mobility of rhenium platinum group elements and organic carbon during black shale weathering this study investigates the effects of black shale weathering on the re os isotope system platinum group element concentrations and the degradation of organic matter samples from a weathering profile in late devonian 365 myr ohio shale show a pronounced decrease 77 in organic carbon corg near the present soil surface relative to the interior portion of the outcrop a similar trend is observed for total n 67 loss conversely organic phosphorus porg concentrations increase by 59 near the soil surface the decrease in corg is accompanied by a pronounced decrease in re 99 and to a lesser extent os 39 palladium and pt do not appear to be significantly mobile the effects of re and os mobility on the re os isotope system are significant none of the samples plots on a 365 myr isochron rather the samples define a trend with a slope corresponding to an age of 18 myr with an initial 187os 188os of 6 1 this indicates recent disturbance of the re os system isotope mass balance calculations imply that the labile fraction of os is significantly more radiogenic 187os 188os of 7 8 than the average of the unweathered samples 187os 188os of 6 4 based on data from this study the molar ratio of labile re to corg in ohio shale is estimated at 7 10 8 we estimate the present day riverine black shale derived re flux to seawater using literature data on re burial in anoxic marine sediments and assuming steady state between re release during black shale weathering and re burial in anoxic marine sediments then the labile re corg observed in this study implies that 0 5 tmol of corg is released annually from weathering of black shales a trace lithology in the continental crust this flux corresponds to 12 of the estimated annual co2 flux from oxidative weathering of sedimentary rocks the labile molar re os of 270 indicates that black shale weathering releases 130 mol os per year which accounts for 7 of the riverine os input to seawater the data from this study support the notion that the crustal cycles of labile corg re and os are tightly coupled gray shales which are less corg re and os rich but much more abundant in the continental crust than black shales are likely to be even more important continental sources of re and os to seawater

geochemistry of major and trace elements and pb sr isotopes of a weathering profile developed on the lower cambrian black shales in central hunan china abstract this paper reports a geochemical study on the major and trace elements and pb sr isotopes of a weathering profile developed in the lower cambrian black shales in central hunan china six weathering horizons were identified and sampled vertically throughout the profile the chemical composition of the profile consists of variable concentrations of the major elements fe2o3 feo mno mgo cao na2o and p2o5 and of less variable concentrations of sio2 tio2 al2o3 and k2o the chemical change caused by weathering is estimated by mass balance calculations and the results show that the element mobility is characterised by substantial loss of sio2 feo cao k2o na2o loi cr v ba cs rb sr u and th and moderate loss of al2o3 mgo fe2o3 ni cu pb tl sn sc ge and ree y the high field strength elements tio2 sn sc u ga ge zr hf nb and ta were immobile during weathering the chemical changes and the pb sr isotopic data suggest that four types of chemical reactions occurred the oxidation of sulphide minerals e g pyrite and organic carbon os the dissolution of less resistant clinochlore ia calcite and p bearing minerals dl the dissolution of detrital albite and microcline da and the transformation of clay tc minerals e g muscovite and illite smectite these chemical reactions then led to two stages of geochemical processes an early stage of chemical differentiation and a later stage of chemical homogenisation the chemical differentiation dominated by the os dl and da reactions led to the leaching of mobile elements e g mgo na2o k2o p2o5 sr and ree and the redistribution of some less mobile elements e g sio2 and al2o3 in contrast the chemical homogenisation which was caused by tc reactions led to the leaching of both mobile and less mobile elements from the system and ultimately transformed the weathered black shales into soil soils derived from black shales in south china might result from the above two geochemical processes

role of plutonism in low pressure metamorphic belt formation wickham and oxburgh1 recently proposed that low pressure high temperature low p high t metamorphism in the eastern pyrenees and possibly all low p high t metamorphic belts resulted from anomalously high mantle heat flow brought about by rifting their model is largely constrained by the presence of nearby synmetamorphic rift related sedimentary rocks and the interpretation that the migmatites and granites are the product of in situ melting in the presence of an anomalously steep geotherm here we present an alternative model in which low p high t metamorphism pro grade reactions at pressures near or below the al2sio5 triple point results from contact effects near sill like igneous intrusions at intermediate crustal levels low p high t conditions can be achieved through this process in regions of continent continent collision with normal mantle heat flux as well as in zones of extension our model is based on studies of the low p high t metamorphic terrane in the new england appalachians

sm nd evidence for diachronous crustal accretion in the lewisian complex of northwest scotland sm nd whole rock analyses of several cogenetic rock suites from the late archaean lewisian complex of northwest scotland yield chronological data for a crustal accretion differentiation superevent cads in this terrane three layered mafic ultramafic bodies predate badcallian high grade metamorphism 2660 ma but their temporal relationship to the igneous precursors of the host quartzofeldspathic gneiss complex remains unclear regression of data from these samples yield the following achiltibuie 2850 95 ma with nd t 1 93 0 52 drumbeg 2910 55 ma with nd t 1 70 0 32 scouriemore 2670 110 ma with nd t 0 98 0 73 these data suggest that contemporaneous sub lewisian mantle had a long term light rare earth element depleted history relative to a chondritic reservoir composition three suites of quartzofeldspathic gneisses the pyroxene granulites of scourie the hornblende granulites of gruinard bay and the amphibolites of the northern region north of loch laxford have small ranges of sm nd ratios and do not yield precise regression results if these gneisses were derived from a relatively homogeneous source region perhaps represented by the mafic ultramafic bodies then sm nd model ages suggest a diachronous sequence of crustal generation decreasing in age from scourie terrane average tdm 2930 ma through gruinard bay 2860 ma to the northern region 2780 ma a diachronous sequence such as this suggests that for a cads in which separate accretion and differentiation episodes may be resolved final high grade metamorphism may not be related to magmatic crustal generation processes

release of heavy metals during weathering of the lower cambrian black shales in western hunan china weathering of heavy metal enriched black shales may be one of the most important sources of environmental contamination in areas where black shales are distributed heavy metal release during weathering of the lower cambrian black shales lcbs in western hunan china was investigated using traditional geochemical methods and the icp ms analytical technique concentrations of 16 heavy metals 8 trace elements and p were measured for samples from selected weathering profiles at the taiping vanadium ore mine tp the matian phosphorous ore mine mt and taojiang stone coal mine tj the results show that the bedrock at these three profiles is enriched with sc v cr co ni cu zn pb th u mo cd sb tl and p based on mass balance calculation the percentages of heavy metals released in loss relative to immobile element nb were estimated the results show significant rates of release during weathering of v cr co ni cu zn u mo cd sn sb and tl for the tp profile sc cr mn co ni cu zn pb th cd and sn for the mt profile and sc mn co ni zn th cd sn and tl for the tj profile among these heavy metals co ni zn cd and sn show very similar features of release from each of the three weathering profiles the heavy metals released during weathering may affect the environment especially topsoil and surface waters and are possibly related to an observed high incidence of endemic diseases in the area

effects of black shale weathering on the mobility of rhenium and platinum group elements radiogenic os from the continents dominates the late cenozoic marine os budget a variety of proposed radiogenic sources includes organic rich sediments precambrian shields and re rich sulfides identifying the dominant sources of radiogenic os to the oceans has a strong impact on past climate models because weathering of silicates acts as a net sink of co 2 whereas weathering of organic matter acts as a source here we investigate the effects of black shale weathering on the integrity of the re os isotope system and release of re and platinum group elements time correlative pairs of fresh drill core and weathered outcrop black shales of late ordovician age utica shale magnafacies quebec were analyzed for re os ir pt and pd as well as total s n and c as c carb and c org the results indicate that 25 64 of the initial re budget 45 90 of the os budget 14 65 of the ir budget 60 77 of the pt budget 69 86 of the pd budget and 44 96 of the c org budget are lost during weathering we use positive correlations of os pt and pd with c org and n to calculate the respective platinum group element concentrations in the unweathered organic matter end member as 3 ng g os 9 ng g pt and 11 24 ng g pd although black shales make up

a field study of the chemical weathering of ancient sedimentary organic matter weathering profiles developed on organic carbon rich black shales were studied to examine the loss and degradation of organic matter om during weathering and its role in the geochemical carbon cycle analysis of weathered shales reveals between 60 and nearly 100 total organic carbon toc loss in highly weathered samples relative to initial unweathered toc content pyrite loss coincides with or precedes organic carbon loss elemental analysis and flash pyrolysis gas chromatography py gc of kerogen concentrates indicate that there is little or no selective enrichment or depletion of norg containing sorg containing alkylaromatic branched alkyl or long chain n alkyl moieties in most profiles during weathering kerogen o c ratios consistently increase with toc and pyrite loss infrared spectroscopy ir reveals an increase in the relative abundance of c c and c o bonds relative to alkyl c h bonds in progressively weathered samples these results suggest a two component model for kerogen weathering largely non selective oxidation and hydration followed by cleavage dissolution of oxidized kerogen fragments the extent of weathering in a given outcrop is likely limited by a combination of the rate of physical erosion and exposure of the rock to oxidizing surface waters with om type composition playing a lesser role

the occurrence and dispersion of potentially toxic elements in areas covered with black shales and slates in korea abstract potentially toxic heavy metals together with other elements are present in some natural geological materials and the okchon black shale in korea provides an important example of this the dispersion of these elements in the rocks and soils derived from this shale are examined geochemical surveys were undertaken in 11 study areas in the okchon zone underlain by black shales slates phyllites and limestones after appropriate preparation of rocks and soils samples were analysed for multi elements by inaa icp aes and icp ms some potentially toxic elements are highly enriched in the okchon black shales and soils developed from these shales in the dukpyungri and majeonri areas in particular mean concentrations in soils in the dukpyungri area are 34 g g as 43 g g mo and 3 4 g g se which are significantly higher than the worldwide average for soils the degree of enrichment decreases in the order forest upland farm paddy playground soils and discriminant analysis by geochemical characteristics separates soils in the black shale area from those in other rock areas in terms of se zn mo and cd

synchronous peak barrovian metamorphism driven by syn orogenic magmatism and fluid flow in southern connecticut usa recent work in barrovian metamorphic terranes has found that rocks experience peak metamorphic temperatures across several grades at similar times this result is inconsistent with most geodynamic models of crustal over thickening and conductive heating wherein rocks which reach different metamorphic grades generally reach peak temperatures at different times instead the presence of additional sources of heat and or focusing mechanisms for heat transport such as magmatic intrusions and or advection by metamorphic fluids may have contributed to the contemporaneous development of several different metamorphic zones here we test the hypothesis of temporally focussed heating for the wepawaug schist a barrovian terrane in connecticut usa using sm nd ages of prograde garnet growth and u pb zircon crystallization ages of associated igneous rocks peak temperature in the biotite garnet zone was dated via sm nd on garnet at 378 9 1 6 ma 2r whereas peak temperature in the highest grade staurolite kyanite zone was dated via sm nd on garnet rims at 379 9 6 8 ma 2r these garnet ages suggest that peak metamorphism was pene contemporaneous within error across these metamorphic grades ion microprobe u pb ages for zircon from igneous rocks hosted by the metapelites also indicate a period of syn metamorphic peak igneous activity at 380 6 4 7 ma 2r indistinguishable from the peak ages recorded by garnet a 388 6 2 1 ma 2r garnet core age from the staurolite kyanite zone indicates an earlier episode of growth coincident with ages from texturally early zircon and a previously published monazite age along the prograde regional metamorphic t t path the timing of peak metamorphism and igneous activity as well as the occurrence of extensive syn metamorphic quartz vein systems and pegmatites best supports the hypothesis that advective heating driven by magmas and fluids focussed major mineral growth into two distinct episodes the first at c 389 ma and the second corresponding to the regionally synchronous peak metamorphism at c 380 ma

thermal evolution and exhumation in obliquely convergent transpressive orogens most p t t path models to date have considered a linear erosion rate for exhumation from burial depth related to isostatic readjustment of crustal thickness a few have discussed extension enhanced exhumation erosional exhumation can only restore lower crustal rocks from the thickened mountain root to their previous original depth in the pre collisional crust one major assumption of all models to date is that the compressive forces responsible for crustal thickening cease before elevation and erosion begins however compression is often still active even if the crustal thickening has stopped further compression of the thickened and strongly deformed orogenic root is responsible for forceful exhumation extrusion of softened rocks upwards hence the rate of exhumation is related to the rate of convergence of colliding plates extrusional exhumation can elevate buried rocks to any depth depending on the action of fault shear systems in the extrusional exhumation models examined here the ascending rocks cool faster because they approach the zero temperature surface conditions more rapidly than by isostatic erosion the exhumation rate is also governed by the angle between the plate boundary and the displacement vector implying that the convergent plate boundaries are regarded as complex transpressive systems in which the degree of obliquity can be expressed by the ratio of pure to simple shear components a low ratio of pure simple shear typical for wrench dominated plate boundaries implies long distance horizontal transport from the buried position in the original orogen and longer periods during which metamorphic heating occurs a high ratio of pure simple shear characteristic for frontal like convergence implies a rapid exhumation without significant heating thus granulites barrovian type and blueschist facies metamorphism are characterised by increasing angle of obliquity 10 30 90 respectively the high temperature limit at low ratio of pure simple shear is the geotherm t and lies at temperatures that would commonly be taken to indicate that addition of mantle heat was required to generate hot geotherms and p t t paths wrench faulting over 100 s of kilometres at reasonable slow convergence rates could lead to extensive dehydration melting and granulite formation in large scale collisional orogens

geochemistry of soils derived from black shales in the ganziping mine area western hunan china the geochemistry of major and trace elements including heavy metals and rare earth elements of the fresh and weathered black shales and the soils derived from black shales in the ganziping mine area in western hunan province china were studied using the following techniques x ray fluorescence xrf inductively coupled plasma mass spectrometer icp ms and x ray diffraction xrd the results show that the black shale soils are significantly enriched with al2o3 and fe2o3 and depleted of mobile elements cao na2o and k2o the soils are also highly enriched with heavy metals u v ni ba cu zn and pb that may cause potential heavy metal contamination of the soils composition of the soils is homogeneous compared to the weathered black shales for which the concentrations of major elements except cao and na2o and trace elements except heavy metals u v ni ba cu zn and pb as well as the mobile sr show lower variations than in the weathered black shales ratios of zr hf ta nb y ho nd sm and ti ti zr of the soils are also less variable with values constantly similar to that of the fresh and weathered black shales correspondingly thus components of the soils are believed to be contributed from the parent black shales through weathering and pedogenesis it is concluded that the soils were formed by at least two stages of geochemical processes the early stage of chemical differentiation and the later stage of chemical homogenization the chemical differentiation that was taken during black shale weathering might have caused the depletion of cao and na2o and the enrichment of al2o3 and fe2o3 while the chemical homogenization that was taken during pedogenesis led to the depletion of sio2 and k2o and to the further enrichment of al2o3 and fe2o3 the heavy metal enrichment contamination of the soils was then genetically related to the enrichment of al2o3 and fe2o3 in the soils

sm nd dating and cooling history of scourian granulites sutherland the scourian gneisses of the lewisian complex of north west scotland have been the subject of many geochronological investigations sm nd whole rock measurements suggest that the protoliths of the lewisian complex differentiated 2 92 0 05 gyr ago from an approximately chrondritic mantle1 rb sr and pb pb whole rock ages between 2 8 and 2 6 gyr reflect subsequent depletion in rb and u refs 2 3 which has generally been associated with granulite facies metamorphism zircons which are thought to have crystallized during this metamorphism have also given u pb ages of 2 66 gyr ref 4 this granulite facies metamorphism involving pressures in excess of 10 kbar and peak temperatures estimated between 820 50 c ref 5 and 1 250 c refs 6 7 affects a terrain including supracrustal rocks7 and thus implies a major tectonic event we report here the first geochronological data measured on mineral assemblages that have also provided estimates of the conditions of metamorphism such measurements are possible because the major minerals of granulite facies assemblages show an unusually favourable spread in sm nd ratios garnet especially is strongly enriched in sm ref 8 data for three garnetiferous basic gneiss assemblages suggest that closure of the sm nd system occurred significantly later than the peak of the metamorphism

weathering of the new albany shale kentucky usa i weathering zones defined by mineralogy and major element composition abstract comprehensive understanding of chemical and mineralogical changes induced by weathering is valuable information when considering the supply of nutrients and toxic elements from rocks here minerals that release and fix major elements during progressive weathering of a bed of devonian new albany shale in eastern kentucky are documented samples were collected from unweathered core parent shale and across an outcrop excavated into a hillside 40 year prior to sampling quantitative x ray diffraction mineralogical data record progressive shale alteration across the outcrop mineral compositional changes reflect subtle alteration processes such as incongruent dissolution and cation exchange altered primary minerals include k feldspars plagioclase calcite pyrite and chlorite secondary minerals include jarosite gypsum goethite amorphous fe iii oxides and fe ii al sulfate salt efflorescence the mineralogy in weathered shale defines four weathered intervals on the outcrop zones a c and soil alteration of the weakly weathered shale zone a is attributed to the 40 a exposure of the shale in this zone pyrite oxidization produces acid that dissolves calcite and attacks chlorite forming gypsum jarosite and minor efflorescent salt the pre excavation active weathering front zone b is where complete pyrite oxidation and alteration of feldspar and organic matter result in increased permeability acidic weathering solutions seep through the permeable shale and evaporate on the surface forming abundant efflorescent salt jarosite and minor goethite intensely weathered shale zone c is depleted in feldspars chlorite gypsum jarosite and efflorescent salts but has retained much of its primary quartz illite and illite smectite goethite and amorphous fe iii oxides increase due to hydrolysis of jarosite enhanced permeability in this zone is due to a 14 loss of the original mass in parent shale denudation rates suggest that characteristics of zone c were acquired over 1 ma compositional differences between soil and zone c are largely attributed to illuvial processes formation of additional fe iii oxides and incorporation of modern organic matter

u pb dating of major and accessory minerals formed during metamorphism and deformation of metapelites abstract u pb isotope analyses on major and accessory minerals from pelitic schists in of southwestern connecticut are used to date metamorphism and deformation most of the major minerals have 206 pb 204 pb ratios less than 100 however u pb mineral isochron and mineral whole rock isochrons constructed using aliquots of the same mineral yield concordant ages with uncertainties as low as 5 ma staurolite kyanite and garnet are older than metamorphic monazites and zircons these data are summarized below 5 mineral 206 pb 204 pb system the straits schist trap falls fm monazite zircon 207 pb 206 pb 379 384 ma 380 2 ma staurolite 48 623 238 u 206 pb 394 400 ma 398 5 ma garnet 22 46 238 u 206 pb 383 ma 414 10 ma 235 u 207 pb 418 ma 207 pb 206 pb 623 ma kyanite 21 27 238 u 206 pb 399 ma chlorite anatase ilmenite 20 27 238 u 206 pb 350 370 ma apatite quartz kspar 18 19 transposed pegmatitic intrusions in the straits schist yield monazites with u pb ages analytically indistinguishable from those of metamorphic monazites and zircons in the schists growth of monazite and zircon in the schists may be related to high t fluid influx associated with pegmatite intrusion age discordance in the garnets from the straits schist is most consistent with continuous loss of intermediate daughter products of the 238 u decay chain from about 420 ma to 380 ma garnets from the adjacent trap falls formation do not display this behavior

early ordovician orogenic event in galicia nw spain evidence from u pb ages in the uppermost unit of the ordenes complex new u pb data zircon monazite and rutile obtained from rocks of the uppermost allochthon in the variscan belt of nw spain indicate that the hangingwall to the suture includes an allochthonous unit with a pre variscan tectonothermal evolution this evolution is characterised by an early ordovician 498 500 ma bimodal magmatism followed almost immediately 493 498 ma by a barrovian style metamorphism up to the granulite facies the metamorphism subsequent to the igneous intrusions requires convergence and crustal thickening in order to generate the barrovian facies pattern shown by the lithologies of the uppermost allochthon the almost coeval magmatism and metamorphism and the chemistry of the metabasites suggest an accretionary complex probably related to a volcanic arc as the most probable setting for the origin of the uppermost unit the implications of the existence of early ordovician convergent plate boundaries are discussed in the context of gondwana laurentia avalon interactions

tectonic controls on metamorphism partial melting and intrusion timing and duration of regional metamorphism and magmatism in the nigde massif turkey protracted heating and melting of orogenic middle crust followed by emplacement of a syn extensional pluton during decompression and cooling are demonstrated for a metamorphic core complex in central turkey new geochronologic data for the nigde massif of the central anatolian crystalline complex document an interval of melting crystallization and pb loss at elevated ambient temperature 85 92 ma determined by u pb shrimp within a single sample of peraluminous granite crustal melting was syn to post peak metamorphism 725 c dated at 91 0 2 0 ma by shrimp analysis of zircon rims in sillimanite schist that is part of the country rock to the pluton metamorphic monazite in sillimanite schist yields a younger age of 84 7 0 7 ma for matrix grains and inclusions in garnet hornblende 40ar 39ar ages from amphibolites interlayered with the sillimanite schists coincide with the timing of emplacement of magma into metamorphic country rock that had experienced cooling and decompression to 12 km and 550 c the similarity of 40ar 39ar ages for biotite in the pluton 79 ma and hornblende 79 81 ma biotite 74 76 ma and muscovite 78 83 ma in the metamorphic country rock document rapid cooling 100 c my following intrusion the coincidence of the youngest u pb magmatic zircon ages and the oldest 40ar 39ar ages combined with structural evidence for normal sense shearing and tectonic unroofing in the late cretaceous suggests that intrusion was driven by extension we propose that crustal melting occurred in the middle crust during prograde metamorphism and or initial decompression and that ascent and emplacement of magma as a pluton were only triggered once extension occurred and removed upper crustal rocks

interpretation of monazite ages obtained via in situ analysis abstract monazite grains from nepal and vietnam were compositionally analyzed with an electron microprobe and dated th pb with an ion microprobe five sources of uncertainty explain age distributions from single samples that appear inconsistent with a single population 1 pb loss due to diffusion 2 dissolution reprecipitation reactions along a retrograde path 3 analytical uncertainties 4 analyses of overlapping age domains and 5 episodic monazite growth the influence of these factors is sample dependent but can be evaluated 1 using peak metamorphic conditions and x ray element maps to assess potential polymetamorphism or retrogression 2 obtaining other geochronologic data including previous work or dating other minerals in the sample 3 evaluating any method related uncertainty including counting statistics for electron microprobe analyses or calibration reproducibility for ion microprobe analyses and 4 ascertaining the potential growth mechanism of the monazite grain including dissolution of detrital grains or production from rare earth element ree oxide or allanite chemical contents of monazite grains analyzed in this study fail to reflect timing information or mineral growth mechanisms instead of relying on monazite chemical composition major mn fe mg ca and minor y element garnet zoning patterns and peak p t conditions should be used to facilitate age interpretation this thermobarometric data records the sample s thermal history changes in garnet growth rate and mechanisms and accessory mineral breakdown

quantification of loss of calcite pyrite and organic matter due to weathering of toarcian black shales and effects on kerogen and bitumen characteristics abstract comparison of geochemical data on posidonia shale early toarcian from a shallow unweathered core and from adjacent weathered exposures of the same fades was performed results revealed that quantitatively the most affected petrographic constituent is pyrite and that organic matter and carbonate were also altered by weathering due to this process of weathering the bulk composition of organic matter especially the molecular composition of soluble organic matter and the fluorescence colour of organic particles are changed estimates of weathering rates reveal that the annual release of sulphur and organic carbon from black shales may significantly add to anthropogenic pollution

isotopic dating in metamorphic belts isotopic dating in metamorphic rocks is concerned with the timing of processes whose operation is controlled by continually changing physical conditions of these temperature has a pervasive influence and the use of physical models to elucidate the ways in which temperature is likely to vary is briefly reviewed the central concept of closure temperature is critically discussed and quantitative estimates for biotite and hornblende are evaluated in order to illustrate the factors which control closure temperatures and limit their application in practice the possibility of dating crystallization using minerals which crystallize below their respective closure temperatures is examined taking examples involving k ar rb sr sm nd and u pb analyses the indirect dating of metamorphism via structurally dated plutons is briefly considered and the problems of interpreting both discordant u pb zircon ages and rb sr whole rock isochrons in metamorphosed granites are discussed the value of near concordant zircon ages is emphasized the extent of isotopic equilibration during metamorphism specifically of sr isotopes in metasediments is shown not to be a simple function of metamorphic grade the flow of fluids produced by metamorphic reactions appears to be crucial and there is a potential for dating metamorphism using whole rock samples where such flow can he demonstrated independently the concluding discussion briefly examines existing data for the dalradian and indicates the potential for further progress using both well established and novel approaches

absolute ages aren t exactly the time scales of important events and processes in geology and archaeology are ascertained through measurements of radioisotopes the accuracy of the dating depends critically on how well known the radioactive decay constants are in their perspective renne karner and ludwig discuss the role that discrepancies in decay constants play in the accuracy of radioisotope dating as dating measurements become increasingly precise geochronologists will have to confront these kinds of systematic errors

natural constraints on metamorphic reaction rates abstract quantitative constraints on the rates at which metamorphic reactions proceed in nature are now available from several sources most common are predictions made on the basis of laboratory kinetic data however the applicability of such laboratory based predictions has long been questioned and many observations in the field now suggest much slower rates here published quantitative field based constraints on high temperature 400 c reaction rates are assembled from a variety of sources reaction rates attending regional metamorphism are four to seven orders of magnitude slower than most laboratory based predictions a general rate law for regional metamorphism has been derived which best describes these field based data log 10 r net 0 0029 t 9 6 1 where r net is the net reaction rate g cm 2 a and t is temperature c at the same time natural reaction rates attending contact metamorphism differ from laboratory based predictions by less than two orders of magnitude and are in close agreement at higher temperatures thus while existing laboratory based kinetic data may be judiciously applied to some contact metamorphic systems laboratory based kinetic predictions clearly misrepresent regional metamorphism to explain this kinetic discrepancy regional metamorphic reaction rates may be limited by slow intergranular transport due to comparatively limited or transient availability of aqueous fluid in the intergranular medium the general field based rate law may be applied to regional metamorphic and other environments i e ultrahigh pressure or ultrahigh temperature metamorphism if similar system characteristics mainly low aqueous fluid content can be inferred

shear zones at the laxford front nw scotland and their significance in the interpretation of lower crustal structure the lewisian rocks in the scourie laxford region nw scotland show variations in shear strains and associated structures on the southern upper margin of a zone of intense laxfordian reworking the scourian block was thrust a large distance obliquely northwards over the northern laxfordian gneisses as part of a laxfordian episode of crustal thickening this was followed by crustal extension during which time the scourian block moved down to the south granite sheets were intruded along the main shear zone in a dilational region at the base of a rotational extensional block the laxfordian contractional and extensional deformation occurred under amphibolite facies conditions and analogies can be made with middle crustal structures inferred from deep seismic data for example structures produced during late laxfordian crustal spreading can be compared to those seen on the birps offshore scottish data which formed during devonian basin development following caledonian crustal thickening the scourie laxford structures give an idea of fault kinematics at the brittle ductile transition in the middle to lower crust steep faults pass down into more gently dipping ductile shears and then to a zone of anastomosing shears which accommodate the strains and rotations at the base of the rigid upper crust the shears may concentrate along a more planar zone of deformation forming a detachment or decoupling zone below which the extension may be variable depending on the mode of lithospheric stretching

environmental impact of mineralised black shales abstract black shales are sedimentary rocks containing 0 5 of organic carbon they host polymetallic deposits which have been mined for cu ni zn mn p mo v u au and pge platinum group elements even sub economic occurrences provide potential risk of acid rock drainage when exposed to oxic surface environment the natural acid neutralisation potential varies depending on the adjacent rock units especially on the presence of calcareous rocks the chemical and mineralogical composition of black shale is reflected in the quality of the surface waters and groundwater cu ni pb u and zn are recognised as major pollutants though the environmental impact is characteristically polymetallic just like the black shale occurrences hence the environmental impacts have to be evaluated in each occurrence the proterozoic ni zn cu co deposit at talvivaara finland is reviewed in more detail as an example of a large low grade deposit that is currently exploited with open pit mining and a bioleaching process together with the proterozoic central african copperbelt the cambrian u mo deposits in sweden the cambrian ni mo pge deposits in china and the cambrian ordovician u deposits in south korea the devonian ni zn pge occurrences in yukon canada and kentucky usa and the permian cu ag deposits in poland and germany the mineralised horizons may be merely few centimetres thick like in yukon or hundreds of metres thick like at talvivaara both natural and anthropogenic environmental impacts of black shales are reviewed world wide and based on the overview of the state of the art an integrated research approach is suggested for the comprehensive assessment of the risk black shales are natural sources of soil and water contamination at talvivaara the geochemical background includes higher than average concentrations of ni cu zn and mn in glacial till peat surface waters and groundwater as well as in stream and lake sediments bioaccumulation by plants has been reported in china and korea even endemic diseases have been proposed to be linked with the contamination derived from the weathering and leaching of harmful elements from black shale anthropogenic actions exposing the black shale bedrock and associated soils to oxic conditions further intensifies acid rock drainage regional or nation wide mapping of the black shales is recommended to detect potential risk areas finland has recently completed the country wide mapping program of black shales with airborne geophysics integrated with geological petrophysical and geochemical studies the black shale database is actively used in regional planning and by environmental authorities research institutes and consulting companies in the case of the historical black shale mining areas like in the kupferschiefer in germany restoration measures have been applied to prevent further acid mine drainage in active and future mining projects a comprehensive environmental impact assessment with effective monitoring programmes and closure plans play a crucial role in the prevention of acid mine drainage from the black shale associated deposits

fast tectonometamorphism and exhumation in the type area of the barrovian and buchan zones the beginning of the grampian episode of tectonometamorphism in scotland is dated by collision and obduction of the ballantrae ophiolite complex at 478 8 ma for the first time we have used zircon and garnet to radiometrically date the peak of the caledonian buchan and barrovian tectonometamorphism in their type areas as contemporaneous at 467 2 5 ma detrital garnet from the neighboring southern uplands flysch terrane has the same radiometric age and occurs in 465 2 5 ma molasse in the midland valley we show that the entire grampian episode lasted 15 2 5 m y and that it took fewer than 7 6 m y to expose high grade rocks following the peak of metamorphism those who study precambrian orogeny should note the brevity of this scottish tectonometamorphic episode and the speed of exhumation

crustal channel flows 2 numerical models with implications for metamorphism in the himalayan tibetan orogen 1 results from a thermal mechanical model ht1 that includes midcrustal channel flow are compatible with many features of the himalayan tibetan system radioactive self heating and rheological weakening of thickened model orogenic crust lead to the formation of a hot low viscosity midcrustal channel and a broad plateau channel material corresponding to the greater himalayan sequence ghs flows outward from beneath the plateau in response to topographically induced differential pressure at the plateau flank it is exhumed by focused surface denudation and juxtaposed with cooler newly accreted material corresponding to the lesser himalayan sequence lhs the model channel is bounded by coeval thrust and normal sense ductile shear zones interpreted to represent the main central thrust mct zone and south tibetan detachment system respectively inverted metamorphism associated with the model mct zone results from distributed ductile shear along the mct and extrusion of the hot channel a variety of model p t t path styles resembling those observed in the ghs and lhs are produced for points traveling through contrasting tectonic regimes that coexist in different parts of the model predicted times of peak metamorphism cooling and erosion of metamorphic facies are generally compatible with observations although model ghs cooling ages are too young the times of m1 and m2 metamorphic events observed in the ghs correspond to model times of maximum burial and maximum heating respectively the results highlight the need to integrate tectonics and metamorphism in continental collision models and demonstrate the importance of lateral transport of both heat and material in large hot orogens

continental thermal and tectonic regimes during the archaean metamorphic pressures estimated from mineral assemblages in archaean high grade terrains may be used to constrain geothermal regimes in the archaean continental crust in two ways first they may be combined with temperature estimates to yield bounds on the heat flux during the thickening events that produced the metamorphism the pressure temperature data do not require any greater supply of heat to the base of the continental crust in the archaean than is supplied at the present day second the pressures alone may be used to infer the height of archaean mountains these mountains appear to have had elevations comparable with those of present day mountain belts it seems probable that the elevation of present day belts is limited by the creep strength of the lithosphere and in view of the strong temperature dependence of creep in earth materials this second observation also implies that archaean continental thermal regimes were similar to present day ones these observations together with the common

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 4 0 ar 3 9 ar cooling ages of amphibole and muscovite from rocks of the bronson hill terrane in connecticut and central massachusetts reflect a late paleozoic alleghanian overprinton 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 4 0 ar 3 9 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

sm nd dating of spatially controlled domains of garnet single crystals a new method of high temperature thermochronology ganguly and tirone meteorit planet sci 36 2001 167 175 recently presented a method of determining the cooling rates of rocks from the difference between the core and bulk ages of a crystal as determined by a single decay system here we present the first application of the method using the core and bulk ages of garnet single crystals according to the sm nd decay system in two rock samples with contrasting cooling rates which can be constrained independently the samples belong to the metamorphic core complex valhalla british columbia and the mid crustal magmatic arc exposure of the salinian terrane california we have micro sampled the garnet crystals over specific radial dimensions and measured the nd isotopes of these small sample masses as ndo via solid source mass spectrometry to determine the sm nd age difference between the core and bulk crystals using a peak metamorphic p t condition of 8 1 kbar 820 30 c spear and parrish j petrol 37 1996 733 765 the core 67 3 2 3 ma and bulk 60 9 2 1 ma ages of the british columbian garnet sample yield a cooling rate of 2 13 c myr which is in very good agreement with the cooling rates that we have derived by modeling the retrograde fe mg zoning in the same garnet and assuming the same peak metamorphic p t condition considering earlier cooling rate data derived from closure temperature vs age relation of multiple geochronological systems spear and parrish j petrol 37 1996 733 765 a cooling rate of v15 20 c myr seems most reasonable for the valhalla complex diffusion kinetic analysis shows that the sm nd core age of the selected garnet crystal could not have been disturbed during cooling consequently the core age of the garnet crystal 67 3 2 3 ma corresponds to the peak metamorphic age of the valhalla complex the salinian sample on the other hand yields indistinguishable core 78 2 2 7 ma and bulk 77 9 2 9 ma ages as expected from its fast cooling history which can be constrained by the results of earlier studies the sm nd decay system in garnet has relatively high closure temperature usually s 650 c therefore the technique developed in this paper fills an important gap in thermochronology since the commonly used thermochronometers are applicable only at lower temperatures simultaneous modeling of the retrograde fe mg zoning in garnet spatially resolved sm nd ages of garnet single crystals and resetting of the bulk garnet sm nd age

prograde temperature time evolution in the barrovian type locality constrained by sm nd garnet ages from glen clova scotland abstract the timing of garnet growth during metamorphism associated with the grampian orogeny in the sillimanite zone of the barrovian type locality in glen clova scotland was determined by sm nd geochronology two high precision garnet whole rock ages were achieved by employing hf partial dissolution of garnet separates to optimize purity multiple garnet growth generations were identified on the basis of the geochronology and detailed textural and chemical data an early stage at 472 9 2 9 ma during d 2 deformation under garnet zone conditions c 500 550 c and a later stage at 464 8 2 7 ma during or slightly after d 3 deformation mostly under sillimanite zone conditions peak temperature of c 660 c but possibly including some growth during kyanite zone conditions when combined with recently published garnet ages from the kyanite and garnet zones the data suggest that peak metamorphic temperatures in at least these three of barrow9s zones were achieved roughly contemporaneously the difference between garnet zone and sillimanite zone peak temperature attainment is 2 8 3 7 ma the near contemporaneity of peak temperature attainment in different metamorphic zones requires an additional source of heat beyond thermal relaxation of a variably over thickened crust we suggest that local igneous intrusions with synmetamorphic ages provided that additional heat

metamorphism of the scourian complex nw scotland the rocks of the scourian complex have been intensively studied but there is still no consensus as to the conditions of the granulite facies metamorphism preserved in these rocks recent estimates of these conditions fall into two groups one at 820 920 c and ca 11 kbar and the second at ca 1000 c and 12 kbar investigation of a variety of rocks shows that the recorded conditions vary with grain size with higher grade conditions recorded by the cores of coarser ca 10 mm crystals and lower grade conditions recorded by the rims of coarser grains and by finer grains this observation suggests that re equilibration during recovery of these rocks to the surface has been important which may account for the discrepancy in estimated p t conditions revised estimates of the equilibration conditions of the scourian complex of t 1000 c and p 8 5 kbar are presented the conditions suggested for the peak of metamorphism mean that the role of anatexis in the genesis of these rocks must be considered and the nature of the fluid phase thoroughly investigated

mineralogical and geochemical constraints on environmental impacts from waste rock at taojiang mn ore deposit central hunan china the mineralogy and geochemistry of the waste rocks distributed at taojiang mn ore deposit central hunan province china were studied using x ray powder diffraction xrd electron microprobe analysis empa fitted with energy dispersive spectrometer eds and inductively coupled plasma mass spectrum atomic emission spectra icp ms aes with the aim of predicting the environmental impacts of weathering of the waste rocks the mineralogical results from microscope observation and xrd and empa studies show that the waste rock is composed of black shale and minor mn carbonates the oxidation of sulfide minerals such as galena pyrite and chalcopyrite is accompanied by decomposition of mn carbonates and k feldspar during exposure to atmospheric o2 the geochemical characteristics of major rare earth elements ree and trace elements of the waste rocks also show that the waste rock can be divided into black shale and mn carbonate and both of them are currently under chemical weathering the major alkalies and alkaline elements ca mg na k rb sr and cs and major elements fe s and p and heavy metals sc v cr th u sn co ni cu zn pb mo cd sb an tl are being released during weathering the mobility of alkalis and alkaline elements ca mg na k rb sr and cs is controlled by decomposition of mn carbonates the dispersion of cr sc and th u might be related to weathering of k feldspar and the release of the heavy metals co ni cu zn pb mo cd sb and tl is dominated by the breaking of sulfide minerals the ree of the waste rocks and surrounding soils and the spidery distribution patterns of heavy metals in the waste rocks the surrounding soils and the surface waters show that weathering of the waste rocks and bedrock might be the sources of heavy metal contamination for the surrounding soils and surface water system for the mining area this is predicted by the mass balance calculation by using zr as an immobile element therefore it is urgently necessary take measures to treat the waste rocks distributed throughout the area for the local environmental protection

statistical empirical index of chemical weathering in igneous rocks a new tool for evaluating the degree of weathering abstract chemical weathering indices are useful tools in characterizing weathering profiles and determining the extent of weathering however the predictive performance of the conventional indices is critically dependent on the composition of the unweathered parent rock to overcome this limitation the present paper introduces an alternative statistical empirical index of chemical weathering that is extracted by the principal component analysis pca of a large dataset derived from unweathered igneous rocks and their weathering profiles the pca analysis yields two principal components pc1 and pc2 which capture 39 23 and 35 17 of total variability respectively the extent of weathering is reflected by variation along pc1 primarily due to the loss of na 2 o and cao during weathering in contrast pc2 is the direction along which the projections of unweathered felsic intermediate and mafic igneous rocks appear to be best discriminated therefore pc1 and pc2 represent independent latent variables that correspond to the extent of weathering and the chemistry of the unweathered parent rock subsequently pc1 and pc2 were then mapped onto a ternary diagram mfw diagram the m and f vertices characterize mafic and felsic rock source respectively while the w vertex identifies the degree of weathering of these sources independent of the chemistry of the unweathered parent rock the w index has a number of significant properties that are not found in conventional weathering indices first the w index is sensitive to chemical changes that occur during weathering because it is based on eight major oxides whereas most conventional indices are defined by between two and four oxides second the w index provides robust results even for highly weathered sesquioxide rich samples third the w index is applicable to a wide range of felsic intermediate and mafic igneous rock types finally the mfw diagram is expected to facilitate provenance analysis of sedimentary rocks by identifying their weathering trends and thereby enabling a backward estimate of the composition of the unweathered source rock

rare earth diffusion kinetics in garnet experimental studies and applications abstract we determined the diffusion coefficient of sm in almandine garnet as function of temperature at 1 bar and fo 2 corresponding to that of wustite iron buffer and to a limited extent that of a few other selected rare earth elements in almandine and pyrope garnets both garnets were demonstrated to have metastably survived the diffusion annealing at conditions beyond their stability fields the experimental diffusion profiles were analyzed by secondary ion mass spectrometry and in addition by rutherford back scattering spectroscopy for two samples transmission electron microscopic study of an almandine crystal that was diffusion annealed did not reveal any near surface fast diffusion path using reasonable approximations and theoretical analysis of vacancy diffusion the experimental data were used to develop an expression of rare earth element ree diffusion coefficient in garnet as a function of temperature pressure fo 2 ionic radius and matrix composition calculation of the closure temperature for the sm nd decay system in almandine garnet in a metamorphic terrain shows very good agreement with that constrained independently modeling of the ree evolution in melt and residual garnet suggests that for dry melting condition the ree pattern in the melt should commonly conform closely to that expected for equilibrium melting however for much lower solidus temperatures that would prevail in the presence of a h 2 o co 2 fluid the concentration of light ree in the melt could be significantly lower than that under equilibrium melting condition a reported core and rim differences in the ree content of a garnet crystal in a mantle xenolith in kimberlite have been reproduced by assuming that the ree zoning was a consequence of entrapment in a magma derived from an external source for 32 000 yr before the eruption

fluid heterogeneity during granulite facies metamorphism in the adirondacks stable isotope evidence the preservation of premetamorphic whole rock oxygen isotope ratios in adirondack metasediments shows that neither these rocks nor adjacent anorthosites and gneisses have been penetrated by large amounts of externally derived hot co2 h2o fluids during granulite facies metamorphism this conclusion is supported by calculations of the effect of fluid volatilization and exchange and is also independently supported by petrologic and phase equilibria considerations the data suggest that these rocks were not an open system during metamorphism that fluid rock ratios were in many instances between 0 0 and 0 1 that externally derived fluids as well as fluids derived by metamorphic volatilization rose along localized channels and were not pervasive and thus that no single generalization can be applied to metamorphic fluid conditions in the adirondacks

pressure temperature time paths of regional metamorphism i heat transfer during the evolution of regions of thickened continental crust the development of regional metamorphism in areas of thickened continental crust is investigated in terms of the major controls on regional scale thermal regimes these are the total radiogenic heat supply within the thickened crust the supply of heat from the mantle the thermal conductivity of the medium and the length and time scales of erosion of the continental crust the orogenic episode is regarded as consisting of a relatively rapid phase of crustal thickening during which little temperature change occurs in individual rocks followed by a lengthier phase of erosion at the end of which the crust is at its original thickness the principal features of pressure temperature time ptt paths followed by rocks in this environment are a period of thermal relaxation during which the temperature rises towards the higher geotherm that would be supported by the thickened crust followed by a period of cooling as the rock approaches the cold land surface the temperature increase that occurs is governed by the degree of thickening of the crust its conductivity and the time that elapses before the rock is exhumed sufficiently to be affected by the proximity of the cold upper boundary for much of the parameter range considered the heating phase encompasses a considerable portion of the exhumation decompression part of the ptt path in addition to the detailed calculation of ptt paths we present an idealized model of the thickening and exhumation process which may be used to make simple calculations of the amount of heating to be expected during a given thickening and exhumation episode and of the depth at which a rock will start to cool on its ascent path an important feature of these ptt paths is that most of them lie within 50 c of the maximum temperature attained for one third or more of the total duration of their burial and uplift and for a geologically plausible range of erosion rates the rocks do not begin to cool until they have completed 20 to 40 per cent of the total uplift they experience considerable melting of the continental crust is a likely consequence of thickening of crust with an average continental geotherm a companion paper discusses these results in the context of attempts to use metamorphic petrology data to give information on tectonic processes 1984 oxford university press

oxygen isotope geochemistry of the scourian complex northwest scotland the scourian complex of northwest scotland underwent granulite facies metamorphism at 2 7 ga granulite facies orthogneisses have whole rock 18o values similar to those of igneous rocks of comparable compositions ultrabasic gneisses 5 5 5 9 basic gneisses 6 4 6 8 tonalitic gneisses 9 5 9 7 and steep 18o gradients of up to 3 in 10cm are recorded at two lithological contacts these data suggest that large volumes of pervasive metamorphic fluids have not infiltrated the rocks but do not preclude localized fluid rock interaction scourian paragneisses have lower 18o values 8 5 9 9 than typical metasediments and may have undergone fluid hosted isotopic exchange with the surrounding orthogneisses felsic sheets within tonalitic and basic gneisses have similar 18o values to their hosts these data combined with petrological and geochemical information suggest that the sheets were formed by local anatexis during granulite facies metamorphism fluid infiltration during the 2 5 ga amphibolite facies inverian retrogression caused homogenization of 18o values of the scourian gneisses unaltered tholeiitic scourie dykes have low 18o values of 2 0 it is unlikely that heated surface derived fluids infiltrated the scourian complex and these dykes were probably emplaced as low 18o magmas