Bacteriohopanepolyol signatures of bacterial populations in Western Canadian soils

Bacteriohopanepolyols (BHPs) are naturally occurring compounds derived from bacteria. Their quantity and diversity in five Western Canadian soils, which vary mostly in vegetative cover, were examined using high performance liquid chromatography – atmospheric pressure chemical ionization – mass spectrometry (HPLC–APCI–MS). Eighteen BHP compounds including tetra-, penta- and hexa-functionalised components, as well as composite components, were identified. Concentrations were highest in the forest-grassland transition soil [515 μg/g organic carbon (OC)], followed by the forest soil (431 μg/g OC) and the grassland soils (333–306 μg/g OC). The distribution trends measured using HPLC–ACPI–MS agree with hopanoid measurements using gas chromatography–mass spectrometry (GC–MS) but intact BHPs were detected at a concentration that was an order of magnitude higher using HPLC–APCI–MS. Adenosylhopane was the most abundant BHP in all the samples and comprised on average 27% of total BHPs, supporting earlier work indicating that adenosylhopane is an excellent soil-specific biomarker. The soil samples vary in vegetative cover and this is likely one of the main reasons for observing variation in BHP composition, suggesting that BHP biomarkers may be a valuable tool for assessing bacterial community structure in soil when used in cooperation with other molecular microbial ecology methods (such as DNA genotyping).     

Predicting C aromaticity of biochars based on their elemental composition

Three models were examined to predict C aromaticity (f_a) of biochars based on either their elemental composition (C, H, N and O) or fixed C (FC) content. Values of f_a from solid state ¹³C nuclear magnetic resonance (NMR) analysis with Bloch-decay (BD) or direct polarisation (DP) techniques, concentrations of total C, H, N, and organic O, and contents of FC of 60 biochars were either compiled from the literature (dataset 1, n = 52) or generated in this study (dataset 2, n = 8). Models were first calibrated with dataset 1 and then validated with dataset 2. All models were able to fit dataset 1 when atomic H to C ratio (H/C) < 1 (except two ash rich biochars) and to estimate f_a of HF treated biochars (H/C < 1). Model 1, which was based on values of H/C only and calibrated with a root mean square of error (RMSE) of 0.04 f_a-unit (n = 41), could predict the experimental data with a RMSE = 0.02 f_a-unit (n = 6). Model 2, which was based on biochar elemental composition data, showed the most accurate prediction, with a RMSE of 0.03 f_a-unit (n = 41) for the calibration data, and of 0.02 f_a-unit (n = 6, H/C < 1) for the validation data. Model 3, which was based on contents of FC and C, and modified with a correction factor of 0.96, displayed the highest RMSE (0.06 f_a-unit, n = 19) among the three models. Models 1 and 2 did not work properly for samples having either an H/C ratio > 1, high concentrations of carbonate or high inorganic H. These models need to be further tested with a wider range of biochars before they can be recommended for classification of biochar stability.     

Tropical northeast Africa in the middle–late Eocene: Paleomagnetism of the marine-mammals sites and basalts in the Fayum province,Egypt

The mid-late Eocene “Valley of Whales” in the Fayum province of Egypt contains hundreds of marine-mammals’ skeletons. Given its paleontological importance, we carried out a paleomagnetic study of the fossil-bearing formations. A sequence of basalts directly overlying the upper Eocene rocks in three distant clusters within a 25 km-long NW–SE graben in the southwestern part of the area was also studied. Thermal demagnetization of three-axis IRM was used to identify and eliminate sites dominated by hematite and/or goethite as potential remanence carriers. Progressive thermal demagnetization of the NRM isolated a characteristic NNE–SSW dual-polarity direction with a shallow inclination that passes both tilt and reversal tests. The mean tilt-corrected direction of the sedimentary formations is D/I = 16°/30° (k = 50, α₉₅ = 3°) yielding a paleomagnetic pole at 70°N/159°E. The anisotropy of magnetic susceptibility (AMS) indicated that the observed inclinations were free from inclination shallowing, as did the nearly identical characteristic remanence of the overlying basalt flows (with a tilt-corrected reversed-polarity direction of D/I = 198°/−28° (k = 38, α₉₅ = 7°) and a pole at 68°N/158°E). The new paleopoles place the Fayum province at a lower paleolatitude (15–17°N) than today (29.5°N), and point to the possible prevalence of tropical climate in northeast Africa during mid-late Eocene times. This tropical position is nearly identical to the paleolatitudes extrapolated from the mean of 36 coeval poles rotated from the other major cratons and from Africa itself. The declinations show a minor easterly deviation from those predicted by extrapolation from other continents. This is interpreted as due to a small clockwise rotation internal to NE Africa, possibly related to Red Sea/Gulf of Suez rifting after the late Eocene. The alternative explanation that the geomagnetic field had a non-zonal non-dipole field contribution is not favored.     

Proterozoic paleomagnetism in the Nipigon Embayment of northern Ontario: Pillar Lake Lava,Waweig Troctolite and Gunflint Formation tuffs

By using unusual combinations of demagnetization techniques, Proterozoic paleomagnetic vectors and paleopoles are provided for two recently discovered post-tectonic Proterozoic units near Armstrong, northern Ontario, and also for well-dated Gunflint Formation, which by previous techniques yielded problematical paleomagnetic data. The first paleomagnetic data are provided also for the Seagull Pluton and Inspiration Sills. Characteristic remanent magnetizations (ChRM) for the Pillar Lake Lavas indicate a Keweenawan age, more specifically ∼1000–1040 Ma by comparison with the well-established APWP for the Late Proterozoic Superior craton. Four combinations of demagnetization techniques yield declinations in the range 108–133° and inclinations in the range −65 to −70° (n = 100), which define paleopoles near 200 W/48 N corresponding to a location on the Keweenawan APWP near ∼1040 Ma. In the underlying basement a recently discovered Proterozoic igneous complex, the Waweig Troctolitic Complex, yields new paleomagnetic data with declination and inclination 42/−54 (n = 14) defining a paleopole at 238 W/09 N. Its ages may be 1400–1600 or ∼2000 Ma by comparison with the presently available, ambiguous and sparsely populated APWP. The first paleomagnetic results for the Seagull Pluton (U–Pb age 1113 Ma) yield a mean declination of 87.4/−75.7 (n = 32) corresponding to a Keweenawan paleopole near 233/42 N, consistent with other paleopoles near ∼1200 Ma. Tuffs of the oft studied but problematical Gunflint Formation (U–Pb age1878 Ma) yielded stable and presumably primary vectors using several different demagnetization techniques on the same specimens. Their mean primary declination and inclination ∼303/+48.8 (n = 17) yields a paleopole now located near 178 W/42 N, comparable with the published locations of paleopoles of ∼2000 Ma. Of broader interest, we recognized that low temperature demagnetization preceding conventional demagnetization techniques enhanced the isolation of characteristic vectors. Combining the conventional techniques (thermal and AF demagnetization) also improved the resolution of characteristic vectors not achieved by other means. Low grade metamorphism affected the non-tectonized Proterozoic cover to the Canadian shield, due to burial or hydrothermal effects, obfuscating or erasing primary vectors in some lithologies and especially at certain sites.     

Distribution of glycerol dialkyl glycerol tetraether lipids along an altitudinal transect on Mt. Xiangpi,NE Qinghai-Tibetan Plateau,China

The distribution of glycerol dialkyl glycerol tetraethers (GDGTs) can reflect continental environmental changes. Recently, the distribution of branched GDGTs (bGDGTs) has been proposed as a novel tool for paleoelevation reconstructions. Here we report the variation in TEX₈₆ (tetraether index of 86 carbon atoms) of isoprenoidal GDGTs (iGDGTs) and MBT (methylation of branched tetraether index) of bGDGTs along an altitudinal transect on Mt. Xiangpi, NE Qinghai-Tibetan Plateau. Both TEX₈₆ and MBT values of surface soils showed significant linear decreases with altitude (TEX₈₆: R² = 0.65; n = 50; MBT: R² = 0.69; n = 24). We suggest that the apparent relationships between the two indices and altitude may be related to temperature. Our preliminary investigation suggests that the TEX₈₆ index can potentially be applied as a paleoelevation indicator in addition to the MBT index on the Qinghai-Tibetan Plateau.     

Geochemical and oxygen isotope signatures of mantle corundum megacrysts from the Mbuji-Mayi kimberlite,Democratic Republic of Congo,and the Changle alkali basalt,China

Oxygen isotope signatures of ruby and sapphire megacrysts, combined with trace-element analysis, from the Mbuji-Mayi kimberlite, Democratic Republic of Congo, and the Changle alkali basalt, China, provide clues to specify their origin in the deep Earth. At Mbuji-Mayi, pink sapphires have δ¹⁸O values in the range 4.3 to 5.4‰ (N = 10) with a mean of 4.9 ± 0.4‰, and rubies from 5.5 to 5.6‰ (N = 3). The Ga/Mg ratio of pink sapphires is between 1.9 and 3.9, and in rubies, between 0.6 and 2.6. The blue or yellow sapphires from Changle have δ¹⁸O values from 4.6 to 5.2 ‰, with a mean of 4.9 ± 0.2‰ (N = 9). The Ga/Mg ratio is between 5.7 and 11.3. The homogenous isotopic composition of ruby suggests a derivation from upper mantle xenoliths (garnet lherzolite, pyroxenite) or metagabbros and/or lower crustal garnet clinopyroxenite eclogite-type xenoliths included in kimberlites. Data from the pink sapphires from Mbuji-Mayi suggest a mantle origin, but different probable protoliths: either subducted oceanic protolith transformed into eclogite with δ¹⁸O values buffered to the mantle value, or clinopyroxenite protoliths in peridotite. The Changle sapphires have a mantle O-isotope signature. They probably formed in syenitic magmas produced by low degree partial melting of a spinel lherzolite source. The kimberlite and the alkali basalt acted as gem conveyors from the upper mantle up to the surface.     

Combining boron isotopes and carbamazepine to trace sewage in salinized groundwater: A case study in Cap Bon,Tunisia

The Korba aquifer on the east coast of Cape Bon has been overexploited since the 1960s with a resultant reversal of the hydraulic gradient and a degradation of the quality due to seawater intrusion. In 2008 the authorities introduced integrated water resources planning based on a managed aquifer recharge with treated wastewater. Water quality monitoring was implemented in order to determine the different system components and trace the effectiveness of the artificial recharge. Groundwater samples taken from recharge control piezometers and surrounding farm wells were analyzed for their chemical contents, for their B isotopes, a proven tracer of groundwater salinization and domestic sewage, and their carbamazepine content, an anti-epileptic known to pass through wastewater treatment and so recognized as a pertinent tracer of wastewater contamination. The system equilibrium was permanently disturbed by the different temporal dynamics of continuous processes such as cation exchange, and by threshold processes linked to oxidation–reduction conditions. The B isotopic compositions significantly shifted back-and-forth due to mixing with end-members of various origin. Under the variable contribution of meteoric recharge, the Plio-Quaternary groundwater (δ¹¹B of 35–40.6‰, a mean B concentration of 30 μmol/L, no carbamazepine, n = 7) was subject to seawater intrusion that induced a high δ¹¹B level (δ¹¹B of 41.5–48.0‰, a mean B concentration of 36 μmol/L, and n = 8). Fresh groundwater (δ¹¹B of 19.89‰, B concentration of 2.8 μmol/L, no carbamazepine) was detected close to the recharge site and may represent the deep Miocene pole which feeds the upper Plio-Quaternary aquifer. The managed recharge water (δ¹¹B of 10.67–13.8‰, n = 3) was brackish and of poor quality with a carbamazepine content showing a large short term variability with an average daily level of 328 ± 61 ng/L. A few piezometers in the vicinity of the recharge site gradually acquired a B isotopic composition close to the wastewater signature and showed an increasing carbamazepine content (from 20 to 910 ng/L). The combination of B isotopic signatures with B and carbamazepine contents is a useful tool to assess sources and mixing of treated wastewaters in groundwaters. Effluent quality needs to be greatly improved before injection to prevent further degradation of groundwater quality.     

Geological and isotopic constraints on the origin of the Anle carbonate-hosted Zn–Pb deposit in northwestern Yunnan Province,SW China

The Anle Zn–Pb deposit, hosted by Upper Cambrian dolostone, is located in the southern Songpan–Ganzi Block in southwest China. In this deposit, ore bodies occur as stratiform lenses and consist of galena, sphalerite and pyrite as ore minerals, and quartz, dolomite and calcite as gangue minerals. The mineralization shows mainly vein, banded and brecciated structures. Four ore bodies have been found in the Anle deposit, with a combined 2.0 million tonnes (Mt) of sulfide ores at average grades of 1.64 wt.% Pb, 6.64 wt.% Zn and 45 g/t Ag. Brown, brownish-yellow and yellow sphalerite samples have δ⁶⁶Zn values ranging from + 0.08 to + 0.10‰ (average + 0.09‰, n = 3), + 0.12 to + 0.38‰ (average + 0.24‰, n = 8) and + 0.40 to + 0.50‰ (average + 0.46‰, n = 3), respectively. We interpret the progressively heavier Zn isotopes from brown to yellow sphalerite as being led by kinetic Raleigh fractional crystallization. Calcite samples have δ¹³C_PDB and δ¹⁸O_SMOW values ranging from − 4.8 to − 0.2‰ (average − 1.7‰, n = 7) and + 17.9 to + 21.4‰ (average + 19.6‰, n = 7), respectively. Whole-rock δ¹³C_PDB and δ¹⁸O_SMOW values of the Cambrian ore-hosting dolostone range from + 0.1 to + 1.1‰ (average + 0.6‰, n = 3) and + 23.2 to + 24.1‰ (average + 23.6‰, n = 3), respectively. This suggests that carbon in the ore-forming fluids was provided by the host dolostone through carbonate dissolution. δ³⁴S_CDT values of sulfide samples range between − 1.3‰ and + 17.8‰ with an average value of + 6.3‰ (n = 25), lower than evaporites (such as barite + 19.8‰) in the overlaying Lower Ordovician sedimentary strata. The data suggest that sulfur in the hydrothermal fluids were derived from evaporites by thermo-chemical sulfate reduction (TSR). ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios for sulfide minerals range from 17.63 to 17.86, 15.58 to 15.69 and 37.62 to 37.95, respectively. The data are similar to those of the age-corrected Cambrian ore-hosting dolostone (²⁰⁶Pb/²⁰⁴Pb = 17.70–17.98, ²⁰⁷Pb/²⁰⁴Pb = 15.58–15.65 and ²⁰⁸Pb/²⁰⁴Pb = 37.67–38.06), but lower than those of age-corrected Ordovician sandstone and slate (²⁰⁶Pb/²⁰⁴Pb = 18.54–19.58, ²⁰⁷Pb/²⁰⁴Pb = 15.73–15.81 and ²⁰⁸Pb/²⁰⁴Pb = 38.44–39.60). This indicates that ore Pb was most likely to be derived from the Cambrian ore-hosting dolostone. Therefore, our new geological and isotopic evidence suggests that the Anle Zn–Pb deposit is best classified to be an epigenetic carbonate-hosted Mississippi Valley-type (MVT) deposit.     

Re–Os ages for molybdenum mineralization in the Fengning region of northern Hebei Province,China: New constraints on the timing of mineralization and geodynamic setting

A recently recognized molybdenum (Mo) metallogenic belt is present within and adjacent to the northern part of the North China Craton (NCC). More than 20 Mo deposits are present in the belt, including the Sadaigoumen and Dacaoping porphyry deposits located in the Fengning region of the northern part of Hebei Province. The Sadaigoumen deposit has a Re–Os molybdenite weighted mean age of 236.5 ± 2.2 Ma (MSWD = 1.4, n = 6), which is more reliable than existing dates and is interpreted as the precise age for formation of the deposit. The Dacaoping Mo deposit is about 100 million years younger, with a Re–Os molybdenite isochron age of 140.1 ± 3.4 Ma (2σ, MSWD = 0.26, n = 5), which is within error of the weighted mean age of 139.4 ± 0.9 Ma. The ages of the two deposits show that there are at least two episodes of Mo porphyry formation in the Fengning region. In combination with the regional geological evolution of this part of the craton margin, we propose that the Triassic Mo event at Sadaigoumen is associated with a collisional event during the closure of the ancient Asian Ocean, whereas the Early Cretaceous Mo event at Dacaoping is associated with lithospheric thinning of the NCC.     

Mesoproterozoic granulites of the Shillong–Meghalaya Plateau: Evidence of westward continuation of the Prydz Bay Pan-African suture into Northeastern India

Thermo-chronologic considerations in the Australo-Antarctic domains suggest that the Prydz Bay Pan-African suture of East Antarctica continues westward into India. However, the location of the suture within Eastern India has so far been uncertain because of a lack of adequate thermo-chronological information. In this study, electron microprobe (EPMA) monazite dates and mineral paragenesis of granulite facies metapelites are reported from two areas of the Shillong–Meghalaya gneissic complex (SMGC), a crustal block located in the extreme northeast of the Indian shield close to the Australo-Antarctic block in Neoproterozoic-Cambrian paleomagnetic reconstructions of the Rodinia supercontinent. In the Garo-Goalpara Hills region, a well constrained Mesoproterozoic age of 1596 ± 15 Ma (n = 103) is correlated with a counterclockwise pressure–temperature path with near peak conditions of 7–8 kbar and 850 °C. Rare matrix monazite rims record younger ages (1032–1273 Ma). At Sonapahar region, 50 km ESE of Garo-Goalpara Hills, homogenous monazite grains in granulite facies metapelites yield EPMA dates tightly clustered at 500 ± 14 Ma (n = 36) irrespective of their textural setting in a well-annealed mineral matrix. In a few zoned monazite grains, the cores yield older ages of 1078 ± 31 Ma (n = 10) and 1472 ± 38 Ma (n = 13). The 500 Ma date corresponds with the ca. 880–480 Ma Rb–Sr dates of porphyritic granites that predominantly intruded the east-central part of the SMGC. We propose that the progressively eastward dominance of Cambro-Ordovician ages in the SMGC indicates a Pan-African final amalgamation of the Indian plate with the Australo-Antarctic plate and a northward extension of the Prydz Bay suture through the SMGC, with the western boundary of the suture possibly located between the Garo-Goalpara Hills and Sonapahar areas.     

A combined CDB-MAGIC method for the determination of phosphorus associated with sedimentary iron oxyhydroxides

A combined CDB-MAGIC method for the determination of sedimentary Fe-oxyhydroxide-bound P in citrate–dithionite–bicarbonate (CDB) reducing solutions is described. Quantitative removal of P from solution is accomplished through the alkaline precipitation of Mg(OH)₂ (brucite) with 10 M NaOH. After subsequent separation by centrifugation and two washings with 10% NH₄OH, the precipitate is re-dissolved in 10% HCl. The P concentration in the sample is subsequently measured by the conventional molybdate blue technique using a UV–vis spectrophotometer. The detection limit of the method is 1.2 μM with precision within 1.3–8.1% in the 6–30 μM P concentration range. The results obtained using the CDB-MAGIC protocol were equivalent to those obtained using ICP-AES (r² = 0.860; p ⩽ 0.001; n = 29; with a linear slope of 1.19 ± 0.09). The CDB-MAGIC method provides then a simple, low cost alternative to the current methods based on ICP quantification.     

Geochronological and geochemical constraints on the petrogenesis of alkaline ultramafic dykes from southwest Guizhou Province,SW China

Geochronological, geochemical and whole-rock Sr–Nd isotopic analyses have been completed on a suite of alkaline ultramafic dykes from southwest (SW) Guizhou Province, China with the aim of characterising their petrogenesis. The Baiceng ultramafic dykes have a LA-ICP-MS zircon ²⁰⁶Pb/²³⁸U age of 88.1 ± 1.1 Ma (n = 8), whereas two phlogopites studied by ⁴⁰Ar/³⁹Ar dating methods give emplacement ages of 85.25 ± 0.57 Ma and 87.51 ± 0.45 Ma for ultramafic dykes from Yinhe and Lurong, respectively. In terms of composition, these Late Mesozoic ultramafic dykes belong to the alkaline magma series due to their high K₂O (3.31–5.04 wt.%) contents. The dykes are characterised by enrichment of light rare earth element (LREE) and large-ion lithosphile elements (LILEs) (Rb and Ba), negative anomalies in high field strength elements (HFSEs), such as, Nb, Ta and Ti relative to primitive mantle, low initial ⁸⁷Sr/⁸⁶Sr ratios (0.7060–0.7063) and positive ε_Nd(t) values (0.3–0.4). Such features suggest derivation from low degree (< 1%) partial melting of depleted asthenospheric mantle (garnet-lherzolite), and contamination to various degrees (～ 10%) by interaction with upper crustal materials.     

Mercury deposition and methylmercury formation in Narraguinnep Reservoir,southwestern Colorado,USA

Narraguinnep Reservoir in southwestern Colorado is one of several water bodies in Colorado with a mercury (Hg) advisory as Hg in fish tissue exceed the 0.3 μg/g guideline to protect human health recommended by the State of Colorado. Concentrations of Hg and methyl-Hg were measured in reservoir bottom sediment and pore water extracted from this sediment. Rates of Hg methylation and methyl-Hg demethylation were also measured in reservoir bottom sediment. The objective of this study was to evaluate potential sources of Hg in the region and evaluate the potential of reservoir sediment to generate methyl-Hg, a human neurotoxin and the dominant form of Hg in fish. Concentrations of Hg (ranged from 1.1 to 5.8 ng/L, n = 15) and methyl-Hg (ranged from 0.05 to 0.14 ng/L, n = 15) in pore water generally were highest at the sediment/water interface, and overall, Hg correlated with methyl-Hg in pore water (R² = 0.60, p = 0007, n = 15). Net Hg methylation flux in the top 3 cm of reservoir bottom sediment varied from 0.08 to 0.56 ng/m²/day (mean = 0.28 ng/m²/day, n = 5), which corresponded to an overall methyl-Hg production for the entire reservoir of 0.53 g/year. No significant point sources of Hg contamination are known to this reservoir or its supply waters, although several coal-fired power plants in the region emit Hg-bearing particulates. Narraguinnep Reservoir is located about 80 km downwind from two of the largest power plants, which together emit about 950 kg-Hg/year. Magnetic minerals separated from reservoir sediment contained spherical magnetite-bearing particles characteristic of coal-fired electric power plant fly ash. The presence of fly-ash magnetite in post-1970 sediment from Narraguinnep Reservoir indicates that the likely source of Hg to the catchment basin for this reservoir has been from airborne emissions from power plants, most of which began operation in the late-1960s and early 1970s in this region.     

Combined paleomagnetic and geochronological study on Cretaceous strata of the Qiangtang terrane,central Tibet

A combined paleomagnetic and geochronological investigation has been performed on Cretaceous rocks in southern Qiangtang terrane (32.5°N, 84.3°E), near Gerze, central Tibetan Plateau. A total of 14 sites of volcanic rocks and 22 sites of red beds have been sampled. Our new U–Pb geochronologic study of zircons dates the volcanic rocks at 103.8 ± 0.46 Ma (Early Cretaceous) while the red beds belong to the Late Cretaceous. Rock magnetic experiments suggest that magnetite and hematite are the main magnetic carriers. After removing a low temperature component of viscous magnetic remanence, stable characteristic remanent magnetization (ChRM) was isolated successfully from all the sites by stepwise thermal demagnetization. The tilt-corrected mean direction from the 14 lava sites is D = 348.0°, I = 47.3°, k = 51.0, α₉₅ = 5.6°, corresponding to a paleopole at 79.3°N, 339.8°E, A₉₅ = 5.7° and yielding a paleolatitude of 29.3° ± 5.7°N for the study area. The ChRM directions isolated from the volcanic rocks pass a fold test at 95% confidence, suggesting a primary origin. The volcanic data appear to have effectively averaged out secular variation as indicated by both geological evidence and results from analyzing the virtual geomagnetic pole (VGP) scatter. The mean inclination from the Late Cretaceous red beds, however, is 13.1° shallower than that of the ~ 100 Ma volcanic rocks. After performing an elongation/inclination analysis on 174 samples of the red beds, a mean inclination of 47.9° with 95% confidence limits between 41.9° and 54.3° is obtained, which is consistent with the mean inclination of the volcanic rocks. The site-mean direction of the Late Cretaceous red beds after tilt-correction and inclination shallowing correction is D = 312.6°, I = 47.7°, k = 109.7, α₉₅ = 3.0°, N = 22 sites, corresponding to a paleopole at 49.2°N, 1.9°E, A₉₅ = 3.2° (yielding a paleolatitude of 28.7° ± 3.2°N for the study area). The ChRM of the red beds also passes a fold test at 99% confidence, indicating a primary origin. Comparing the paleolatitude of the Qiangtang terrane with the stable Asia, there is no significant difference between our sampling location in the southern Qiangtang terrane and the stable Asia during ~ 100 Ma and Late Cretaceous. Our results together with the high quality data previously published suggest that an ~ 550 km N–S convergence between the Qiangtang and Lhasa terranes happened after ~ 100 Ma. Comparison of the mean directions with expected directions from the stable Asia indicates that the Gerze area had experienced a significant counterclockwise rotation after ~ 100 Ma, which is most likely caused by the India–Asia collision.     

Shifting zonal patterns of the southern boreal forest in eastern Canada associated with changing fire regime during the Holocene

This research aims at uncovering the stand-scale Holocene fire history of balsam fir forest stands from two bioclimatic zones of the boreal forest and assessing the existence of a sub-continental shift in past fire activity that could have triggered a change in the Holocene zonal pattern. In eastern Canada, the extant closed-crown boreal forest corresponds to two ecological regions separated along 49°N, the northern black spruce zone and the southern balsam fir zone. We sampled balsam fir stands from the southern fir zone (n = 7) and among the northernmost patches of fir forest located far beyond the fir zone boundary, into the spruce zone (n = 6). Macrofossil analysis of charcoal in mineral soils was used to reconstruct both the stand-scale and regional Holocene fire histories. Data were interpreted in the context of published palaeoecological evidence. Stands of the balsam fir zone were submitted to recurrent fire disturbances between c. 9000 and 5000 cal. yr B.P. Local fire histories suggested that four sites within the fir zone escaped fire during the Holocene. Such fire protected sites allowed the continuous maintenance of the balsam fir forest in the southern boreal landscape. Stands of the spruce zone have been affected by recurrent fires from 5000 cal. yr B.P. to present. Local fire histories indicated that no site escaped fire in this zone. Published palaeoecological data suggested that balsam fir migrated to its current northern limit sometime between 7300 and 6200 cal. yr B.P. A change of the fire regime 5000 years ago caused the regional decline of an historical northern balsam fir forest and its replacement by black spruce forest. The consequence was a sub-continental reshuffling of the fir and spruce zones within the closed-crown boreal forest. The macrofossil analysis of charcoal in mineral soils was instrumental to the reconstruction of stand-scale Holocene fire history at sites where no other in situ fire proxies were available.     

Microblock amalgamation in the North China Craton: Evidence from Neoarchaean magmatic suite in the western margin of the Jiaoliao Block

The Archaean Earth is considered to have been characterized by microcontinents that formed, dominantly, through the accretion of oceanic arcs and plateaus. The North China Craton (NCC) provides a typical case where at least seven ancient microcontinental nuclei with distinct lithological features and independent tectonic histories were amalgamated into the cratonic framework at the end of the Archaean. Here we investigate a suite of magmatic rocks developed at the periphery of one of these microblocks, the Jiaoliao Block that forms part of the composite Eastern Block of the NCC. We present petrological, geochemical and zircon U–Pb geochronological data from the Taipingzhai charnockite suite, and associated amphibolites, metagabbros and orthogneisses from the Qianxi Complex. Geochemically the rocks show a wide range of SiO₂ (charnockite suite: 52.57–75.50 wt.%; metagabbro: 43.71 wt.%; amphibolite: 50.24 wt.%; garnet-bearing biotite: 63.73 wt.%), and MgO (charnockite suite: 0.89–5.01 wt.%; metagabbro: 3.99 wt.%; amphibolite: 6.23 wt.%; garnet-bearing biotite: 2.08 wt.%). The composition of the felsic units straddle from diorite through syeno-diorite to granite with both alkalic and subalkalic affinity, with dominantly magnesian composition and arc-related features. Their immobile trace element relationships suggest calc-alkaline affinity. They show positive Pb, Ba, La, Nd, and Gd and negative Nb, Ta, Sr, Th and Ti anomalies with slightly negative anomalies of Ce and Y, attesting to arc-related features. In tectonic classification diagrams, the rocks plot in the VAG + syn-COLG field or the VAG area suggesting subduction-related origin.The dominant population of zircons in all these rocks displays magmatic crystallization features including high Th/U values with core-rims textures indicating subsequent thermal events. The zircon U–Pb data yield upper intercept ages of 2587 ± 10 Ma to 2543 ± 17 Ma and ²⁰⁷Pb/²⁰⁶Pb mean ages of 2578 ± 7.3 Ma to 2536 ± 8 Ma for the charnockite suite, marking the timing of emplacement of the arc magmas. The overgrowth rims as well as discrete neoformed grains are interpreted as dating subsequent metamorphism and yield ²⁰⁷Pb/²⁰⁶Pb ages between 2533 Ma to 2490 Ma. Zircons in the metagabbro preserve upper intercept ages of 2556 ± 20 Ma representing the crystallization age of this rock. The younger ages of 2449 ± 58 Ma (upper intercept age) and 1845 ± 25 Ma (²⁰⁷Pb/²⁰⁶Pb spot age) are interpreted to represent subsequent multiple thermal events in this area. Zircons in the amphibolite preserve the ²⁰⁷Pb/²⁰⁶Pb mean age of 2539 ± 9 Ma, representing the crystallization age of this rock. The garnet-bearing biotite gneiss shows an upper intercept age of 2562 ± 10 Ma (MSWD = 0.66; N = 36) and the ²⁰⁷Pb/²⁰⁶Pb mean age of 2561 ± 9 Ma (MSWD = 0.63; N = 33) which is taken to represent the crystallization age of this rock. Some inherited zircons are also identified with ²⁰⁷Pb/²⁰⁶Pb ages of 2664 ± 26 Ma and 2628 ± 26 Ma. Zircon Lu–Hf data show dominantly positive εHf(t) values and combined with crustal residence ages, the results suggest Mesoarchean to Neoarchean juvenile crust formation in the NCC. We interpret the data presented here to represent a phase of major late Neoarchaean arc magmatism along the western margin of the Jiaoliao Block related to the birth of microcontinental nuclei within the NCC. Our data suggest that the Western and Eastern Blocks might not have existed as discrete crustal blocks, and that the construction of the NCC is a result of the assembly of several microblocks or terranes at the end of Archaean. Similar Archean cratonic nuclei in other regions of the world might have formed part of a primitive supercontinent in the early Earth.     

The geographic distribution of Sr isotopes from surface waters and soil extracts over the island of Bornholm (Denmark) – A base for provenance studies in archaeology and agriculture

In this paper we report the Sr isotope signatures, and Sr, Al and Na concentrations of 30 surface waters (lakes/ponds and rivers/creeks) and 19 soil sample extracts from the island of Bornholm (Denmark) and present a categorized ⁸⁷Sr/⁸⁶Sr value distribution map that may serve as a base for provenance studies, including archaeological migration and authenticity proof for particular food products. The Sr isotopic compositions of surface waters range from ⁸⁷Sr/⁸⁶Sr = 0.7097–0.7281 (average 0.7175 ± 0.0049; 1σ), whereas 0.1 M HNO₃, 0.05 M HNO₃, and 0.01 M CaCl₂ soil extracts range from ⁸⁷Sr/⁸⁶Sr = 0.7095–0.7197 and define somewhat lower but statistically indistinguishable averages of 0.7125 ± 0.003 (1s). These compositions are lower than the values expected from the Precambrian granitoid basement (⁸⁷Sr/⁸⁶Sr = 0.758–0.944), and from the overlying, mainly clastic Paleozoic sediments. Combined Sr isotope composition vs. Sr, Na and Al concentration relationships of soil extracts imply that lowering of the isotopic composition of leachable Sr on Bornholm results as a consequence of significant admixture to this fraction of Sr deposited as marine salts (aerosols), and that rainwater only has a minor influence on the Sr budget of the surface waters. Positively correlated Al/Na and [1/Sr] vs. ⁸⁷Sr/⁸⁶Sr relationships in soil extracts and surface waters indicate that the surface run-off on Bornholm is characterized by two predominant sources, namely marine aerosols (sea salts) with high Sr and low ⁸⁷Sr/⁸⁶Sr values, and a source with lower [Sr] delivering radiogenic Sr to the surface waters, which we equate with Sr leached from the products of mineral weathering (soils).A feasibility study for using Sr isotopic compositions of surface waters and soil extracts as a proxy for bioavailable Sr signatures was performed with a few samples collected in the vicinity of the eleventh century AD Ndr. Grødbygård cemetery site in SW Bornholm, from where Sr isotope compositions of modern fauna samples and tooth enamel of humans buried in the cemetery have been reported. Waters and soil extracts studied herein from around this site range from ⁸⁷Sr/⁸⁶Sr = 0.7104–0.7166 and correspond to Sr compositions extracted from snail shells in this area which span a range of ⁸⁷Sr/⁸⁶Sr = 0.7095–0.7160. Some human tooth enamel is characterized by more radiogenic values (⁸⁷Sr/⁸⁶Sr up to 0.718) which points to a possible provenance of these humans from the granite–gneiss terrain in the north of the island and/or to immigration of these humans in their childhood from other places (for example from mainland Sweden) to Bornholm. If the total compositional range of ⁸⁷Sr/⁸⁶Sr = 0.709–0.718 (n = 44) recorded in human enamel from the Ndr. Grødbygård site is considered representative for the variation of bioavailable Sr on Bornholm, then our soil leachate and surface water data entirely covers this range. We therefore propose that the combination of Sr isotope analyses of surface waters and soil leachates are an easy, fast and relatively cost efficient way to characterize a local bioavailable ⁸⁷Sr/⁸⁶Sr signature, and consequently propose that the overall average of ⁸⁷Sr/⁸⁶Sr = 0.7153 ± 0.0048 (1σ; n = 50) can be taken as a band for bioavailable Sr fractions suitable to discriminate between local and non-local signatures in provenance studies in the field of archaeology and for food and plant authenticity control in agricultural applications.     

Paleomagnetic data and K–Ar ages from Mesozoic units of the Santa Marta massif: A preliminary interpretation for block rotation and translations

We report 6 K–Ar ages and paleomagnetic data from 28 sites collected in Jurassic, Lower Cretaceous and Paleocene rocks of the Santa Marta massif, to test previous hypothesis of rotations and translations of this massif, whose rock assemblage differs from other basement-cored ranges adjacent to the Guyana margin. Three magnetic components were identified in this study. A first component has a direction parallel to the present magnetic field and was uncovered in all units (D = 352, I = 25.6, k = 57.35, a95 = 5.3, N = 12). A second component was isolated in Cretaceous limestone and Jurassic volcaniclastic rocks (D = 8.8, I = 8.3, k = 24.71, a95 = 13.7, N = 6), and it was interpreted as of Early Cretaceous age. In Jurassic sites with this component, Early Cretaceous K–Ar ages obtained from this and previous studies are interpreted as reset ages. The third component was uncovered in eight sites of Jurassic volcaniclastic rocks, and its direction indicates negative shallow to moderate inclinations and northeastward declinations. K–Ar ages in these sites are of Early (196.5 ± 4.9 Ma) to early Late Jurassic age (156.6 ± 8.9 Ma). Due to local structural complexity and too few Cretaceous outcrops to perform a reliable unconformity test, we only used two sites with (1) K–Ar ages, (2) less structural complexity, and (3) reliable structural data for Jurassic and Cretaceous rocks. The mean direction of the Jurassic component is (D = 20.4, I = −18.2, k = 46.9, a95 = 5.1, n = 18 specimens from two sites). These paleomagnetic data support previous models of northward along-margin translations of Grenvillian-cored massifs. Additionally, clockwise vertical-axis rotation of this massif, with respect to the stable craton, is also documented; the sense of rotation is similar to that proposed for the Perija Range and other ranges of the southern Caribbean margin. More data is needed to confirm the magnitudes of rotations and translations.     

Neoarchean convergent margin tectonics associated with microblock amalgamation in the North China Craton: Evidence from the Yishui Complex

Archean tectonic history of the North China Craton (NCC) involved complex processes of amalgamation of microcontinents along multiple subduction zones prior to the consolidation of the major crustal blocks and their assembly into unified cratonic architecture. Here we report a suite of granitoids, diabase, metabasalts, volcanic tuff, banded iron formations and quartzite from the Yishui Complex along the southern margin of the Jiaoliao microblock within the Eastern Block of the NCC. The geochemical features of the magmatic suite are consistent with calc-alkaline magmatism in a convergent margin setting. In tectonic discrimination diagrams, the mafic suite shows variable IAB, MORB and OIB affinities typical of rocks formed in an arc-related subduction environment. Zircon grains in most of the rocks from Yishui Complex display core–rim texture with the cores showing magmatic crystallization and the narrow structureless rims corresponding to metamorphic overgrowth. The ²⁰⁷Pb/²⁰⁶Pb ages of magmatic zircons show 2504 ± 19 Ma for the volcanic tuff, 2581 ± 21 Ma for the granitoid, 2501 ± 19 Ma for the metavolcanics, 2537 ± 38 Ma for the pyroxenite, and 2506 ± 13 Ma for the diabase. Metamorphism is constrained from the 2451 ± 18 Ma and 2466 ± 23 Ma age groups in the metavolcanics and (meta-) pyroxenites. Zircons from BIF show multiple population with the oldest showing a spot age of 2503 Ma, followed by a number of distinct groups of Paleoproterozoic zircons corresponding to later thermal events. The oldest population of magmatic zircons from the quartzite shows ²⁰⁷Pb/²⁰⁶Pb mean age of 2495 ± 24 Ma. The dominantly positive εHf(t) values of the magmatic zircons from the Yishui suite are broadly consistent with a depleted mantle source with only minor input of crustal components. Their Hf crustal residence ages (T_DM^C) range from 2586 to 3181 Ma and Hf depleted mantle model ages (T_DM) are in the range of 2548–2927 Ma. The data indicate that magma production involved Meso- to Neoarchean juvenile sources within a continental arc setting, suggesting the Jiaoliao microblock as one of the ancient continental nuclei in the NCC. We trace the continuity of a Neoarchean subduction system along the western and southern margins of the Jiaoliao microblock with convergence of the Qianhuai and Xuhuai microblocks towards the Jiaoliao microblock with subduction–accretion–collision during the Archean–Proterozoic transition.     

Organic matter quality in reclaimed boreal forest soils following oil sands mining

Following surface mining of the Athabasca Oil Sands deposits in northeastern Alberta, Canada, land reclamation entails the reconstruction of soil-like profiles using salvaged soil materials such as peat and mining by-products. The overall objective of this research was to assess soil organic matter (SOM) quality in different reclamation practices as compared to undisturbed soils found in the region. Soil samples (0–10 cm) were taken from 45 plots selected to represent undisturbed reference ecosites and reclamation treatments. Soil OM pools were isolated using a combination of acid hydrolysis and physical separation techniques. Chemical composition of the low density fractions was characterized using ramped cross polarization (RAMP-CP) ¹³C nuclear magnetic resonance (NMR). Differences between disturbed and undisturbed sites reflected the influence of different botanical inputs (peat vs. forest litter) to SOM composition. Reconstructed soils were characterized by significantly lower alkyl over O-alkyl carbon (ALK/O-ALK) ratios (0.3) than undisturbed sites (0.5). For these reconstructed soils, a significantly higher proportion of soil carbon was present in the sand associated (Heavy sand) pool (49.2 vs. 37.3) and in the acid-unhydrolyzable residue (AUR) fraction (61.3 vs. 54.7). These SOM parameters were significantly related to time since reconstruction, with the AUR (p value = 0.012) and Heavy sand (p value = 0.05) fractions decreasing with time since reconstruction, while the ALK/O-ALK ratio increased (p value = 0.006). These findings suggest that the ALK/O-ALK, AUR, and Heavy sand parameters are suitable indicators for monitoring SOM quality in these reconstructed soils following oil sands mining.