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R. P. Wintsch

Publications and source records attributed to R. P. Wintsch.

18 recordsLinked to original sources
USGS2016

Reaction softening by dissolution–precipitation creep in a retrograde greenschist facies ductile shear zone, New Hampshire, USA

We describe strain localization by a mixed process of reaction and microstructural softening in a lower greenschist facies ductile fault zone that transposes and replaces middle to upper amphibolite facies fabrics and mineral assemblages in the host schist of the Littleton Formation near Claremont, New Hampshire. Here, Na-poor muscovite and chlorite progressively replace first staurolite, then garnet, and finally biotite porphyroblasts as the core of the fault zone is approached. Across the transect, higher grade fabric-forming Na-rich muscovite is also progressively replaced by fabric-forming Na-poor muscovite. The mineralogy of the new phyllonitic fault-rock produced is dominated by Na-poor muscovite and chlorite together with late albite porphyroblasts. The replacement of the amphibolite facies porphyroblasts by muscovite and chlorite is pseudomorphic in some samples and shows that the chemical metastability of the porphyroblasts is sufficient to drive replacement. In contrast, element mapping shows that fabric-forming Na-rich muscovite is selectively replaced at high-strain microstructural sites, indicating that strain energy played an important role in activating the dissolution of the compositionally metastable muscovite. The replacement of strong, high-grade porphyroblasts by weaker Na-poor muscovite and chlorite constitutes reaction softening. The crystallization of parallel and contiguous mica in the retrograde foliation at the expense of the earlier and locally crenulated Na-rich muscovite-defined foliation destroys not only the metastable high-grade mineralogy, but also its stronger geometry. This process constitutes both reaction and microstructural softening. The deformation mechanism here was thus one of dissolution–precipitation creep, activated at considerably lower stresses than might be predicted in quartzofeldspathic rocks at the same lower greenschist facies conditions.

New Hampshire↗
USGS2010

Contrasting P‐T‐t paths: Thermochronologic evidence for a Late Paleozoic final assembly of the Avalon Composite Terrane in the New England Appalachians

Strongly contrasting pressure‐temperature‐time paths for the Avalon composite terrane and the structurally overlying Putnam‐Nashoba zone in eastern New England obtained from thermochronologic and thermobarometric data are best explained by a late Paleozoic underthrusting of cover rocks by the Avalon composite terrane. We present new Ar and U‐Pb thermochronologic data that show that in the southern Hope Valley zone, Permian (280 Ma) anatectic metamorphic conditions of 700°C and 6 kbar were quenched by relatively rapid cooling (12°C/m.y.) and exhumation (0.5 km/m.y.) for ∼40 m.y. In contrast, peak metamorphic conditions in the Putnam‐Nashoba zone predate Silurian intrusions, and slower cooling (3.5°C/m.y.) began at about 400 Ma. One‐dimensional thermal modeling suggests that these two belts were not in thermal equilibrium during the Permian metamorphism of the Avalon composite terrane. Because of the absence of high‐grade Alleghanian metamorphism in rocks overlying the Avalon terrane, we conclude that high‐grade Alleghanian metamorphism in the Avalon terrane occurred east of rocks now overlying it and that significant motion between Avalon and this cover occurred after peak Alleghanian metamorphism. Similarly contrasting metamorphic histories between Avalon inliers (Willimantic window, Massabesic complex gneiss, Pelham dome) and their cover rocks reveals the regional significance of this boundary. The core rocks all show Permian cooling, but the cover rocks show post‐Acadian cooling ages decreasing from east to west to the Pelham area, where hornblende ages in Avalon and cover differ by only 35 rather than 80 m.y. Model calculations show that thermal equilibrium between instantaneously thrusted blocks of rocks is generally obtained in tens of millions of years. Consequently, underthrusting of Avalon is constrained to be middle Mississippian or younger. Because the leading edge of the underthrusting block would have been heated the longest and would have most closely approached thermal equilibrium with its cover, core rocks of the Pelham dome must have been relatively close to this leading edge. Thus Carboniferous to Permian underplating from a generally eastward direction best explains these thermochronologic relationships.

Connecticut, Maine, Massachusetts, New Hampshire, ↗
USGS2009

40Ar/39Ar dating of Silurian and late Devonian cleavages in lower greenschist-facies rocks in the Westminster terrane, Maryland, USA

40 Ar/ 39 Ar dating of muscovite, biotite, and K-feldspar combined with microstructural analysis of lower greenschist-facies, polymetamorphic, phyllitic rocks, and marbles were successfully used to decipher the thermal and tectonic histories of the Westminster and adjacent terranes in western Maryland. The presence of unreset detrital muscovite in some samples demonstrates that temperatures in these rocks never exceeded the closure temperature for argon diffusion in muscovite, ∼350 ± 50 °C. Minor biotite in some arkoses constrains the minimum metamorphic temperatures to ≥∼320 °C. These data show an Early Silurian (ca. 430 Ma) cleavage in the western part of the Westminster terrane and a Late Devonian event (ca. 370 Ma) in the eastern Westminster and adjacent Potomac terranes. These two cleavage domains are separated by the NE-trending, newly identified Parrs Ridge fault zone. We propose that the sinistral transpressive collision of the Carolina terrane with Laurentia emplaced the western portion of the Westminster terrane in the Pennsylvania embayment along the Martic fault where it was folded and cleaved at ca. 430 Ma but otherwise largely sheltered from later deformation. The later Late Devonian dextral transpressive accretion of the outboard Potomac terrane thrust rocks of the eastern Westminster and Potomac terranes to the west, causing Late Devonian (360–370 Ma) S 2 cleavage in these rocks, but only minimal discrete overprinting S 3 cleavages in rocks farther west. Final juxtaposition and thermal convergence of these terranes occurred along reactivated dextral strike-slip faults in the Alleghanian at ca. 300 Ma.

Maryland↗
USGS2009

Chitin: 'Forgotten' source of nitrogen: From modern chitin to thermally mature kerogen: Lessons from nitrogen isotope ratios

Chitinous biomass represents a major pool of organic nitrogen in living biota and is likely to have contributed some of the fossil organic nitrogen in kerogen. We review the nitrogen isotope biogeochemistry of chitin and present preliminary results suggesting interaction between kerogen and ammonium during thermal maturation. Modern arthropod chitin may shift its nitrogen isotope ratio by a few per mil depending on the chemical method of chitin preparation, mostly because N-containing non-amino-sugar components in chemically complex chitin cannot be removed quantitatively. Acid hydrolysis of chemically complex chitin and subsequent ion-chromatographic purification of the "deacetylated chitin-monomer" D-glucosamine (in hydrochloride form) provides a chemically well-defined, pure amino-sugar substrate for reproducible, high-precision determination of δ 15 N values in chitin. δ 15 N values of chitin exhibited a variability of about one per mil within an individual's exoskeleton. The nitrogen isotope ratio differed between old and new exoskeletons by up to 4 per mil. A strong dietary influence on the δ 15 N value of chitin is indicated by the observation of increasing δ 15 N values of chitin from marine crustaceans with increasing trophic level. Partial biodegradation of exoskeletons does not significantly influence δ 15 N values of remaining, chemically preserved amino sugar in chitin. Diagenesis and increasing thermal maturity of sedimentary organic matter, including chitin-derived nitrogen-rich moieties, result in humic compounds much different from chitin and may significantly change bulk δ 15 N values. Hydrous pyrolysis of immature source rocks at 330°C in contact with 15 N-enriched NH 4 Cl, under conditions of artificial oil generation, demonstrates the abiogenic incorporation of inorganic nitrogen into carbon-bound nitrogen in kerogen. Not all organic nitrogen in natural, thermally mature kerogen is therefore necessarily derived from original organic matter, but may partly result from reaction with ammonium-containing pore waters.

ACS Symposium Series↗
USGS2007

Scales of equilibrium and disequilibrium during cleavage formation in chlorite and biotite-grade phyllites, SE Vermont

Detailed electron microprobe analyses of phyllosilicates in crenulated phyllites from south-eastern Vermont show that grain-scale zoning is common, and sympathetic zoning in adjacent minerals is nearly universal. We interpret this to reflect a pressure-solution mechanism for cleavage development, where precipitation from a very small fluid reservoir fractionated that fluid. Multiple analyses along single muscovite, biotite and chlorite grains (30–200 μ m in length) show zoning patterns indicating Tschermakitic substitutions in muscovite and both Tschermakitic and di/trioctahedral substitutions in biotite and chlorite. Using cross-cutting relationships and mineral chemistry it is shown that these patterns persist in cleavages produced at metamorphic conditions of chlorite-grade, chlorite-grade overprinted by biotite-grade and biotite-grade. Zoning patterns are comparable in all three settings, requiring a similar cleavage-forming mechanism independent of metamorphic grade. Moreover, the use of 40 Ar/ 39 Ar geochronology demonstrates this is true regardless of age. Furthermore, samples with chlorite-grade cleavages overprinted by biotite porphyroblasts suggest the closure temperatures for the diffusion of Al, Si, Mg and Fe ions are greater than the temperature of the biotite isograd (>∼400 °C). Parallel and smoothly fanning tie lines produced by coexisting muscovite–chlorite, and muscovite–biotite pairs on compositional diagrams demonstrate effectively instantaneous chemical equilibrium and probably indicate simultaneous crystallization. These results do not support theories suggesting cleavages form in fluid-dominated systems. If crenulation cleavages formed in systems in which the chemical potentials of all major components are fixed by an external reservoir, then the compositions of individual grains defining these cleavages would be uniform. On the contrary, the fine-scale chemical zoning observed probably reflects a grain-scale process consistent with a pressure-solution mechanism in which the aqueous activities of major components are defined by local dissolution and precipitation. Thus the role of fluids was probably limited to one of catalysing pressure-solution and fluids apparently did not drive cleavage development.

Journal of Metamorphic Geology↗
USGS2007

Ages and origins of rocks of the Killingworth dome, south-central Connecticut: Implications for the tectonic evolution of southern New England

The Killingworth dome of south-central Connecticut occurs at the southern end of the Bronson Hill belt. It is composed of tonalitic and trondhjemitic orthogneisses (Killingworth complex) and bimodal metavolcanic rocks (Middletown complex) that display calc-alkaline affinities. Orthogneisses of the Killingworth complex (Boulder Lake gneiss, 456 ?? 6 Ma; Pond Meadow gneiss, ???460 Ma) were emplaced at about the same time as eruption and deposition of volcanic-sedimentary rocks of the Middletown complex (Middletown Formation, 449 ?? 4 Ma; Higganum gneiss, 459 ?? 4 Ma). Hidden Lake gneiss (339 ?? 3 Ma) occurs as a pluton in the core of the Killingworth dome, and, on the basis of geochemical and isotopic data, is included in the Killingworth complex. Pb and Nd isotopic data suggest that the Pond Meadow, Boulder Lake, and Hidden Lake gneisses (Killingworth complex) resulted from mixing of Neoproterozoic Gander terrane sources (high 207Pb/204Pb and intermediate ??Nd) and less radiogenic (low 207Pb/204Pb and low ??Nd) components, whereas Middletown Formation and Higganum gneiss (Middletown complex) were derived from mixtures of Gander basement and primitive (low 207Pb/204Pb and high ??Nd) sources. The less radiogenic component for the Killingworth complex is similar in isotopic composition to material from Laurentian (Grenville) crust. However, because published paleomagnetic and paleontologic data indicate that the Gander terrane is peri-Gondwanan in origin, the isotopic signature of Killingworth complex rocks probably was derived from Gander basement that contained detritus from non-Laurentian sources such as Amazonia, Baltica, or Oaxaquia. We suggest that the Killingworth complex formed above an east-dipping subduction zone on the west margin of the Gander terrane, whereas the Middletown complex formed to the east in a back-arc rift environment. Subsequent shortening, associated with the assembly of Pangea in the Carboniferous, resulted in Gander cover terranes over the Avalon terrane in the west; and in the Middletown complex over the Killingworth complex in the east. Despite similarities of emplacement age, structural setting, and geographic continuity of the Killingworth dome with Oliverian domes in central and northern New England, new and published isotopic data suggest that the Killingworth and Middletown complexes were derived from Gander crust, and are not part of the Bronson Hill arc that was derived from Laurentian crust. The trace of the Ordovician Iapetan suture (the Red Indian line) between rocks of Laurentian and Ganderian origin probably extends from Southwestern New Hampshire west of the Pelham dome of northcentral Massachusetts and is coverd by Mesozoic rocks of the Hartford basin.

American Journal of Science↗
USGS2007

SHRIMP U-Pb evidence for a Late Silurian age of metasedimentary rocks in the Merrimack and Putnam-Nashoba terranes, eastern New England

U-Pb ages of detrital, metamorphic, and magmatic zircon and metamorphic monazite and titanite provide evidence for the ages of deposition and metamorphism of metasedimentary rocks from the Merrimack and Putnam-Nashoba terranes of eastern New England. Rocks from these terranes are interpreted here as having been deposited in the middle Paleozoic above Neoproterozoic basement of the Gander terrane and juxtaposed by Late Paleozoic thrusting in thin, fault-bounded slices. The correlative Hebron and Berwick formations (Merrimack terrane) and Tatnic Hill Formation (Putnam-Nashoba terrane), contain detrital zircons with Mesoproterozoic, Ordovician, and Silurian age populations. On the basis of the age of the youngest detrital zircon population (???425 Ma), the Hebron, Berwick and Tatnic Hill formations are no older than Late Silurian (Wenlockian). The minimum deposition ages of the Hebron and Berwick are constrained by ages of cross-cutting plutons (414 ?? 3 and 418 ?? 2 Ma, respectively). The Tatnic Hill Formation must be older than the oldest metamorphic monazite and zircon (???407 Ma). Thus, all three of these units were deposited between ???425 and 418 Ma, probably in the Ludlovian. Age populations of detrital zircons suggest Laurentian and Ordovician arc provenance to the west. High grade metamorphism of the Tatnic Hill Formation soon after deposition probably requires that sedimentation and burial occurred in a fore-arc environment, whereas time-equivalent calcareous sediments of the Hebron and Berwick formations probably originated in a back-arc setting. In contrast to age data from the Berwick Formation, the Kittery Formation contains primarily Mesoproterozoic detrital zircons; only 2 younger grains were identified. The absence of a significant Ordovician population, in addition to paleocurrent directions from the east and structural data indicating thrusting, suggest that the Kittery was derived from peri-Gondwanan sources and deposited in the Fredericton Sea. Thus, the Kittery should not be considered part of the Laurentian-derived Merrimack terrane; it more likely correlates with the early Silurian Fredericton terrane of northeastern New England and Maritime Canada.

American Journal of Science↗
USGS2007

Origin of the Lyme Dome and implications for the timing of multiple Alleghanian deformational and intrusive events in southern Connecticut

Geologic mapping, structural analysis, and geochronology in the area of the Lyme dome, southern Connecticut provides constraints on the origin of the rocks in the core of the dome, the absolute timing of the principal deformational and thermal events attributed to Alleghanian orogenesis, and the processes that generated the dome. Detrital zircon geochronology in combination with ages on intrusive rocks brackets the deposition of quartzite in the core of the dome sometime between ca. 925 and 620 Ma. Granite and granodiorite intruded the Neoproteorozic metasedimentary rocks in the core of the dome at ca. 620 to 610 Ma. Four major early Permian events associated with the Alleghanian orogeny affected the rocks in the Lyme dome area. Syn-tectonic migmatization and widespread penetrative deformation (D1, ca. 300 - 290 Ma) included emplacement of alaskite at 290 ?? 4 Ma during regional foliation development and aluminosilicate-orthoclase metamorphic conditions. Rocks of the Avalon terrane may have wedged between Gander cover rocks and Gander basement in the core of the Lyme during D1. Limited structural evidence for diapiric uplift of the Lyme dome indicates that diapirism started late in D1 and was completed by D2 (ca. 290 - 280 Ma) when horizontal WNW contractional stresses dominated over vertical stresses. Second sillimanite metamorphism continued and syn-tectonic D2 granite pegmatite (288 ?? 4 Ma) and the Joshua Rock Granite Gniess (284 ?? 3 Ma) intruded at this time. North-northwest extension during D3 (ca. 280 - 275 Ma) led to granitic pegmatite intrusion along S3 cleavage planes and in extensional zones in boudin necks during hydraulic failure and decompression melting. Intrusion of a Westerly Granite dike at 275 ?? 4 Ma suggests that D3 extension was active, and perhaps concluding, by ca. 275 Ma. Late randomly oriented but gently dipping pegmatite dikes record a final stage of intrusion during D4 (ca. 275 - 260 Ma), and a switch from NNW extension to vertical unloading and exhumation. Monazite and metamorphic zircon rim ages record this event at ca. 259 Ma. The evolution of the Lyme dome involved D1 mylonitization, intrusion, and migmatization during north-directed contraction, limited late D1 diapirism, D2 migmatization during WNW contraction with associated flexural flow and fold interference, D3 NNW horizontal extension and decompression melting, and final D4 vertical extension and rapid exhumation. Late regional uplift, extension, and normal faulting at higher crustal levels may have been caused by diapiric rise of the lower crust, below the structural level of the Lyme dome. The rocks record no evidence of Acadian metamorphism or deformation, suggesting that the Gander zone here was not tectonically juxtaposed with Avalon until the Alleghanian orogeny.

American Journal of Science↗
USGS2005

Contrasting tectonothermal domains and faulting in the Potomac terrane, Virginia-Maryland - Discrimination by 40Ar/39Ar and fission-track thermochronology

New 40Ar/39Ar data reveal ages and thermal discontinuities that identify mapped and unmapped fault boundaries in the Potomac terrane in northern Virginia, thus confirming previous interpretations that it is a composite terrane. The rocks of the Potomac terrane were examined along the Potomac River, where it has been previously subdivided into three units: the Mather Gorge, Sykesville, and Laurel Formations. In the Mather Gorge Formation, at least two metamorphic thermal domains were identified, the Blockhouse Point and Bear Island domains, separated by a fault active in the late Devonian. Early Ordovician (ca. 475 Ma) cooling ages of amphibole in the Bear Island domain reflect cooling from Taconic metamorphism, whereas the Blockhouse Point domain was first metamorphosed in the Devonian. The 40Ar/39Ar data from muscovites in a third (eastern) domain within the Mather Gorge Formation, the Stubblefield Falls domain, record thrusting of the Sykesville Formation over the Mather Gorge Formation on the Plummers Island fault in the Devonian. The existence of two distinctly different thermal domains separated by a tectonic boundary within the Mather Gorge argues against its status as a formation. Hornblende cooling ages in the Sykesville Formation are Early Devonian (ca. 400 Ma), reflecting cooling from Taconic and Acadian metamorphism. The ages of retrograde and overprinting muscovite in phyllonites from domain-bounding faults are late Devonian (Acadian) and late Pennsylvanian (Alleghanian), marking the time of assembly of these domains and subsequent movement on the Plummers Island fault. Our data indicate that net vertical motion between the Bear Island domain of the Mather Gorge complex and the Sykesville Formation across the Plummers Island fault is east-side-up. Zircon fission-track cooling ages demonstrate thermal equillbrium across the Potomac terrane in the early Permian, and apatite fission-track cooling ages record tilting of the Potomac terrane in the Cretaceous or later with the west side up at least 1 km. ?? 2005 Geological Society of America.

Geological Society of America Bulletin↗
USGS2005

Foliation development and reaction softening by dissolution and precipitation in the transformation of granodiorite to orthogneiss, Glastonbury Complex, Connecticut, U.S.A

Textures, microstructures, and patterns of chemical zoning in minerals in a granodioritic orthogneiss in the Glastonbury Complex, Connecticut, lead to the interpretation that foliation development was facilitated by retrograde hydration reactions in the presence of an aqueous fluid. Incomplete replacement of the metastable magmatic minerals K-feldspar + hastingsite + magnetite produced foliation-defining biotite + epidote + quartz. These reaction products did not replace K-feldspar – hastingsite interfaces; rather, either biotite or epidote replaced the amphibole, and plagioclase replaced K-feldspar. Biotite and epidote precipitated syntectonically in discrete layers that define the foliation in the orthogneiss, whereas quartz precipitated primarily in ribbons, further enhancing the fabric. Metastable REE-rich igneous titanite also dissolved, and was incompletely replaced by REE-poor, Al-bearing metamorphic titanite. The similar concentrations of the REE in epidote and titanite show that the REE released by titanite dissolution were precipitated locally as the allanite component in adjacent grains of epidote. The entire process was syntectonic, with most grains showing multiple overgrowths in the direction of extension as defined by stretched xenoliths. Sufficient U was present in the titanite overgrowths to allow SHRIMP dating of cores, mantles, and rims. These results suggest at least three retrograde Alleghanian events of growth in a span of ~30 m.y. Thus the dissolution – transportation –precipitation process not only describes the reaction mechanism but also leads to the redistribution of reaction products into nearly monomineralic layers, thus contributing to metamorphic differentiation and to the development of the foliation. The resulting orthogneiss was much weaker that the granodiorite protolith, owing to this reaction and textural softening.

Connecticut↗
USGS2004

Deciphering multiple Mesoproterozoic and Paleozoic events recorded in zircon and titanite from the Baltimore Gneiss, Maryland: SEM imaging, SHRIMP U-Pb geochronology, and EMP analysis

The Baltimore Gneiss , exposed in antiforms in the eastern Maryland Piedmont, consists of a suite of felsic and mafic gneisses of Mesoproterozoic age. Zircons from the felsic gneisses are complexly zoned, as shown in cathodoluminescence imaging ; most zircon grains have multiple overgrowth zones, some of which are adjacent and parallel to elongate cores. Sensitive high-resolution ion microprobe ( SHRIMP ) analyses of oscillatory-zoned cores indicate that the volcanic protoliths of the felsic gneisses crystallized at ca. 1.25 Ga. These rocks were subsequently affected by at least three Mesoproterozoic growth events , at ca. 1.22, 1.16, and 1.02 Ga. Foliated biotite granite intruded the Baltimore Gneiss metavolcanic sequence at ca. 1075 Ma. The Slaughterhouse Granite (renamed herein) also is Mesoproterozoic , but extremely discordant U-Pb data from high-U, metamict zircons preclude calculating a precise age. The 1.25 Ga rocks of the Baltimore Gneiss are coeval with rocks emplaced in the Grenville Province during the Elzevirian orogeny, and the 1.22 Ga zircon overgrowths are coincident with a later stage of this event . Younger zircon overgrowths formed during the Ottawan phase of the Grenville orogeny. Backscattered electron imaging of titanites from felsic gneisses and foliated biotite granite reveals that many of the grains contain cores, intermediate mantles, and rims. Electron microprobe traverses across zoned grains show regular variations in composition. SHRIMP ages for titanite from the foliated biotite granite are 374 ± 8, 336 ± 8, and 301 ± 12 Ma. The ca. 374 Ma age suggests growth of titanite during a thermal event following the Acadian orogeny, whereas the late Paleozoic titanite growth ages may be due to greenschist-facies replacement reactions associated with Alleghanian metamorphism and deformation.

Maryland↗
USGS2003

P-T-t paths and differential Alleghanian loading and uplift of the Bronson Hill terrane south central New England

Late Paleozoic U-Pb ages of sphene and 40 Ar/ 39 Ar cooling ages of amphibole and muscovite from rocks of the Bronson Hill terrane in Connecticut and central Massachusetts reflect a late Paleozoic (Alleghanian) overprint on Acadian metamorphic rocks. Prograde Alleghanian sphenes crystallized during the Late Pennsylvanian, and eliminate the possibility that amphibole ages reflect delayed Permian cooling from Devonian Acadian metamorphism. Fourteen new amphibole ages from Connecticut form a north-to-south trend of decreasing age from 294 to 245 Ma, while in Massachusetts four new amphibole ages together with three others from the literature produce a random Carboniferous pattern. Seven new muscovite ages support existing data indicating uniform cooling throughout the Bronson Hill terrane through ∼350°C in the Early Triassic. The rate of Permian cooling defined by amphibole-muscovite pairs increases from ∼4°C/my in northern Connecticut to ∼50°C/my near Long Island Sound. Hinged loading and hinged but delayed exhumation in the southern part of the Bronson Hill terrane (with the hinge in central Connecticut) explain these ages and cooling rates as well as a southerly increasing metamorphic field gradient. One-dimensional thermal modeling indicates that loading of Bronson Hill rocks must have begun by the Late Mississippian. The time of peak Alleghanian metamorphic temperature decreases southward from Early Permian in northern Connecticut to Late Permian to the south. These results demonstrate that the metamorphic effects of the Alleghanian orogeny are not restricted to the Avalon terrane of southeastern New England. On the contrary, the Alleghanian orogeny reset 40 Ar/ 39 Ar mineral ages, recrystallized minerals, partially melted felsic rocks, and transposed fabrics at least as far west as the Bronson Hill terrane in south-central New England.

American Journal of Science↗
USGS2002

U-Pb geochronology of zircon and polygenetic titanite from the Glastonbury Complex, Connecticut, USA: An integrated SEM, EMPA, TIMS, and SHRIMP study

U-Pb ages for zircon and titanite from a granodioritic gneiss in the Glastonbury Complex, Connecticut, have been determined using both isotope dilution thermal ionization mass spectrometry (TIMS) and the sensitive high resolution ion microprobe (SHRIMP). Zircons occur in three morphologic populations: (1) equant to stubby, multifaceted, colorless, (2) prismatic, dark brown, with numerous cracks, and (3) elongate, prismatic, light tan to colorless. Cathodoluminescence (CL) imaging of the three populations shows simple concentric oscillatory zoning. The zircon TIMS age [weighted average of 207Pb/206Pb ages from Group 3 grains-450.5 ?? 1.6 Ma (MSWD=1.11)] and SHRIMP age [composite of 206Pb/238 U age data from all three groups-448.2 ?? 2.7 Ma (MSWD = 1.3)], are interpreted to suggest a relatively simple crystallization history. Titanite from the granodioritic gneiss occurs as both brown and colorless varieties. Scanning electron microscope backscatter (BSE) images of brown grains show multiple cross-cutting oscillatory zones of variable brightness and dark overgrowths. Colorless grains are unzoned or contain subtle wispy or very faint oscillatory zoning. Electron microprobe analysis (EMPA) clearly distinguishes the two populations. Brown grains contain relatively high concentrations of Fe2O3, Ce2O3 (up to ~ 1.5 wt.%), Nb2O5, and Zr. Cerium concentration is positively correlated with total REE + Y concentration, which together can exceed 3.5 wt.%. Oscillatory zoning in brown titanite is correlated with variations in REE concentrations. In contrast, colorless titanite (both as discrete grains and overgrowths on brown titanite) contains lower concentrations of Y, REE, Fe2O3, and Zr, but somewhat higher Al2O3 and Nb2O5. Uranium concentrations and Th/U discriminate between brown grains (typically 200-400 ppm U; all analyses but one have Th/U between about 0.8 and 2) and colorless grains (10-60 ppm U; Th/U of 0-0.17). In contrast to the zircon U-Pb age results, SHRIMP U-Pb data from titanite indicate multiple growth episodes. In brown grains, oscillatory zoned cores formed at 443 ?? 6 Ma, whereas white (in BSE) cross-cutting zones are 425 ?? 9 Ma. Colorless grains and overgrowths on brown grains yield an age of 265 ?? 8 Ma (using the Total Pb method) or 265 ?? 5 Ma (using the weighted average of the 206Pb/238U ages). However, EMPA chemical data identify zoning that suggests that this colorless titanite may preserve three growth events. Oscillatory zoned portions of brown titanite grains are igneous in origin; white cross-cutting zones probably formed during a previously unrecognized event that caused partial dissolution of earlier titanite and reprecipitation of a slightly younger generation of brown titanite. Colorless titanite replaced and grew over the magmatic titanite during the Permian Alleghanian orogeny. These isotopic data indicate that titanite, like zircon, can contain multiple age components. Coupling SHRIMP microanalysis with EMPA and SEM results on dated zones as presented in this study is an efficient and effective technique to extract additional chronologic ?? 2002 Elsevier Science B.V. All rights reserved.

Chemical Geology↗
USGS2001

Experimental controls on D/H and 13C/12C ratios of kerogen, bitumen and oil during hydrous pyrolysis

Large isotopic transfers between water-derived hydrogen and organic hydrogen occurred during hydrous pyrolysis experiments of immature source rocks, in spite of only small changes in organic 13C/12C. Experiments at 330 ??C over 72 h using chips or powder containing kerogen types I and III identify the rock/water ratio as a main factor affecting ????D for water and organic hydrogen. Our data suggest that larger rock permeability and smaller rock grain size increase the H-isotopic transfer between water-derived hydrogen and thermally maturing organic matter. Increasing hydrostatic pressure may have a similar effect, but the evidence remains inconclusive. ?? 2001 Elsevier Science Ltd. All rights reserved.

Organic Geochemistry↗
USGS1999

D/H isotope ratios of kerogen, bitumen, oil, and water in hydrous pyrolysis of source rocks containing kerogen types I, II, IIS, and III

Immature source rock chips containing different types of kerogen (I, II, IIS, III) were artificially matured in isotopically distinct waters by hydrous pyrolysis and by pyrolysis in supercritical water. Converging isotopic trends of inorganic (water) and organic (kerogen, bitumen, oil) hydrogen with increasing time and temperature document that water-derived hydrogen is added to or exchanged with organic hydrogen, or both, during chemical reactions that take place during thermal maturation. Isotopic mass-balance calculations show that, depending on temperature (310–381°C), time (12–144 h), and source rock type, between ca. 45 and 79% of carbon-bound hydrogen in kerogen is derived from water. Estimates for bitumen and oil range slightly lower, with oil–hydrogen being least affected by water-derived hydrogen. Comparative hydrous pyrolyses of immature source rocks at 330°C for 72 h show that hydrogen in kerogen, bitumen, and expelled oil/wax ranks from most to least isotopically influenced by water-derived hydrogen in the order IIS > II ≈ III > I. Pyrolysis of source rock containing type II kerogen in supercritical water at 381°C for 12 h yields isotopic results that are similar to those from hydrous pyrolysis at 350°C for 72 h, or 330°C for 144 h. Bulk hydrogen in kerogen contains several percent of isotopically labile hydrogen that exchanges fast and reversibly with hydrogen in water vapor at 115°C. The isotopic equilibration of labile hydrogen in kerogen with isotopic standard water vapors significantly reduces the analytical uncertainty of D/H ratios when compared with simple D/H determination of bulk hydrogen in kerogen. If extrapolation of our results from hydrous pyrolysis is permitted to natural thermal maturation at lower temperatures, we suggest that organic D/H ratios of fossil fuels in contact with formation waters are typically altered during chemical reactions, but that D/H ratios of generated hydrocarbons are subsequently little or not affected by exchange with water hydrogen at typical reservoir conditions over geologic time. It will be difficult to utilize D/H ratios of thermally mature bulk or fractions of organic matter to quantitatively reconstruct isotopic aspects of paleoclimate and paleoenvironment. Hope resides in compound-specific D/H ratios of thermally stable, extractable biomarkers (“molecular fossils”) that are less susceptible to hydrogen exchange with water-derived hydrogen.

Geochimica et Cosmochimica Acta↗
USGS1996

40Ar/39Ar whole-rock data constraints on Acadian diagenesis and Alleghanian cleavage in the Martinsburg formation, eastern Pennsylvania

A comparison of 40 Ar/ 39 Ar age spectra of whole-rock mudstone and slate samples from the Ordovician Martinsburg Formation at Lehigh Gap, Pennsylvania and stratigraphic and thermal constraints support Alleghanian age for regional slaty cleavage and a late Acadian age for diagenesis in these rocks. Age spectra from mud-stones have a sigmodal shape, with slopes that climb steeply from apparent Mesozoic ages to intermediate saddle regions with Devonian apparent ages, and then climb steeply again to Late Proterozoic apparent ages. The steps with these oldest apparent ages are interpreted to be dominated by late Proterzoic detrial muscovite. The saddle region of the mudstone samples gives very Late Silurian to earliest Devonian ages, which are maximum ages of diagenetic micas and which eliminate a Taconic age for the cleavage. The ages of saddle regions of the slate samples constraining cleavage-forming muscovite is <~375. This is the maximum age of this mica and requires an Alleghanian age for the cleavage. These age constraints are supported by ages of individual mica components calculated with knowledge of the total gas ages and mass fractions of the micas and by predictions from thermal modeling. We conclude that the Taconic orogeny in the Martinsburg Formation in eastern Pennsylvania was a very mild event. Not only is the cleavage in these rocks not Taconic in age, but even the mild (~100C) diagenetic growth of illite was Silurian of younger. Thus the Taconic event in these rocks in limited to loading of lass than about 3 km.

Connecticut, Delaware, Maryland, Pennsylvania, New↗