Sedimentology (2004) 51, 885897

doi: 10.1111/j.1365-3091.2004.00656.x

Scale and timing of Rare Earth Element redistribution in the Taconian foreland of New England
BARBARA BOCK 1 , J. A. HUROWITZ, S. M. MCLENNAN and G. N. HANSON Department of Geosciences, ESS Building, State University of New York at Stony Brook, Stony Brook, NY, 11794-2100, USA
ABSTRACT

Clastic sedimentary rocks, deposited on eastern North America in response to the Taconian Orogeny, commonly have Sm/Nd isotope relationships indicating substantial isotope disturbance near or subsequent to the time of sedimentation that may be associated with severe depletion in light rare earth elements (LREE). Affected units [Normanskill Formation (Austin Glen and Pawlet Members), Frankfort Formation and Perry Mountain Formation] are widely separated both geographically (western New York to western Maine) and stratigraphically (Middle Ordovician to Silurian). A model is proposed for the most likely explanation of the observed REE and Sm/Nd isotope relationships involving a two-stage process. In the rst stage, REE are redistributed on a mineralogical scale (dissolution/precipitation on a sample scale) often with the involvement of REE-enriched trace phases such as apatite and monazite. This stage typically takes place during diagenesis but may also take place later during metamorphism and/or recent weathering, and results in isotope re-equilibration on a sample scale. The second stage occurs when one or more of these phases is redissolved and REE are transported on large advective scales. Where LREE-enriched phases are involved, this gives rise to LREE depletion in whole rocks. The timing of this second stage cannot be constrained from Sm/Nd isotope data and may take place at any time subsequent to the isotope re-equilibration. Such complex histories of REE redistribution may result in serious errors in estimating Nd model ages but not in estimating the Nd isotope composition at the age of sedimentation. Thus, Sm/Nd ratios even of unmetamorphosed sedimentary rocks have to be carefully evaluated before the calculation of depleted mantle model ages for the provenance. Keywords Nd isotope resetting, provenance, Rare Earth Element redistribution, Taconian Orogeny, USA. INTRODUCTION Rare earth elements (REEs) are generally thought to be immobile during weathering, transport and sedimentation (e.g. McLennan, 1989). Although redistribution of REEs on a mineralogical scale is to be expected where recrystallization has taken place during diagenesis or metamorphism (Ohr
1

Present address: IFM-Geomar, Leibniz-Institut fu r Meereswissenschaften, Dienstgeba ude Ostufer, Wischhofstr. 13, 24148 Kiel, Germany (E-mail: bbock@geomar.de)

et al., 1991), some studies have also demonstrated REE transport on a much larger scale. Fractionation of the REE has been attributed to diagenesis and/or early metamorphism (McLennan & Taylor, 1979; Milodowski & Zalasiewicz, 1991; Ohr et al., 1991; Bock et al., 1994) as well as to weathering (Nesbitt, 1979; Baneld & Eggleton, 1989; McDaniel et al., 1994; Hannigan & Sholkovitz, 2001). In some cases, this fractionation clearly leads to a substantial disturbance of the Sm-Nd isotope system (Zhao et al., 1992; Bock et al., 1994, 1996; McDaniel et al., 1994; Lev et al., 1998, 1999). 885

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B. Bock et al. carbonate platform along the east coast of Laurentia. As a result of thrust loading and bending of the continental margin, the carbonate platform of the passive margin (Trenton Group; Fig. 1) was overstepped from the east rst by deeper water shales, which are themselves overstepped by a ysch sequence. This overstepping occurred diachronously in space and time. Therefore, the ysch deposited to the east (Austin Glen Member of the Normanskill Formation) is older than the ysch deposited further west (Schenectady and Frankfort Formation) in the foreland basin (Rowley & Kidd, 1981; Stanley & Ratcliffe, 1985; Bradley, 1989). In the studies by Bock et al. (1994, 1998) and Hurowitz (2001) of the Austin Glen and the Pawlet Members, the uppermost units of the Normanskill Formation were analysed (Fig. 1). Both the Austin Glen and the Pawlet Members are thought to be derived from sources to the east (Rowley & Kidd, 1981). As shown in Fig. 2, samples of the Austin Glen and Pawlet Members were collected from southern and northern New York State, respectively, so it is difcult to establish the relative stratigraphic positions of the samples. The Austin Glen and Pawlet Members are sedimentologically indistinguishable from one another and, for the purpose of this study, both members will be considered to be about 465 Ma (graptolite zone Nematograptus gracilis according to Riva, 1974). The Late Ordovician (Ashgill, c. 440 Ma) Frankfort Formation, analysed in a study by Andersen & Samson (1995), was also derived from easterly sources and deposited in western New York State (Fig. 2). The Frankfort Formation is autochthonous but sedimentologically indistinguishable from the allochthonous ysch (Rowley & Kidd, 1981). The Rangeley and Perry Mountain Formations are part of the Silurian clastic wedge, which was deposited on top of a thick Late Ordovician clastic sequence in the Merrimack Synclinorium (Osberg et al., 1968; Moench, 1971). The REE and Nd isotope data of these formations were published by Cullers et al. (1997). The Early Silurian Rangeley Formation is considered to be a yschtype deposit. The Perry Mountain Formation is more uniform than the Rangeley Formation and is supposedly more reworked than the former. Both formations are interpreted as being derived from the Taconian highlands in the west, so that they may have a provenance similar to that of the older rocks deposited in the Taconian foreland basin (Osberg et al., 1989).

The Middle Ordovician Taconian Orogeny affected much of the New England region of North America. During the Middle Ordovician to Silurian, clastic sedimentary rocks were derived from the Taconian Orogen and deposited in the foreland on eastern North America. In this paper, the results of several regional REE and Nd isotope studies are reviewed to show that the redistribution of REE appears to be a widespread process (geographically and stratigraphically) within the Taconian foreland. The data that are reviewed and discussed in this paper were published by Bock et al. (1994, 1998; Austin Glen Member), Andersen & Samson (1995; Frankfort Formation), Cullers et al. (1997; Rangeley and Perry Mountain Formation) and Hurowitz (2001; Pawlet Member). In addition, new data are presented from one hand specimen of a late Middle Ordovician greywacke from the Normanskill Formation that shows an extreme example of small-scale REE redistribution. It is the purpose of this paper to demonstrate that: (1) rare earth redistribution and disturbance of the Sm/Nd isotope system was widespread, both geographically (from Maine to New York State) and stratigraphically (from the Ordovician to the Silurian, about 40 million years), within the sedimentary successions of the Taconian foreland; (2) - substantial Sm/Nd isotope re-equilibration at a mineralogical scale is likely to have occurred typically near the time of sedimentation; and (3) open-system transport of REE, occurring on greater than whole rock scale, affected these rocks. Such multiple and complex REE redistribution histories may be difcult to unravel in detail, but a schematic model shows how these processes may occur and the consequences for the calculation of mantle model ages. The calculation of eNd at the time of sedimentation will allow the evaluation of the presence or absence of Nd isotope re-equilibration events. Systematic variations in the Sm/Nd ratios with depleted model ages are an indicator of disturbances on large scales (larger than sample size). If such events go unrecognized, the undifferentiated use of Nd isotopes will lead to aberrant mantle model ages and possibly incorrect provenance inferences.

GEOLOGICAL BACKGROUND The Taconian Orogeny (Middle to Late Ordovician) caused increased subsidence and drowning of the Cambrian to Early Ordovician stable

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Fig. 1. Stratigraphic relations of the Normanskill, Frankfort, Rangeley and Perry Mountain Formations (modied from Rowley & Kidd, 1981).

METHODS Most of the REE abundances and Nd isotope data discussed in this paper were collected in the isotope laboratory at SUNY Stony Brook and are therefore of comparable quality. Samples from Bock et al. (1994, 1998) and the previously unpublished data from the hand specimen of the Normanskill Formation were analysed by TIMS for REE abundances and Nd isotopes. For details on sample preparation, see the original publications. The total analytical uncertainties on the REE abundances are < 1%, and the uncertainty on eNd is better than 03 at the 2 r level. Sm and Nd concentrations and Nd isotope measurements on the Rangeley and Perry Mountain Formation published by Cullers et al. (1997) were also performed in the isotope laboratory at SUNY Stony Brook. Therefore, the methods and errors are the same as the ones stated above. The error quoted by Andersen & Samson (1995) on their Nd isotope measurements is 03 e at the 2 r level. All 143Nd/144Nd ratios were normalized to 146 Nd/144Nd 07219, and those analysed in the isotope laboratory of SUNY Stony Brook (all data

except those from Andersen & Samson, 1995) were corrected to correspond to a 143Nd/144Nd ratio of 0511865 for the La Jolla Nd-Standard. eNd (the deviation of the Nd isotopes relative to the chondritic uniform reservoir) is calculated as ( 143Nd/ 144Nd sample / 143 Nd/ 144 Nd Chur ) 1)*10 000 with 143 Nd/ 144 Nd Chur 0 512638; T DM (the depleted mantle model age) is calculated as 1/ k* ln[( 143Nd / 144 Nd sample ) 0 51315)/(147 Sm / 144 Nd sample ) 0 217) + 1].

REE REDISTRIBUTION AND ITS EFFECTS ON Nd ISOTOPES REE patterns and Sm/Nd isotope data are widely used in clastic sedimentary rocks as a provenance indicator because REE are generally regarded as the least mobile elements during sedimentary processes. Although this is generally the case, recent studies have demonstrated that, under certain conditions of weathering, diagenesis and perhaps low-grade metamorphism, REEs may be mobilized on mineralogical and/or advective scales from REE-rich trace

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Fig. 2. Modied map (after Bradley, 1989) showing the approximate sample locations. (1) Rangeley and Perry Mountain Formations from Cullers et al. (1997). (2) Frankfort Formation from Andersen & Samson (1995). (3) Pawlet Member from Hurowitz (2001). (4) Austin Glen Member from Bock et al. (1994, 1998). (5) Hand specimen from the Normanskill Formation.

phases, organic matter, clay minerals and labile rock fragments (McLennan & Taylor, 1979; Eldereld et al., 1981; Eldereld & Sholkovitz, 1987; Baneld & Eggleton, 1989; German & Eldereld, 1989; Milodowski & Hurst, 1989; Leventhal, 1990; Milodowski & Zalasiewicz, 1991; Murray et al., 1991, 1992; Ohr et al., 1991, 1994; Zhao et al., 1992; McLennan et al., 1993; Bock et al., 1994; McDaniel et al., 1994; Rasmussen & Glover, 1994; Bouch et al., 1995; Sturesson, 1995; Cullers et al., 1997; Lev et al., 1998, 1999; Kidder et al., 2003). A common feature among most studies is that REE redistributions are strongly controlled by dissolution and/or reprecipitation of phosphatic trace minerals (apatite, monazite, orencite and rhabdophane) and petrogenetically related diagenetic minerals (e.g. calcite). The most detailed studies of mineralogical scale redistribution of REE and Sm/Nd isotopes are those by Ohr et al. (1991) and Lev et al. (1998,

1999). In these studies, there is strong evidence of REE redistribution on a mineralogical scale as a result of reactions among organic matter, clay minerals, apatite, calcite and REE-enriched phosphatic minerals (monazite, rhabdophane, orencite). In the areas studied by Ohr et al. (1991, 1994), the geochemical system was thought to be essentially closed on a whole rock scale because of reduction of pore space and uid volumes with increasing depth. However, a number of other studies (Bock et al., 1994, 1996; McDaniel et al., 1994; Cullers et al., 1997; Lev et al., 1998, 1999) have demonstrated nearly contemporaneous (or subsequent) transport of REE, leading to partial resetting of the Sm/Nd isotope system on greater than whole rock scale. In each of these cases, mass balance of REE strongly suggested the redistribution of trace phosphatic phases as the cause of the isotopic disturbance. In the case of Lev et al. (1998), the inferences from mass balance were conrmed by petrographic

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REE redistribution in the Taconian foreland identication of diagenetic reactions involving apatite and monazite.

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Austin Glen and Pawlet Members

Combined REE and Sm/Nd isotope data for the Austin Glen Member have been published by Bock et al. (1994, 1998). Many of the samples show substantial LREE depletion with 147 Sm/144Nd ratios commonly being > 013, which compares with ratios of 0105012 for most clastic sedimentary rocks (McLennan & Hemming, 1992) and the remainder of the Austin Glen. Sm/Nd isotope data calculated at the time of sedimentation (about 465 Ma) provide uniform eNd values of )80 06 (n 23), indicating an old age of mantle extraction,  18 Ga (Bock et al., 1994). However, when data are plotted on a Sm-Nd evolution diagram (Fig. 3), they scatter about a 465 Ma reference line, and the trend is distinct from a 18 Ga or any signicantly older reference line. Samples taken from a single 70 m stratigraphic section are especially coherent in Fig. 3, and a regression of these data (solid line in Fig. 3) provides an age of 547 76 Ma, which is only slightly older than the sedimentation age

(about 465 Ma) and indicates a substantial degree of disturbance of the Sm/Nd isotope system. The Pawlet Member samples display a range of 147 Sm/144Nd from 00985 to 01390 (Hurowitz, 2001). Values for eNd calculated at 465 Ma range from )82 to )97 (n 8). The model age calculated for one sample with a normal 147Sm/144Nd ratio (01089) is 18 Ga, consistent with results for undisturbed samples from the Austin Glen Member (Bock et al., 1994). The remaining Pawlet Member samples dene a range in TDM from 17 to 24 Ga. A regression through the data from the Pawlet Member (Fig. 4) yields an age of 493 240 Ma (with the exception of one anomalous sample), indicating Sm-Nd isotopic disturbance at around the time of sedimentation. The anomalous Pawlet Member sample (Fig. 4) has most probably undergone a later, or more protracted, diagenetic disturbance, such that the age of Nd isotopic resetting is considerably younger than the sedimentation age. Such a diagenetic history would also explain the low eNd of this sample when calculated back to the time of sedimentation ()97 at 465 Ma). Bock et al. (1994) demonstrated with mass balance calculations that the LREE-depleted character of Austin Glen Member samples was inconsistent with removal of a detrital phase or mixing of an unusual provenance component. Instead, a two-stage process best explains the Sm/Nd isotope systematics shown in Figs 3 (Austin Glen

Fig. 3. Sm-Nd isochron diagram for sediments from the Austin Glen Member (data from Bock et al., 1994, 1998). The solid line is a regression of samples from a single stratigraphic section that gives an age of 547 76 Ma. Dashed lines are reference isochrons of 1800 and 465 Ma, designed to intersect the isochron at 147 Sm/144Nd of about 0115, a 147Sm/144Nd ratio typical of average shale. Note that the regional samples, which are more poorly stratigraphically constrained, have greater scatter with most scatter from a single location near Wappinger Falls.

Fig. 4. Sm-Nd isochron diagram for sediments from the Pawlet Member (Hurowitz, 2001). The solid line is a regression of samples that gives an age of 493 240 Ma. The dashed line is a reference isochron of 1800 Ma, designed to intersect the regression line at 147 Sm/144Nd of about 0115.

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Member) and 4 (Pawlet Member). In the rst stage, the Sm/Nd isotope system is essentially reequilibrated on an unknown scale. No observable mineralogical relationships are preserved in these samples that indicate the exact character of this re-equilibration event. However, other studies of REE redistribution in clastic sedimentary rocks (e.g. Milodowski & Zalasiewicz, 1991; Ohr et al., 1994; Evans & Zalasiewicz, 1996; Lev et al., 1998, 1999) have pointed to the breakdown of various relatively labile provenance components, such as volcanic glass, organic matter, Fe-Mn oxyhydroxides and so forth, to form clay minerals and various trace phosphatic phases (such as apatite, monazite, rhabdophane, orencite) during diagenesis and/or very early metamorphism. The second stage of this process involves loss of an LREE-enriched component that leads to the dramatic increase in whole rock Sm/Nd ratios. These samples show no evidence of substantial change in geochemical composition apart from REE patterns (Bock et al., 1994, 1998). This led Bock et al. (1994) to suggest that loss of an LREEenriched trace phase was probably the major cause of changing Sm/Nd ratios, and this is consistent with other studies of similar rocks (Milodowski & Zalasiewicz, 1991; Evans & Zalasiewicz, 1996; Lev et al., 1998, 1999). This second stage may occur essentially contemporaneously with the rst stage or may post-date it by some time. The fact that the data align so closely to the age of sedimentation does not necessarily imply that the loss of LREE must have occurred very close to the time of sedimentation, but only that the isotopic re-equilibration took place at that time. This is discussed further below.

Fig. 5. Sm-Nd isochron diagram for sedimentary rocks and leachates from the Frankfort Formation (data from Andersen & Samson, 1995). The solid line is a regression of whole rock/leachate/residue for sample OC-4, which gives an age of 450 40 Ma. Note that a regression of the whole rock data would give rise to a younger, but statistically indistinguishable, age.

Frankfort Formation
Sm/Nd isotope systematics of the Frankfort Formation in western New York State were investigated by Andersen & Samson (1995) as part of a regional provenance study of Taconian sedimentary rocks. The Frankfort Formation lies far to the west of the Austin Glen Member and is in the order of 20 Ma younger based on graptolite zonations (early Ashgill or about 445440 Ma). Whole rock Sm/Nd ratios display a similar range to those seen in the Austin Glen Member, and Sm/Nd isotope data align along a slope that approximates the age of sedimentation, indicating that the Sm/ Nd isotope system has been strongly disturbed (Fig. 5). REE mobility was not an issue in this study and, to avoid any complications related to REE disturbance, the authors reported only eNd

values at the time of sedimentation eNd (T) and no TDM values, which may be severely affected. Andersen & Samson (1995) conducted a leaching experiment on one sample, and isotope results are shown in Fig. 5. The Sm/Nd systematics of the leach/whole rock/residue set are almost identical to those found by Ohr et al. (1994) for Ordovician shales from Wales, where the leachates reect the presence of early diagenetic apatite. Although complete REE patterns are not available for these rocks, Fig. 6 shows that the process giving rise to variable Sm/Nd ratios is different for the Frankfort Formation than for the Austin Glen/Pawlet Member and the Perry Mtn Formation. In the Austin Glen/Pawlet/Perry Mtn samples, high Sm/Nd ratios correspond to severe depletion of LREE in whole rocks, leading to a negative correlation between Nd concentration and Sm/Nd ratio, which led Bock et al. (1994) to suggest loss of a highly LREE-enriched phase, such as monazite, to be the cause of the change in Sm/Nd ratio for the Austin Glen Member (Fig. 6). In contrast, Sm/Nd ratios in the Frankfort Formation whole rocks vary essentially independently of Nd concentration (Fig. 6). Thus, for the Frankfort Formation, there is no necessity for a strongly LREE-enriched phase to be involved, and the data can be explained by redistribution among various diagenetic phases with generally similar REE concentrations but variable Sm/Nd ratios.

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Fig. 6. Plot of Nd vs. 147Sm/144Nd. Samples from the Austin Glen and Pawlet Member and Perry Mountain Formation form a negative correlation consistent with the change in Sm/Nd ratio being dominated by loss of LREE. In contrast, the Frankfort Formation shows no correlation between Nd abundances and 147Sm/144Nd, suggesting that resetting of the Sm/Nd system is controlled by redistribution of REE without substantial loss of LREE.

Fig. 7. Sm-Nd isochron diagram for metasedimentary rocks from the Silurian Rangeley and Perry Mountain Formations (data from Cullers et al., 1997). Shown for reference are 18 Ga, 420 Ma and 250 Ma reference isochrons designed to intersect at the average Sm/Nd ratio of the three Rangeley Formation samples with lowest Sm/Nd. The Perry Mountain Formation samples are highly scattered with very high Nd model ages that correlate with Sm/Nd ratios, suggesting a complex history of Sm/Nd isotopic redistribution.

The slope of the leachate/whole rock/residue in Fig. 5 is consistent with a mineralogical scale redistribution of REE at about the time of sedimentation (c. 450 Ma). Whole rock data appear to dene a slightly shallower trend than the leachate/residue, but the slopes are statistically indistinguishable. A shallower slope might indicate that the whole rock disturbance took place over an extended period of time, consistent with a late diagenetic resetting of the isotope system.

Perry Mountain Formation

The Silurian Rangeley and Perry Mountain Formations are exposed in western Maine (Fig. 2) and are signicantly younger than the Austin Glen/Pawlet Members or the Frankfort Formation (Fig. 1). They also differ substantially from the Austin Glen/Pawlet Members and the Frankfort Formation in that they were later metamorphosed to garnetstaurolite grade during the Acadian and/or Alleghenian Orogenies. REE and Sm/Nd isotope characteristics were studied by Cullers et al. (1997). The REE data show substantial depletion of the LREE in samples from the Perry Mountain Formation, generally similar to samples of the Austin Glen/Pawlet Members, but far more complex in detail (e.g.

variable Ce and Eu anomalies). Sm/Nd isotope data for the LREE-depleted samples of the Perry Mountain Formation are highly scattered (Fig. 7) but, for the most part, clearly distinct from any reasonable 18 Ga reference line and indicative of substantial isotopic disturbance close to and/or subsequent to the age of sedimentation (c. 420 Ma). Cullers et al. (1997) suggested that these rocks were most probably affected by more than one episode of Sm/Nd disturbance. The most likely times when this may have occurred are during diagenesis (c. 420 Ma), metamorphism (Acadian and perhaps Alleghenian) and perhaps even recent weathering.

Recent REE redistribution in the Normanskill Formation

A sample from the Normanskill Formation displays incipient exfoliationcorestone relationships characteristic of weathering. This weathering appears to be relatively recent, probably occurring since the last glaciation (Pleistocene). The hand specimen has a grey, non-porous, apparently unweathered core of about 10 cm diameter surrounded by an  2 cm wide weathered porous rim (porosity resulting from the loss of 2030% carbonate). The grain size of the sample is

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B. Bock et al. entirely pristine but also underwent signicant post-depositional changes (i.e. carbonate replacement). Minor phases are chlorite, biotite, apatite, zircon and rutile. A few monazite grains 30 10 lm in size were observed in both core and rim.

medium to ne sand (125250 lm) graded across the sample. The hand specimen was cut into about 1 cm thick slices for thin section chips and also to facilitate separating the rim from the core. The core was crushed and then aliquoted for analysis, whereas the rim was sampled according to grain size. A composite as well as pieces of coarse- and ne-grained weathered rim material were analysed for REE abundances. A soft (cold 1 N HCl) leachate of powdered core and its residue were analysed for REE abundances (Table 1). The brownish colour of the weathered rim results from iron coatings that surround quartz grains. The Fe may be derived from ankerite that was observed in the core. The major difference between rim and core is the increased porosity of the rim due to the loss of the abundant carbonate component that is present in the core (2030%) as large twinned single crystals and as smaller grains replacing feldspar. Notable features observed in the core are small rhombs that show high luminescence. These rhombs are surrounded by thin iron-rich, non-luminescent rims and have a very brightly luminescent core that does not have a crystal shape. This relationship may indicate that an earlier dolomite or ankeritic rhomb-shaped crystal was replaced by the carbonate. Accordingly, it is clear that the core is not

Rare earth element abundances Rare earth element and Sm/Nd isotope data for the core and rim of the Normanskill Formation sample are given in Tables 1 and 2. Chondritenormalized REE patterns for three core samples and the rim composite and various grain sizes are shown in Fig. 8a. The main differences between the patterns are the 7% higher Sm-Nd ratio of the weathered rim and the negative Ce anomaly of the core. The rim samples (Table 1) differ in absolute abundances, but the shapes of the patterns are similar and none shows negative Ce anomalies. In Fig. 8b, the rim composite and the results from the 10 N HCl leaching experiment are shown. Samples plotted in Fig. 8b are normalized to the average core composition, so the positive Ce anomalies are artifacts of the negative Ce anomaly present in the core (Fig. 8a), but the core leachate has a chondrite-normalized negative Ce anomaly (Ce/Ce* 075). The difference in REE patterns between core and rim results largely from the loss of a soluble middle REE-enriched phase(s) with

Table 1. REE abundances (p.p.m.) of a hand specimen from the Normanskill Formation. Core La Ce Nd Sm Eu Gd Dy Er Yb Sum Sm/Nd Ce/Ce* Eu/Eu* 2351 3767 2567 563 127 640 508 348 330 112 0219 074 065 Core 2234 3596 2518 553 127 670 526 317 267 108 0220 074 064 Core 1984 3754 2695 603 134 663 599 336 292 111 0224 082 064 Core av. 2190 3706 2593 573 129 658 544 334 296 110 0221 076 064 Rim comp. 1928 4451 2420 580 127 580 527 302 292 112 0240 102 067 Rim coarse 1798 4053 2030 476 104 471 445 257 249 99 0235 103 067 Rim ne 2892 5700 3433 883 211 960 830 480 431 158 0257 089 070 Rim vs. ne 2698 6138 3540 906 213 951 848 468 445 162 0256 099 070 Rim av. 2329 5086 2856 711 164 741 663 377 354 133 0249 098 069 Core leach 2434 4841 4966 1388 320 1492 1173 685 463 178 0280 075 068 Core residue 1431 3304 1401 231 045 195 225 160 168 72 0165 111 064

Table 2. Nd isotopes of a hand specimen from the Normanskill Formation. Sample Core Core Rim composite Sm (p.p.m.) 553 603 580 Nd (p.p.m.) 2518 2695 2420
147

Sm/144Nd

143

Nd/144Nd

eNd (0) )122 )122 )125

01330 01347 01443

0512012 0512011 0511997

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held in the carbonate component, but also removed REEs from other sites (perhaps REEs absorbed on clays); or (2) the leaching removed only the carbonate component, but the difference between residue and rim results from more complex processes such as preferential retention and/or loss of the REEs by other minerals present in the rock. The leaching experiment has shown that the REE component that is most easily removed from the core has a high Sm/Nd ratio.

Timing and character of Sm/Nd isotope re-equilibration The Sm/Nd isotope data are given in Table 2 and plotted in Fig. 9 where they are compared with samples from the single stratigraphic section in the Austin Glen Member. Rim and core have differing Sm/Nd ratios but essentially identical 143 Nd/144Nd ratios consistent with recent isotopic re-equilibration and REE redistribution. It is worth noting that the intersection of the 0 Ma reference isochron and any reasonable 465 Ma reference isochron is at relatively high 147 Sm/144Nd (> 012) and 143Nd/144Nd ratios consistent with an earlier disturbance of these samples. The cause of the re-equilibration event is not obvious but probably related to the recent weathering that affected these samples. On the other hand, the presence of Ce anomalies is not necessarily the direct result of recent weathering. Where fractionation of the REEs

Fig. 8. (a) Chondrite-normalized REE pattern for a rim composite, various grain sizes of the rim and three analyses of the core. (b) Average core-normalized REE pattern of a soft (1 N HCl) leach, its residue and, for comparison, the rim composite.

chondrite-normalized negative Ce anomalies. Mass balance calculations show that mixing 30% of leachate and 70% of residue results in an REE pattern similar to the core. These proportions agree with the estimated carbonate component based on petrography. The loss of the carbonate component cannot be responsible for the attening of the REE pattern of the rim because the Sm/Nd ratio of the leached core (residue) is 0165, which is lower than the Sm/Nd ratio of the unleached core (0221) and much lower than the Sm/Nd ratio of the rim (0249) (Table 1). Thus, the leaching experiment did not result in a residue that is representative of the rim composition. This could be interpreted in two ways: (1) the leaching removed not only REEs

Fig. 9. 143Nd/144Nd vs. 147Sm/144Nd for the core and rim. Also shown are 18 Ga, 465 Ma and 0 Ma reference isochrons as well as the data points of the single stratigraphic section of the Austin Glen Member (open circles).

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B. Bock et al. common situation (Stille & Clauer, 1986; Bros et al., 1992). However, in the Perry Mountain Formation, isotopic disturbance may have occurred during diagenesis and again later during Acadian and/or Alleghenian metamorphism. In the extreme case of the corerim sample, the disturbance appears to be essentially recent and may result from weathering. Thus, in sedimentary successions that are susceptible to Sm/Nd isotopic disturbance, the disturbance can occur at whatever time(s) at which the appropriate conditions come into existence, whether that be during diagenesis, metamorphism or weathering. In the study of Early Silurian turbidites in Wales, Ohr et al. (1991) recognized Sm/Nd reequilibration but saw no evidence that samples were affected on anything greater than a mineralogical scale. This is probably because conditions that give rise to mineral dissolution and changes to whole rock Sm/Nd ratios did not occur, as is the case for the Taconian samples. In cases where changes in Sm/Nd ratios (thus permitting the recognition of isotopic disturbance on a whole rock scale) result simply from dissolution of one or more phases (e.g. monazite, apatite), the timing of the REE mobility may post-date the isotopic reequilibration by any amount of time. The exact timing of this second stage cannot be evaluated by REE or Sm/Nd isotope data alone and must be inferred from petrographic, geochemical and other independent data. This can be seen in the schematic isochron diagram presented in Fig. 10a. In a simplied case, a sample has had the Sm/Nd system fully re-equilibrated among the various minerals at time T0. If, at some intermediate time (T1), one of the phases is lost, the effect on the whole rock is to change both Sm/Nd ratio and Nd isotope composition such that the whole rock remains on the isochron. Of note, however, is that this stage of REE loss gives rise to variable Sm/Nd ratios that permit the entire disturbance (both isotopic and REE loss) to be identied on a whole rock scale. The complications that these processes may impose on any interpretation of provenance are illustrated in Fig. 10b. Here, it can be seen that the change in bulk rock Sm/Nd results in an estimate of mantle extraction age (generally equated to mean age of provenance) that is aberrant. On the other hand, it is valid to calculate the Nd isotope composition of the whole rock back to the time of re-equilibration (T0). Where this is essentially equivalent to the age of sedimentation (i.e. diagenetic resetting), the estimate of eNd at the time of sedimentation

occurs during weathering processes in an oxidizing environment, Ce anomalies may be found (Baneld & Eggleton, 1989; Braun et al., 1990; Marsh, 1991) and can be attributed to the oxidation of Ce3+ to the less mobile Ce4+, which is coprecipitated with oxyhydroxides or precipitated as the extremely insoluble CeO2 (cerianite; Braun et al., 1990). Therefore, weathering residues often exhibit positive Ce anomalies (Ce/Ce* < 1), whereas weathering products are commonly depleted in Ce (Ce/Ce* < 1). However, carbonate minerals may also carry a negative Ce anomaly, which is generally interpreted as being inherited from sea water (Eldereld et al., 1981). As the core is interpreted as relatively unweathered, the presence of a Ce anomaly is unexpected. One possibility is that the core is only apparently unweathered; for example, Price et al. (1991) noted that incipient alteration often causes the most erratic REE patterns (see also Baneld & Eggleton, 1989), whereas more severely altered samples more closely reect the unaltered material. The presence of carbonate with a pronounced negative Ce anomaly in the core (indicated by the leach; see Fig. 8) is the alternative explanation, and the REE pattern of the rim supports this conclusion as the rim is carbonate-free and has no chondrite-normalized negative Ce anomaly.

DISCUSSION The data reviewed and discussed in this paper clearly establish that isotopic re-equilibration of the Sm/Nd system and redistribution of REE on larger than hand sample scales are not necessarily isolated effects. In the Taconian foreland of New England, tectonically and sedimentologically related sedimentary rocks that are separated in time (sedimentation ages range from c. 465 to c. 420 Ma) and space (western New York to western Maine) have been affected. That is not to say, however, that all units within this tectonostratigraphic sequence have been so affected as there are a number of published data from stratigraphic units that show no evidence for REE redistribution (e.g. Andersen & Samson, 1995; Cullers et al., 1997). Nevertheless, it is remarkable that evidence for REE redistribution has been found in so many tectonically related stratigraphic units. The exact timing of re-equilibration appears to be variable. In the Austin Glen/Pawlet Members and Frankfort Formation, re-equilibration is probably diagenetic, and this appears to be the most

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Fig. 10. (a) and (b). Schematic Sm/Nd isochron diagram illustrating the effects of mineral scale Sm/Nd isotope reequilibration in a single sample and subsequent dissolution of an REE-bearing mineral (mineral A). Where a certain mineral(s) contain(s) a substantial fraction of the rocks REE budget and an Sm/Nd ratio signicantly different from the whole rock, loss of the mineral will result in a changed Sm/Nd ratio of the whole rock. The earlier resetting event will still be recorded in the remaining minerals, and the eNd at the time of the resetting will also remain unchanged. (b) However, the Nd model age will be disturbed to a degree controlled by the REE characteristics (Sm/Nd, Nd content) of the REE-bearing mineral and the time of its dissolution.

will be robust and can be compared with potential provenance reservoirs. As pointed out by Ohr et al. (1991), regardless of whether or not Nd isotopic re-equilibration has occurred, as long as there is no open system transport of REE, the whole rock Sm/Nd isotope systematics remain intact. In cases such as those described in this paper, that is obviously not the case. In Fig. 11, TDM is plotted against Sm/Nd, and it can be seen that there is a strong relationship, providing an important test for open system transport of REE. In effect, where a correlation exists between model age and Sm/Nd ratio, disturbance of the Sm/Nd isotope system should

be suspected and evaluated with more thorough petrographic and geochemical studies.

CONCLUSIONS In this paper, it has been demonstrated that rare earth redistribution and disturbance of the Sm/ Nd isotope system were widespread both geographically (from Maine to New York State) and stratigraphically (from the Ordovician to the Silurian, about 40 million years) within the sedimentary successions of the Taconian foreland.

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B. Bock et al.
Baneld, J.F. and Eggleton, R.A. (1989) Apatite replacement and rare earth mobilization, fractionation, and xation during weathering. Clays Clay Minerals, 37, 113127. Bock, B., McLennan, S.M. and Hanson, G.N. (1994) Rare earth element redistribution and its effects on the neodymium isotope system in the Austin Glen Member of the Normanskill Formation, New York, USA Geochim. Cosmochim. Acta, 58, 52455253. Bock, B., McLennan, S.M. and Hanson, G.N. (1996) The Taconian orogeny in southern New England: Nd-isotope evidence against addition of juvenile components. Can. J. Earth Sci., 33, 16121627. Bock, B., McLennan, S.M. and Hanson, G.N. (1998) Geochemistry and provenance of the Middle Ordovician Austin Glen Member (Normanskill Formation) and the Taconian Orogeny in New England. Sedimentology, 45, 635655. Bouch, G.C., Hole, M.J., Trewin, N.H. and Morton, A.C. (1995) Low-temperature aqueous mobility of the rare earth elements during sandstone diagenesis. Geol. Soc. London, 152, 985998. Bradley, D.C. (1989) Taconic plate kinematics as revealed by fore deep stratigraphy, Appalachian Orogen. Tectonics, 8, 10371049. Braun, J.-J., Pagel, M., Muller, J.-P., Bilong, Michard, A. and Guillet, B. (1990) Cerium anomalies in lateritic proles. Geochim. Cosmochim. Acta, 54, 781795. Bros, R., Stille, P., Gauthier-Lafaye, F., Weber, F. and Clauer, N. (1992) Sm-Nd isotopic dating of Proterozoic clay material: An example from the Francevillian sedimentary series, Gabon. Earth Planet. Sci. Lett., 113, 207218. Cullers, R.L., Bock, B. and Guidotti, C. (1997) Elemental distributions and neodymium isotopic compositions of Silurian metasediments, western Maine, USA: redistribution of the rare earth elements. Geochim. Cosmochim. Acta, 61, 18471861. Eldereld, H. and Sholkovitz, E.R. (1987) Rare earth elements in the pore waters of reducing nearshore sediments. Earth Planet. Sci. Lett., 82, 280288. Eldereld, H., Hawkesworth, C.J. and Greaves, M.J. (1981) Rare earth element geochemistry of oceanic ferromanganese nodules and associated sediments. Geochim. Cosmochim. Acta, 5, 513528. Evans, J. and Zalasiewicz, J. (1996) U-Pb, Pb-Pb and Sm-Nd dating of authigenic monazite: implications for the diagenetic evolution of the Welsh Basin. Earth Planet. Sci. Lett., 144, 421433. German, C.R. and Eldereld, H. (1989) Rare earth elements in Saanich Inlet, British Columbia, a seasonally anoxic basin. Geochim. Cosmochim. Acta, 53, 25612571. Hannigan, R.E. and Sholkovitz, E. (2001) The development of middle rare earth element enrichments in freshwaters: weathering of phosphate minerals. Chem. Geol., 175, 495 508. Hurowitz, J.A. (2001) The Geochemical and Nd-Isotopic Evolution of the Eastern Margin of North America in New England: Late Proterozoic to Middle Ordovician. MS Thesis, Stony Brook, State University of New York, 137 pp. Kidder, D.L., Krishnaswamy, R. and Mapes, R.H. (2003) Elemental mobility in phosphatic shales during concretion growth and implications for provenance analysis. Chem. Geol., 198, 335353. Lev, S.M., McLennan, S.M., Meyers, W.J. and Hanson, G.N. (1998) A petrographic approach for evaluating trace-element mobility in a black shale. J. Sed. Res., 68, 970980.

Fig. 11. Plot of TDM vs. 147Sm/144Nd for samples from the Taconian foreland. Hatched area encloses approximate range of TDM and 147Sm/144Nd for samples unaffected by REE redistribution. Note that changes in Sm/Nd result in geologically unreasonable model ages, and such a pattern is a good indicator of disturbance on the Sm/Nd isotope system in clastic sedimentary rocks.

Furthermore, it has been demonstrated that substantial Sm/Nd isotope re-equilibration at a mineralogical scale is likely to have occurred typically near the time of sedimentation because the eNd values converge to homogeneous values when back-calculated to the time of sedimentation. And, nally, it was observed that open-system transport of REE, occurring on greater than whole rock scale, affected these rocks. This can be recognized by the REE patterns that deviate from average upper crustal REE patterns and by the positive relationship of Sm/Nd ratios and TDM values.

ACKNOWLEDGEMENTS This study was funded by an NSF grant (EAR8957784) to S. M. McLennan. Thanks to S. Samson, M. Schoonen and D. Davis for reading an earlier version. Thanks to R. Hannigan and R. Cullers for their thorough reviews, which helped to improve the manuscript.

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Manuscript received 28 July 2003; revision accepted 23 February 2004.

2004 International Association of Sedimentologists, Sedimentology, 51, 885897