Biodegradation of forest floor organic matter bound to minerals via different binding mechanisms

Mineral-associated organic matter (OM) represents a large reservoir of organic carbon (OC) in natural environments. The factors controlling the extent of the mineral-mediated OC stabilization, however, are poorly understood. The protection of OM against biodegradation upon sorption to mineral phases is assumed to result from the formation of strong bonds that limit desorption. To test this, we studied the biodegradation of OM bound to goethite (α-FeOOH), pyrophyllite, and vermiculite via specific mechanisms as estimated from OC uptake in different background electrolytes and operationally defined as ‘ligand exchange’, ‘Ca²⁺ bridging’, and ‘van der Waals forces’. Organic matter extracted from an Oa forest floor horizon under Norway spruce (Picea abies (L.) Karst) was reacted with minerals at dissolved OC concentrations of ∼5-130 mg/L at pH 4. Goethite retained up to 30.1 mg OC/g predominantly by ‘ligand exchange’; pyrophyllite sorbed maximally 12.5 mg OC/g, largely via ‘van der Waals forces’ and ‘Ca²⁺ bridging’, while sorption of OM to vermiculite was 7.3 mg OC/g, mainly due to the formation of ‘Ca²⁺ bridges’. Aromatic OM components were selectively sorbed by all minerals (goethite ? phyllosilicates). The sorption of OM was strongly hysteretic with the desorption into 0.01 M NaCl being larger for OM held by ‘Ca²⁺ bridges’ and ‘van der Waals forces’ than by ‘ligand exchange’. Incubation experiments under aerobic conditions (initial pH 4; 90 days) revealed that OM mainly bound to minerals by ‘ligand exchange’ was more resistant against mineralization than OM held by non-columbic interactions (‘van der Waals forces’). Calcium bridges enhanced the stability of sorbed OM, especially for vermiculite, but less than the binding via ‘ligand exchange’. Combined evidence suggests that the extent and rate of mineralization of mineral-associated OM are governed by desorption. The intrinsic stability of sorbed OM as related to the presence of resistant, lignin-derived aromatic components appears less decisive for the sorptive stabilization of OM than the involved binding mechanisms. In a given environment, the type of minerals present and the solution chemistry determine the operating binding mechanisms, thereby the extent of OM sorption and desorption, and thus ultimately the bioavailability of mineral-associated OM.     

Highly evolved juvenile granites with tetrad REE patterns: the Woduhe and Baerzhe granites from the Great Xing'an Mountains in NE China

In NE China, voluminous granitoids were emplaced in late Paleozoic and Mesozoic times. We report here Sr–Nd–O isotopic and elemental abundance data for two highly evolved granitic plutons, Woduhe and Baerzhe, from the Great Xing'an Mountains. They show a rather “juvenile” Sr–Nd isotopic signature and a spectacular tetrad effect in their REE distribution patterns as well as non-CHARAC (charge-and-radius-controlled) trace element behavior. The emplacement ages are constrained at 130±4 Ma for the Woduhe and 122±5 Ma for the Baerzhe granites by Rb–Sr and Sm–Nd isotope analyses. Both granites are also characterized by low but imprecise initial ⁸⁷Sr/⁸⁶Sr ratios of about 0.703. The Nd–Sr isotope data argue for their generation by melting of dominantly juvenile mantle component with subordinate recycled ancient crust. This is largely compatible with the general scenario for much of the Phanerozoic granitoids emplaced in the Central Asian Orogenic Belt. The parental magmas for both the Woduhe and Baerzhe granites have undergone extensive magmatic differentiation, during which intense interaction of the residual melts with aqueous hydrothermal fluids (probably rich in F and Cl) resulted in the non-CHARAC trace element behavior and the tetrad effect of REE distribution. Both the Woduhe and Baerzhe granites show the characteristic trace element patterns of rare-metal granites, but their absolute abundances differ by as much as two orders of magnitude. The oxygen isotope compositions of the two granites have been severely disturbed. Significant ¹⁸O depletion in feldspar, but not so much in quartz, suggests that the hydrothermal alteration took place in a temperature condition of 300–500 °C. This subsolidus hydrothermal alteration is decoupled from the late-stage magma–fluid interaction at higher temperatures. Despite the two distinct and intense events of “water–rock” interaction, the Rb–Sr and Sm–Nd geochronological systems seem to have maintained closed, hence, suggesting that the two events occurred shortly after the plutonic emplacements.     

Major and trace element, and Sr-Nd isotope constraints on the origin of Paleogene volcanism in South China prior to the South China Sea opening

Paleogene volcanic rocks crop out in three sedimentary basins, namely, Sanshui, Heyuan and Lienping, in the attenuated continental margin of south China. Lavas from the Sanshui basin which erupted during 64-43 Ma are bimodal, consisting of intraplate tholeiitic basalt and trachyte/rhyolite associations. Similar to Cretaceous A-type granites from the nearby region, the felsic member shows peralkaline nature [Na₂O + K₂O ≈ 10–12%; (Na + K)/Al≈ 0.98−1.08], general enrichment in the incompatible trace elements and significant depletion in Ba, Sr, Eu, P and Ti. Although both types of the Sanshui lavas have rather uniform Nd isotope compositions [_Nd(T) ≈ +6 to +4]that are comparable to Late Cenozoic basalts around the South China Sea, the felsic rocks possess apparently higher initial Sr isotope ratios (I_Sr up to 0.713) and form a horizontal array to the right in the Nd vs. Sr isotope plot. Closed system differentiation of mantle-derived magmas in a ‘double diffusive’ magma chamber is considered for the bimodal volcanism, in which the trachytes and rhyolites represent A-type melts after extensive crystal fractionation in the upper portion of the chamber. Such A-type melts were later contaminated by small amounts (1–3%) of upper crustal materials during ascent. On the other hand, composition of lavas in the other two basins varies from tholeiitic basalt to andesite. Their Sr and Nd isotope ratios [I_Sr ≈ 0.705 to 0.711; _Nd(T) ≈ +1 to − 5] and generally correlative Nb-Ta depletions suggest a distinct magma chamber process involving fractional crystallization concomitant with assimilation of the country rock. We conclude that these Paleogene volcanic activities resulted from the lithospheric extension in south China that migrated southwards and eventually led to opening of the South China Sea during 30-16 Ma.     

Plastic deformation of orthoenstatite and the ortho- to high-pressure clinoenstatite transition: a metadynamics simulation study

Atomic-scale mechanisms of plastic deformation in orthoenstatite, MgSiO₃ are studied by computer simulation methods. The combined use of metadynamics and molecular dynamics allows a direct observation of the structural changes during the creation of stacking faults in the (100) plane. A sequence of slip deformations in two different (100) planes at P = 15 GPa and T = 1,000 K reveals a probable transformation mechanism for the ortho- to high-pressure clinopyroxene transition. Each of the observed slips consists of at least four partial deformations crossing high-energy intermediate structures. In agreement with experimental studies, both (100)[010] and (100)[001] slip systems are activated in the deformation process. The observation of a dominant (100)[001] single slip system in pyroxenes may be related to the fact that high-energy intermediate dislocations with (100)[010] component are not stable on geological or experimental timescales.     

Setouchi high-Mg andesites revisited: geochemical evidence for melting of subducting sediments

In order to evaluate the mechanism of production of unusual high-Mg andesite (HMA) magmas, Pb–Nd–Sr isotopic compositions were determined for HMAs and basalts from the Miocene Setouchi volcanic belt in the SW Japan arc. The isotopic compositions of Setouchi rocks form mixing lines between local oceanic sediments and Japan Sea backarc basin basalts, suggesting a significant contribution of the subducting sediment component to the HMA magma generation. Mixing calculations using compositions of an inferred original mantle and local oceanic sediments suggest that a sediment-derived melt, neither an H₂O-rich fluid nor an amphibolite/eclogite-derived melt, could have been produced first and served as a plausible metasomatic agent for the HMA magma source. The unusual tectonic setting, including subduction of a newly-borne hence hot plate, may be responsible for melting of subducting sediments.     

Paleoproterozoic age of the Zeya Group,Stanovoy Complex of the Dzhugdzhur–Stanovoy Superterrane (Central Asian mobile belt): Results of Sm–Nd isotopic and U–Th–Pb geochronological (LA-ICP-MS) аnalyses

Geochemical Sm–Nd isotope and U–Th–Pb geochronological (LA-ICP-MS) studies have demonstrated that the Zeya Group of the Stanovoy Complex of the Dzhugdzhur–Stanovoy Superterrane (Central Asian fold belt) is not Paleoarchean, as was previously thought, but Paleoproterozoic in age.     

Komatiites of the Onverwacht Group,S. Africa: REE geochemistry,Sm/Nd age and mantle evolution

Komatiites of the Tjakastad Subgroup of the Onverwacht Group (S. Africa) were dated by the Sm/Nd method. A whole-rock isochron yields an age of 3.56±0.24 (2) AE, with initial ¹⁴³Nd/¹⁴⁴Nd ratio of 0.50818±23 (2), corresponding to _Nd(T)= + 1.9±4.5. This age is interpreted as the time of initial Onverwacht volcanism. This result agrees with earlier Sm/Nd data of Hamilton et al. (1979) and is consistent with the Rb-Sr result of Jahn and Shih (1974).Komatiites may be divided into 3 groups based on the typology of heavy REE distributions (Jahn and Gruau 1981). According to this scheme, the Onverwacht komatiites of the present study belong to two groups: the predominant Group II rocks showing (Gd/Yb)_N1.4, CaO/Al₂O₃ = 1.33, Al₂O₃/TiO₂10.6; and the subordinate Group III rocks with (Gd/Yb)_N<1.0; CaO/Al₂O₃0.6 and A1₂O₃/ TiO₂40. This contrasting feature is best explained by garnet fractionation within the mantle sources.Younger komatiites (2.7 AE) from Finland, Canada, Rhodesia, and Australia have (Gd/Yb)_N1.0, CaO/ Al₂O₃<1.1 and Al₂O₃/TiO₂21 based on 58 analyses. These ratios are nearly chondritic or of the bulk earth value (Anders 1977). It appears that some late Archean komatiites are different in chemistry from many early Archean komatiites. This may imply that the upper mantle chemistry has evolved through Archean times. However, the age connotation of the chemical parameters, such as CaO/Al₂O₃, (Gd/Yb)_N or Al₂O₃/TiO₂ ratio has not been firmly established. The characteristic high CaO/Al₂O₃ or (Gd/Yb)_N ratios in many Onverwacht Group rocks can also be explained as a result of local short-term mantle heterogeneity.     

Archean granulite gneisses from eastern Hebei Province,China: rare earth geochemistry and tectonic implications

The granulite gneisses and their retrograded products of the Qianxi Group from eastern Hebei Province, China, have been investigated for their isotope and trace element geochemistry. A consistent age of about 2.5 AE has been obtained by the Rb-Sr and Sm-Nd whole-rock isochron methods, in agreement with the zircon U-Pb data (Pidgeon 1980; D.Y. Liu, unpubl.). Geochemical arguments from initial isotopic ratios (I_Sr and I_Nd) and elemental distribution patterns have led us to conclude that this age of about 2.5 AE represents the time of granulite facies metamorphism, which must have followed closely the primary emplacement of their protoliths. Previous claims for early Archean ages (>3.5 AE) of these granulites are not substantiated. The mineral isotope systematics register an important thermal event at about 1.7 AE, roughly corresponding to the time of the widespread Luliang Orogeny (Ma and Wu 1981) or Chungtiao Movement (Huang 1978).The granulites of the Qianxi Group have diverse compositions ranging from ultrabasic through basic-intermediate to acid. Discriminant function calculations suggest that most analyzed samples have igneous parentage. Only a few show characteristics of metasedimentary rocks. The igneous protoliths apparently belong to two series — tholeiitic and calc-alkaline, with the latter dominating in abundance. The majority of the acid granulites have compositions corresponding to tonalite-granodiorite.Except for ultrabasic and metasedimentary rocks, all REE patterns are significantly fractionated with LREE enrichment. The degree of fractionation, as measured by the (La/Yb)_N ratios, is most important in the acid granulites. These rocks often show positive Eu anomalies and HREE depletions that are typical of Archean TTG rocks (tonalitetrondhjemite-granodiorite).The existence of komatiites has been previously reported in this region. Although a few rocks have a major element chemistry similar to that for peridotitic komatiites, the lack of associated members in a komatiitic series and the scarcity of REE data have not confirmed the true komatiite occurrence in this region.Many Qianxi granulites are highly depleted in Rb relative to K and Sr. This preferential Rb depletion during granulite facies metamorphism has led to very high K/Rb and very low Rb/Sr ratios. The most comparable case is found in Lewisian granulites.Although the fractionated REE patterns of the basic granulites somewhat resemble those of continental flood basalts, the highly different abundances in other incompatible elements (Ti, Zr, and Ba) readily distinguish them from each other. Nevertheless, the LREE enriched patterns of the basic granulites may suggest an origin of their protoliths by partial melting of LREE-enriched mantle sources. On the other hand, the REE patterns of acid granulites suggest that their protoliths could be derived by partial melting of quartz eclogite, amphibolite or basic granulite.The close time relationship for a series of geologic events, namely, from initial melting of mantle peridotites, through fractional crystallisation of basaltic magmas, to granulite facies metamorphism, seems to occur in many granulite terrains. This relationship, together with the juxtaposition of lithologies of different origins and the exceptionally high pressure conditions (>10 Kb) can be best explained by crustal underplating combined with intracrustal thin-skinned thrusting and stacking of crustal slices. The andesitic or island arc model for the formation of the lower continental crust is not in good agreement with the present geochemical data.     

NdSr isotope and REE geochemistry of alkali basalts from the Massif Central,France

Nd and Sr isotopic compositions as well as trace element concentrations have been determined on a suite of alkali basalts from the Massif Central, in France. Samples show a typical enrichment in incompatible elements. In particular, the REE patterns exhibit a strong fractionation characterized by a ($\text{La}\text{Yb}\text{)}{}_{\mathrm{<mtext>N</mtext>}}$ ratio of about 20. The Yb_N content is about 10 times chondrite. The $\text{143}\text{Nd}\text{144}\text{Nd}$ ratios exhibit a range from 0.512775 to 0.512989, values quite comparable to those from oceanic island basalts. The $\text{87}\text{Sr}\text{86}\text{Sr}$ ratios vary between 0.70338 and 0.70458 and are anti-correlated with the Nd isotopic ratio.The isotopic and the trace element (in particular REE) data have been used in order to quantitatively model the genesis of the alkali basalts. Among the several types of models tested here, the most likely one appears to be the model of mantle metasomatism. A semi-quantitative approach shows that the source of alkali basalts from the Massif Central was metasomatized prior to melting. In such a model, the basalts could be produced by rather high degrees of partial melting (such as 10 or 15%) of the metasomatically enriched mantle.     

Geomorphological modelling and nature protection in arctic and subarctic environments

Geomorphological processes of the cold climate zone can be divided into natural and accelerated. In the former group the following processes are being discussed: frost weathering, mass wasting, solifluction, landslides, slopewash and linear erosion and wind action. Processes of accelerated action are due to natural and artificial stimuli. To the former belong for instance heavy rains which sometimes occur in polar zones (as in Spitsbergen in July 1972). More frequent however, are, artificial causes which are connected with man's activities.The action of geomorphological processes is indicated by the denudational balance which can be either positive or negative. The author has determined this balance for some regions of the Arctic and Subarctic, especially for Siberia. The balance is positive (degradation) in the zone of polar desert and in the oceanic part of the Arctic, and also in high mountains of this zone. Negative denudation balance prevails in the continental section of the Subarctic. The areas of positive denudational balance are threatened with nature destruction and therefore particularly deserve to be covered by a nature protection scheme.