application of zn isotopes in environmental impact assessment of zn pb metallurgical industries a mini review abstract zn and pb smelters are the major contributors to zn and pb emissions among all anthropogenic sources thus it is essential to understand zn isotopic variations within the context of metallurgical industries as well as its fractionation in different environments impacted by smelting activities this mini review outlines the current state of knowledge on zn isotopic fractionation during the high temperature roasting process in zn and pb refineries 66 zn values variations in air emissions slags and effluents from the smelters in comparison to the geogenic zn isotopic signature of ores formation and weathering in order to assess the environmental impact of these smelters the available and measured 66 zn values are compiled for smelter impacted natural water bodies groundwater stream and river water sediments lake and reservoir and soils peat bog soil inland soil finally the discussion is extended to the fractionation induced during numerous physicochemical reactions and transformations i e adsorption precipitation as well as both inorganic and organic surface complexation

disruption of the geochemical metal cycle during mining multiple isotope studies of lake sediments from schefferville subarctic quebec iron mining in schefferville 1939 1977 in subarctic quebec has left behind large numbers and quantities of tailing deposits the impact of past mining activity on aquatic ecosystems in the schefferville area has been studied using geochemical and isotopic pb zn and fe analyses of lake sediments ore deposits tailings and epiphytic lichens analysis of two sediment cores from lakes dauriat and oksana reveals that the surface geochemical cycle of the schefferville area has been profoundly disturbed by anthropogenic activity such as mining disturbances were particularly abrupt at the transitions from pre mining to mining and mining to post mining periods elemental and isotopic analyses of the lake sediments reveal four different end member contributions to the lake sedimentation with changes in terms of sources and source contribution observed throughout the sedimentation history end members were identified using pb zn and fe isotopes and are consistent for each element lead isotope ratios vary from highly radiogenic 206pb 204pb 27 to less radiogenic 206pb 204pb 17 7 from the bottom to the top of the sediment cores iron isotope compositions vary from 0 2 to 1 the latter value remaining constant throughout the sedimentary history of lake oksana a systematic difference in the zn isotope ratios of the two lakes is also observed and can be explained by local differences in basin lithology in order to identify pollution sources samples from ores and tailings and epiphytic lichens were measured as proxies of mining activity lithology and atmospheric deposition respectively the impact of anthropogenic activity is clearly evident in the sediment records and results from mining activity as well as local urban and industrial activities waste water inputs long range atmospheric deposition also accounts for some of the variations in isotopic composition measured in the sediments the systematic coupling of pb isotopes with zn or fe isotopes allows us to identify and constrain the metal sources that contributed to sediment contamination this study demonstrates that disturbance due to mining activities is very effective in rapidly modifying lake sediment composition though the disturbances remained local in terms of geographic extent the damage to the aquatic ecosystem has been significant and may persist for decades

isotope variations of dissolved zn in the rio grande watershed usa the role of adsorption on zn isotope composition abstract in order to better understand the factors influencing zinc zn isotope composition in hydrological systems we analyzed the 66 zn of dissolved zn in the streams and groundwater of the upper and middle rio grande watershed in colorado and new mexico united states the stream water samples have a wider variation of 66 zn 0 57 to 0 41 relative to the jmc 3 0749 lyon standard than groundwater samples 0 13 to 0 12 and than samples from streams that are in close proximity to abandoned mining sites 0 24 to 0 40 regional changes of bedrock geology from primarily igneous rocks to primarily sedimentary rocks have no resolvable effect on the 66 zn of aqueous samples instead an increase in water ph from 7 5 to 8 5 corresponds to a considerable decrease in the 66 zn of dissolved zn r 2 0 37 p 0 003 n 22 consequently we link the observed zn isotope variations to the process of adsorption of zn onto suspended sediment and bedrock minerals average 66 zn adsorbed dissolved 0 31 our results are in good agreement with previous experimental and empirical studies suggesting that zn adsorption leads to a residual dissolved pool enriched in light zn isotopes given that anthropogenic zn sources can also be responsible for lowering of 66 zn and may overlap with the ph adsorption effect on 66 zn the latter needs to be carefully considered in future studies to differentiate between natural and anthropogenic factors influencing zn isotopes in this and other aquatic systems

zinc isotope systematics in snow and ice accretions in central european mountains abstract zinc zn pollution negatively affects human and ecosystem health we quantified atmospheric zn inputs at six remote mountain top locations in the czech republic central europe and used 66 zn isotope ratios to identify zn from different pollution sources the study sites were located at an elevation of approximately 1000 m near the state borders with germany and poland during two winter seasons 2009 2010 over 400 samples of vertical deposition snow and horizontal deposition ice accretions were collected zinc pollution levels were generally low zinc concentrations in snow and ice accretions were less than twice as high in the east compared to the west across the sites over 90 of zn was present in a weak acid soluble form zinc concentrations were 5 times higher in ice accretions which formed from small droplets originating in the basal cloud layer rich in pollutants than in snow in contrast droplets resulting in snow formation were larger and scavenged less pollution due to their smaller surface area 66 zn of pribram sphalerite west and smelter derived fly ash west were low 0 23 and 0 47 respectively olkusz sphalerite east had a higher 66 zn of 0 02 66 zn of snow ranged from 0 60 to 0 68 ice accretions had 66 zn between 0 67 and 0 14 at the three eastern sites 66 zn of ice accretions was lower than 66 zn of snow suggesting the presence of volatilized smelter derived or coal burning derived zn 66 zn of ice accretions at two of the three western sites was higher than 66 zn of snow different 66 zn values of snow and ice accretions from the same site reflected different pollution sources which may have been situated at different distances from the receptor site 66 zn of the soluble zn fraction was higher than 66 zn of the insoluble zn fraction possibly also indicating a different origin of these two zn fractions zinc isotope heterogeneity in the atmosphere of remote areas indicates that 66 zn can be a useful tool in pollution provenance studies

the estuarine geochemical reactivity of zn isotopes and its relevance for the biomonitoring of anthropogenic zn and cd contaminations from metallurgical activities example of the gironde fluvial estuarine system france abstract zinc stable isotopes measurements by mc icp ms validated by laboratory intercalibrations were performed on wild oysters suspended particles and filtered river estuarine water samples to provide new constraints for the use of zn isotopes as environmental tracers the samples selected were representative of the long range 400 km transport of metal zn cd etc contamination from former zn refining activities at decazeville i e 66 zn 1 and its phasing out recorded during 30 years in wild oysters from the gironde estuary mouth rno rocch sample bank the study also addresses additional anthropogenic sources urban and viticulture and focuses on geochemical reactivity of zn in the turbidity gradient and the maximum turbidity zone mtz of the fluvial gironde estuary in this area dissolved zn showed a strong removal onto suspended particulate matter spm and progressive enrichment in heavy isotopes with increasing spm concentrations varying from 66 zn 0 02 at 2 mg l to 0 90 at 1310 mg l these signatures were attributed to kinetically driven adsorption due to strongly increasing sorption sites in the turbidity gradient and mtz of the estuary oysters from the estuary mouth contaminated sediments from the lot river and spm entering the estuary showed parallel historical evolutions 1979 2010 for zn cd ratios but not for 66 zn values oysters had signatures varying from 66 zn 1 43 in 1983 to 1 18 in 2010 and were offset by 66 zn 0 6 0 7 compared to past 1988 and present spm from the salinity gradient isotopic signatures in river borne particles entering the gironde estuary under contrasting freshwater discharge regimes during 2003 2011 showed similar values 66 zn 0 35 0 03 1sd n 15 i e they were neither related to former metal refining activities at least for the past decade nor clearly affected by other anthropogenic sources therefore the zn isotopic signatures in gironde oysters reflect the geochemical reactivity of zn in the estuary rather than signatures of past metallurgical contaminations in the watershed as recorded in contaminated river sediments the study also shows that the isotopic composition of zn is strongly fractionated by its geochemical reactivity in the gironde estuary representative of meso macrotidal estuarine systems

atmospheric deposition and isotope biogeochemistry of zinc in ombrotrophic peat abstract zinc isotope ratios were measured in the top sections of dated ombrotrophic peat cores in finland to investigate their potential as proxies for atmospheric sources and to constrain post depositional processes affecting the geochemical record the peat deposits were located in hietajarvi a background site well away from any point pollution source and representing background conditions in outokumpu next to a mining site and in harjavalta next to a smelter measured total concentrations calculated excess concentrations and mass balance considerations suggest that zinc is subjected to important biogeochemical cycling within the peat significant isotopic variability was found in all three peat bogs with heavier zinc in the deeper and lighter zinc in the upper sections isotope ratios and concentrations correlated in the two peats located next to dominant point sources i e the smelting and mining site suggesting that zinc isotopes trace pollution sources concentration and isotope peaks were offset from the period of mining and smelting activity supporting migration of zinc down the profile the 66znjmc where 66zn 66zn 64zn sample 66zn 64zn jmc standard 1 103 of the top section sample at the remote hietajarvi site was 0 9 and we suggest this represents the regional background isotope signature of atmospheric zinc the deeper sections of the peat cores show isotopically heavier zinc than any potential atmospheric source indicating that post depositional processes affected the isotopic records the large variations encountered up to 1 05 for 66zn and rayleigh modelling imply that multiple fractionation of zinc during diagenetic alterations occurs and nutrient recycling alone cannot explain the fractionation pattern we propose that zinc isotopes are amenable to identify different atmospheric zinc sources including zinc derived from anthropogenic activities such as mining and smelting but multiple biogeochemical processes seriously affect the record and they need to be evaluated and assessed carefully if zinc isotopes are used in terrestrial paleorecords

approaching raw material functionality in the upper magdalenian of coimbre cave asturias spain through geometric morphometrics abstract coimbre cave penamellera alta asturias is an upper palaeolithic site in northern spain spanning an occupation sequence from the gravettian to the magdalenian periods the upper layers layer i and ii corresponding to the upper magdalenian register the highest intensity of human activity in this paper we analyse raw material functionality at the site through the study of cut marks found on bone remains at coimbre we have documented mainly quartzite followed by flint other raw materials are found in very low frequencies there are several types of local quartzite that appear mainly as flaking debitage and stone tools such as burins and scrappers on the other hand flint is mainly knapped to elaborate blades and bladelets as well as specialised implements such as different types of side scrappers retouched flakes on flint are relatively more abundant than those made on quartzite in this paper we employ the use of photogrammetry geometric morphometrics and statistics to analyse the cut marks from the upper magdalenian assemblage of coimbre cave our aim is to determine the lithic raw material preferentially used for carcass processing at the site

a global assessment of zn isotope fractionation in secondary zn minerals from sulfide and non sulfide ore deposits and model for fractionation control abstract we investigated extent and direction of zn isotope fractionation in secondary zinc minerals formed during low temperature hydrothermal and or supergene oxidation of primary sulfide deposits zinc isotope data have been obtained from non sulfide zinc mineral separates willemite zn2sio4 smithsonite znco3 hemimorphite zn4 si2o7 oh 2 h2o hydrozincite zn5 co3 2 oh 6 and sauconite na0 3zn3 si al 4o10 oh 2 4h2o collected from several zn deposits in ireland belgium poland namibia peru yemen and zambia the data are compared with zn isotope compositions measured on zn sulfides collected in the same areas and or derived from the existing literature to establish the controls of direction and likely extent of any fractionations we find that willemite has the greatest compositional variability with measured 66znjcm lyon values ranging from 0 42 to 1 39 spanning the entire range of terrestrial variation in zn isotopes recorded to date overall significant fractionations in positive and negative directions are recorded relative to the precursor phase primary sphalerite or an earlier secondary phase with primary sphalerite falling in a relatively narrow range of isotopic values approximately 0 1 to 0 4 most of the data observed on willemite hemimorphite and hydrozincite can be explained with a model of isotopic fractionation in which partial dissolution of primary sphalerite is followed by precipitation of an initial secondary phase that preferentially incorporates heavy zn isotopes smithsonite instead preferentially incorporates light zn isotopes this reflects the variation in the zn x bond strengths of these secondary phases with respect to the original sulfides we also observed that isotope compositions do not depend only on the difference between the fractionation factors of the involved phases but also on the amount of the secondary mineral precipitated after dissolution of primary sulfide and that the greatest fractionations occur when only small amounts of secondary mineral are precipitated progressive precipitation from migrating fluids that form phases enriched in heavy zinc isotopes would lead to a gradual decrease in the 66zn values of such phases and the fluids involved in time and space strong negative isotopic shifts are almost only observed for late crystallizing phases such as those in vugs these are interpreted to reflect precipitation from residual isotopically light fluids that are the inevitable highly fractionated product of the above described process where a more complete replacement of primary sulfide has occurred such as in the high grade core of non sulfide zinc orebodies there is limited net isotopic fractionation because dissolved primary zinc is nearly quantitatively reprecipitated locally in addition in only one case yanque peru we observed that the fringes of non sulfide zinc deposit were characterized by isotopically fractionated compositions with highly negative values implying extensive precipitation earlier or elsewhere of isotopically heavy secondary phases the higher grade ore zones where complete breakdown of primary sulfides and quantitative reprecipitation of zinc have occurred show instead less fractionated compositions

evidence for zn isotopic fractionation at merapi volcano abstract fumarolic gases rocks and condensate samples from merapi volcano indonesia have been analyzed by multiple collector inductively coupled plasma mass spectrometry mc icp ms for their zn isotopic compositions the variation observed expressed as 66 zn 66 zn 66 zn 64 zn sample 66 zn 64 zn jmc 3 049l 1 10 3 ranges from 0 05 to 1 68 the overall reproducibility was found to be better than 0 10 2sd the 66 zn of andesitic rock samples are homogeneous with a mean value of 0 24 which is comparable to previously reported basalt data 66 zn in the woro fumerolic field are ranging from 0 05 to 0 85 and 1 48 to 1 68 in fumarolic gases and condensates respectively upon cooling from 590 to 297 c gaseous zn concentrations decrease and become increasingly enriched in the lighter zn isotopes while the condensates become increasingly enriched in the heavier isotopes gas and condensate isotopic compositions can be explained with a rayleigh condensation model with temperature dependent isotope fractionation factor solid vapor over the 574 c to 297 c range of observations 1000 ln solid vapour c 1 c 2 t c 3 t 2 with c 1 0 c 2 0 88 10 3 c 3 1 00 10 6 and t in degrees kelvin which corresponds to solid vapor of 1 00033 to 1 00153 respectively at the indicated temperatures

zn isotopic evolution in early ediacaran ocean a global signature abstract the zn isotope composition of sedimentary archives reveals key biosphere lithosphere interactions throughout geologic history a recent zn isotope study of ediacaran cap carbonates from south australia revealed that the local isotopic profile reflects global changes in oceanic chemistry to examine this critical assumption this study investigates a high resolution zinc isotope profile of marinoan post glacial cap carbonates from the yangtze platform south china stratigraphic variations in zn isotope data from this study are similar to previously reported sections in south australia and south china the remarkable isotopic similarity between the two sections that were deposited on distant geographically separated continental blocks demonstrates that the zn isotopic variations reflect changing global signatures of the early ediacaran ocean this study highlights the value of zn isotopes in sediments as a global proxy for paleoceanographic studies we interpret the systematic stratigraphic changes in the zn isotope composition of the studied post glacial marinoan carbonates as a global oceanic trend controlled mainly by varying inputs and outputs of zn to the ocean decreasing 66zn values in the lowermost part of the section are attributed to the global precipitation of carbonate enriched in the heavier zn isotope a positive shift in the middle part of the section is explained by the non quantitative removal of isotopically lighter zn by sulfide minerals lower 66zn values in the uppermost part likely reflect the changing contributions of continental weathering and sulfide precipitation our data suggest that non quantitative removal of zn by sulfides is a previously unrecognized sink for zinc in the oceans

evidence of zn isotopic fractionation in a soil plant system of a pristine tropical watershed nsimi cameroon abstract the objective of this study is to determine for the first time the zinc zn isotopic composition of different soil horizons parent rocks litter and plants from a single pristine watershed three soil profiles from nsimi zoetele site south cameroon africa have been investigated the 66zn 66zn 66zn 64zn sample 66zn 64zn jmc 3 0749l 1 103 measured in the soils and rocks range from 0 05 to 0 64 in a typical hillslope soil profile developed in situ from a granitic parent rock we observe two important and systematic trends i a weathering regime in the saprolite horizon that involves strong zn depletion with no or slight fractionation compared to the fresh igneous rock and ii a shallower weathering regime with significant depletion in heavy zn isotopes in the most superficial soil horizons in contrast the soil profile of the swamp zone does not exhibit isotopic fractionation between the soil and the parent rock six plants and two litter samples were analyzed for their zn isotopic compositions 66zn varied from 0 75 to 0 91 among all samples plant roots and shoots are generally enriched in heavy isotopes 66zn of 0 42 to 0 76 relative to the litter layer 0 12 to 0 25 and most superficial soils similar to the controlled plant growth study of weiss et al weiss d j mason t f d zhao f j kirk g j d coles b j and horstwood m s a 2005 isotopic discrimination of zinc in higher plants new phytologist 165 703 710 negative 66zn values were obtained for tree leaves the most aerial part of the tree based on biomass data for the tropical forest vegetation is on average enriched in light isotopes compared to the litter and the superficial soil horizons which are the nutrients reservoirs due to the age of these soils and the complexity of pedogenetic processes it is difficult to explain the isotopic composition of the soils at present however the transformation of the saprolite horizon into a ferruginous horizon is associated with an enrichment in light zn isotopes this observation may be due to the adsorption of zn onto clays surfaces the uptake of zn by roots in the soils leads to an enrichment in heavy isotopes once the zn is in the xylem it will be transported within the plant during this transport both diffusion and active uptake of heavy isotopes by cells out of the xylem favour the mobility of light isotopes to the most aerial parts of the plants the difference in zn isotopic composition between the deep horizons and the superficial horizons of soils suggests that zn isotopes can be used to discriminate the source of zn and other metals leaving the catchment by river water

contrasting isotopic signatures between anthropogenic and geogenic zn and evidence for post depositional fractionation processes in smelter impacted soils from northern france abstract zinc isotopes have been studied along two smelter impacted soil profiles sampled near one of the largest pb and zn processing plants in europe located in northern france about 50 km south of lille mean 66zn values along these two soil profiles range from 0 22 0 17 2 to 0 34 0 17 2 at the lowest horizons and from 0 38 0 45 2 to 0 76 0 14 2 near the surface the 66zn values in the lowest horizons of the soils are interpreted as being representative of the local geochemical background mean value 0 31 0 38 whereas heavier 66zn values near the surface of the two soils are related to anthropogenic zn this anthropogenic zn occurs in the form of franklinite znfe2o4 bearing slag grains originating from processing wastes at the smelter site and exhibiting 66zn values of 0 81 0 20 2 the presence of franklinite is indicated by exafs analysis of the topsoil samples from both soil profiles as well as by micro xanes analysis of the surface horizon of a third smelter impacted soil from a distant site these results indicate that naturally occurring zn and smelter derived zn exhibit significantly different 66zn values which suggests that zinc isotopes can be used to distinguish between geogenic and anthropogenic sources of zn in smelter impacted soils in addition to a possible influence of additional past sources of light zn likely zn sulfides and zn sulfates directly emitted by the smelter the light 66zn values in the surface horizons compared to smelter derived slag materials are interpreted as resulting mainly from fractionation processes associated with biotic and or abiotic pedological processes zn bearing mineral precipitation zn complexation by organic matter and plant uptake of zn this conclusion emphasizes the need for additional zn isotopic studies before being able to use zn isotopes to trace sources and pathways of this element in surface environments

micro photogrammetric characterization of cut marks on bones in the last few years the study of cut marks on bone surfaces has become fundamental for the interpretation of archaeological sites and prehistoric butchery practices due to the difficulties in the correct identification of cut marks many criteria for their description and classifications were suggested this article presents an innovative methodology which supplements the microscopic study of cut marks despite the benefits of using scanning electron microscopy sem for the two dimensional identification of these marks it has a number of drawbacks such as the high costs and consequently the limited sample studied in this article a low cost technique for the analysis of cut mark micromorphology from a tri dimensional perspective is introduced it provides a high resolution approach to cut mark characterisation such as morphology depth width and angle estimation as well as section determination measured directly on the marks on bones macro photogrammetry records quantitative and qualitative information which can be statistically processed with standard multivariate and geometric morphometric tools

tracing of anthropogenic zinc sources in coastal environments using stable isotope composition abstract the use of zinc isotopes to trace anthropogenic sources in coastal areas has been tested in this study we determined the stable isotopic composition of zinc in sediment cores suspended particulate matter spm and rocks collected at the sepetiba bay southeastern brazil an estuarine lagoon heavily impacted by metallurgic activities these isotopic signatures were compared with those from willemite ore which represent the main mineral refined by the major industrial source of zinc the aim was to test if this tracer system enables to identify sources and sinks of anthropogenic zinc and to reconstruct the temporal and spatial evolution of zinc contamination the zinc isotopic compositions expressed using the 66zn notation relative to the jmc 3 0749 l solution showed significant variations in the sediment cores the spm and willemite ore minerals ranging between 0 01 and 1 15 spatial and temporal analysis of sediments samples fit well in a model of mixing involving three main end members i terrestrial background 66znjmc 0 28 0 12 2 ii marine detrital material 66znjmc 0 45 0 03 2 and iii a major anthropogenic source associated with electroplating wastes released into the bay 66znjmc 0 86 0 15 2 sediment cores collected in the mud flats showed high correlation between 66zn and zinc enrichment factors suggesting good preservation of the isotopic records of natural and anthropogenic sources the sediment core sampled from a mangrove wetland located in a zone impacted by the metallurgy presented levels of zinc up to 4 sediment dry weight and preserved the isotopic signatures of electroplating wastes despite evidences that post depositional processes slightly changed the isotopic signatures in some layers from this core toward heavier 66znjmc values above 1 0 a two component mixing model suggests contributions of this major anthropogenic zn source up to nearly 80 during periods of electroplating activities our work suggests that zn isotope compositions of sediments are reliable tracers of anthropogenic sources and therefore can be useful to improve environmental monitoring efforts in coastal systems

zn and cu isotopic variability in the alexandrinka volcanic hosted massive sulphide vhms ore deposit urals russia abstract copper and zn isotope ratios of well characterized samples from three ore facies in the devonian alexandrinka volcanic hosted massive sulphide vhms deposit southern urals were measured using multi collector icp ms mc icp ms and show variations linked to depositional environment and mineralogy the samples analysed derived from a hydrothermal metasomatic vein stockwork b a hydrothermal vent chimney and c reworked clastic sulphides as the deposit has not been significantly deformed or metamorphosed after its formation it represents a pristine example of ancient seafloor mineralization variations in 65 cu where 65 cu 65 cu 63 cu sample 65 cu 63 cu standard 1 1000 and 66 zn where 66 zn 66 zn 64 zn sample 66 zn 64 zn standard 1 1000 of 0 63 and 0 66 respectively are significantly greater than analytical uncertainty for both isotope ratios 0 07 2 very limited isotopic fractionation is observed in primary cu minerals from the stockwork and chimney whereas the zn isotopic composition of the stockwork varies significantly with the mineralogy chalcopyrite bearing samples from the stockwork have lighter 66 zn by 0 4 relative to sphalerite dominated samples which may be due to equilibrium partitioning of isotopically light zn into chalcopyrite during its precipitation 66 zn also showed significant variation in the chimney with an enrichment in heavy isotopes toward the chimney rim of 0 26 which may be caused by changing temperature hence fractionation factor or raleigh distillation post depositional seafloor oxidative dissolution and re precipitation in the clastic sediments possibly coupled with leaching led to systematic negative shifts in cu and zn isotope compositions relative to the primary sulphides copper shows the most pronounced fractionation consistent with the reduction of cu ii to cu i during supergene mineralization however the restricted range in 65 cu is unlike modern sulphides at mid oceanic ridges where a large range of cu isotope of up to 3 has been observed rouxel o fouquet y ludden j n 2004 copper isotope systematics of the lucky strike rainbow and logatchev sea floor hydrothermal fields on the mid atlantic ridge econ geol 99 585 600 zhu x k o nions r k guo y belshaw n s rickard d 2000 determination of natural cu isotope variation by plasma source mass spectrometry implications for use as geochemical tracers chem geol 163 139 149

size matters an evaluation of descriptive and metric criteria for identifying cut marks made by unmodified rocks during butchery one of the key concerns in human evolution studies is tracing the development of stone tool use by early hominins to acquire meat it has been suggested that the earliest tools used for this purpose might have been unmodified naturally sharp rocks however it has proven challenging to distinguish marks on bones made by hominins using humanly unmodified rocks hurs for butchery from marks made by natural processes here we present the results of a study aimed at comparing marks made by hurs during butchery versus marks made by the same hurs through simulated natural processes specifically the fluvial tumbling of bones with naturally sharp rocks replicated here using a rock tumbler the results of this study in which the lithological effector is held constant while the actor is varied confirm earlier studies suggesting that many existing categorical attributes do not effectively distinguish between marks made by hurs versus those made by other tools or trampling however we also present a novel way of measuring mark depths which shows that marks made by the human actor are much deeper and longer than those made by natural processes the size of marks therefore matters this knowledge may help us assess the likelihood that marks on bone surfaces may have been produced by natural forces as opposed to by humans using unmodified rocks for butchery

roman road pollution assessed by elemental and lead isotope geochemistry in east belgium the ability of inorganic geochemistry to record environmental change and especially human impact has been evidenced by several studies across europe especially in peat where it is possible to record the impact of agriculture mining and other industries however despite the numerous investigations on the impact of ancient human activities such as ore mining and smelting little attention has been paid to geochemistry as a tool to solve problems of palaeopollution in the surroundings of archaeological sites this paper presents geochemical evidence of the impact of a possible early roman road built in se belgian peatland increased zn and pb concentrations suggest that pb zn ores were transported on the road lead isotope analyses suggest that these ores are locally derived being compatible with those found in the nearby pb zn ore deposits from east belgium present results provide direct evidence that east belgian pb zn ores were already being mined during roman times i e earlier than previously suspected i e 14th century and that zn appears to be relatively immobile here on a broader scale it also demonstrates that such an early road already had an impact on the environment in terms of metal pollution this paper enlarges on the range of possibilities offered by geochemistry in the field of geoarchaeology

zinc isotope variations in deep sea carbonates from the eastern equatorial pacific over the last 175 ka the carbonate fraction of sediment core odp 849 leg 138 located in the eastern equatorial pacific mostly consisting of coccoliths was separated and analyzed for its zn isotopic composition the overall variation in zn isotopic composition as determined by multiple collector magnetic sector inductively coupled plasma mass spectrometry was found to be on the order of 1 expressed in 66zn where xzn xzn 64zn sample xzn 64zn standard 1 103 and x 66 67 or 68 over the last 175 ka the analytical precision was 0 04 and the overall reproducibility was usually better than 0 07 the zn isotopic composition signal exhibits several marked peaks and a high frequency variability a periodogram of the 66zn signal showed two periodicities of 35 2 and 21 2 ka we suggest that the latter is caused by the precession of the earth s axis of rotation the periodogram exhibits a minimum at 41 1 ka thus showing that the zn isotopic composition is independent of the obliquity in the eastern equatorial pacific the range of 66zn values observed for the carbonate fraction of odp 849 overlaps with the range observed for fe mn nodules in the world s oceans which suggests that seawater carbonate zn isotope fractionation is weak we therefore assume that most of the zn isotope variability is a result of the selective entrainment of the light isotopes by organic matter in the surface ocean the odp 849 66zn record seems to follow the changes in the insolation cycles changes in the late summer fall equatorial insolation modulate the intensity of the equatorial upwelling hence the mixing between deep and surface waters we propose that during decreased summer fall equatorial insolation when a steep thermocline can develop el nino like conditions the surface waters cannot be replenished by deep waters and become depleted in the lighter zn isotopes by biological activity thus resulting in the progressive increase of the 66zn values of the carbonate shells presumably in equilibrium with surface seawater

application of iron and zinc isotopes to track the sources and mechanisms of metal loading in a mountain watershed abstract here the hydrogeochemical constraints of a tracer dilution study are combined with fe and zn isotopic measurements to pinpoint metal loading sources and attenuation mechanisms in an alpine watershed impacted by acid mine drainage in the tested mountain catchment 56fe and 66zn isotopic signatures of filtered stream water samples varied by 3 5 and 0 4 respectively the inherent differences in the aqueous geochemistry of fe and zn provided complimentary isotopic information for example variations in 56fe were linked to redox and precipitation reactions occurring in the stream while changes in 66zn were indicative of conservative mixing of different zn sources fen environments contributed distinctively light dissolved fe 0 4 acidic drainage from mine wastes contributed heavier dissolved fe 0 5 and lighter zn 0 2 isotopes relative to the fen upwelling of fe rich groundwater near the mouth of the catchment was the major source of fe 56fe 0 leaving the watershed in surface flow while runoff from mining wastes was the major source of zn the results suggest that given a strong framework for interpretation fe and zn isotopes are useful tools for identifying and tracking metal sources and attenuation mechanisms in mountain watersheds

isotopic composition of zinc copper and iron in lunar samples abstract we determined by icp ms the concentrations and isotopic ratios of fe cu and zn in the ti rich lunar basalt 74275 in the lunar orange glass 74220 and in up to 10 lunar soils namely 14163 15231 64501 66041 68841 69941 70011 72501 75081 and 76501 two analyses of zinc in lunar basalt 74275 give 66 zn 0 17 and 0 75 values within the range of those measured in terrestrial basalts copper in lunar basalt 74275 has 65 cu 1 4 which is isotopically heavier than values observed in terrestrial basalts in the orange glass we measured 56 fe 0 24 65 cu 0 42 and 66 zn 3 6 these values of are more negative than those obtained for 74275 and for typical lunar basalts but for cu comparable to those observed in terrestrial sulfides and meteorites in lunar soils we found 0 11 56 fe 0 51 2 6 65 cu 4 5 and 2 2 66 zn 6 4 insofar as we can generalize from a small sample set s fe cu zn and cd show similar trends in isotopic fractionation on the moon lunar basalts have nearly terrestrial isotopic ratios relative to the lunar basalt 74275 the pyroclastic glass 74220 is enriched in the lighter isotopes of fe cu and zn and the soils are enriched in the heavier isotopes of fe cu and zn the patterns in the basalts are likely inherited from the source material the light isotope enrichments seen in the orange glass originated during lava fountaining or less probably during partial condensation of vapor and the heavy isotope enrichments in the lunar soils were likely created by a combination of processes that included micrometeorite vaporization and sputtering in the orange glass the light isotope enrichments relative to lunar basalts of zn are larger than those of cu if these enrichments reflect accurately the isotopic composition of the gas they suggest that cu is more volatile than zn in the liquid from which the gas derived a simple model built on the known flux of micrometeorites to the lunar surface and a published estimate that micrometeorites generate 10 times their own mass of vapor predicts heavy isotope enrichments comparable to those observed in soils but only if the regolith gardening rate is set at about one twentieth of the generally accepted value of 1 cm my this discrepancy may reflect the difference in the time constants for micrometeorite milling and decimeter scale gardening or the importance of sputtering

zinc and copper behaviour at the soil river interface new insights by zn and cu isotopes in the organic rich rio negro basin abstract the complex behaviour of zn and cu at the soil river interface was investigated in soil and riverine water samples from the rio negro basin a secondary tributary of the rio amazonas using their stable isotope compositions this acidic and organic river drains two types of intensely weathered terrains podzols in its upstream part and lateritic soils downstream bulk soil particles suspended particulate matter spm as well as colloidal fractions were sampled across the whole basin during low and high water stages in the basin zn and cu are mostly exported from lateritic soils and transported by organic colloids where significant losses are observed in the downstream part of the river the use of 66zn and 65cu measurements reveals distinct stories for these two metals in suspended sediments and colloids in the colloids the constant 66zncoll across the basin is induced by the same weak association mode between zn and organic ligands regardless of the origin of the water by contrast in spm the speciation of zn and thus 66znspm differ according to the type of drained soils zn is associated with organic complexes in particles exported with water draining podzol whereas zn2 is incorporated in the structure of the remaining kaolinite clays in lateritic output the stronger reactivity of cu than zn with organic ligands induces its complete complexation copper is controlled by refractory particulate organic matter pom and by reactive colloidal organic matter the latter being enriched in 65cu due to stronger binding interactions than in pom while the cu content remains constant in the upstream part of the rio negro downstream the decrease of spm and colloidal cu fluxes is associated with a constant 65cuspm and with an increase of 65cucoll at the rio negro outlet geochemical mass balance modelling based on spm cu and zn fluxes in spm and their associated isotopic signatures confirms distinct host phases for zn and cu and identifies the most probable places where losses of these two metals occur in colloids the observed cu isotope fractionation from 0 24 to 0 45 superimposed on the significant cucoll loss is assumed to result from a new isotopic equilibrium in a low velocity and high productivity zone cu rich colloids enriched in 63cu aggregate and settle down whereas the remaining heavy cu is partially complexed on strong organic ligands secreted by phytoplankton forming new cu colloids

taphonomic identification of cut marks made with lithic handaxes an experimental study abstract recent experimental studies have developed new diagnostic criteria to differentiate between trampling and cut marks within cut marks these diagnostic criteria have been useful to differentiate between marks made with simple and retouched flakes the present study expands the application of these criteria using a multivariate analysis to discriminate marks created with handaxes from those made with stone tool flakes a discriminant analysis resulted in a selection of specific variables which can successfully differentiate cut marks made with handaxes from those created with retouched flakes in more than 80 of occasions the utility of this analogical taphonomic signature created by handaxes is discussed in the light of their potential value as butchering tools

tracing cadmium zinc and lead sources in bivalves from the coasts of western canada and the usa using isotopes abstract environmental monitoring and remediation require techniques to identify the source and fate of metals emissions the measurement of heavy metal isotopic signatures made possible by the advent of the mc icp ms is a powerful new geochemical tool which may be used to trace the source of these metals in the environment in a multi tracer study cd zn and pb isotopic compositions mc icp ms and elemental concentrations hr icp ms are used to distinguish between natural and anthropogenic sources of these metals in bivalves collected from western canada british columbia hawaii and the usa east coast variability in the 114 110cd values of bivalves 1 20 to 0 09 is attributed to differences in the relative contributions of cd from natural and anthropogenic sources between sites cadmium isotopic compositions 114 110cd 0 69 to 0 09 identify high cd levels in b c oysters as primarily natural i e upwelling of cd rich intermediate waters in the north pacific with some variability attributed to anthropogenic sources e g mining and smelting variability in the 66 64zn values exhibited by the b c bivalves is relatively small 0 28 0 36 despite the low pb levels found in b c oysters pb isotopes are used to identify emissions from industrial processes and the consumption of unleaded gasoline and diesel fuel as significant metal sources although the cd concentrations of the usa east coast bivalves are primarily lower than those of b c oysters their relatively light cd isotopic compositions 114 110cd 1 20 to 0 54 indicate the significance of anthropogenic cd sources and are attributed to the high prevalence of industry on this coast the 114 110cd values of usa east coast bivalves include the lightest ever reported with the exception of values reported for extraterrestrial materials in addition the pb isotopic compositions of bivalves from the usa east coast indicate pb emissions from the combustion of coal are an important source of pb consistent with the high consumption of coal for power production on this coast this study demonstrates the effective use of cd and zn isotopes to trace anthropogenic sources in the environment and the benefit of combining these tools with pb fingerprinting techniques

historical variations in the isotopic composition of atmospheric zinc deposition from a zinc smelter abstract in order to test the usefulness of stable zinc isotopes as an atmospheric source tracer we analyzed the zinc isotopic composition of two sediment cores taken at 1 km distance of the former zinc smelter in lommel belgium the peat bog lake sediments accumulate mainly atmospheric particles have high organic matter contents 12 60 wt are anoxic and highly contaminated with heavy metals up to 4 7 wt zn and 1 1 wt pb with a sulfide mineralogical control on mobility down core variations in 66 zn relative to the jmc 3 0749l standard were small ranging from 0 07 to 0 39 but are nevertheless eight times the external reproducibility of 0 04 good agreement was found between the two cores and despite 30 zn mobilization to deeper layers no evidence of associated diagenetic zn isotope fractionation was found sediments deposited in the early 20th century have 66 zn of 0 30 0 05 2sd n 5 and a shift takes place between 1945 and 1950 to 66 zn values of 0 14 0 09 2sd n 7 in the 2nd half of the century in order to understand this shift in 66 zn we analyzed 32 ore grade sphalerite zns samples from african australian and european origin together with 29 published 66 zn values for ore grade zns we find remarkably homogeneous isotopic compositions which when averaged for mining location gives 66 zn of 0 16 0 20 2sd n 10 mines n 61 analyses early 20th century zn deposition with 66 zn of 0 30 is significantly different p 66 zn of 0 16 we suggest that this reflects the presence of an atmospheric smelting residue slag component enriched in the heavy zn isotopes due to rayleigh type fractionation during zn refining

cadmium isotope fractionation within the soil profile complicates source identification in relation to pb zn mining and smelting processes abstract many cadmium species are among the most toxic of environmental contaminants because cd in many forms is mobile in the environment identifying its sources is a crucial aspect of remedial intervention data from the literature suggest that cd isotopes could be a useful tool for such identification but no data about cd isotopes through entire soil profiles has yet been published we compared in this paper the cd isotope composition of three forest and two meadow soil profiles affected by different contamination sources near the olkusz pb zn smelter in southern poland together with the main industrial source of possible contamination at that location in the contaminated forest soil profile the upper soils reflected the heaviest cd isotope compositions while the deeper soil humus layer had the lightest cd isotope compositions we found that the overall cd isotope heterogeneity in industrial wastes was overlapped by the overall cd isotope fractionation within the forest soil profile near the smelter e 114 110 cd nist3108 values of 5 14 compared to 11 8 respectively both meadow soil profiles had approximately a cd isotope composition corresponding to the processed ore olkusz sphalerite

the zinc stable isotope signature of waste rock drainage in the canadian permafrost region leachate from a well instrumented experimental scale waste rock pile test pile at the diavik diamond mine northwest territories was monitored the well characterized waste rock consists of granite pegmatitic granite and biotite schist with an average total sulfur and carbonate carbon concentration of 0 053 and 0 027 wt respectively the leachate emerging from the southern basal drain of the waste rock pile has been monitored since 2007 the zinc stable isotope footprint was characterized alongside standard monitoring parameters during two field seasons may to november 2011 and 2012 the ph ranged between 4 3 and 6 8 and carbonate alkalinity was low or undetectable 35 mg l 1 caco3 the ph was governed by the oxidation of sulfide minerals and the dissolution of primary carbonate minerals and secondary al and fe oxyhydroxysulfates and hydroxides dissolved al and fe concentrations averaged 6 78 mg l 1 and 175 g l 1 respectively the main processes controlling zn concentrations in the range of 0 4 and 4 7 mg l 1 average 2 2 mg l 1 were the oxidative dissolution of sphalerite zns and the attenuation by secondary fe and al hydroxides zinc isotopes were fractionated mass dependently zinc isotope ratios ranging between 0 16 and 0 18 average 0 05 n 43 were consistent with values reported for sphalerite from other deposits the deviations in isotope ratios 0 36 were significant in comparison to analytical uncertainties 0 06 zinc isotope ratios and concentrations were largely uncorrelated suggesting that the processes affecting zn mobility had little or no impact on the zn isotope signature these data suggest that the zn isotope ratios of the waste rock leachate may be used as a fingerprint to track anthropogenic mine derived zn sources in an environment under fluctuating ph temperature and ionic strength

tsunami waveform inversion for sea surface displacement following the 2011 tohoku earthquake importance of dispersion and source kinematics this paper considers the importance of model parameterization including dispersion source kinematics and source discretization in tsunami source inversion we implement single and multiple time window methods for dispersive and nondispersive wave propagation to estimate source models for the tsunami generated by the 2011 tohoku oki earthquake our source model is described by sea surface displacement instead of fault slip since sea surface displacement accounts for various tsunami generation mechanisms in addition to fault slip the results show that tsunami source models can strongly depend on such model choices particularly when high quality open ocean tsunami waveform data are available we carry out several synthetic inversion tests to validate the method and assess the impact of parameterization including dispersion and variable rupture velocity in data predictions on the inversion results although each of these effects has been considered separately in previous studies we show that it is important to consider them together in order to obtain more meaningful inversion results our results suggest that the discretization of the source the use of dispersive waves and accounting for source kinematics are all important factors in tsunami source inversion of large events such as the tohoku oki earthquake particularly when an extensive set of high quality tsunami waveform recordings are available for the tohoku event a dispersive model with variable rupture velocity results in a profound improvement in waveform fits that justify the higher source complexity and provide a more realistic source model

the isotopic composition of some common forms of anthropogenic zinc abstract anthropogenic sources account for much of the zinc zn in the environment constraining the isotopic composition of anthropogenic zn is therefore essential to understanding the environmental biogeochemical cycling of zn isotopes this study examines the isotopic variability in several different categories of anthropogenic zn pure zn metal and zn dust are the raw materials used in many zn containing products we have measured 66 zn for zn dust purified by thermal distillation electrochemically purified zn metal and us pennies which are made from the most common grade of zn metal special high grade zn in galvanized steel and electroplated hardware was studied because this is a common use of zn and zn in these products may be easily released into the environment through corrosion vitamins were studied because they are more highly purified than typical zn metals and are made from processed chemical compounds such as zn oxide or zn gluconate the isotopic composition of samples measured in this study are as follows reported as 66 zn compared to lyon jmc zn laboratory standards seven samples 9 15 to 0 17 zn metal dust purified by thermal distillation three samples 0 09 to 0 19 zn metal shot purified by electrochemically one sample 0 22 special high grade zn as represented in us pennies six samples 0 14 to 0 31 galvanized steel three samples 0 12 to 0 58 electroplated hardware three samples 0 56 to 0 20 and health products five samples 0 09 to 0 24 based on these results we suggest that the isotopic composition of common anthropogenic zn products ranges from 0 1 to 0 3 all samples studied here had 66 zn values within this range except four laboratory standards all electroplated hardware samples and a single galvanized steel sample the isotopic range for common anthropogenic zn is much smaller than the total 66 zn range found in zn ore field hydrothermal samples demonstrating the effects of zn isotope homogenization during ore processing and purification laboratory standards may have anomalously light 66 zn values because they undergo extra purification steps and zn recovery during these steps is not quantitative electroplated hardware was also isotopically light consistent with previous studies showing that lighter isotopes are electroplated more quickly than heavy isotopes our results suggest that isotopically heavy zn may be incorporated into the waste stream during the electroplating process by defining the range of 66 zn values that is typical for some common zn products and discovering some kinds of products that fall outside this range we will be better able to use zn isotopes to trace different anthropogenic zn sources

tumbling effects on bone surface modifications bsm an experimental application on archaeological deposits from the barranc de la boella site tarragona spain abstract tumbling is defined as a process in which hyper concentrated flows alter bone remains producing changes in their morphology and original structure although the process is well known little experimental research has focused on describing the effects this process has on bone surface modifications bsm which can subsequently be applied to the fossil record water currents may have played an important role in altering the surfaces of bones from barranc de la boella which were deposited in a deltaic fan context striae of undetermined origin have been documented on bones at the la mina locality and possible cut marks found on bones at pit 1 locality in our experiments both fresh and dry bones with reproduced trampling striae and cut marks were tumbled in a tumbling machine combining different types of movement and proportions of water to sediment the bones were examined after each of the five cycles of the modification process which lasted 30 30 1 h 2 h and 4 h our results show a considerable diminishing of trampling striae while the majority of cut marks were preserved the marks on fresh bones were more severely altered than those on dry bones based on the results of this experiment the marks from pit 1 appear to be morphologically close to the experimentally altered cut marks while the majority of those from la mina are more similar to the altered trampling striae

a new method for the quantitative analysis of cutmark micromorphology abstract cutmarks found on the fossilised bones of butchered animals provide direct evidence for the procurement of meat through technological means as such they hold some of the oldest available information on cognitive ability and behaviour in human evolution here we present a new method that allows a three dimensional reconstruction of cutmark morphology and the quantification of profile parameters we have tested this new technique on cutmarks that were experimentally inflicted on a pig rib using a steel knife and an un retouched flint flake at different angles the method allows for the cross sectional shape the sharpness and depths of the resulting cutmarks to be quantified the data show that knife mark sections are characterised by a v shape or shape depending on the inclination of the knife cutmarks produced with the flint flake were less clearly defined and generally less sharp than those produced by the knife we discuss the method s potential to provide new information on butchery technique and cognitive abilities developed by the human lineage from the earliest tool using hominins through to modern homo sapiens

taphonomy of palaeloxodon antiquus at castel di guido rome italy proboscidean carcass exploitation in the lower palaeolithic field investigations at castel di guido revealed a middle pleistocene open air site containing macrofaunal remains associated with acheulean industry the large majority of the remains lay at the bottom of a depressed area which probably evolved into a low energy freshwater basin after the deposition of the assemblage to quantify the importance of the natural processes compared to the anthropogenic ones in the formation of the site a full taphonomic analysis of the macromammal assemblage was carried out a geoarchaelogical study together with a taphonomic analysis of the lithic and bone implements is ongoing this paper discusses the results of the study of elephant bones the taphonomic analysis has documented traces of different modifying agents on the specimens indicating the important role of syn and post depositional factors in the accumulation and modification of bones nevertheless evidence of utilization of carcasses for subsistence and for tool production was detected the study provides new data for the exploitation of elephants by hominins during the lower palaeolithic

zinc isotope and transition element dynamics accompanying hydrozincite biomineralization in the rio naracauli sardinia italy abstract the rio naracauli in sw sardinia drains part of the ingurtosu zn pb mining district and contains extreme concentrations of dissolved zn at near neutral ph in the upper reaches of the stream ph alkalinity and zn concentrations are such that hydrozincite zn 5 co 3 2 oh 6 precipitates in a biologically mediated process facilitated by a microalga chlorella sp and a cyanobacterium scytonema sp values of 66 zn in water and solid samples ranged from 0 35 to 0 5 relative to the jmc 3 0749 lyon standard and closely follow a mass dependent fractionation line two composite samples of sphalerite the primary ore mineral in the ingurtosu deposits had an average 66 zn of 0 15 similar to sphalerite measured elsewhere in hydrothermal mineral deposits zinc isotope measurements of the stream water and the hydrozincite forming in the stream show a consistent preference for the heavy isotope 66 zn in the hydrozincite relative to 64 zn synthetic hydrozincites produced without added bacteria have 66 zn identical to the dissolved zn thus suggesting a biologically mediated mineralization process in rio naracauli the average fractionation hdz water is 0 35 the magnitude of which is consistent with other studies and suggests an extracellular mechanism of the biomineralization process zinc concentration and dissolved 66 zn steadily decrease in the reach of the stream where the biomineralization occurs the biomineralization process also leads to the sequestration of pb cu and ni in the hydrozincite lattice and the coeval precipitation of an amorphous cdco 3 solid prompting the suggestion that if optimized the biomineralization process might represent a feasible passive remediation strategy for streams with high zn and other metals and with near neutral ph

the behaviour of cu and zn isotopes during soil development controls on the dissolved load of rivers abstract the stable isotopes of copper cu and zinc zn are finding increasing applications in surface earth geochemistry an important early observation is that aqueous pools of cu rivers and oceans are isotopically heavier than rocks of the continental crust for zn the global average 66 zn for rivers is identical to estimates of the upper continental crust but the oceans are slightly heavier here we study cu and zn abundances and isotopes in soils to assess how processes in the weathering environment control isotopic values of rivers and ultimately the oceans we investigated a range of soils developed on granitoid scotland and basaltic hawaiian islands rock substrates representing soil development times from 0 1 to 400 kyr mean annual temperatures of 6 16 c and mean annual precipitation map of 1060 5050 mm soils developed on the island of maui over 400 kyr and under high rainfall show the clearest chemical weathering signatures here in oxic soils cu and zn are both depleted by 50 90 with preferential loss of heavy cu 65 cu up to 1 2 lower than parent material and small shifts in 66 zn we attribute this to equilibrium fractionation between aqueous organic species that are removed from the soil versus sorption to residual fe oxyhydroxides in soils that are 0 1 150 kyr old in scotland and hawaii this same pattern is overprinted by biological cycling and the addition of mineral aerosol cu and zn with heavier isotope compositions in reducing soils on maui developed under the highest rainfall cu and zn are almost completely stripped from the soil leaving a very small residual pool with 65 cu and 66 zn values that range from those for the oxic soils back to and beyond parent material this removal of the light sorbed cu seen in oxic soils is attributed to the dissolution of fe oxides under anaerobic conditions perhaps microbially mediated leaving a very small residual isotopically heavier pool overall these data suggest that processes in soils create significant variability in cu isotopes with the heavy isotope exported from oxic soils in contrast small isotope fractionations of zn are generated in the soil environment these observations are consistent with those made previously for cu and zn isotopes in rivers but the maximum amount of cu and zn stored by world soils equates to only 30 130 years of the dissolved riverine flux soils cannot be the ultimate repository of the residual cu and zn required balancing the riverine flux and this must ultimately reside in the erosive products of soil formation in continental and ocean margin sediments

zinc isotope variation in hydrothermal systems preliminary evidence from the irish midlands ore field little is known about the range or controls on the zinc isotope composition of terrestrial materials and no systematic studies have been carried out on ore forming systems we have obtained zinc isotope data from 19 sphalerite samples formed over a range of well constrained precipitation conditions from the irish zn pb ore field the results reveal variation in 66zn where 66zn 66zn 64zn sample 66zn 64zn standard 1 1000 from 0 17 to 1 33 per mil relative to the lyon jmc 3 0749l zinc standard this variation is significant compared to the external reproducibility 0 12 2 and the data show very good mass dependency with 67zn and 68zn values thus natural variations in the zinc isotope composition of these ore minerals can be resolved our results span the entire range of 66zn values measured on terrestrial geologic samples to date the data suggest that variations in the primary source rock composition or precipitation temperature are unlikely to be important controls on the zinc isotope composition of sphalerite in the ore field we suggest that the variation is most likely due to a kinetic fractionation involving the preferential incorporation of light zinc isotopes in sphalerite precipitated rapidly under disequilibrium conditions however we cannot rule out the possibility of mixing of zinc derived from two isotopically distinct sources the significant variation in zinc isotope compositions we have observed in the irish ore field confirms that such fractionations can provide new insights into mineralizing processes in the earth s crust

nickel isotope fractionation during laterite ni ore smelting and refining implications for tracing the sources of ni in smelter affected soils abstract nickel isotope ratios were measured in ores fly ash slags and feni samples from two metallurgical plants located in the goias state brazil barro alto niquel ndia this allowed investigating the mass dependent fractionation of ni isotopes during the ni laterite ore smelting and refining feeding material exhibits a large range of 60 ni values from 0 02 0 10 to 0 20 0 05 n 7 explained by the diversity of ni bearing phases and the average of 60 ni feeding materials was found equal to 0 08 0 08 2sd n 7 both 60 ni values of fly ash 60 ni 0 07 0 07 n 10 and final feni produced 0 05 0 02 n 2 were not significantly different from the feeding materials ones these values are consistent with the very high production yield of the factories however smelting slags present the heaviest 60 ni values of all the smelter samples with 60 ni ranging from 0 11 0 05 to 0 27 0 05 n 8 soils were also collected near and far from the niquel ndia metallurgical plant to evaluate the potential of ni isotopes for tracing the natural vs anthropogenic ni in soils the ni isotopic composition of the non impacted topsoils developed on ultramafic rocks ranges from 0 26 0 09 to 0 04 0 05 n 20 on the contrary the ni isotopic composition of the non ultramafic topsoils collected close to the plant exhibit a large variation of 60 ni ranging from 0 19 0 13 up to 0 10 0 05 n 4 this slight but significant enrichment in heavy isotopes highlights the potential impact of smelting activity in the surrounding area as well as the potential of ni isotopes for discerning anthropogenic samples heavier 60 ni values from natural ones lighter 60 ni values however given the global range of published 60 ni values from 1 03 to 2 5 and more particularly those associated to natural weathering of ultramafic rocks from 0 61 to 0 32 the use of ni isotopes for tracing environmental contamination from smelters will remain challenging

cutmarks made by stone tools on bones from olduvai gorge tanzania fossils from olduvai gorge tanzania show cutmarks which establish that hominids were using stone tools on animal tissues during the lower pleistocene in africa we identified cutmarks by elimination of other likely causes of the marks on the bone surfaces for example gnawing or chewing by carnivores or rodents and damage made by tools of excavators or preparators this was achieved by comparing the marks on the fossils with those produced by known causes on modern bones using scanning electron microscopy sem because the fossils occur as part of accumulations of animal remains in relatively undisturbed geological contexts we conclude that there is a functional association between the stone artefacts and bones at these sites rather than an accidental postmortem association1 2

determining provenance of marine metal pollution in french bivalves using cd zn and pb isotopes abstract cadmium zn and pb isotopic compositions mc icp ms and elemental concentrations hr icp ms have been used to distinguish between natural and anthropogenic sources of these metals in bivalves collected from the coastlines of france english channel atlantic and mediterranean coasts the cd isotopic signatures 114cd 1 08 to 0 52 exhibited by bivalves from the coastlines of france excluding those from ne france are within the range of those exhibited by bivalves from the usa east coast 114cd 1 20 to 0 54 this indicates the high prevalence of industry as well as the low natural contributions of cd from north atlantic waters in both regions thus the significance of anthropogenic cd sources is similar these significant anthropogenic contributions are identified for bivalves with a large range in tissue cd concentrations importantly french bivalves from the gironde estuary and marennes oleron basin regions of historic and modern importance for oyster farming respectively exhibited the highest cd levels of the study their cd isotopic signatures indicate historical smelting emissions remain the primary cd source despite the cessation of local smelting activities in 1986 and subsequent remedial efforts no significant variability is observed in the 66zn values of the french bivalves 0 53 with the exception of the much heavier compositions exhibited by oysters from the polluted gironde estuary 1 19 1 27 lead isotopes do not fractionate during processing like cd and zn they can therefore be used to identify emissions from industrial processes and the consumption of unleaded gasoline and diesel fuel as metal sources to french bivalves cadmium and zn isotopes are successfully used here as tracers of anthropogenic processing emissions and are combined with pb isotope fingerprinting techniques to identify metal sources

zn isotopes as tracers of anthropogenic pollution from zn ore smelters the riou mort lot river system article i nfo zn values up to 1 49 zn extraction yields for these samples were calculated using presumable conservative elements fe ca mg k na and mn and vary from 95 4 to 99 4 extraction yields are related to the intensity of zn isotopic fractionation different rayleigh isotope fractionation scenarios for zn refining yielded ore tailings ranging from 1 00012 to 1 00062 the 66 zn of the riou mort sediments downstream from

lead concentrations and isotope ratios in speleothems as proxies for atmospheric metal pollution since the industrial revolution abstract lead concentrations and isotope ratios from two speleothems from the han sur lesse cave in southern belgium were measured in order to study the ability of speleothems to act as archives of atmospheric pollution to address this aim we analyzed trace elemental al and pb compositions by la icp ms and icp ms as well as pb isotopes by mc icp ms the results help to identify three intervals characterized by particularly high enrichment of pb from 1880 to 1905 ad from 1945 to 1965 ad and from 1975 to 1990 ad the speleothem record shows similar changes as the known historical atmospheric pollution level in belgium lead isotope ratios discriminate between pb sources and confirm that coal and gasoline combustion combined with regional metallurgical activities were the predominant pb pollution sources in the stalagmites during the last 250 years this study opens possibilities to determine anthropogenic versus natural metal sources in well dated speleothem archives

use of isotope ratios to assess sources of pb and zn dispersed in the environment during mining and ore processing within the orlovka spokoinoe mining site russia element concentrations element ratios and pb and zn isotope data are reported for different geologic samples barren and ore bearing granites and host rocks technogenic products ore concentrates and tailings and biologic samples lichens and birch leaves from the orlovka spokoinoe mining district eastern transbaikalia russia with the aim to trace the sources of pb and zn at a local level within the mining site lichens and birch leaves were used as receptors of contamination within the mining site pb zr and zn zr values indicated pb and zn enrichment relative to host rocks zn isotope data of 15 geologic and 11 lichen samples showed different zn isotopic signatures with the total range for the geologic suite of 0 4 to 1 2 and for lichens of 0 4 to 1 4 in 66zn relative to lyon jmc zn standard the source of isotopically heavy zn within the orlovka spokoinoe mining site could be potentially associated with long range atmospheric aerosols that also contributed pb to the studied mining site our results demonstrated that zn isotopes might be used as new tools for zn source assessment

new taphonomic data of the 1 myr hominin butchery at untermassfeld thuringia germany abstract untermassfeld has provided a butchered bone assemblage and a mode 1 lithic record demonstrating hominin presence at a site which was classically viewed as paleontological this archaeological record was found during fieldwork and surveying in fluvial river banks and low to medium energy channel erosion sediments paleomagnetism and biostratigraphy has yielded an age for this hominin occupation close to the onset of the jaramillo subchron ca 1 07 myr in this paper we present new taphonomic data of the cut marked and hammer related bone material corresponding mainly to large sized herd species i e bison but also from cervids eucladoceros giulii and cervus s l nestii vallonnetensis and megafaunal species i e stephanorhinus hundsheimensis and hippopotamus amphibius antiquus distribution of skeletal elements and bone surface features suggests that this bone assemblage consists of animal remains with different taphonomic origins the assemblage formed during at most two or three sediment laden floods transporting both lithic tools and remains of animals that died of natural causes or were killed by predators the new taphonomic results presented here are important to analyze hominin colonization and adaptation to european mid latitude environments at 1 myr in competition for meat resources with large carnivores i e pachycrocuta brevirostris and panthera onca gombaszoegensis

cut marks and raw material exploitation in the lower pleistocene site of bell s korongo bk olduvai gorge tanzania a geometric morphometric analysis the lower pleistocene site of bell s korongo bk in olduvai gorge tanzania has been a key site for the study of the origin of human behaviour the lower archaeological levels of bk are characterized by anthropogenic activity related to the exploitation of megafauna elephant hippopotamus sivatherium and smaller game zebra wildebeest and antelopes these remains display a high frequency of cut marks the exceptional state of preservation of the bk fossil assemblage has allowed a wide range of different analyses that among other things detected the use of quartzite in butchering activities through the study of cut marks following up previous analyses this paper presents the study of a series of cut marks from the bk faunal assemblage using a 3d geometric morphometric methodological approach in order to determine the mineralogical properties of the quartzite used at the site bk cut marks are compared with experimentally produced cut marks using 9 mineralogically different quartzite types from olduvai gorge this comparative analysis provides valuable hints about the exact nature of the raw materials used in butchering activities the results presented here identify a preferential use of quartzite with a finer granular composition suggesting that hominin populations were already selecting the best raw materials for their use in specific activities 1 3 mya