronite revealed an IT band near 730 nm (13,700 cm−1). Both the intensity and position of this band were affected by the extent of Fe reduction. The intensity increased until the Fe2+ content approached 40% of the total Fe, then decreased slightly with more Fe2+. The position of the band also shifted to lower energy as the extent of reduction increased.

Variable-temperature magnetic susceptibility measurements showed that the magnetic exchange in unaltered nontronite is frustrated antiferromagnetic, but ferromagnetic in reduced samples. Magnetic ordering temperatures are in the range 10–50 K, depending on the extent of reduction. The ferromagnetic component in the magnetization curve increased with increasing Fe2+ in the crystal structure. The positive paramagnetic interaction likely is due to electron charge transfer from Fe2+ to Fe3+ through such structural linkages as Fe2+-O-Fe3+ (perhaps following a double exchange mechanism), which is consistent with the visible absorption spectra.

Synthetic 2-line and 6-line ferrihydrite samples prepared from ferric nitrate solutions have the bulk compositions Fe4(O,OH,H2O)12 and Fe4,6(O,OH,H2O)12, respectively. The composition depends on crystal size, which averages 20 Å for 2-line and 35 Å for 6-line ferrihydrite. X-ray absorption edge spectra indicate the presence of tetrahedral Fe3+, a conclusion supported by heating experiments which show the development of maghemite after heating to 300°C in the presence of N2, followed by the formation of hematite at higher temperatures. These two reactions are recorded on differential thermal analysis traces by exotherms at 350° and 450°C. Transmission electron microscopy shows that 2-line ferrihydrite has no Z-axis regularity but does show hexagonal 2.54-Å lattice fringes. Six-line ferrihydrite forms faceted crystals having 9.4-Å c-parameter only detectable in dark field. In bright field, 2.54-Å lattice fringes indicate greater atomic regularity than in 2-line ferrihydrite. Analysis of the X-ray powder diffraction pattern of 6-line ferrihydrite suggests a structure based on double-hexagonal close-packed oxygens, containing 36% Fe in tetrahedral sites. Selective chemical dissolution, surface area measurements, and magnetic susceptibility are consistent with the recorded properties of ferrihydrite.

Many soils developed from volcanic rocks in southern Brazil exhibit spontaneous magnetization caused by the presence of fine-grained maghemite (γ-Fe2O3), but few attempts were made to quantify or characterize this important soil component. To that end, clays were separated from freely drained soils derived from acid (≥63% SiO2), intermediate (54–62% SiO2), and basic (≤53% SiO2) igneous rocks produced by the Paraná flood volcanism. The sample set included soils with a wide range of pedogenic development on different landscape positions. The Fe oxide mineralogy of these samples was examined by using a combination of selective dissolution, magnetic susceptibility, and X-ray diffraction (XRD) techniques. Hematite and maghemite were the primary Fe oxides in mature soils (Oxisols, Ultisols, and Alfisols) developed from basic rocks; whereas goethite was dominant in all other soils, especially those formed from acid-intermediate rocks. The association of maghemite with basic rock materials suggests that it was primarily formed by oxidation of lithogenic magnetite. A strong, positive correlation (R2 = 0.89) was obtained between mass specific magnetic susceptibility (χ) of the clay fractions and maghemite contents estimated by XRD. Either method could be used for quantitative analyses, but χ was more sensitive than XRD at low maghemite concentrations (<2 wt. %). The clay-sized maghem-ites were superparamagnetic with an estimated value for the mass specific magnetic susceptibility (χlf) value of 91,000 × 10−8 m3 kg−1 and frequency dependent variations of 10–15%. The maghemites also had low unit cell constants, which, if attributed entirely to replacement of Fe by Al, would correlate with Al substitutions in the range of 5–16 mole %. Selective dissolution of the soil maghemites was achieved by treatment of Fe oxide concentrates with 1.8 M H2SO4 at 75°C for 2 h.

Eight kaolinite and 2 halloysite samples were analyzed using 27Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, chemical analysis and magnetic susceptibility to understand the effect of isomorphously substituted Fe3+ and secondary Fe phases on the NMR signal. Known additions of goethite and hematite were made to determine the response of kaolinite 27Al MAS NMR spectra and sample magnetic susceptibilities.

Results from high field (11.7 T) NMR studies show positive correlations between 1) Fe content, 2) magnetic susceptibility and 3) relative intensity of the spinning side band (SSB) to central band (CB) ratio. No correlation is observed between the mass-corrected NMR spectral intensity and Fe content. Comparative high/low field (11.7 T/8.46 T) NMR studies show a decrease in the relative ratio of line broadening with increasing Fe content. Projected trends of known additions of hematite and goethite versus magnetic susceptibility extrapolate back to zero y intercepts that have Fe concentrations higher than actually measured.

Absolute intensity observations have negative implications for the use of 27Al MAS NMR spectroscopy in assessing Fe-ordering in kaolinites. First, high-energy, short (1/6 of π/2 solutions) pulse sequences do not produce reliable quantitative data needed to assess paramagnetic line-broadening affects caused by different Fe-ordering clustering scenarios. The lack of perfect correlation between SSB/CB, Fe content and magnetic susceptibility indicates that differences exist with respect to 1) the amount of isomorphously substituted Fe, 2) the ordering of the Fe within kaolinite, 3) the concentration of secondary Fe phases and 4) magnetic susceptibility of the secondary Fe assemblage. Variability of line-width ratios at different field strengths indicates an increasing second-order quadrupole effect (SOQE) with increasing Fe. Finally, the difference between the observed Fe content and that predicted from magnetic susceptibility measurements suggest that magnetic domain properties of secondary Fe phases behave differently from Fe domains bound in kaolinite.

The characterization of magnetic minerals and the relationship of these minerals to the magnetic susceptibility of soils that have developed on various parent materials can provide valuable information to various disciplines, such as soil evolution and environmental science. The aim of the study reported here was to investigate variations in the magnetic susceptibility (χ) of soils in western Iran due to differences in lithology and to examine the relationship of χ to ferrimagnetic minerals. Eighty samples were collected from eight parent materials taken from both intact rocks and associated soils. The soil parent materials included a range of igneous and sedimentary rocks, such as ultrabasic rocks (Eocene), basalt (Eocene), andesite (Eocene), limestone (Permian), shale (Cretaceous), marl (Cretaceous), and the Qom formation (partially consolidated fine evaporative materials, early Miocene). The 80 samples were analyzed for χ using a dual-frequency magnetic sensor and for mineralogy using X-ray diffraction (XRD). The highest χ values were found in the ultrabasic rocks and associated soils, while the lowest χ values were observed in the limestone rocks and associated soils. The pedogenic processes significantly enhanced the χ values of soils developed on the sedimentary rocks due to the formation of ferrimagnetic minerals. In contrast, χ values decreased as a result of pedogenic processes in soils developed on igneous rocks due to the dilution effects of diamagnetic materials, such as halite, calcite, phyllosilicates, and organic matter. The significant positive correlation between the XRD peak intensity of the maghemite/magnetite particles and χ values confirmed that χ values in soils are largely controlled by the distribution and content of ferrimagnetic minerals. These results show that χ measurements can be used to quantify low concentrations of ferrimagnetic minerals in the soils of semiarid regions.

To ascertain weathering, provenance, and paleoclimate of the last ca. 29 ka in mainland Gujarat, western India, a sedimentary profile of ~7.5 m was measured, described, and sampled at Pratappura and a multiproxy analysis was conducted. To determine weathering, silty-sand and sandy-silt facies were analyzed, and log Na2O/K2O versus log SiO2/Al2O3 was plotted, which shows clustering in the quartz arenite and sub-litharenite categories, indicating low to moderate weathering. The chemical index of alteration (CIA) is 55–74, and was plotted versus the index of chemical variability (ICV) of 1.50, with samples clustered mainly between subalkali basalt and picrite, indicating the dominance of a mafic component. While depleted chondrite normalized light rare earth element (REE) (La/Yb <1) levels suggest the prevalence of a mafic source in the catchment, identical chondrite normalized REE patterns indicate that sediments were well homogenized. Using multiple proxies, the measured profile was subdivided into five paleoclimatic zones. Zone-I (29–18 ka) exhibits decreasing moisture, Corg, χlf, Al2O3, TiO2, and Fe2O3 trends, while higher values of CO3−2 and δ13C indicate a change from a warm-humid to semiarid climate. Zone-II (18–11 ka) shows signs of the beginning of aridity ca. 18 ka during the Last Glacial Maximum (LGM). Several proxies in zone-III show wetter climatic conditions from the early Holocene (ca. 11–4 ka) due to the onset of the SW monsoon, with the trend continuing in zone-IV (4–2 ka). In zone-V, the climate appears to have been similar to the modern conditions in the area from 2 ka–present.

The loess deposits in Shandong Province in eastern China potentially provide valuable insights into past environmental changes. However, their precise provenance and paleoclimatic implications are unclear. We studied three loess sections located in the piedmont of the Central Shandong Mountains (PCSM) and in an offshore island in Bohai Gulf. Both the glacial loess and interglacial paleosol units are characterized by a coarse grain size, indicating a proximal sediment source. Using the “grain size–transport distance” model established for the Chinese Loess Plateau (CLP), the estimated source-sink distance is ~200–300 km for the PCSM loess and ~100–200 km for the coastal loess. This suggests that fluvial deposits of the Yellow River system in the North China Plain and sediments on the adjacent continental shelf are the major provenance for the Shandong loess. In contrast to the CLP, the Shandong loess does not show a consistent pattern of coarse grain size and low magnetic susceptibility values in glacial loess compared with interglacial paleosols, likely due to frequent changes in dust sources caused by diversions of the Yellow River and local hydroclimatic conditions. Nevertheless, the loess-paleosol alternations in the Shandong loess are a product of global glacial–interglacial cycles.

Integrating geophysical survey with the study of community settlement patterns can be challenging because of cultural and environmental factors including (1) site formation and house preservation, (2) the coordination of domestic tasks at extra-household scales, and (3) the survey environment of the study area. In this article, we present the results of a program of geophysical survey comprising magnetic susceptibility and magnetometry at Weeden Island (8Pi1)—a shell-bearing, wooded site with nearly pure sand soils on the Gulf Coast of Florida. Combining remote sensing techniques mitigated some of the challenges of surveying forested terrain while providing insight into community organization at a site with minimal preserved structural remains. Compared with previous traditional surveys of the area, the geophysical survey extended the recognized boundaries of occupational activity, provided additional definition to the spatial structure of deposits, and allowed us to identify specific domestic features. Excavations at each area of intensive occupation provided evidence about the organization of the domestic economy at the site and showed the potential of this approach to reveal significant patterns of community settlement.

The Lung Cam expanded stratigraphic succession in Vietnam is correlated herein to the Meishan D section in China, the GSSP for the Permian–Triassic boundary. The first appearance datum of the conodont Hindeodus parvus at Meishan defines the Permian–Triassic boundary, and using published graphic correlation, the Permian–Triassic boundary level has been projected into the Lung Cam section. Using time-series analysis of magnetic susceptibility (χ) data, it is determined that H. parvus arrived at Lung Cam ∼18 kyr before the Permian–Triassic boundary. Data indicate that the Lung Cam section is expanded by ∼90 % relative to the GSSP section at Meishan. Given the expanded Lung Cam section, it is possible to resolve the timing of significant events during the Permian–Triassic transition with high precision. These events include major stepped extinctions, beginning at ∼135 kyr and ending at ∼110 kyr below the Permian–Triassic boundary, with a duration of ∼25 kyr, followed by deposition of Lung Cam ash Bed + 13, which is equivalent to Siberian Traps volcanism is graphically correlated to a precession Time-series model, placing onset of this major volcanic event at ~242 kyr before the PTB. The Meishan Beds 25 and 26, at ∼100 kyr before the Permian–Triassic boundary. In addition, the elemental geochemical, carbon and oxygen isotope stratigraphy, and magnetostratigraphy susceptibility datasets from Lung Cam allow good correlation to other Permian–Triassic boundary succession. These datasets are helpful when the conodont biostratigraphy is poorly known in sections with problems such as lithofacies variability, or is undefined, owing possibly to lithofacies exclusions, anoxia or for other reasons. The Lung Pu Permian–Triassic boundary section, ∼45 km from Lung Cam, is used to test these problems.

Depositional changes are studied in three sections encompassing the Danian–Selandian transition, Loubieng (France), Zumaia (Spain) and Sidi Nasseur (Tunisia), using magnetic susceptibility as a proxy. Additional rock-magnetic analyses are used to avoid ambiguous interpretation of magnetic susceptibility. The magnetic susceptibility, measured on 90 to 270 samples per section, is mainly controlled by paramagnetic minerals and linked to detrital input. Major increases in the detrital input are correlated to the end of the Latest Danian Event, a hyperthermal, and to the Danian–Selandian boundary. In Loubieng, two gradual increases in magnetic susceptibility within limestones beds precede the major detrital input increases, and start synchronously with the beginning of the Latest Danian Event and the onset of haematite deposition around the Danian–Selandian boundary, respectively. This haematite is suspected to be of primary origin based, among other things, on low magnetic viscosity values, which is used here as an indicator of diagenetic origin in haematite and goethite. The red levels where haematite is interpreted to be of primary origin could be linked to the hyperthermal event previously hypothesized for the basal Selandian. The comparison of the magnetic susceptibility, chemo- and biostratigraphic data between the three sections highlights the condensed nature of the sedimentation around the Danian–Selandian boundary in the sections of the Atlantic realm. The lower part of the Selandian shows a particularly low sedimentation rate at Zumaia compared to Loubieng and Sidi Nasseur. The latter displays the most complete record of the three.

Changes in the palaeoenvironment are investigated in two representative Frasnian sections of the NW Algerian Sahara, integrating sedimentology and magnetic susceptibility (MS). The Ben Zireg section is characterized by condensed and ferruginous calcareous deposits; in the South Marhouma section the sedimentation rate is high, dominated by muddy nodular limestones with several hypoxic shale intervals. In both sections, sediments were mostly emplaced on pelagic outer ramps below the limit of storm wave-base, evolving through time from proximal to distal setting. Investigations of the temporal evolution of facies and MS data permit a first estimate of the local sea-level trends in NW Algeria. These trends match the overall long-term rise of sea level recognized worldwide from Frasnian Zone 5 upwards. Noteable positive excursions of the sea-level curve related to the semichatovae transgression, as well as to the late Frasnian transgression prior to the late Kellwasser event, can be established in this area. Although the sharp regression of sea level at the upper Kellwasser level can be confirmed from our data, no particular trend is depicted at the transition of conodont zones (Frasnian Zones 12–13) where the presence of the lower Kellwasser level has not yet been clearly recognized.

Coal slag and ash, obtained from burning coal in a textile factory in Duga Resa (Croatia) was discharged directly into the Mrežnica River for 110 y (1884–1994), from where it travelled to the Korana River and further to the Kupa River at Karlovac, a total of ~50km from its source. Of 54 elements determined by inductively coupled plasma mass spectrometry (ICP-MS) in the <2 mm sediment fraction, a number of anomalously high levels were recorded. The geoaccumulation index (Igeo) for the anomalous elements were: Hg (1.88), B (4.05), Na (1.44), Al (2.05), V (1.65), Cr (1.20), Fe (1.18), Ni (2.10), Cu (2.37), Sr (0.97), Zr (3.27), Mo (3.34) and U (4.03). Low-field magnetic susceptibility (MS) was measured for each sample. The Igeo for MS in the anomalous region is 5.85. Correlation analysis showed good correlation (>0.90) of MS with: B (0.96), U (0.95), Zr (0.94), Sr (0.93), Na (0.92), Mo (0.92) and Ni (0.90). Cluster analysis of R-modality indicates that MS is linked to B, Mo, Na and U. Low correlation of MS with Fe (0.36) suggests that Fe in stream sediments is not in a ferromagnetic form. Neither maghemite, nor magnetite phases were identified by X-ray diffraction (XRD) in the sediments. Low-field magnetic susceptibility provides an indicator of contamination of river sediments by transported coal slag and ash, although it cannot be prescribed to a single element.

We examined the top 135 m, that is, the entire Pleistocene, of the classic Luochuan section on the Chinese Loess Plateau with a diffuse reflectance spectrophotometer from the near ultraviolet, through the visible, and into the near infrared. From the reflectance data we calculated sample brightness which, with some caveats, is a reasonable proxy for magnetic susceptibility. Mineralogic changes were identified by factor analyzing the first derivative of the percent reflectance data and examining samples with high factor scores. Two factors which explain about 96% of the cumulative variance are distinguished by the relative proportion of hematite and goethite, the minerals that are responsible for the color changes in the loess sequence. Both hematite and goethite are present in both loess and paleosol but goethite dominates in loess whereas hematite dominates in paleosol. The goethite factor exhibits an inverse correlation with magnetic susceptibility; the hematite factor exhibits a weak positive correlation with susceptibility. Paleoclimatic interpretations are drawn from comparison of susceptibility to the concentration of spectrally identified hematite. Based on this comparison, paleosols in the early Pleistocene Wucheng Formation are characterized by conditions that are drier than today, a “dry summer monsoon”, whereas later Pleistocene paleosols are characterized by a “wet summer monsoon”.

An ∼8400 cal yr record of vegetation change from the northern Peten, Guatemala, provides new insights into the environmental history of the archaeological area known as the Mirador Basin. Pollen, loss on ignition, and magnetic susceptibility analyses indicate warm and humid conditions in the early to mid-Holocene. Evidence for a decrease in forest cover around 4600 cal yr B.P. coincides with the first appearance of Zea mays pollen, suggesting that human activity was responsible. The period between 3450 cal yr B.P. and 1000 cal yr B.P. is characterized by a further decline in forest pollen types, includes an abrupt increase in weedy taxa, and exhibits the highest magnetic susceptibility values since the early Holocene, all of which suggest further agricultural disturbance in the watershed. A brief drop in disturbance indicators around 1800 cal yr B.P. may represent the Preclassic abandonment of the area. Changing pollen frequencies around 1000 cal yr B.P. indicate a cessation of human disturbance, which represents the Late Classic collapse of the southern Maya lowlands.

Core A9-EB2 from the eastern Bransfield Basin, Antarctic Peninsula, consists of pelagic (diatom ooze-clay couplets and bioturbated diatom ooze) and hemipelagic (bioturbated mud) sediments interbedded with turbidites (homogeneous mud and silt–clay couplets). The cyclic and laminated nature of these pelagic sediments represents alternation between the deposition of diatom-rich biogenic sediments and of terrigenous sediments. Sediment properties and geochemical data explain the contrasting lamination, with light layers being finer-grained and relatively rich in total organic carbon and biogenic silica content. Also, the high-resolution magnetic susceptibility (MS) variations highlight distinct features: high MS values coincide with clastic-rich sections and low MS values correspond to biogenic sections. The chronology developed for core A9-EB2 accounts for anomalous ages associated with turbidites and shows a linear sedimentation rate of approximately 87 cm/103 yr, which is supported by an accumulation rate of 80 cm/103 yr calculated from 210Pb activity. The late Holocene records clearly identify Neoglacial events of the Little Ice Age (LIA) and Medieval Warm Period (MWP). Other unexplained climatic events comparable in duration and amplitude to the LIA and MWP events also appear in the MS record, suggesting intrinsically unstable climatic conditions during the late Holocene in the Bransfield Basin of Antarctic Peninsula.

The middle Wisconsinan Gilman Canyon Formation at the Buzzard's Roost type locality in southwestern Nebraska was investigated to document the stratigraphy and to reconstruct the environmental and climate record. The Gilman Canyon Formation was subdivided into three loess units and three soils, with radiocarbon ages constraining it between about 40 ka and 25 ka. Stable carbon isotope ratios, magnetic susceptibility, and carbon content were used to define and characterize soils within both the Gilman Canyon Formation and underlying Illinoian Loveland Loess. At the height of soil development within the Gilman Canyon Formation, climate was supporting C4-dominated grassland, with July temperatures equal to or exceeding those of today. Soil-forming intervals within the Loveland Loess, including the Sangamon Soil, also exhibited relative increases in C4 biomass. Climate, as recorded in the Gilman Canyon Formation, is corroborated by regional proxy data. The formation accumulated during MIS 3, and concurrent soil formation coincided with a summer insolation maximum.

Grayscale intensity profiles from photographic images offer a rapid means of obtaining paleoclimate proxy records from Chinese loess, dune sand, and paleosols. Although the data can be obtained using conventional 35-mm film images, a digital camera and laptop computer will produce a high-resolution grayscale profile at a field site within minutes. Comparison of grayscale profiles with profiles of magnetic susceptibility measured down loess and dune-sand sections at sites on the Loess Plateau and Tibetan Plateau in a range of altitudes and climatic regimes shows that the two parameters are highly correlated. Therefore, grayscale intensity is a convenient alternative to magnetic susceptibility for generating paleoclimatic data in the loess and desert-margin regions of China. The resolution of both grayscale and susceptibility profiles ultimately is limited by bioturbation, which is most pronounced in paleosols.

Eemian lake deposits in Grande Pile and Ribains, France, correlate with marine isotope substages (MIS) 5e and 5d as delimited in two pollen-bearing deep-sea cores off Portugal. The Eemian forests in France lasted for approximately 20 millennia, from at least 126,000 to ca. 107,000 yr B.P. Oscillatory climate deteriorations began about 115,000 yr ago. An intense cold spell affected the region approximately 110,000 yr ago.

The Vyazivok loess sequence from the Dnieper Plain, Ukraine, documents regional environmental changes during the late Pleistocene and Holocene. Pedological and palynological analyses and low-field magnetic susceptibility document changes from dense temperate forest during the last interglacial maximum to open, harsh, loess–steppe during the latest Pleistocene. The Vyazivok section overlies hillwash derived from a lower Pleistocene terrace and consists of two stratified soil complexes (Kaydaky and Pryluky; marine isotope stage [MIS] 5 equivalent) separated by a layer of eolian dust (Tyasmyn silt). The lower soils in both complexes formed within forest. These soils are overlain by the Uday (MIS4) and Bug (MIS2) loess units, which are separated by boreal soils of the Vytachiv (MIS3) complex. The coldest conditions within the record occurred in the youngest loess. Holocene soils cap the Bug loess. The Vyazivok section shows remarkable similarities with other classical loess sequences in western Europe, the Czech Republic, and Austria. The Kaydaky, Pryluky, and Vytachiv deposits, correlate with the PKIII, PKII, and PKI soil complexes, respectively, of the Czech Republic. The Tyasmyn and Prylyky silt layers correspond to marker horizons from central Europe.