Controls on metamorphic equilibration: the importance of intergranular solubilities mediated by fluid composition

A dramatic demonstration of the role of intergranular solubility in promoting chemical equilibration during metamorphism is found in the unusual zoning of garnet in pelitic schist exposed at Harpswell Neck, Maine, USA. Many garnet crystals have irregular, patchy distributions of Mn, Cr, Fe and Mg in their inclusion‐rich interiors, transitioning to smooth, concentric zoning in their inclusion‐poor outer rims; in contrast, zoning of Ca and Y is comparatively smooth and concentric throughout. We re‐assess the disputed origin of these zoning features by examining garnet growth in the context of the thermal and structural history of the rocks, and by evaluating the record of fluid–rock interaction revealed in outcrop‐scale veining and fluid‐inclusion assemblages. The transition in the character of garnet zoning correlates with the onset of a synkinematic, simple‐shear‐dominated phase of garnet growth and with a shift in the composition of the intergranular fluid from CO₂‐rich to H₂O‐rich. Compositional variations in garnet are therefore best explained by a two‐stage growth history in which intergranular diffusive fluxes reflect differences in the concentration of dissolved species in these two contrasting fluids. Interiors of garnet crystals grew in the presence of a CO₂‐rich fluid, in which limited solubility for Mn and Cr (and perhaps Fe and Mg) produced patchy disequilibrium overprint zoning, while appreciable solubility for Ca and Y permitted their rock‐wide equilibration. Rims grew in the presence of an H₂O‐rich fluid, in which high intergranular concentrations for all elements except Cr enabled diffusion over length scales sufficient for rock‐wide equilibration. This striking example of partial chemical equilibrium during reaction and porphyroblast growth implies that thermal effects may commonly be subsidiary in importance to solubilities in the intergranular medium as determinants of length scales for metamorphic equilibration.     

ISA model: A constitutive model for soils with yield surface in the intergranular strain space

In this article, a new constitutive model for soils is proposed. It is formulated by means of plasticity, but in contrast to the precedent works, it presents a yield function describing a surface within the intergranular strain space. This latter is a state variable providing information of the recent strain history. An expression for the plastic strain rate has been proposed to guarantee the stress rate continuity. Under the application of medium or large strain amplitudes, the constitutive equation becomes independent of the intergranular strain and delivers a mathematical structure similar to some Karlsruhe hypoplastic models. Some simulations of monotonic and cyclic triaxial test are provided to evaluate and analyze the model performance. Copyright © 2015 John Wiley & Sons, Ltd.     

Calibration of paired watersheds: Utility of moving sums in presence of externalities

Historically, paired watershed studies have been used to quantify the hydrological effects of land use and management practices by concurrently monitoring 2 similar watersheds during calibration (pretreatment) and post‐treatment periods. This study characterizes seasonal water table and flow response to rainfall during the calibration period and tests a change detection technique of moving sums of recursive residuals (MOSUM) to select calibration periods for each control–treatment watershed pair when the regression coefficients for daily water table elevation were most stable to minimize regression model uncertainty. The control and treatment watersheds were 1 watershed of 3–4‐year‐old intensely managed loblolly pine (Pinus taeda L.) with natural understory, 1 watershed of 3–4‐year‐old loblolly pine intercropped with switchgrass (Panicum virgatum), 1 watershed of 14–15‐year‐old thinned loblolly pine with natural understory (control), and 1 watershed of switchgrass only. The study period spanned from 2009 to 2012. Silvicultural operational practices during this period acted as external factors, potentially shifting hydrologic calibration relationships between control and treatment watersheds. MOSUM results indicated significant changes in regression parameters due to silvicultural operations and were used to identify stable relationships for water table elevation. None of the calibration relationships developed using this method were significantly different from the classical calibration relationship based on published historical data. We attribute that to the similarity of historical and 2010–2012 leaf area index on control and treatment watersheds as moderated by the emergent vegetation. Although the MOSUM approach does not eliminate the need for true calibration data or replace the classic paired watershed approach, our results show that it may be an effective alternative approach when true data are unavailable, as it minimizes the impacts of external disturbances other than the treatment of interest.     

The Late Cretaceous Klepa basalts in Macedonia (FYROM)—Constraints on the final stage of Tethys closure in the Balkans

The waning stage(s) of the Tethyan ocean(s) in the Balkans are not well understood. Controversy centres on the origin and life‐span of the Cretaceous Sava Zone, which is allegedly a remnant of the last oceanic domain in the Balkan Peninsula, defining the youngest suture between Eurasia‐ and Adria‐derived plates. In order to investigate to what extent Late‐Cretaceous volcanism within the Sava Zone is consistent with this model we present new age data together with trace‐element and Sr–Nd–Pb isotope data for the Klepa basaltic lavas from the central Balkan Peninsula. Our new geochemical data show marked differences between the Cretaceous Klepa basalts (Sava Zone) and the rocks of other volcanic sequences from the Jurassic ophiolites of the Balkans. The Klepa basalts mostly have Sr–Nd–Pb isotopic and trace‐element signatures that resemble enriched within‐plate basalts substantially different from Jurassic ophiolite basalts with MORB, BAB and IAV affinities. Trace‐element modelling of the Klepa rocks indicates 2%–20% polybaric melting of a relatively homogeneously metasomatised mantle source that ranges in composition from garnet lherzolite to ilmenite+apatite bearing spinel–amphibole lherzolite. Thus, the residual mineralogy is characteristic of a continental rather than oceanic lithospheric mantle source, suggesting an intracontinental within‐plate origin for the Klepa basalts. Two alternative geodynamic models are internally consistent with our new findings: (1) if the Sava Zone represents remnants of the youngest Neotethyan Ocean, magmatism along this zone would be situated within the forearc region and triggered by ridge subduction; (2) if the Sava Zone delimits a diffuse tectonic boundary between Adria and Europe which had already collided in the Late Jurassic, the Klepa basalts together with a number of other magmatic centres represent volcanism related to transtensional tectonics.     

Groundwater recharge in an arid grassland as indicated by soil chloride profile and multiple tracers

Previous studies have shown that shallow groundwater in arid regions is often not in equilibrium with near‐surface boundary conditions due to human activities and climate change. This is especially the case where the unsaturated zone is thick and recharge rate is limited. Under this nonequilibrium condition, the unsaturated zone solute profile plays an important role in estimating recent diffuse recharge in arid environments. This paper combines evaluation of the thick unsaturated zone with the saturated zone to investigate the groundwater recharge of a grassland in the arid western Ordos Basin, NW China, using the soil chloride profiles and multiple tracers (²H, ¹⁸O, ¹³C, ¹⁴C, and water chemistry) of groundwater. Whereas conventional water balance and Darcy flux measurements usually involve large errors in recharge estimations for arid areas, chloride mass balance has been widely and generally successfully used. The results show that the present diffuse recharge beneath the grassland is 0.11–0.32 mm/year, based on the chloride mass balance of seven soil profiles. The chloride accumulation age is approximately 2,500 years at a depth of 13 m in the unsaturated zone. The average Cl content in soil moisture in the upper 13 m of the unsaturated zone ranges from 2,842 to 7,856 mg/L, whereas the shallow groundwater Cl content ranges from 95 to 351 mg/L. The corrected ¹⁴C age of shallow groundwater ranges from 4,327 to 29,708 years. Stable isotopes show that the shallow groundwater is unrelated to modern precipitation. The shallow groundwater was recharged during the cold and wet phases of the Late Pleistocene and Holocene humid phase based on palaeoclimate, and consequently, the groundwater resources are nonrenewable. Due to the limited recharge rate and thick unsaturated zone, the present shallow groundwater has not been in hydraulic equilibrium with near‐surface boundary conditions in the past 2,500 years.     

New P–T constraints on the Tamayen glaucophane‐bearing rocks,eastern Taiwan: Perple_X modelling results and geodynamic implications

New pseudosection modelling was applied to better constrain the P–T conditions and evolution of glaucophane‐bearing rocks in the Tamayen block of the Yuli belt, recognized as the world's youngest known blueschist complex. Based on the predominant clinoamphibole, textural relationships, and mineral compositions, these glaucophane‐bearing high‐P rocks can be divided into four types. We focused on the three containing garnet. The chief phase assemblages are (in decreasing mode): amphibole + quartz + epidote + garnet + chlorite + rutile/titanite (Type‐I), phengite + amphibole + quartz + garnet + chlorite + epidote + titanite + biotite + magnetite (Type‐II), and amphibole + quartz + albite + epidote + garnet + rutile + hematite + titanite (Type‐III). Amphibole exhibits compositional zoning from core to rim as follows: glaucophane → pargasitic amphibole → actinolite (Type‐I), barroisite → Mg‐katophorite/taramite → Fe‐glaucophane (Type‐II), glaucophane → winchite (Type‐III). Using petrographic data, mineral compositions and Perple_X modelling (pseudosections and superimposed isopleths), peak P–T conditions were determined as 13 ± 1 kbar and 550 ± 40 °C for Type‐I, 10.5 ± 0.5 kbar and 560 ± 30 °C for Type‐II (thermal peak) and 11 ± 1 kbar and 530 ± 30 °C for Type‐III. The calculations yield higher pressures and temperatures than previously thought; the difference is ~1–6 kbar and 50–200 °C. The three rock types record similar P–T retrograde paths with clockwise trajectories; all rocks followed trajectories with substantial pressure decrease under near‐isothermal conditions (Type‐I and Type‐III), with the probable exception of Type‐II where decompression followed colder geotherms. The P–T paths suggest a tectonic environment in which the rocks were exhumed from maximum depths of ~45 km within a subduction channel along a relative cold geothermal gradient of ~11–14 °C km^?1.     

Intragrain oxygen isotope zoning in titanite by SIMS: Cooling rates and fluid infiltration along the Carthage‐Colton Mylonite Zone,Adirondack Mountains,NY, USA

Oxygen isotopes are an attractive target for zoning studies because of the ubiquity of oxygen‐bearing minerals and the dependence of mineral ¹⁸O/¹⁶O ratios on temperature and fluid composition. In this study, subtle intragrain oxygen isotope zoning in titanite is resolved at the 10‐μm scale by secondary ion mass spectrometry. The patterns of δ¹⁸O zoning differ depending on microstructural context of individual grains and reflect multiple processes, including diffusive oxygen exchange, partial recrystallization, grain‐size reduction, and grain growth. Using the chronological framework provided by structural relations, these processes can be related to specific events during the Grenville orogeny. Titanite was sampled from two outcrops within the Carthage‐Colton Mylonite Zone (CCMZ), a long‐lived shear zone that ultimately accommodated exhumation of the Adirondack Highlands from beneath the Adirondack Lowlands during the Ottawan phase (1090–1020 Ma) of the Grenville orogeny. Titanite is hosted in the Diana metasyenite complex, which preserves three sequentially developed fabrics: an early NW‐dipping protomylonitic fabric (S₁) is crosscut by near‐vertical ultramylonitic shear zones (S₂), which are locally reoriented by a NNW‐dipping mylonitic fabric (S₃). Texturally early titanite (pre‐S₂) shows diffusion‐dominated δ¹⁸O zoning that records cooling from peak Ottawan, granulite‐facies conditions. Numerical diffusion models in the program Fast Grain Boundary yield good fits to observed δ¹⁸O profiles for cooling rates of 50 ± 20 °C Ma^?1, which are considerably faster than the 1–5 °C Ma^?1 cooling rates previously inferred for the Adirondack Highlands from regional thermochronology. High cooling rates are consistent with an episode of rapid shearing and exhumation along the CCMZ during gravitational collapse of the Ottawan orogen at c. 1050 Ma. Texturally later titanite (syn‐S₂) has higher overall δ¹⁸O and shows a transition from diffusion‐dominated to recrystallization‐dominated δ¹⁸O zoning, indicating infiltration of elevated‐δ¹⁸O fluids along S₂ shear zones and continued shearing below the blocking temperature for oxygen (~≤500 °C for grain sizes at the study site). The texturally latest titanite (post‐S₃) has growth‐dominated δ¹⁸O zoning, consistent with porphyroblastic grain growth following cessation of shearing along the Harrisville segment of the CCMZ.     

Effect of bed surface roughness on longitudinal dispersion in artificial open channels

In several empirical and modelling studies on river hydraulics, dispersion was negatively correlated to surface roughness. In this study, it was aimed to investigate the influence of surface roughness on longitudinal dispersion under controlled conditions. In artificial flow channels with a length of 104 m, tracer experiments with variations in channel bed material were performed. By use of measured tracer breakthrough curves, average flow velocity, mean longitudinal dispersion, and mean longitudinal dispersivity were calculated. Longitudinal dispersion coefficients ranged from 0·018 m² s^?1 in channels with smooth bed surface up to 0·209 m² s^?1 in channels with coarse gravel as bed material. Longitudinal dispersion was linearly related to mean flow velocity. Accordingly, longitudinal dispersivities ranged between 0·152 ± 0·017 m in channels with smooth bed surface and 0·584 ± 0·015 m in identical channels with a coarse gravel substrate. Grain size and surface roughness of the channel bed were found to correlate positively to longitudinal dispersion. This finding contradicts several existing relations between surface roughness and dispersion. Future studies should include further variation in surface roughness to derive a better‐founded empirical equation forecasting longitudinal dispersion from surface roughness. Copyright © 2011 John Wiley & Sons, Ltd.