Editor Associate Editors

VOLUME 27 / NUMBER 1 / 1985

Published by THE AMERICAN JOURNAL OF SCIENCE

Editor MINZE STUIVER

Associate Editors To serve until January 1, 1989 STEPHEN C PORTER Seattle, Washington

To serve until January 1, 1986 W G MOOK Groningen, The Netherlands HANS OESCHGER Bern, Switzerland

To serve until January 1, 1987 RONALD B DAVIS Orono, Maine

To serve until January 1, 1990 ANDREW MOORE

Managing Editor RENEE S KRA

Kline Geology Laboratory Yale University New Haven, Connecticut 06511 ISSN: 0033-8222 TWELFTH INTERNATIONAL RADIOCARBON CONFERENCE June 24-28, 1985 Trondheim, Norway The Twelfth International Radiocarbon Conference will be held from June 24 to 28, 1985 at the Norwegian Institute of Tech- nology, Trondheim, Norway.

PROGRAM Natural 14C variations: time-scale calibrations climatic change cosmic ray flux The carbon cycle: anthropogenic 14C variations CO2 and other tracers Advances in dating techniques and overlapping dating methods Advances and applications in accelerator mass spectrometry 14C in archaeology and natural sciences 14C data bases

PAPERS Acceptance of papers will be based on extended summaries of approximately 200 words. Papers may be submitted for oral presentation or poster sessions. Papers will be selected for publication in a special proceedings issue of RADIOCAR- BON.

For further information, write: The 12th International Radiocarbon Conference Attn: Pat Ueland Studies and Academic Administration The Norwegian Institute of Technology N-7034 Trondheim-NTH, Norway NOTICE TO READERS AND CONTRIBUTORS

Since its inception, the basic purpose of Radiocarbon has been the publication of compilations of 14C dates produced by various laboratories. These lists are extremely useful for the dissemination of basic 14( information. In recent years, Radiocarbon has also been publishing technical and interpretative articles on all aspects of 14C. We would like to encourage this type of publication on a regular basis. In addition, we will be publishing compilations of published and unpublished dates along with interpretative text for these dates on a regional basis. Authors who would like to compose such an article for his/her area of interest should contact the Managing Editor for information. Our new associate editor for Archaeology, Andrew Moore, is a prehistoric archaeologist who recently became an assistant professor in the Department of Anthropology at Yale University. He received his doctorate from Oxford University and has also taught at the University of Arizona. His research is mainly concerned with the origins of agriculture and sedentary life in Southwest Asia. He is interested, further, in the prehistory of Europe, prehistoric economies, and theory and method in archaeology. Another section is added to our regular issues, "Notes and Comments." Authors are invited to extend discussions or raise pertinent questions to the results of scientific investigations that have appeared on our pages. The section includes short, technical notes to relay information concerning innovative sample preparation procedures. Laboratories may also seek assistance in technical aspects of radiocarbon dating. Book reviews will also be included for special editions. Manuscripts of radiocarbon papers should follow the recommendations in Suggestions to Authors* and RADIOCARBON Style Guide (R, 1984, v 26, p 152-I 58). Our deadline schedule is For Date Vol 27, No. 3, 1985 May 1, Vol 28, No. 1, 1986 Sept 1, Vol 28, No. 2, 1986 Jan 1, Half life of'4C. In accordance with the decision of the Fifth Radiocarbon Dating Conference, Cambridge, 1962, all dates published in this volume (as in previous volumes) are based on the Libby value, 5570 ± 30 yr, for the half life. This decision was reaffirmed at the l 1 th International Radiocarbon Conference in Seattle, Washington, 1982. Because of various uncertainties, when 14C measurements are expressed as dates in years BP the accuracy of the dates is limited, and refinements that take some but not all uncertainties into account may be misleading. The mean of three recent determinations of the half life, 5730 ± 40 yr, (Nature, v 195, no. 4845, p 984, 1962), is regarded as the best value presently available. Published dates in years BP can be converted to this basis by multiplying them by 1.03. AI)/BC Dates. In accordance with the decision of the Ninth International Radiocarbon Con- ference, Los Angeles and San Diego, 1976, the designation of AI)/BC, obtained by sub- tracting Al) 1950 from conventional BP determinations is discontinued in Radiocarbon. Authors or submitters may include calendar estimates as a comment, and report these estimates as AD/BC, citing the specific calibration curve used to obtain the estimate. Meaning of b14C. In Volume 3, 1961, we endorsed the notation 0 (Lamont VIII, 1961) for geochemical measurements of '4C activity, corrected for isotopic fractionation in samples and b14C in the NBS oxalic-acid standard. The value of that entered the calculation of was to Lamont VI, 1959, and was corrected for age. This fact has been lost defined by reference b14C sight of, by editors as well as by authors, and recent papers have used as the observed deviation from the standard. At the New Zealand Radiocarbon Dating Conference it was recommended to use 514C only for age-corrected samples. Without an age correction, the value should then be reported as percent of modern relative to 0.95 NBS oxalic acid (Pro- ceedings 8th Conference on Radiocarbon Dating, Wellington, New Zealand, 1972). The Ninth International Radiocarbon Conference, Los Angeles and San Diego, 1976, recommended that the reference standard, 0.95 times NBS oxalic acid activity, be normalized to 5°C = -19'00. 8140 In several fields, however, age corrections are not possible. and , uncorrected for age, have been used extensively in oceanography, and are an integral part of models and theories. For the present, therefore, we continue the editorial policy of using notations for samples not corrected for age. *Suggestions to Authors of the Reports of the United States Geological Survey, 6th ed, 1978, Supt of Documents, U S Govt Printing Office, Washington, DC 20402.

i RADIOCARBON

Editor: MINZ1'. STU[VER Managing Editor: REN1:E S KRA Published by THE AMERICAN JOURNAI. OF SCIENCE Editors: Jot IN ROnGERS, jOIIN H OSTROM, ROBERT A BERNER Managing Editor: MARIE C CASEY

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11 Vol 27, No. I Radiocarbon 1985

CONTENTS

25 Years of Tropospheric 14C Observations in Central Europe Ingeborg Levin, Bernd Kromer, Hildegard Schoch-Fischer, Michael Brun.s, Marianne Munnich, I)ietrich Berdau, John C Vogel, and Karl Otto Munnich ...... ]

La Jolla Measurements of Radiocarbon in South German Oak Tree-Ring Chronologies T W Linuk, H F Suess, and Bernd Becker ...... 20 Contamination Studies on Mollusk Shell Samples Tomasz Go,slar and Mieczys?"aw F Pazdur ...... Woods Hole Oceanographic Institution Radiocarbon Laboratory: Sample Treatment and Gas Preparation Sheila Griffin and Fllen H M i)ruffel ...... 43

DATE LISTS Gd Mieczyshiw F Pazdur, Rommald Awsiuk, Andrzej Bluszcz, Tomasz Goslar, Anna Pazdur, Adam Walanus, and Andrezej Zastawny (:liwice Radiocarbon Dates X.... `

HAR A f Walker and R L Otlet Harwell Radiocarbon Measurements IV ...... 74

PRL D P Agrawal, R V Krishnamurthy, and Sheela Kusumgar Physical Research Laboratory Radiocarbon Date List V ...... 95

NOTES, COMMENTS, AND REMARKS Amplitude of Sunspot-I)ependent Radiocarbon Variations: I)ata from Corals and Wine Mordeckai Magaritz, Israel Carrni, and 7w Sirkes ...... 111

111

[RADIOCARBON, Vol. 27, No. 1, 1985, P 1-19] Radiocarbon

1985

25 YEARS OF TROPOSPHERIC 14C OBSERVATIONS IN CENTRAL EUROPE INGEBORG LEVIN, BERND KROMER, HILDEGARD SCHOCH-FISCHER, MICHAEL BRUNS*, MARIANNE MUNNICH, DIETRICH BERDAU**, JOHN C VOGELt, and KARL OTTO MUNNICH Institut fur Umweltphysik, Universitat Heidelberg, Federal Republic of Germany

station series of tropospheric 14C data for the period ABSTRACT. A long-term mountain 14C 1959 to 1984 is presented. This series is considered representative of the higher altitude 14C level over central Europe. Even tree-ring levels from a rural ground level site in southern Germany are consistently lower (by a14Cde ression = -15%o if compared with the mountain station summer average in atmospheric C02). The rural tree-ring series is considered to represent the additional continental Suess effect at ground level without local contamination. This Suess effect decreases gradually with the distance from the ground (ie, source) level. We therefore estimate the additional continental Suess effect in the vegetation period to be S%o for the mountain station and 200/so for a rural ground level site, respec- &4Cdepression - - - 14C tively. Based on this assumption, yearly mean tropospheric levels corrected for fossil fuel contamination and representative of the Northern Hemisphere are provided for use in global carbon cycle models. INTRODUCTION With the beginning of extensive atmospheric nuclear bomb testing in 1954, the Heidelberg Radiocarbon Laboratory was one of the first institutions to continuously measure 14C in atmospheric CO2 samples. Until now the data have partly been published in graphs (Munnich & Vogel, 1963; Levin, Munnich & Weiss, 1980) but never in tabulated form. We intend to 14C fill this gap and provide a complete data base-to replace "data read from graph"-and to complement the data from Nydal and Lovseth (1983), also compiled by Tans (1981). The new data base might be useful for the testing of recent carbon cycle models (see, eg, Enting & Pearman, 1982; Pearman, Hyson, & Fraser, 1983; Fung et al, 1983).

SAMPLING LOCATIONS In the first years of tropospheric 14002 observations (1955 to 1967) several stations were maintained in central and southern Europe (Heidel- berg, 49° N, Schleswig, 55° N, Hohenpeij3enberg, 48° N, Bergen, 60° N, Trapani, 38° N, Vermunt, 47° N). Since 1977 Schauinsland, 48° N, was added. We consider the 14C levels at the Schauinsland and Vermunt sam-

*Present address: Technischer Uberwachungsverein Baden eV, Dudenstr 28, 6800 Mannheim, FRG **Present address: Blutenweg 10a, 6900 Heidelberg, FRG tPresent address: National Physics Research Laboratory, PO Box 395, Pretoria, South Africa

1 2 Levin et al pling sites representative of the "true 14C level" of the Northern Hemi- sphere or, at least, central European continental background air. Some early (1959-1961) data from Hohenpeij3enberg and Bergen also are included. Recent studies (Levin, Munnich, & Weiss, 1980; Segl et al, 1983) have shown, that, especially in winter months, there is considerable "contamination" from fossil fuel sources of the Heidelberg 14C level and conceivably also that of other urban stations, such as Schleswig, northern Germany, and Trapani, Sicily. In addition to Northern Hemisphere 14C data, we present some of the early Pretoria data, 26° S, collected by J C Vogel and measured in the Hei- delberg Radiocarbon Laboratory. These data are corrected like all the other Heidelberg data (see below) and presented in tabular form.

Vermunt Station, Austria (470 N, 10 ° E) 1959-1983 The Vermunt sampling location was established in a remote electric power station situated at the upper water reservoir of the Ill-Werke (Par- tenen, Austria) at 1800m asl. Local fossil fuel contamination can only result from local traffic on a nearby private road open only during the summer. The samples were collected at the top of the building ca l Om above ground level (see table 1).

Schauinsland Station, W Germany (48° N, 8° E) 1977-1984 The Schauinsland samples were collected at the Background Air Pollu- tion Monitoring station of the German Federal Environmental Agency on the Schauinsland mountain top 1205m asl. The station is an isolated house with electrical heating only. There can only be occasional contamination from local traffic (station personel). The sample air was collected from a heated stack with the air inlet ca 5m above the ground (see table 2).

Hohenpeif3enberg Station, W Germany (48° N, 11 ° E) 1959-1961 CO2 samples were collected at the Meteorological Observatory of the Deutscher Wetterdienst, Hohenpeij3enberg, 975m asl (see table 3).

Bergen Station, Norway (60° N, 50 E) 1959-1961 CO2 samples were collected at the Geophysical Institution of the Uni- versity of Bergen (see table 4).

Pretoria Station, South Africa (26° S, 28° E)1959-1961 CO2 samples were collected at the Radioactivity Division, National Physics Research Laboratory, ca 15km east of Pretoria. The site should be free of contamination by fossil CO2, except for occasional smog from the city of Pretoria (Vogel,1970) (see table 5).

SAMPLING AND ANALYSIS TECHNIQUES The sampling technique was modified twice during the period of observation: 25 Years of Tropospheric'4C Observations in Central Europe 3 1959-Nov 1965 Three dishes with 1.5L of a 0.5n sodium hydroxide solution were exposed to the atmosphere for ca 3 days. The method has been described by Munnich and Vogel (1959).

Nov 1965-May 1975 Samples were collected by pumping fresh air continuously for 10 days through a box containing 1.5L of a 0.5n sodium hydroxide solution. With this method the atmospheric CO2 is absorbed nearly quantitatively in the NaOH solution.

May 1975-the present Air is pumped through a rotating glass tube filled with a packed bed of Raschig rings (hardglass) to enlarge the surface of the absorbing NaOH solution (200m1 of 4n NaOH). The CO2 absorption is quantitative. The sampling technique is described by Levin, Munnich, and Weiss (1980). The samples represent mean values of 10 days to 2 weeks. The samples were extracted from the NaOH solution' in the laboratory in a vacuum system by adding hydrochloric or sulphuric acid. The CO2 gas samples were purified over charcoal and counted in a proportional counter. All the laboratory procedures have been described by Munnich (1957); Schoch et al (1980); and Levin, Munnich, and Weiss (1980).

CALIBRATIONS All a14C data are referred to NBS oxalic acid corrected for decay (Stuiver & Polach, 1977). They were also adjusted to the new Heidelberg calibration scale (Kromer, 1984). The data were corrected for isotopic fractionation on the basis of '3C analysis of the sample CO2. The b' 3C values are given relative to the PDB standard (Craig, 1957). These values do not represent the true atmospheric ''C level because of isotopic fractionation in the early period (till 1975) and small fractiona- during sample collection ''C tion (up to b' 3C = ± 0.2 1 o) in the laboratory procedures. was not measured for some of the early samples (1959 to 1961). We took the mean value b' 'C (mean) = -22.7x of all samples collected by the same sampling technique from 1959 to 1965. Because the standard deviation of the b' 3C values, observed in the tray samples of this period, is the assumed cor- 014C rection may lead to an additional error (not included in table 1) of = +4%o in the data marked by an asterisk (*).

RESULTS AND DISCUSSION

Evaluation and Interpretation of the Data The results from the Vermunt station are plotted in figure 1. In the early 1960's marked seasonal variations, up to ca a14C = 2000,4o, were observed in the tropospheric 14C level resulting mainly from spring-time injections of bomb G from the stratosphere. The observed C variations

The Pretoria samples were precipitated as BaC33 for shipment to the laboratory. 4 Levin et al

1000 Vermunt 800

600

400

200

Ye a r 0 I 1 I I I 59 61 63 65 67 69 71 73 75 77 79 81 83 Fig I. Tropospheric 14C variations (with la error bars) at the Vermunt station, Austria (47° N, 10° F) with the calculated spline function.

Schauinsland 350

300

250

200

150 77 78 79 014C Fig 2. Tropospheric variations (with 1 a error bars) at the Schauinsland station, W Germany (48° N, 8° E). The solid line is a calculated spline function through these data; the dotted line represents the corresponding spline function through the Vermunt data (see fig 1). The periodic variations observed at both stations are mainly due to a general (seasonally varying) "European Suess effect". 14C 25 Years of Tropospheric Observations in Central Europe 5 014C in later years (peak to peak variations in = 2O'6o) from 1976 onwards are, to a great extent, due to seasonal variations of the contribution of fossil fuel CO2 at the sampling location. In 1978 (and 1981) there may have been some artificial '4C variation resulting from the most recent Chinese bomb tests The 14C data at the Schauinsland station from 1976 to 1984 are plotted in figure 2. The solid line is a calculated spline function (Reinsch, 1967) through this data set. We have also added the spline function through the corresponding Vermunt data from the same period (dotted line). The sur- prisingly close agreement between the two data sets from two different sampling locations 200km apart (in the Alps and Black Forest) indicates that the data indeed represent the '4C level of tropospheric CO2 above central Europe. 14C The question is now, "How representative are these data of the level of this latitude?" Evidence of an additional 14C depression on the European continent 14C was given in several studies. Stuiver and Quay (1981) compared tree- ring data from supposedly uncontaminated trees grown on the U S west coast with those from Dutch trees (Tans, de Jong, & Mook, 1979). For the 14C 14C period, 1920 to 1950, they found a depletion of up to = -10'4>o in the Dutch trees. Referring to the west coast tree-ring series, de Jong and 014C Mook (1982) found a 14C depletion of ca = - 54o in tree-ring samples from southern Germany. Using the energy consumption data from Rotty (1983), we can roughly assume that from the period, 1920-1950, to the present the yearly fossil fuel combustion rate has increased by a factor of 4-5. In addition to the 14C depletion, the "European Suess effect" should global increase of the 14C have increased by approximately this factor, ie, to ca 5°ho * (4 to 5) _ -20 to -25%o. Assuming the fossil fuel depression is lowest during the summer due to intensive vertical mixing of the atmosphere and better dilu- tion of anthropogenic C02, Tans (1981) proposed that the upper envelope of his selected data set represented the Northern Hemisphere 14C level. On the basis of the arguments made above, a brief data analysis of the Schauinsland 14C data of 1980, and 1982-1983, that are probably not '4C influenced by additional bomb released during this interval, offers an independent estimate of representative tropospheric 14C levels. Assuming that all negative deviations from the "upper envelope" of the Schauinsland '4C data are due to fossil fuel contamination, we use a "straight line upper envelope" to the 1980-1983 Schauinsland data and compare the bulk of 14C data with this line. By this procedure, we obtain a mean anthropogenic depletion for the Schauinsland station of ca & 4C = - 9%o (- 5°,i6o in summer and -13 ii o in winter); presumably, these numbers are reliable within a ±30% range. Based on other atmospheric tracer data for the same site (eg, CO2 concentration and 222 Radon activity), we seem to have good reasons to believe that our upper envelope in fact represents the 14C level of the latitu- dinal belt beyond local or regional influence by fossil CO2 sources. 14C In this context, it is also worth noting a single ring study (see table 6 Levin et al Delta C-14 1000 Tree Obrigheim 800 Spline fct. Vermunt

600

400

200

Year - 59 61 63 65 67 69 71 73 75 77 79 81 83 Fig 3. Spline function through the Vermunt data (fig 1) together with the tree-ring data from a pine (minus nigra) grown near Obrigheim, 14Csouthern Germany (49° N, 9° E). Except for 1970 and 1975 (see text), a mean depression of is found in 14C = - 15o the tree rings as compared to the level in tropospheric COz at the mountain stations in summer. 6: 1966-1982) on a tree (Pines nigra) grown near Obri heim2 in a rural area in southern Germany. There we found a mean 0 C depression of - 20%o compared to the "upper envelope" of the Schauinsland and Ver- munt data (fig 3). This presumably means an average 204,o fossil CO2 contribution at ground level and daytime during the growing season, due to the average mesoscale source density of fossil fuel CO2 ("continental effect"). The preceding estimates support the assumption of Tans (1981), that 14C the "clean air" level of the Northern Hemisphere is represented by the "upper envelope" of the 14C values, observed at European (continental) ' stations. The mean 4C level at our mountain stations 14C seems to be depleted from the true background by only ca = 94o in the 1980's. The 14C - larger deviations in the ground level plant material may be due to the fact that it grows within the polluted layers influenced by anthropogenic CO2 sources at ground level. At higher altitudes or rather at mountain tops reaching out of the ground layer at least in summer, the anthropogenic sig- 4140 nal is reduced to only ca = - 5%. Proposed "Clean Air" '4C Levels In order to find representative 14C levels suitable for carbon cycle modeling, we calculate a mean 14C activity for each year of observation and

z This tree-ring analysis originally was performed to study the influence of reactor 14C on plant material in the surroundings of the nuclear power plant Obrigheim (49° N, 9° E) pres- surized water reactor, 300 MW electric power 14C (see, eg, Levm, Munnich, & Weiss,1980). Reac- tor in tree rings collected at a distance of 1 km from the reactor stack is significant. This tree is grown at 4km distance, and we do not expect to find additional reactor 4C here. This assumption is based on dispersion model estimates, which include release rates from the reactor stack, and experience gathered at similar reactor sites (Segl et al, 1983). We can not, however, exclude slight contamination for the years 1970 and 1975, when we also found high 14( excess values at the sampling site closer to the reactor. 25 Years of Tropospheric14C Observations in Central Europe 7 subtract for 1980 to 1983 a yearly mean fossil fuel contamination due to anthropogenic continental sources of &4CdeprCSJiOn = _90/)o, ie, we repro- duce and use the previous "upper envelope." We derive the fossil fuel 014C contribution for the period prior to 1980 by linear interpolation of the 14C depression values of 1980 to 1983 and of 1959, respectively. We assume that the 14C depression in 1959 is half that of 1980, based on a fossil fuel CO2 release that is also half in 1959 of that in 1980 (Rutty, 1983). Thus, we arrive at the assumed "clean air" 14C levels for the period between 1959 and 1983 listed in table 6. Our "clean air levels" obtained by this procedure agree within 0140 ±20%o with the values proposed by Tans (1981) for the period from 1964 to 1977. Just prior to 1964, there is a discrepancy in the "clean air" levels proposed by Tans (1981), although he used essentially the same data set (Munnich & Vogel, 1963; Ostlund & Engstrand, 1963) as we did in the present paper. His interpretations of "clean air" levels seem to be up to 0140 = 14041o too high compared to the fossil fuel corrected data presented here. This might be due to the fact that Tans, even in this period with maximum bomb 14C production, took the upper envelope of the seasonally varying '4C data. However, the extent to which the seasonal modulation in the late 1960's and early 1970's is due to fossil fuel contamination or to seasonal stratospheric injection is not known.

ACKNOWLEI)GMENTS This study was supported by the Heidelberg Academy of Sciences and by the Federal Minister of the Interior, Bonn. We wish to thank the following people for their help in obtaining the numerous samples: F Brugger, Vorarlberger Ill-Werke, Schruns, Austria, R Graul, Federal Environmental Agency, Kirchzarten, FRG, the staffs of the sampling stations at Hohen- pei,3enberg, Bergen, and Pretoria, C Junghans for running the 13C measurements, and M Segl and M Barabas for the data documentation. Special thanks go to Minze Stuiver for helpful suggestions during the revision of this paper.

TABLE I Tropospheric 0140 activities at the Vermunt station, Austria (47°N, 10°E) b'3C * = assumed = -22.7i&), see text.

ANALYSIS SAMPLE PERIOD OF EXPOSURE No. No. ddmmyy - ddmmyy %(PDB)

Hd- 611 Ver- 2 130259 3 Hd- Ver- 7 Hd- Ver- 5 7 6 6

Ver- 7 130459 7 Hd- 661 Ver- 8 230459 7 Hd- 688 Ver- 180559 9 Hd- 691 Ver- 180659 7 Hd- 836 Ver- 80759 * 7 Hd- 721 Ver- 180859 Hd- 747 Ver- 180959 6 8 Levin et al

TABLE 1 (continued)

ANALYSIS SAMPLE PERIOD OF EXPOSURE 1'C No. No. ddmmyy - ddmmyy (PDB)

Hd- 801 Ver- 25 51059 - 81059 * 9 Hd- 757 Ver- 26 151059 - 181059 9 Hd- 179 Ver- 29 151159 - 181159 * 4 Hd- 824 Ver- 31 151259 - 181259 * 7 Hd- 832 Ver- 34 160160 - 190160 * 1 Hd- 953 Ver- 48 250260 - 280260 * 5 lid- 954 Ver- 49 50 360 - 80360 * 7 lid- 841 Ver- 46 150360 - 180360 * 8 lid- 853 Ver- 39 200460 - 230460 * 7 lid- 872 Ver- 41 150560 - 180560 * 6 Hd- 900 Ver- 44 150660 - 180660 * 5 Hd- 913 Ver- 51 150760 - 180160 * 6 11d- 927 Ver- 54 150860 - 180860 * 7 Hd- 931 Ver- 51 150960 - 180960 * 8 lid- 957 Ver- 60 151060 - 181060 * 1 Hd- 959 Ver- 63 151160 - 181160 * 1 Hd-1061 Ver- 66 151260 - 181260 * 7 lid- 998 Ver- 68 150161 - 180161 * 1 lid-1004 Ver- 71 150261 - 180261 * 9 lid-1014 Ver- 74 150361 - 180361 * 8 Hd-1060 Ver- 77 150461 - 180461 * 1 Hd-1036 Ver- 80 150561 - 180561 * 8 11d-1069 Ver- 83 150661 - 180661 * 8 lid-1079 Ver- 86 150761 - 180761 * 7 Hd-1087 Ver- 89 150861 - 180861 * 6 11d-1108 Ver- 92 200961 - 230961 * 7 Hd-1178 Ver- 95 151061 - 181061 6 Hd-1180 Ver-101 151261 181261 6

Hd-1222 Ver-104 160162 190162 7 lid-1224 Ver-108 250262 280262 5 lid-1242 Ver-111 250362 280362 6 lid-1270 Ver-116 170562 200562 6 lid-1307 Ver-125 250762 280762 6 lid-1308 Ver-121 150862 180862 6 Hd-1344 Ver-128 150962 180962 8 lid-1363 Ver-131 151062 181062 6 Hd-1381 Ver-134 151162 181162 6 Hd-1404 Ver-131 150163 180163 6 Hd-1416 Ver-142 150263 180263 00 5 Hd-1551 Ver-144 50363 80363 1 Hd-1430 Ver-145 160363 190363 4 Hd-1574 Ver-141 50463 80463 6 Hd-1442 Ver-148 150463 180463 6 Hd-1561 Ver-150 50563 80563 5 Hd-1410 Ver-151 150563 180563 5 Hd-1560 Ver-153 50663 80663 5 Hd-1480 Ver-154 150663 180663 6 Hd-1555 Ver-156 50763 80163 7 lid-1495 Ver-151 150163 180163 6 Hd-1561 Ver-159 50863 80863 6 Hd-1506 Ver-160 150863 180863 6 Hd-1564 Ver-162 50963 80963 6 Hd-1518 Ver-163 150963 180963 5

Hd-1540 Ver-166 151063 181063 5 Hd-1554 Ver-169 151163 181163 6 Hd-1595 Ver-172 151263 181263 6 Hd-1611 Ver-175 150164 180164 6 Hd-1611 Ver-178 150264 180264 6 lid-1622 Ver-181 150364 180364 6 25 Years of Tropospheric 14C Observations in Central Europe 9

TABLE 1 (continued)

ANALYSIS SAMPLE OF EXPOSURE No. No. ddmmyy - ddmmyy %(PDB)

Hd-1624 Ver-184 150464 6 Hd-1640 Ver-187 150564 6 Hd-1657 Ver-190 150664 6 Hd-1615 Ver-193 150764 7 Hd-1677 Ver-196 150864 6 Hd-1684 Ver-202 150964 6 Hd-1705 Ver-205 151064 6 Hd-1718 Ver-198 151164 7 Hd-1139 Ver-208 151264 6 Hd-1741 Ver-211 150165 7 tid-1172 Ver-214 170265 6 Hd-1176 Ver-217 150365 70 6 Hd-1187 Ver-220 150465 6 6 6 6 6

1 Hd-1850 Ver-239 161165 6 Hd-1861 Ver-243 151265 6 Hd-1895 Ver-246 250166 6 Hd-1887 Ver-248 150266 6 Hd-1908 Ver-255 150366 6 Hd-1916 Ver-258 150466 6 Hd-1929 Ver-261 150566 6 Hd-1951 Ver-264 150666 6 Hd-1962 Ver-267 150166 7 Hd-1973 Ver-270 150866 6 Hd-2003 Ver-273 150966 5 5 Hd-2009 Ver-219 151166 5 6 6

5 5 Hd-2113 Ver-293 150461 6 Hd-2118 Ver-294 250461 7 Hd-2121 Ver-297 150761 6 6 6 6 6 6 6 6 6 6 Hd-2261 Ver-321 250468 79 6 Hd-2295 Ver-326 150568 6 Hd-2296 Ver-329 150668 6 Hd-2316 Ver-333 150768 1 Hd-2371 Ver-332 150868 8 Hd-2378 Ver-335 150968 8 Hd-2379 Ver-338 151068 1 Hd-2380 Ver-341 151168 6 6

1 Hd-2512 Ver-350 250269 7 Levin et al

TABLE 1 (continued)

ANALYSIS SAMPLE OF EXPOSURE No. No. ddmmyy - ddmmyy %(PDB)

Hd-2513 Ver-353 150369 250369 7

Hd-2514 Ver-356 150469 250469 5 Hd-2515 Ver-359 150569 250569 6 Hd-2821 Ver-361 50669 150669 6 Hd-2586 Ver-365 150769 250769 6 Hd-2585 Ver-368 150869 250869 9 Hd-2516 Ver-311 150969 250969 8

Hd-2814 Ver-373 51069 151069 7 Hd-2817 Ver-376 51169 151169 8 Hd-2818 Ver-379 111269 161269

Hd-2819 Ver-382 80170 150170 1 Hd-2828 Ver-384 240170 50270 8 Hd-2820 Ver-385 50370 170370 6 Hd-2821 Ver-388 50470 150470 6

Hd-2822 Ver-391 50570 150570 5 Hd-2823 Ver-394 50670 150670 6 Hd-2824 Ver-397 50110 150710 6

Hd-2829 Ver-400 50870 150870 7

Hd-2830 Ver-403 50970 150970 5 Hd-2831 Ver-406 51070 151070 6

Hd-2832 Ver-409 61170 151170 7 Rd-2833 Ver-412 51270 161270 6

Hd-2834 Ver-415 50171 150171 1

Hd-2835 Ver-418 50271 150271 7 Hd-2836 Ver-420 250271 50371 8 Hd-2837 Ver-423 50471 150411 8 11d-2838 Ver-426 50571 150571 8 Hd-3013 Ver-429 50671 150671 6

Hd-3014 Ver-432 50771 150771 7

Hd-3015 Ver-435 50871 150811 1

Hd-3105 Ver-439 150911 150971 7

Hd-3049 Ver-441 61071 161071 6 Hd-3050 Ver-444 51171 151171 4

Hd-3051 Ver-441 51271 151271 5

Hd-3060 Ver-450 60172 150172 9 Hd-3061 Ver-453 50272 150272 42 5 Hd-3062 Ver-456 50372 150372 6 Hd-3063 Ver-459 50472 150472 6 Hd-3064 Ver-461 50572 150572 6

Hd-3067 Ver-464 250572 50672 5 Hd-3100 Ver-466 150672 250612 6 Hd-3101 Ver-469 150772 250772 4 Hd-3141 Ver-472 150812 260872 6 Hd-3143 Ver-477 151012 261072 5 Hd-3171 Ver-483 151272 261272 0 Hd-3118 Ver-486 150173 250113 6 Hd-3180 Ver-487 250173 50213 6 lid-3184 Ver-488 50273 150273 5 Hd-3170 Ver-489 150273 260273 5 Hd-3185 Ver-490 260273 60313 5

Hd-3184 Ver-488 50213 150273 5

Hd-3170 Ver-489 150273 260273 5 Hd-3185 Ver-490 260213 60313 5 Hd-3187 Ver-491 60313 160313 6 Hd-3190 Ver-492 160313 260373 5 Hd-3201 Ver-493 260373 50473 5

Hd-3202 Ver-494 50413 150413 5

Hd-3225 Ver-491 50573 150573 5

Hd-3261 Ver-504 160773 250773 5 25 Years of Tropospheric'4C Observations in Central Europe 11

TABLE 1 (continued)

ANALYSIS SAMPLE OF EXPOSURE No. No. ddmmyy - ddmmyy (PDB)

Hd-3252 Ver-510 110973 250913 5 Hd-3264 Ver-514 250913 71073 5 Hd-3292 Ver-512 251073 251173 5 Hd-3297 Ver-517 251173 171273 6 H8-3374 Ver-536 50714 250774 4 Hd-3418 Ver-541 250814 160974 6 Hd-3452 Ver-545 31014 261074 38 5 Hd-3471 Ver-548 51114 251114 6 H4-3536 Ver-550 251174 251274 6 Hd-3557 Ver-553 251214 150115 6 Hd-3555 Ver-555 50275 250215 4 Hd-3570 Ver-559 250215 250315 1 Hd-3594 Ver-562 50475 50575 7 Hd-3598 Ver-566 50575 250575 6 Hd-3725 Ver-585 41175 251175 6 Hd-3749 Ver-581 251115 151275 5 Hd-3816 Ver-592 250176 50276 8 Hd-3815 Ver-588 50376 150376 6 Hd-3819 Ver-589 160376 250316 8 Hd-6349 Ver-596 150476 250476 5 Hd-3827 Ver-595 160576 250516 9 Hd-6316 Ver-600 250576 60676 4 Hd-3846 Ver-601 60676 170676 9 Hd-3841 Ver-604 50116 160776 7 Hd-3963 Ver-605 160776 270776 8 Hd-6311 Ver-606 270776 50876 5 Hd-6354 Ver-608 150876 250876 6 Hd-3964 Ver-610 50976 150976 8 Hd-4055 Ver-616 150976 250976 6 Hd-4056 Ver-613 51176 161116 5 Hd-4124 Ver-617 161176 251176 5 Hd-4127 Ver-619 51276 151276 5 Hd-4128 Ver-620 151276 251276 6 Hd-4129 Ver-622 60171 150177 6 H8-4182 Ver-623 150177 260177 4 Hd-4184 Ver-625 50277 150277 5 Hd-4187 Ver-626 150271 250277 5 Hd-4192 Ver-628 50377 150377 5 Hd-4267 Ver-629 180377 260311 5 Hd-4268 Ver-630 260311 150471 5 Hd-4269 Ver-632 150477 70511 5 H8-4313 Ver-635 70577 150577 5 Hd-4406 Ver-638 250577 50677 5 H8-4316 Ver-636 50677 150677 4 Hd-4411 Ver-640 150671 260677 6 Hd-4441 Ver-641 60777 260717 7 Hd-4441 Ver-643 260711 150871 6 Hd-4458 Ver-645 150877 250877 6 Hd-4449 Ver-646 250871 50977 5 Hd-4513 Ver-641 151071 261077 5 H8-4511 Ver-649 261077 51177 6 Hd-4608 Ver-651 91217 151277 7 Hd-4610 Ver-652 151277 261217 7 Hd-4614 Ver-654 70118 150178 6 Hd-4622 Ver-655 150178 250178 4 Hd-4664 Ver-656 250118 60278 5 Hd-4803 Ver-657 60278 150278 6 Hd-4831 Ver-658 150218 260278 6 Hd-4832 Ver-659 260278 60378 5 1 2 Levin et al

TABLE 1 (continued)

ANALYSIS SAMPLE PERIOD OF EXPOSURE No. No. ddmmyy - ddmmyy

Hd-4834 Ver-660 60318 160318 6 Hd-4837 Ver-661 160318 250378 5 Hd-4838 Ver-662 250378 50478 5 kid-4842 Ver-663 50478 160478 5

Hd-4843 Ver-664 160478 260478 5 Hd-4880 Ver-611 260418 10578 4 Hd-4881 Ver-672 10518 60578 5 Hd-4887 Ver-673 160578 250578 8 Hd-4886 Ver-674 250578 60618 6 Hd-4892 Ver-616 150678 250618 8 Hd-4949 Ver-671 250678 50778 9

Hd-4951 Ver-672 50118 150178 7 Hd-5208 Ver-684 60118 250179 6 Hd-4952 Ver-673 150178 250178 7 Hd-4953 Ver-614 250778 50878 8 Hd-4993 Ver-615 50878 160878 8 Hd-4994 Ver-676 160878 260878 6 Hd-5080 Ver-665 260878 50918 Hd-5018 Ver-666 50978 260978 8 Hd-5083 Ver-668 260978 51078

Hd-5090 Ver-669 51018 161078 7 Hd-5091 Ver-670 161018 251018 8 Hd-5108 Ver-617 251078 51118 8

Hd-5112 Ver-678 51178 251118 1

Hd-5112 Ver-680 251178 151278 7 Hd-5206 Ver-683 261278 60179 6 Hd-5209 Ver-686 250179 50279 6

Hd-5226 Ver-681 50279 260279 5 Hd-5239 Ver-689 260219 50319 7 Hd-5240 Ver-690 50379 160379 6

Hd-5242 Ver-691 160319 250379 7 Hd-5243 Ver-692 250319 160479 5

Hd-5406 Ver-695 250479 50579 5 Hd-5411 Ver-696 50579 150519 6

Hd-5418 Ver-691 150579 270579 7 Hd-5422 Ver-698 210519 100679 6 Hd-5423 Ver-699 100679 250619 8 Hd-5441 Ver-701 250679 150779 5 Hd-5450 Ver-703 150119 60879 5 Hd-5451 Ver-705 60819 250819 5 Hd-5520 Ver-701 250819 50979 4

Hd-5531 Ver-108 50919 160919 7 Hd-5548 Ver-709 160919 250979 6 Hd-5550 Ver-710 250979 51079 9 Hd-5714 Ver-711 51019 151019 8

Hd-5124 Ver-715 51119 151179 5

Hd-5712 Ver-116 151119 61279 5 Hd-5791 Ver-720 261279 150180 5 Hd-5812 Ver-723 250180 150280 5 Hd-6002 Ver-733 50580 150580 4 Hd-6043 Ver-735 250580 150680 90 4 Hd-6048 Ver-737 150680 250680 4

Hd-6049 Ver-739 50780 250180 15 5

Hd-6060 Ver-741 250180 150880 5 Hd-6061 Ver-743 150880 60980 5 Hd-6062 Ver-145 60980 250980 5

Hd-6064 Ver-747 250980 51080 7

Hd-6055 Ver-748 51080 161080 7 Hd-6303 Ver-749 161080 51180 6

Hd-6304 Ver-751 51180 141180 5 14C 25 Years of Tropospheric Observations in Central Europe 13

TABLE 1 (continued)

ANALYSIS SAMPLE PERIOD OF EXPOSURE No. No. ddmmyy - ddmmyy

Hd-6331 Ver-152 141180 261180 8 Hd-6342 Ver-153 261180 151280 4 Hd-6355 Ver-155 151280 251280 7 Hd-6356 Ver-756 251280 50181 6 Hd-6362 Ver-157 50181 150181 6 Hd-6316 Ver-158 150181 250181 4 Hd-6377 Ver-159 250181 50281 5 Hd-6506 Ver-160 50281 150281 73 5 Hd-6507 Ver-761 150281 250281 6 Hd-6515 Ver-163 50381 150381 4 Hd-6522 Ver-764 150381 250381 5 Hd-6554 Ver-765 250381 50481 5 Hd-6556 Ver-766 50481 150481 5 Hd-6559 Ver-167 150481 50581 5 Hd-6564 Ver-769 50581 160581 5 Hd-6565 Ver-770 160581 50681 5 111-5555 Ver-172 270581 160681 5

Hd-6727 Ver-173 150681 50181 1 111-6729 Ver-115 50781 250781 5 Hd-6730 Ver-777 250781 150881 4 Hd-6805 Ver-714 240881 150981 5 Hd-6807 Ver-778 51081 261081 4 Hd-6892 Ver-719 71181 251181 4 Hd-6902 Ver-181 21281 151281 5 Hd-6907 Ver-783 151281 50182 5 Hd-6980 Ver-785 150182 60282 74 2 Hd-1012 Ver-788 60282 150282 6 Hd-7025 Ver-790 150282 250282 81 1 Hd-7321 Ver-791 250282 60382 93 5 Hd-7320 Ver-792 60382 250382 5 Hd-7322 Ver-794 250382 50482 87 5 Hd-7323 Ver-195 50482 150482 6 Hd-7308 Ver-196 150482 250482 00 Hd-7410 Ver-797 250482 160582 34 4 Hd-7415 Ver-799 160582 250582 26 4 Hd-1416 Ver-800 250582 50682 5 Hd-1417 Ver-801 50682 150682 5 Hd-1418 Ver-802 150682 250682 17 5 Hd-7546 Ver-803 250682 10782 3 Hd-7559 Ver-805 170782 50882 4 Hd-7521 Ver-807 50882 160882 4 Hd-7560 Ver-808 160882 50982 4 Hd-7677 Ver-810 50982 150982 Hd-1669 Ver-811 150982 250982 4 Hd-1664 Ver-813 271182 61282 3 Hd-7678 Ver-814 61282 151282 39 4 Hd-7670 Ver-815 151282 271282 3 Hd-7821 Ver-816 271282 150183 3 Hd-7806 Ver-812 180283 250283 4 Hd-1822 Ver-822 250283 150383 4 Hd-7901 Ver-818 150383 260383 4 Hd-7908 Ver-819 260383 50483 4 Hd-7909 Ver-820 50483 150483 3 111-7910 Ver-824 150483 250483 4 88-7923 Ver-825 250483 50583 4 Hd-8066 Ver-826 50583 140583 5 Hd-8067 Ver-827 140583 250583 6 Hd-8068 Ver-828 250583 60683 5 Hd-8069 Ver-829 60683 150683 3 14 Levin et al

TABLE 2 Schauinsland station, W Germany (48°N, 8°E)

ANALYSIS SAMPLE PERIOD OF EXPOSURE No. No. ddmmyy - ddmmyy

Hd-4155 Sch- 1 231276

2 60117 5 Hd-4161 Sch- 3 200117 6 Hd-4113 Sch- 4 30277 6

Hd-4178 Sch- 5 170277 8 Hd-4176 Sch- 6 70377

7 7

290377 7 Sch- 9 130477 - Sch- 5

Sch- 5 Sch- 260677 - 5 Sch- 180777 - Sch- 14 5 40977 - 5 Sch- 5

Sch- 17 5 Sch- 251271 - 5 Sch- 19 90318 6

Hd-4885 Sch- 20 290318 5 Hd-4867 Sch- 21 90418 6 Hd-4873 Sch- 22 8 Hd-4814 Sch- 23 50678 8 Hd-4915 Sch- 24 30778 8 Hd-4916 Sch- 25 30778 - 8 Hd-4917 Sch- 26 260778 8 Hd-4920 Sch- 27 6 Hd-4984 Sch- 28 5 29 9 Hd-4986 Sch- 30 260978 Hd-4987 Sch- 31 101078 8 Hd-5003 Sch- 32 231078 Hd-5074 Sch- 33 51178 8 34 8

Sch- 35 11278 9 Hd-5076 Sch- 36 151278

Hd-5088 Sch- 37 311278 7 Hd-5181 Sch- 38 140179 5 Hd-5182 Sch- 39 300179 5 Hd-5183 Sch- 40 120279 5

Hd-5194 Sch- 41 50379 5

Hd-5195 Sch- 42 180379 5 Hd-5258 Sch- 44 130419 6 Hd-5259 Sch- 45 260479 5 Hd-5274 Sch- 46 80579 5

Hd-5215 Sch- 47 210579 5 Hd-5331 Sch- 48 60679 4 Hd-5339 Sch- 49 190619 5 Hd-5340 Sch- 50 30779 5

Hd-5343 Sch- 51 150779 7 Hd-5328 Sch- 52 260779 6 Hd-5485 Sch- 54 240879 4 Hd-5500 Sch- 55 50979 6 Hd-5480 Sch- 56 180979 5 Hd-5501 Sch- 51 11079 6 Hd-5493 Sch- 58 101079 6 Hd-5519 Sch- 59 271079 5 25 Years of Tropospheric'4C Observations in Central Europe 15

TABLE 2 (continued)

13 14 ANALYSIS SAMPLE PERIOD OF EXPOSURE d C A C No. No. ddmmyy - ddmmyy (PDB) Z

Hd-5574 Sch- 60 211079 - 101179 -1.90 6 Hd-5126 Sch- 61 101119 - 241179 -8.02 4 Hd-5581 Sch- 62 241119 - 101279 -8.31 3 Hd-5127 Sch- 63 101219 - 211219 -8.00 4 Hd-5825 Sch- 64 20180 - 180180 -8 29 8 Hd-5807 Sch- 65 180183 - 20280 -8.41 8 Hd-5806 Sch- 66 20280 - 110280 -8 01 6 Hd-5826 Sch- 61 110280 - 30380 -8.95 5 Hd-5935 Sch- 68 110380 - 240380 -8 88 4 Hd-5936 Sch- 69 240380 - 60480 -7.14 3 Hd-5941 Sch- 70 60480 - 190480 -8.90 4 Hd-5942 Sch- 71 200480 - 20580 -8.39 5 Hd-5970 Sch- 73 20680 - 140680 -8.06 2 Hd-5971 Sch- 14 140680 - 240680 -7.71 4 Hd-5956 Sch- 15 240680 - 10780 -8 52 4 Hd-5972 Sch- 16 70780 - 170180 -6 93 6 Hd-5954 Sch- 77 110780 - 40880 -7.35 5 Hd-6038 Sch- 18 10880 - 180880 -1.90 4 Hd-6039 Sch- 79 180880 - 290880 -1.24 5 Hd-6058 Sch- 80 290880 - 80980 -7.81 4 Hd-6059 Sch- 81 80980 - 220980 -1.69 3 Hd-6054 Sch- 82 220980 - 141080 -6.76 3 Hd-6222 Sch- 83 141080 - 271080 -7.95 4 Hd-6223 Sch- 84 211080 - 11180 -9.02 3 Hd-6224 Sch- 85 11180 - 181180 -9.94 4 Hd-6225 Sch- 86 181180 - 11280 -8.91 1 Hd-6210 Sch- 87 101280 - 291280 -8.04 5 Hd-6261 Sch- 88 291280 - 120181 -8.04 4 Hd-6271 Sch- 89 120181 - 220181 -7.85 4 Hd-6388 Sch- 90 220181 - 40281 -8.43 3 Hd-6389 Sch- 91 40281 - 160281 4 lld-6390 Sch- 92 160281 - 10381 3 Hd-6391 Sch- 93 10381 - 130381 5 Hd-6392 Sch- 94 130381 - 270381 3 Hd-6521 Sch- 95 30481 - 160481 4 Hd-6525 Sch- 96 160481 - 300481 4 Hd-6526 Sch- 97 300481 - 150581 55 5 Hd-6814 Sch- 98 100781 - 240181 5 Hd-6815 Sch- 99 240181 - 10881 5 Hd-6952 Sch-101 280182 - 120282 6 Hd-6953 Sch-102 120282 - 20382 3 Hd-1304 Sch-103 30382 - 170382 68 5 Hd-1305 Sch-104 170382 - 10482 5 Hd-1306 Sch-105 10482 - 140482 4 Hd-7307 Sch-106 150482 - 270482 29 3 Hd-7310 Sch-107 210482 - 110582 .97 5 Hd-1422 Sch-108 180582 - 20682 3 Hd-7423 Sch-109 20682 - 160682 4 Hd-7424 Sch-110 160682 - 20782 4 Hd-7425 Sch-111 20182 - 190782 4 Hd-7499 Sch-112 300182 - 170882 4 Hd-7500 Sch-113 110882 - 310882 5 Hd-7508 Sch-114 310882 - 150982 2 Hd-7509 Sch-115 150982 - 71082 2 Hd-7658 Sch-116 71082 - 251082 3 Hd-7659 Sch-117 251082 - 81182 5 Hd-1660 Sch-118 81182 - 291182 5 Hd-1661 Sch-119 291182 - 151282 23 4 16 Levin et al

TABLE. 2 (continued)

ANALYSIS SAMPLE OF EXPOSURE No. No. ddmmyy - ddmmyy (PDB) Z

Hd-1662 Sch-120 151282 100183 4 Hd -1801 Sch-121 260183 150283 2 Hd-7808 Sch-122 150283 70383 3 Hd-7809 Sch-123 10383 60483 3 Hd-7810 Sch-124 60483 290483 6 Hd-7843 Sch-125 290483 90583 4 Hd-1857 Sch-126 90583 190583 4 Hd-8024 Sch-127 10683 160683 4 Hd-8025 Sch-128 160683 10183 4 Hd-8026 Sch-129 10183 220783 4 Hd-8034 Sch-130 220783 120883 4 Hd-8114 Sch-131 120883 240883 4 Hd-8115 Sch-132 240883 50983 4 Hd-8120 Sch-133 50983 160983 4 Hd-8121 Sch-134 160983 270983 4 Hd-8188 Sch-135 270983 71083 4 Hd-8187 Sch-136 71083 211083 4 Hd-8202 Sch-137 211083 91183 3 Hd-8266 Sch-138 91183 251183 4 Hd-8267 Sch-139 251183 71283 4 Hd-8276 Sch-140 11283 201283 4 Hd-8365 Sch-141 201283 20184 4 Hd-8388 Sch-142 20184 100184 4 Hd-8389 Sch-143 100184 230184 4 Hd-8366 Sch-144 260184 20284 5 Hd-8474 Sch-145 70284 130284 4 Hd-8461 Sch-146 130284 200284 4 Hd-8447 Sch-147 200284 50384 3 Hd-8448 Sch-148 50384 190384 4 Hd-8494 Sch-149 190384 20484 4 Hd-8511 Sch-151 60484 160484 3 Hd-3518 Sch-152 160484 300484 3 Hd-8579 Sch-153 70584 140584 3 Hd-8580 Sch-154 140584 250584 3 Hd-8634 Sch-155 250584 110684 4 14C 25 Years of Tropospheric Observations in Central Europe 17 TABLE 3 HohenpeiJ3enberg station, W Germany (48°N, 11 °E)

613C 14C ANALYSIS SAMPLE OF EXPOSURE No. No. ddmmyy - ddmmyy %(PDB)

lid- 613 Hoh- 2 180559 * 7 lid- 199 Hoh- 8 180159 * 6 lid- 800 Hoh- 1 Hd- 837 Hoh- 181259 * 7 lid- 920 Hoh- 80860 * 1 Hd-1005 Hoh- 66 180361 * 8

TABLE 4 Bergen station, Norway (60°N, 5°E)

ANALYSIS SAMPLE PERIOD OF EXPOSURE 613C A14C No. No. ddmmyy - ddmmyy 5(PDB)

* lid- 823 Ber- 12 151259 181259 203+- 8 lid- 831 Ber- 15 250160 280160 * 78+- 9 lid- 844 Ber- 18 150360 190360 * 174+- 8 * lid- 811 Ber- 23 160560 190560 204+- 8 lid- 902 Ber- 26 150660 180660 * 183+- 6 lid- 930 Ber- 34 150860 180860 * 219+-10 * lid- 933 Ber- 31 140960 110960 207+- 7 Hd-1022 Ber- 54 150361 180361 * 196+- 1 lid-1099 Ber- 56 50461 80461 * 110+- 7 Hd-1092 Ber- 58 140661 110661 * 232+- 7 lid-1084 Ber- 59 150761 180761 * 236+- 1

TABLE 5 Pretoria station, South Africa (26°S, 28°E)

813C ANALYSIS SAMPLE PERIOD OF EXPOSURE L 'C No. No. ddmmyy - ddmmyy °(PDB)

* lid- 798 Pre- 2 211159 301159 115+- 6 * lid- 802 Pre- 3 211259 241259 195+- 1 * 7 lid- 813 Pre- 5 250160 250160 194+- * lid- 843 Pre- 1 220260 250260 192+- 8 * lid- 860 Pre- 9 210360 240360 181+- 8 * lid- 908 Pre- 10 110460 140460 118+ 7 * lid- 813 Pre- 11 250460 280460 150+- 6 * lid- 928 Pre- 13 300560 30660 164+- 6 lid- 922 Pre- 14 140660 110660 * 114+- 1 * lid- 929 Pre- 15 280660 10760 169+- 7 lid- 925 Pre- 17 250160 280160 * 113+- 8 * lid- 961 Pre- 20 60960 90960 185+- 1 * lid-1078 Pre- 22 111060 201060 191+- 7 * Hd- 996 Pre- 25 281160 11260 181+- 1 Hd-1077 Pre- 28 310161 30261 * 204+- 1 * lid-1096 Pre- 29 200261 230261 195+- 6 Hd-1091 Pre- 31 210361 240361 * 195+- 1 Hd-1089 Pre- 32 110461 140461 * 194+- 7 Hd-1083 Pre- 34 300561 20661 * 180+- 7 * Hd-1115 Pre- 38 220861 250861 207+- 6 18 Levin et al

TABLE 6 Yearly mean 14C levels observed at the Vermunt and Schauinsland stations, 14C proposed Northern Hemispheric "clean air" level corrected for fossil fuel contamination and the corresponding values, proposed by Tans (1981). The 14C activities observed in recent tree rings from a pine grown near Obrigheim, southern Germany (49°N, 9°E) are also presented. Values with an * presumably are slightly influenced by reactor see text.

Yearly mean " P d a i r rings Vermunt "clean air" Tans (1981) Obrigheim 14 I4 Year Q 1 14 G ( 10) Q ( (%o) . (y (o o) 1959 227 232 60 214 219 61 221 226 62 362 367 63 711 716 64 835 841 65 755 761 66 691 697 67 624 630 4 68 564 570 9 4 70 530 537 5* 71 499 506 5 72 465 472 4 73 429 426 3 74 401 409 5 75 368 376 5* 76 352 360 3 77 334 333 4 4 79 291 295 5 80 261 267 5 81 257 266 4 4 83 225 234 '4C 25 Years of Tropospheric Observations in Central Europe 19

RF:F1 RF:NCES Craig, Harmon, 1957, Isotopic standards for carbon and oxygen and correction factors for mass-spectrometric analysis of carbon dioxide: Geochim et Cosmochim Acta, v 12, p 133- 149. global carbon cycle Enting, 1 (; and Pearman, C I, 1982, I)escription of a one-dimensional model: I)ivision Atmos Physics tech paper no. 42, Commonwealth Sci Industrial Research Org, Melbourne, Australia. Fung, I, Prentice, K, Matthews, E, Lerner, J, and Russel, G, 1983, Three dimensional tracer model study of atmospheric COz: Response to seasonal exchanges with the terrestrial biosphere: Jour Geophys Research, v 88, no. C2, p 1281-1294. Jong, A F M, de and Mook, W C, 1982, An anomalous Suess effect above Europe: Nature, v 641-644. 298, no. 5875, p 14C Kromer, Bernd, 1984, Recalibration of Heidelberg laboratory data: Radiocarbon, v 26, p 148. 14C Levin, I, Munnich, K 0, and Weiss, W, 1980, The effect of anthropogenic CO2 and sources on the distribution of 14(. in the atmosphere, in Stuiver, Minze and Kra, Renee, eds, Inter- natl radiocarbon conf, 10th, Proc: Radiocarbon, v 22, no. 2, p 379-391. Munnich, K 0, (ms), 1957, Messung naturlichen Radiokohlenstofls mit einem ()2-Propor- tionalzahlrohr: Phi) thesis, Univ Heidelberg. in 14C content during the last years: Paper Munnich, K 0 and Vogel, J C, 1959, Variations presented at Internatl carbon-dating conf, 4th, Croningen, Sept 1959. ----- 1963, Investigations of meridional transport in the troposphere by means of measurements, in Symposium on radioactive dating, Proc: IAEA, Vienna. Carbon-14 14( Nydal, R and Ldvseth, K, 1983, Tracing bomb in the atmosphere 1962-1980: Jour Geo- v .. phys Research, 88, no. C6, p 3621-3642. Ostlund, H C and Engstrand, I. (,, 1963, Stockholm natural radiocarbon measurements V: Radiocarbon, v 5, 203-227. p carbon Pearman, G I, Hyson, P, and Fraser, P J, 1983, The global distribution of atmospheric dioxide, 1, Aspects of observations and modeling: Jour Geophys Research, v 88, no. C6, p 3581-3590. Reinsch, C, 1967, Smoothing by spline functions: Numerische Mathematik, v 10, p 177-183. Rotty, R, 1983, I)istribution of and changes in industrial carbon dioxide production: Jour Geophys Research, v 88, no. C2, p 1301-1 308. Schoch, H, Bruns, M, Munnich, K 0, and Munnich, M, 1980, A multicounter system for high precision carbon-14 measurements, in Stuiver, Minze and Kra, Renee, eds, Internatl radiocarbon conf, 10th, Proc: Radiocarbon, v 22, no. 2, p 442-447. Segl, M, Levin, I, Schoch-Fischer, H, Munnich, M, Kromer, B, Tschiersch, J, and Munnich, K 0, 1983, Anthropogenic14C variations, in Stuiver, Minze and Kra, Renee, eds, Inter- natl radiocarbon conf, 11th, Proc: Radiocarbon, v 25, no. 2, p 583-592. 9, Stuiver, M and Polach, H A, 1977, Discussion: Reporting of 'C data: Radiocarbon, v l p 355-363. 14C Stuiver, M and Quay, P I), 1981, Atmospheric changes resulting from fossil fuel release Planetary Sci Letters, v 53, 349-362. and cosmic ray flux variability: Earth p 14C Tans, P P, de Jong, A F M, and Mook, W C, 1979, Natural atmospheric variation and the effect: Nature, v 280, 826-828. Suess p 14f Tans, P P, 1981, A compilation of bomb data for use in global carbon model calculations, in. Bolin, B, ed, Scope 16: Carbon cycle modeling: Chichester, New York, Brisbane, Tor- onto,.J Wiley & Sons. radiocarbon dates IX: Radiocarbon, v 12, no. 2, 444-471. Vogel, J C, 1970, Groningen p [RADIOCARBON, VOL 27, No. 1, 1985, P 20-32] LA JOLLA MEASUREMENTS OF RADIOCARBON IN SOUTH GERMAN OAK TREE-RING CHRONOLOGIES T W LINICK*, H E SUESS Mt Soledad Radiocarbon Laboratory, University of California, San Diego, La Jolla, California 92093 and BERND BECKER Botanisches Institut, Universitat Stuttgart-Hohenheim 7000 Stuttgart 70, West Germany

ABSTRACT. Radiocarbon measurements made by the La Jolla laboratory on tree-ring samples from South German oak chronologies are presented. Several previously separate tree- ring series have been reduced to one absolutely dendro-dated chronology spanning the period from 4066 BC to the present and one still-floating chronology which spans the approximate period 7225 to 4125 BC. Previous estimates of the dendro-years made by the authors are compared with the dendro-years now assigned. From 1974 through 1982, the 14C contents of 575 European oak tree- ring samples were determined at the La Jolla laboratory. The samples came from tree-ring chronologies established by one of us (BB) from sub-fossil oak cross sections collected from South German river deposits. The '4C measurements on these samples provided a substantial basis for a preliminary estimation of the absolute ages of these then-floating Holocene oak tree-ring chronologies. This was accomplished by comparing their 14C variations with those obtained for the absolutely dendro-dated bristlecone-pine chronology using wiggle-matching methods (Kruse et al, 1980). During the past two years, several of the original Hohenheim Holo- cene oak series have been significantly enlarged and successively linked together into longer units. In cooperation with M G L Baillie and J Pilcher, Paleoecology Centre, Queen's University, Belfast, Northern Ireland, and B Schmidt, Dendrochronology Laboratory, University of Cologne, West Ger- many, it was possible to close the long-standing gap in the Hohenheim oak chronology. After correction by 71 years of a tentative, but incorrect, link of the South German series starting at 500 BC (Becker, 1983) and a successful cross-match between the Northern Irish, North German, and South German series from 2000 BC to AD 500 (Pilcher et al, in press), the absolutely dendro-dated Hohenheim oak chronology today extends continuously from the present back to 4066 BC. 14C Suess (1978) published data for the La Jolla analyses of the floating Hohenheim oak series Donau 7/9/12, Main 5, Donau 3/10, and Zug- Sumpf. In 1980 the authors published estimated absolute dendro-years of these series derived from computer-matching of their 14C variations with those in the La Jolla bristlecone-pine absolute chronology (Kruse et al, 1980). Because of the recently established tree-ring-width matches of these individual series into a sinle continuous absolutely dendro-dated sequence, the accuracy of the 4C wiggle-matching method can be checked. As listed in Table 1, the calibrated zero points (years of oldest rings) of the

*Present address: Laboratory of Isotope Geochemistry, Department of Geosciences, Uni- versity of Arizona, Tucson, Arizona 85721

20 La Jolla'4C Dates in South German Oak Tree-Ring Chronologies 21 four previously floating series differ from their absolute dendro-years by less than 10 years, with a range of 3 to 7 years difference. This fact demon- strates once again the validity of absolute radiometric age determinations by matching short-term 14C variations in floating tree-ring series with those in absolutely dated tree-ring chronologies. Progress has also been achieved in linking together the Hohenheim oak series older than 4100 BC. The floating chronologies Donau 6-Main 4/ 11, Main 6/1 3, Donau 11, and Donau 8 have recently been cross-matched (using relative ring widths) into a continuous 3182-year series. These series were initially calibrated individually by wiggle-matching with the bristlecone-pine chronology data. The zero point years estimated for the Donau 8 and Main 613 series were 4870 BC and 6457 BC, respectively. On the basis of an apparent overlap of only ca 150 years of the youngest end of the Donau 6-Main 4/11 series and the oldest end of the ' C-dated bristlecone- pine series, a zero point of 721.5 BC was assigned to the Donau 6-Main 411 series, which spans over 800 years. After the successful connection of these three series (according to ring widths) into a single continuous floating series, the previous wiggle-matching calibrations can be checked. The comparison of previous and new zero points is given in Table 2. If the single continuous floating series is assigned the zero point of the oldest series, Donau 6-Main 4/11, of 7215 BC, the revised zero points of the Main 6/13 and Donau 8 series differ by less than 20 years from their previous values. Recent measurements made by Minze Stuiver, Quaternary Isotope Laboratory, University of Washington, Seattle, and Bernd Kromer, Institut fur Umweltphysik, Universitat Heidelberg, West Germany, on samples from these older Hohenheim series confirm the La Jolla calibrations; details of their calibrations will be presented by Stuiver and Kromer at the 1985 radiocarbon conference in Trondheim, Norway. The zero point of 7215 BC for the Donau 6-Main 4/11-Main 6/13-Donau 8 series can be assumed to be correct to within 20 years. Data for many of the samples listed here were presented in a preliminary publication (Suess,1978). The data for these samples have been recal- culated using 95% of the activity of the original NBS oxalic acid standard as the reference; previously, the decay-corrected activity of mid-to late-19th century Douglas fir tree rings had been used as the reference standard at the La Jolla laboratory. Some of the data for samples from the Donau 6- Main 411 series, which appears to span the period 7225 to 6375 BC, were published by Bruns et al (1983). The La Jolla data for the Hohenheim oak series are presented in two tables, with samples ordered from oldest to youngest. The data for the uni- fied floating series from ca 7225 to 4125 BC are presented in Table 3, while those for the absolutely dendro-dated series covering the period from 4066 BC to AD 250 are given in Table 4. In these two tables, the columns give, from left to right, (1) the ring number, (2) the midpoint dendro-year (AD +, BC -, assigned by wiggle-matching or by absolute dendro-dating), (3) the number of tree rings in the sample, (4) the laboratory number (LJ - ), (5) the b' 3C (%o, PDB) measured on a recombusted aliquot of the acetylene 14C counting gas, (6) the conventional age (years BP, tl/2 = 5568 years) and 22 T W Linick, H E Suess, and Bernd Becker 14C its one standard deviation statistical uncertainty, and (7) the (%o, decay-corrected, based on the dendro-year, using t,/2 = 5730 years) and its one standard deviation statistical uncertainty.

ACKNOWLEDGMENTS The tree-ring studies carried out in Hohenheim were financially supported by the Deutsche Forschungsgemeinschaft. Operations of the Mt Soledad Radiocarbon Laboratory, La Jolla, were financed until 1980 through a grant from the US National Science Foundation, Atmospheric Science Division. However, support from the National Science Foundation was terminated at that time; this has led to a most regrettable delay in publication of these data, as well as final data from 14C dating of the bristlecone- pine chronology (including data for some samples measured after the Suess (1978) publication). Wood samples from the bristlecone-pine chronology were furnished to the La,Jolla laboratory by C W Ferguson, Laboratory of Tree-Ring Research, University of Arizona. We greatly appreciate the support from the Alexander von Humboldt Foundation, West Germany, that provided the possibility for the close cooperation between the European and American investigators and thus enabled completion of this manuscript.

TABLE 1 Comparison between 14C-calibrated zero point years of the previously floating Hohenheim Neolithic and Bronze age oak series and zero points based on linkage of series into absolutely dendro-dated master chronology Name of 14C-calibrated floating series zero point zero point (yr) Donau 7/9/12 Bc BC Main 5 3262 BC 3259 BC +3 Donau 3/10 2871 BC 2875 BC -4 Zug-Sumpf 1238 BC 1241 BC -3

TABLE 2 Comparison between 14C-calibrated zero points of the floating Hohenheim oak series older than 4100 BC and their zero points after linkage of the series into a single continuous floating chronology point after linkage Name of 14C-calibrated into one series starting floating series zero point at 7215 BC

Donau 6-Main 4/11 BC BC Main 6/13 6457 BC 6440 BC Donau 8 4870 BC 4851 BC La Jolla 14C Dates in South German Oak Tree-Ring Chronologies 23

TABLE 3 Floating series, ca 7225 to 4125 BC No. of Ring 13C 14C no. Year rings no. age

16 -7199 3 58 7.9 27 -7188 3 59 8.0 36 -7179 3 41 5.5 46 -7169 3 59 7.9 62 -7153 3 59 7.9 79 -7136 3 58 5 45 6J 104 -7111 3 57 7.7 116 -7099 4 59 7.9 127 -7088 5 57 7.6 137 -7078 3 43 ±5.8 153 -7062 3 52 7.0 164 -7051 3 56 7.6 175 -7040 3 59 8.0 182 -7033 4 57 7.8 198 -7017 4 58 7.8 210 -7005 3 57 7.7 222 -6993 4 60 8.1 279 -6936 2 61 8.1 287 -6928 5 57 7.6 303 -6912 1 55 7.4 314 -6901 2 55 7.4 322 -6893 2 54 7.3 331 -6884 1 56 7.4 346 -6869 2 54 7.3 354 -6861 2 55 7.3 372 -6843 1 55 7.3 380 -6835 2 58 7.6 406 -6809 2 56 7.5 418 -6797 2 55 7.3 433 -6782 4 60 8.0 444 -6771 2 56 7.6 460 -6755 2 55 7.3 472 -6743 5 59 7.9 487 -6728 5 55 7.3 501 -6714 1 44 5.8 514 -6701 6 64 8.5 534 -6681 6 55 7.4 539 -6676 1 56 7.4 566 -6649 2 54 7.1 577 -6638 5 55 7.2 591 -6624 1 55 7.3 614 -6601 1 56 7.4 632 -6583 4 38 5.0 651 -6564 1 54 7.2 688 -6527 1 60 8.0 696 -6519 3 38 5.1 717 -6498 1 56 7.4 729 -6486 5 54 7.2 742 -6473 2 56 7.4 752 -6463 1 54 7.1 755 -6460 1 53 7.0 766 -6449 1 55 7.3 783 -6432 1 44 5.8 795 -6420 1 44 5.9 809 -6406 1 54 7.2 822 -6393 1 53 7.1 1333 -5882 1 51 6.8 1343 -5872 1 51 6.9 1344 -5871 1 37 5.0 24 T W Linick, HE Suess, and Bernd Becker

TABLE 3 (continued)

Ring No. of no. Year rings no. age 14C

1353 -5862 1 55 1353 -5862 1 37 1358 -5857 1 36 1363 -5852 1 52 1365 -5850 1 37 1367 -5848 1 52 1377 -5838 1 52 1377 -5838 1 36 1387 -5828 1 51 1396 -5819 1 36 1397 -5818 1 52 1407 -5808 1 38 1416 -5799 3 52 1417 -5798 1 52 1426 -5789 3 37 1427 -5788 1 52 1435 -5780 4 38 1437 -5778 1 52 1447 -5768 1 51 1461 -5754 1 52 1462 -5753 11 52 1468 -5747 3 38 1475 -5740 6 51 1483 -5732 4 51 1487 -5728 4 51 1496 -5719 3 51 1507 -5708 3 51 1519 -5696 2 37 1527 -5688 1 52 1529 -5686 1 54 1537 -5678 1 51 1537 -5678 1 51 1545 -5670 1 36 1547 -5668 1 52 1557 -5658 2 52 1561 -5654 1 44 1571 -5644 10 52 1577 -5638 1 51 1587 -5628 1 39 1591 -5624 2 54 1604 -5611 1 51 1617 -5598 1 50 1649 -5566 6 50 1677 -5538 1 50 1681 -5534 4 50 1694 -5521 5 49 1702 -5513 1 50 1709 -5506 5 35 1719 -5496 5 44 1727 -5488 1 50 1738 -5477 3 42 1745 -5470 3 46 1759 -5456 5 35 1769 -5446 5 51 1777 -5438 1 39 1779 -5436 5 39 1784 -5431 5 51 1802 -5413 1 49 1807 -5408 2 48 1811 -5404 2 49 1817 -5398 2 51 87.5 ± 6.9 La Jolla '4C Dates in South German Oak Tree-Ring Chronologies 25

TABLE 3 (continued) Ring No. of no. Year rings no. age

1823 -5392 2 44 1827 -5388 1 38 1829 -5386 3 50 1832 -5383 3 44 1843 -5372 3 50 1854 -5361 3 49 1869 -5346 2 51 1873 -5342 2 50 1877 -5338 1 50 1881 -5334 2 43 1888 -5327 1 53 1892 -5323 1 42 1897 -5318 2 49 1899 -5316 6 49 2 50 1911 -5304 2 52 1918 -5297 3 50 1923 -5292 5 51 1924 -5291 3 48 1933 -5282 6 49 1949 -5266 3 40 1965 -5250 6 52 1996 -5219 1 51 2063 -5152 6 35 2073 -5142 4 31 2084 -5131 1 31 2099 -5116 2 35 2124 -5091 1 35 2136 -5079 1 29 2148 -5067 1 35 2176 -5039 1 35 2188 -5027 1 37 2199 -5016 1 35 2218 -4997 1 35 2231 -4984 1 35 2243 -4972 1 34 2253 -4962 1 35 2467 -4748 3 31 2480 -4735 2 49 2492 -4723 2 41 2505 -4710 3 68 2528 -4687 1 31 2540 -4675 4 40 2558 -4657 2 30 2572 -4643 1 39 2587 -4628 1 31 2597 -4618 1 48 2609 -4606 1 32 2619 -4596 1 48 2632 -4583 1 35 2650 -4565 1 49 2660 -4555 1 34 2670 -4545 1 37 2680 -4535 1 30 2691 -4524 1 50 2701 -4514 1 30 2709 -4506 1 37 2720 -4495 1 31 2731 -4484 1 33 2741 -4474 1 30 93.7 ± 4.1 26 T W Linick, HE Suess, and Bernd Becker

TABLE 3 (continued) Ring No. of no. Year rings no. age

2756 -4459 1 39 5.2 2765 -4450 1 31 4.1 2781 -4434 1 46 6.2 2791 -4424 1 30 4.0 2795 -4420 1 47 6.3 2798 -4417 1 48 6.4 2802 -4413 1 45 6.0 2807. -4408 1 47 6.3 2809 -4406 1 47 6.3 2813 -4402 1 46 6.1 2816 -4399 1 47 6.3 2819 -4396 1 48 6.4 2823 -4392 1 47 6.3 2825 -4390 1 47 6.4 2827 -4388 1 47 6.3 2829 -4386 1 63 8.5 2831 -4384 1 47 6.3 2834 -4381 1 70 9.3 2839 -4376 1 47 6.4 2841 -4374 1 47 6.4 2843 -4372 l 46 6.3 2848 -4367 1 47 6.4 2851 -4364 1 47

1 46 6.2 2862 -4353 1 46 6.3 2865 -4350 5 47 6.3 2870 -4345 6 47 4 49 6.7 2879 -4336 4 46 6.3 2884 -4331 3 46 6.2 2889 -4326 3 46 6.2 2892 -4323 1 46 6.2 2894 -4321 1 46 6.2 2896 -4319 1 45 6.1 2900 -4315 3 2902 -4313 1 50 6.8 2904 -4311 6 47 6.4 2905 -4310 l 46 6.1 2908 -4307 1 46 6.1 2910 -4305 1 46 6.2 2914 -4301 l 46 6.2 2916 -4299 1 46 6.2 2920 -4295 1 47 6.3 2923 -4292 l 47 6.4 2926 -4289 l 47 6.4 2928 -4287 1 45 6.1 2933 -4282 1 47 6.4 2941 -4274 1 45 6.1 2947 -4268 l 45 6.1 2948 -4267 9 45 6.1 2950 -4265 1 47 6.3 2957 -4258 8 45 6.1 2960 -4255 1 45 6.1 2964 -4251 1 47 6.3 2964 -4251 7 46 6.2 2969 -4246 1 46 6.2 2969 -4246 3 45

1 2987 -4228 5 46 6.2 2989 -4226 1 46 6.2 La- Jolla'4C Dates in South German Oak Tree-Ring Chronologies 27

TABLE 3 (continued) Ring No. of no. Year rings no. age

1 45 2994 -4221 4 45 2996 -4219 1 47 2998 -4217 1 47 2998 -4217 4 45 3000 -4215 1 46 3001 -4214 3 45 3004 -4211 1 45 3004 -4211 2 45 3006 -4209 1 46 3008 -4207 1 46 3013 -4202 3 45 3014 -4201 1 46

3017 -4198 1 44 3021 -4194 l 44 3024 -4191 4 45 3028 -4187 6 46 3034 --4181 4 45 3042 -4173 4 44 3052 -4163 6 45 3072 -4143 6 46 3078 -4137 6 45

TABI.E 4 Absolutely dendro-dated series, 4066 BC to Al) 250 Ring No. of no. Year rings no. age 14C

88 -3978 3 46 142 -3924 2 46 174 -3892 l 47 197 -3869 1 46 222 -3844 1 46 256 -3810 2 46 276 -3790 2 46 298 -3768 2 47 336 -3730 2 46 370 -3696 6 46 396 -3670 3 45 422 -3644 2 45 446 -3620 2 45 460 -3606 1 46 470 -3596 1 45 480 -3586 1 45 490 -3576 1 48 497 -3569 2 45 500 -3566 1 46 510 -3556 1 46 520 -3546 l 46 530 -3536 1 45 540 -3526 1 45 550 -3516 l 47 560 -3506 1 45 570 -3496 1 45 580 -3486 1 46 590 -3476 1 45 79.0 ± 6.0 a,1IcDQC000Ca,OCCOQ 1cD C6 --oGQ CDO',Q c000 GVGCCG0o0i0,OUOOOOCOa0C11Q,OtI000000Cccct-t ic; ,c, icc ic cc r; r r; r cc cc c c r, cc cc c c . c c c r r cc r cc , c r, c c c c (C cc icc c icc icc cc x Ln c icc cc cc cc c cc icc Lcc cc In icc c ic, Lr +l +I +I +I +I +I +I +I + +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +l +I +I +I +I +I +I +I +l +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I a diQ;c;d"'-CciCICD^;c;CcDoCc,CloCd:M--^ccC--Oc:C ^ncGd+oCC1dCd;;K;c;di>ncDcDcC>n0001--1 cvcucvicc ic cc cc ic dicccci cc CVcc i cc cc cc cc ic cc cc cc tcc t- cc t- cr-cGVcd1cc^^cccCVcccccr-i-r- cc c i cc r- cci- t- ccic;ccccccccci- cxi- xr- r- cc t- cc cc r- t- r- cc t- - t- icc ic;icci.ccc diic)dicc cc icin>rcc r- in r- cc cc cc cc t- cc cc cc inidiicc

i( Ndid,ciccic i)d1ccc CvCvdididiicc ccdicvdidiiccic;i- icdaicccc-isdidd+lc +icxccdiccMcccccccccd,d{ di di di di di d{ icc di d" di di di di di d" di di di di di di di di d' di di di di di di di di d^ di di di di cc +I +I +I +I +I +I +I +I +I +I +I +I +I +I tl +I +I +I +I +I tl +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +I +l +I +I tl +I Icc cicc ^1Lccccc-mod lccccicc cc cci- ccc Lccdcc ir- ict- cc cc cccc -ccc icdccc cccccr- cccccccdcucc i- ccGVGVccccicCVc cicc cicccroc cccf- cc cc ccc -cc cc cvinr- cc cicc cc cc cc cc -war-cc cc cc- wcc cc wcc cicc wcicicc r- cc cc icc ccic- i- i-- i- cccdiicicc inicc icc icc- d"ciccicc iicicccd{Mccc ciciccciNN ci ---+-+-----cc ci GV ccccccci- di

i- ic - cccciccr'- cc 1cdicc cc cc CV-cc d cc cccOci- d'Jccci ciccCCVcc cc cc cc ccii-cc c:icc cid- cci - ccc cc cc iS cicci- c dicccci- ccccccci cc cc cc dicccc ic cc cic i c is Lc ic ic;icdidicr,ccccic;Lc; d',ic;cc cc cc dinic;ic,icc ccLc;ccccd- ic;icc - ic; ic;didid+iccc ci ti cci ti GV ci ci ci ci c-i cci cci ci cicci c-i ci ci c-i ci ci ti ci ci ci ci cci c-i GV ci ci ci ci c-i ci cci tici GV ci CV c-1 c--I cI c-I GV CV ci GV ci GV CV c-i cI c--I c--I G--i c--I c-i ci GV

1 1 1 1 1 1 1 I 1 1 1 1 1 1 1 1 I I I I I I I 11 1 1 I 1 I I I I 1 I I I I I I 1 I I I I I I

I-- i-cc --+ic;cc cc cc cc cc cc cc icc ISCVcccc ccccc cccicccdi ccc w ` cLc;Clr;r,OCR,-.cc;.-^c;,i,--cvi^r;Ci^c;oC^r;cr,x;Cr;Cc--Lc;Lc;C^;c:^c',diCdidiCdidiTdiK;C;dicd'didid'di^;C:diJ:d'di^;diJ;dicc -+cc ciic; - cccccccccccccc - ccc-i cci-- iccd- - c c - cr- cc cc cc cc ic- c--i GVcc CV cccccc-cc-ccccccccc -- cc ccccccic-ic;i-i-i-i-i-i-M, K; ccccic- cicc cc- dc-di c x ccc ccc CV -i M M, M M, cc M M cc; M cc ci cc; cc; ci cc; ccc cc -M, M, cci cc) ci cc c i ci M M cci ccc cc ccc cc; M M cc) M ccc ccc cc cc; cfj M M M chi cc r- cc M d" ccc Q Nv N r1 1 V., bA -M------icvicc---ci--cci-- r-'"----'--c-viicV divivii r+H r-ti r-+r-y r-r r- zV .

cc ccvil`ccccci- iccccici- cc cd- cc d c--i iccc cc iccc cci- c;Ccic C c-V ccci-- ccc i-i-i-i- Cccc-C cIGV cccc C ccic;.cdiccccc-i---ccci-i-i-ccicc- cc;cccc;K;-cc cc cc cc cc cc -cc cccc -cc K,-cc-- cc icc ccc-i ccccic- ucc icd ccr-- ccic-- did -cc didididid dididididicr;MMccc MMMMMMMMccc ccc MM^icicici--cc cc cc cc cc cc cc cc cc cc cccc cc cc cc cc cc cc cc cc cc cc cc i-i-i-i-i-i-- cf;Mcc)cP;Mcc;cc)cc;II(IIIIIillllllillllllllllllllllll cc MMM,MMcc,c,^,McccMMK)MMMMMcccMMcc;McP)cc;MC^cc;ccicicicic1cicic-ic-Ic-ic-1vi iGVcic-iciCV-icicicicic-1ci

bA CGCdiO Ccc^Q ccOdiOa'^c c G11OGVdiCI x cOdiC cCdic)CICQ ^c CC0 0`,ICOdcfludidnOCci p cc ccicicc I-I- cc cc cc cc c -c-icccc;cciciccccci-- Q,ic cc cc;cc cc cc;c;cc cc --ccc ccicc iccc 1- c ciGVGVccc ncc-cciciccdi cccccccccccccccccccccccccccccccccctttl`1`tCC-- 1cc,cccccc------, ---,-GIIGIICVCVc--- ciCVclccccccccc La Jolla "C Dates in South German Oak Tree-Ring Chronologies 29

TABI.E 4 (Continued)

Ring No. of no. Year rings J no.. 4C 5.7 1361 -2705 1 44 1399 -2667 l 60 7.8 5.6 1410 -2656 1 43 1416 -2650 1 61 7.9 5.6 1440 -2626 1 43 1440 -2626 2 44 5.7 1451 -2615 1

1 43 2 44 5.8 4.0 1480 -2586 1 31 5.6 1491 -2575 1 43 1495 -2571 1 43 1 44 5.6 1505 -2561 l 43 5.6 60 7.8 1518 -2548 1 1526 -2540 l 43 5.5 1533 -2533 l 43 5.6 4.0 1555 -251 l 1 31 5.7 1578 -2488 1 44 5.7 1590 -2476 1 43 5.4 1600 -2466 1 42 1610 -2456 l 43 5.6 10.6 1620 -2446 1 81 5.6 1625 -2441 1 43 4.0 1640 -2426 1 31 5.6 1645 -2421 1 43 1656 -2410 2 43 5.6 5.6 1660 -2406 1 43 8.1 1666 -2400 1 62 5.4 1670 -2396 1 42 5.5 1685 -2381 1 42 5.6 1690 -2376 1 43 5.5 1690 -2376 1 43 5.4 1695 -2371 1 42 5.7 1705 -2361 1 44 5.5 1710 -2356 1 42 1715 -2351 l 31 4.0 5.7 1720 -2346 1 44 41 5.3 1732 -2334 1 5.4 1734 -2332 1 42 42 5.4 1746 -2320 1 6.2 1750 -2316 1 48 5.6 1754 -2312 1 43 7.5 1760 -2306 1 58 5.8 1765 -2301 1 45 5.5 1770 -2296 1 42 1775 -2291 l 43 5.5 5.8 1780 -2286 1 45 5.5 1785 -2281 1 43 5.4 1790 -2276 1 42 43 5.5 1794 -2272 1 5.5 1795 -2271 1 42 5.5 1800 -2266 1 42 1805 -2261 l 46 6.0 43 5.6 1810 -2256 1 41 5.3 1815 -2251 1 5.4 1820 -2246 1 42 41 5.3 1825 -2241 1 1831 -2235 3 43

1 46 5.9 30 T W Linick, H E Suess, and Bernd Becker

TABLE. 4 (continued) Ring No. of no. Year rings no. 4C

1840 -2226 1 42 5.4 1840 -2226 1 42 5.5 1845 -2221 1 43 5.5 1850 -2216 1 43 5.6 1855 -2211 1 60 7.7 1866 -2200 I 43 5.6 1875 -2191 l 44 1890 -2176 1 42 5.4 1895 -2171 l 42 5.4 1900 -2166 1 45 5.8 1905 -2161 1 42 5.4 1910 -2156 1 42 5.4 1915 -2151 1 43 1926 -214() 1 43 5.4 1930 -2136 1 43 5.5 1935 -2131 1 44 1940 -2126 1 42 5.4 1940 -2126 1 45 5.8 1945 -2121 1 41 5.3 1955 -21 l l 1 45 5.8 1964 -2102 l 43 5.5 1970 -2096 1 42 5.4 1980 -2086 1 41 5.3 1990 -2076 1 42 5.3 2007 -2059 1 43 5.5 2010 -2056 l 40 5.1 2015 -2051 1 48 6.2 2022 -2044 1 42 5.4 2026 -2040 1 42 5.3 2046 -2020 1 42 5.4 2050 -2016 1 45 5.8 2063 -2003 1 43 5.5 2070 -1996 1 38 4.8 2080 -1986 1 42 5.4 2085 -1981 1 42 5.4 2100 -1966 1 42 5.3 2115 -1951 1 42 5.4 2115 - l 951 l 41 ±5.2 2120 -1946 1 41 5.2 2137 -1929 1 42 5.4 2160 - l 906 1 42 5.4 2165 -1901 1 43 5.4 2165 -1901 l 43 2175 -1891 1 42 5.3 2185 - l 881 1 41 5.3 2190 -1876 1 42 5.4 2198 -1868 1 42 5.3 2217 -1849 3 42 5.3 2225 -1841 1 44 5.6 2240 -1826 l 42 5.3 2250 -1816 1 44 5.6 2260 -1806 2 42 5.3 2280 -1786 1 41 5.2 2290 - l 776 1 42 5.3 2315 -1751 1 42 5.3 2340 - l 726 1 59 7.5 2363 -1703 l 42 5.3 2390 -1676 l 42 5.3_ 2440 -1626 1 41 5.2 2649 -1417 3 41 16.7±5.2 LaJolla '4C Dates in South German Oak Tree-Ring Chronologies 31

TABLE 4 (continued)

Ring No. of 14 no. Year rings J no. age a 2656 -1410 2 41 2676 -1390 2 41 5.2 2698 -1368 2 41 2 41 5.2 2734 -1332 2 40 5.0 2746 -1320 2 41 5.1 2766 -1300 2 40 5.1 2786 -1280 2 41 5.1 5.0 2815 -1251 1 40 41 5.1 2831 -1235 1 41 5.1 2848 - l 218 1 2852 -1214 14 39 4.9 2862 -1204 2 40 5.0 2872 -1194 2 41 5.2 2874 -1192 10 39 4.9 2886 -1180 2 40 5.0 2894 -1172 10 39 4.9 2914 -1152 10 39 2918 -1148 2 40 2932 -1134 l 40 2934 -1132 10 39 2954 -1112 10 26.4 39 2966 -1100 2 40 2974 -1092 10 39 2994 -1072 10 39 2999 -1067 4 40 3014 -1052 10 39 3019 - l 047 3 41 3034 -1032 10 39 3046 -1020 2 40 3059 -1007 3 40 3080 -986 2 40 3084 -982 10 39 3104 -962 10 40 3108 -958 3 40 3130 -936 2 41 3144 -922 2 40 3159 -907 3 40 3169 -897 3 41 3605 -461 10 41 3615 -451 10 41 3623 -443 5 46 3628 -438 5 40 3635 -431 10 41 3645 -421 10 41 10 41 3735 -'331 10 41 1 39 39 3757 -309 1

1 38 38 3761 -305 1 39 3763 -'303 1 1 55 3769 -297 1 39

1 39

1 38 3798 -268 1 38

1 38

1 38 4.8 1 39 32 T W Linick, HE Suess, and Bernd Becker

TABLE 4 (continued) Ring No. of 8130 14C 14C no. Year rings LJ no. age

3853 -213 1 38 4.6 3863 -203 1 39 4.8 3868 -198 1 39 4.8 3879 -187 1 30 3.7 3903 -163 1 38 4.6 3922 -144 I 39 4.8 3953 -113 1 39 4.8 3963 -103 1 39 4.8 3978 -88 1 39 4.8 4003 -63 1 38 4.7 4018 -48 1 39 4.8 4028 -38 1 38 4.7 4053 -13 1 39 4.8 4077 12 1 38 4.7 4082 17 1 39 4.8 4087 22 1 38 4.7 4093 28 1 38 4.7 4102 37 1 57 1 39 4.8 4142 77 1 38 4.7 4162 97 1 39 4.7 4182 117 1 38 4.6 4202 137 1 38 4.7 4222 157 1 38 4.7 4237 172 1 42 5.1 4242 177 1 38 4.6 4258 193 1 39 4.8 4288 223 1 38 4.6 4310 245 6 38 4.7

REFERENCES Becker, Bernd, 1983, The long-term radiocarbon trend of the absolute oak tree-ring chronology, 2800 to 800 BC, in Stuiver, Minze and Kra, R S, eds, International 14C conf, 11th, Proc: Radiocarbon, v 25, no. 2, p 197-203. Bruns, M, Rhein, M, Linick, T W, and Suess, H E, 1983, The atmospheric 14C level in the 7th millenium BC, in Mook, W G and Waterbolk, H T, eds,14C and archeology: PACT, Stras- bourg, v 8, p 511-516. Kruse, H H, Linick, T W, Suess, H E, and Becker, Bernd, 1980, Computer-matched radiocarbon dates of floating tree-ring series, in Stuiver, Minze S, 14C and Kra, R eds, International conf, 10th, Proc: Radiocarbon, v 22, no. 2, p 260-266. Pilcher, J R, Baillie, MG L, Schmidt, B, and Becker, B, 1984, A 7272-year European tree-ring chronology: Nature, v 312, p 150-152. Suess, H E, 1978, La Jolla measurements of radiocarbon in tree-ring dated wood: Radiocar- bon, v 20, p 1-18. [RAntocARBoN, VOL 27, No. 1, 1985, P 33-42] CONTAMINATION STUDIES ON MOLLUSK SHELL SAMPLES TOMASZ GOSLAR and MIECZYSI AW F PAZDUR Radiocarbon Laboratory, Institute of Physics, Silesian Technical University, Krzywoustego 2, PL-44-100 Gliwice, Poland

ABSTRACT. A series of shell samples has been studied to determine the magnitude and mechanisms of carbon exchange between shells and their environment. Laboratory contamination experiments included the storing of shell samples in acid and calcareous environments of different 14C concentrations as well as studies of carbon exchange in the course of thermal recrystallization in solid state in an atomosphere of carbon dioxide. The applicability of differential thermal analysis to studies of the structure and texture of shells is discussed. INTRODUCTION The problem of sample contamination seems to be of special significance in the dating of mollusk shells, as foreign carbon may enter a sample due to the surface exchange between the sample CaCO3 and the environment. Occurring in the same form as the sample material, the contaminant cannot be practically removed by chemical pretreatment. In such a situa- tion one should only try to check if such an exchange has occurred. The mechanisms of shell carbonate contamination have been discussed by numerous authors (Olsson, 1968, 1974; Craig, 1954; Mangerud, 1972; Thommeret, 1976; Polach, 1976). According to Craig (1954) the only mechanism of isotopic exchange fast enough at temperatures found in nature is the recrystallization of shell carbonate by means of solution and its reprecipitation. In the process of recrystallization, primary aragonite, the main component of shell carbonate of most species, is dissolved, and the reprecipitated carbonate has a calcite structure. Calcite itself, however, could exchange carbon atoms with bicarbonates from its environment (Thommeret, 1976). A small exchange can also occur at the shell surface during long storage in open air (Olsson, 1974). There are several criteria which may help to detect the contamination of shell carbonate due to carbon exchange. X-ray examination of the mineralogic structure proves that no recrystallization has taken place, except in shells of a primary aragonite structure. In dating marine shells, the possibility of contamination should be accounted for if b' 3C < - 3% vs PDB (Man- gerud, 1972). An alternative isotopic criterion can be based on o180 values (Craig, 1954). The degree of contamination may also be estimated visually, as stated by some authors, since shells with a good surface texture and well- preserved periostracum are usually recrystallized less than those with weak surface textures (Taft, 1976; Mangerud, 1972). The main aim of our work was to determine the magnitude and mechanisms of carbon exchange between shells and their environment in various artifically produced conditions and to check the potential use of differential thermal analysis in studies of post-depositional changes of the structure and composition of shells.

SAMPLE DESCRIPTIONS The samples designated ZO-1 to ZO-6 are marine shells of Mya trun- catg, Hiatella arctica, and Mytilus edulis, collected 1975 on the marine ter-

33 34 Tomasz Goslar and Mieczysiaw F Pazdur races of King Oscar Land, West Spitsbergen by Jan Szupryczynski, Polish Academy of Science, Torun, and dated for studies of the rate of isostatic uplift after the recession of the Billefjorden ice sheet (Boulton,1979). Sam- ples M79 (Helix pomatia) and M81 (Helix and Cepea sp) were collected by the first author in November 1979 in Bgdzin and in September 1981 in Opole, respectively. The shells were empty, partly filled with soil and sand and covered with dry leaves. Sample J-1-80 consists of shells of freshwater species Lymnaea, collected 1980 in Jaroszow near Walbrzych by Henryk Chmal, Geographic Institute, Wrodaw University, Wrodaw.

CONTAMINATION EXPERIMENTS Limestone Environment A portion of ca 60g of crushed shells of sample M79 was mixed with ca 300g of 14C-free chalk and ca 200g of peat, dated to >42,500, Gd-1076, and >42,900, Gd-1077 (R, 1983, v 25, p 850) and placed with some water in a tightly closed glass jar. The mixture was stored for 133 days at a temperature of 50 to 60°C. The same experiment was repeated with the sample M81. The resulting samples were designated as M79wap and M81wap, respectively.

Acid Environment A portion of 100g of shells of sample ZO-4 was mixed with ca 200g of recent active soil with plant fragments and placed with 200cm3 of diluted citric acid with a pH = 2.5 in a tightly closed glass jar and stored for 133 days at 60-50°C. As the sample ZO-4 was dated to ca 10,500 yr BP (see table 3), any exchange of carbon should produce a younger age of the resulting sample, denoted as ZO-4kwas.

Gaseous CO2 Environment at Elevated Temperatures For studies of carbon exchange during recrystallization in solid state, shells of the ZO-4 sample were subjected to three experiments: 1) ZO-4A/500. The shells were heated for 2 hours at a temperature of 450-550°C (aragonite-calcite transition) in an atmosphere of carbon diox- '4C ide of activity equal to 3300 PM (PM = per cent of modern). 2) ZO-4/500. The shells were heated as above for 8 hours; in the last 15 minutes the temperature was raised to 950°C and the apparatus was open to air. 3) ZO-4900. The shells were heated for 2 hours at a temperature of i4C 800-900°C in an atmosphere of CO2 of activity equal to 187 ± 11 PM. In the last two experiments a small amount of air was present in the CO2 atmosphere.

X-RAY ANALYSES Table 1 presents the results of the mineralogic x-ray analysis of shell samples. Some samples were subjected to additional measurements in order to estimate the size of the crystalline grains. Most of the studied samples have an aragonite structure. Shells of Mya truncata show also traces of TABLE I Identification of the crystalline phases and results of grain size measurements of the studied samples

size Sample Aragonite Calcite CaO, CaO2 indices (urn) M79 ++ <0.3% Helix pomatia ZO-1 MYA ++ Mya truncata ZO-1 HIA ++ Hiatella arctica ZO-2MYT -50% Mytiles edulis ZO-2RES + + other ZO-3NIEB <0.5% only outer part of Mytilus ZO-3PERL mostly inner part of Mytilus ZO-3RES other ZO-4 ++ Mya truncata ZO-S MYA ++ Mya truncata ZO-SRES + + other ZO-6 + + Mya truncata -l-80 J ++ 14 Lymnaea sp 122A 260 ± 130 220,104A 180±70 M79wap ++ <1% 200 ZO-4kwas + + <0.5% ZO-4A 500 + + 1390 1160 >250 7_()-4500 + ++ 1160 >250 ZO-4900 + + + 1160 >400 lO1X 64±7 s + + = main component; + = other component; tr = trace; A = aragonite; C = calcite; X = Ca(OH)2. The calcite and aragonite content was determined by the intensities of (102) and (111) aragonite and (104) calcite diffraction lines (Davies & Hooper, 1963). The grain size diameter was estimated from the line broadening, based on Scherer's equation (Klug & Alexander, 1954). 36 Tomasz Goslar and Mieczyslaw F Pazdur vaterite, which is not found in other shells. The a-quartz lines probably result from minute amounts of sand on the surface of some shells. The samples ZO-2MYT, ZO-3NIEB, and ZO-3PERL consist of species producing a blue calcite layer and pearly aragonite layer (Keith, Anderson, & Eichler, 1964; Thommeret, 1976), so the presence of calcite diffraction lines does not prove their recrystallization. The higher calcite content in the ZO- 1 HIA sample may have been connected with the fact that the surface of the shells was soft and "loose." No correlation was found between the degree of recrystallization and the amount of conchioline. Samples subjected to elevated temperatures were totally recrystallized. The presence of G0, CaO2, and Ca(OH)2 in samples ZO-4/500 and ZO- 4/900 is caused by a partial decomposition of calcite and the subsequent adsorption of water vapor and oxygen from air. The size of the crystalline grains is of the order 102-103nm. The smaller size of calcite grains observed in sample j-1-80 might suggest that this calcite was formed by dissolution and reprecipitation. We did not find out for certain, however, if the size of the crystalline grains changes during the thermally induced transition of aragonite into calcite. The answer to the question whether measurements of the grain size might help to determine the primary or secondary origion of the calcite present in some shells needs additional precise measurements.

THERMAL ANALYSES Thermal analyses of shells were carried out to estimate their chemical composition and crystalline structure and, if possible, the packing of their polycrystalline texture. During the thermal analysis, an investigated sample and appropriate standard reference sample, placed in two pots, are heated at a constant rate, and the temperature of the reference sample together with the difference of temperatures between the reference and investigated samples are plotted as functions of time (curves T and DTA, respectively, fig 1). In an ideal case, curve T should be a straight line. Any endothermic or exothermic transformation of the sample is revealed by a corresponding minimum or maximum of the DTA curve, and, if the reaction heat is suffi- ciently high, a deviation of curve T from linearity could also be observed. Curve TG (fig 1) records the loss of sample mass in the function of time. The DTA curve of calcite has one minimum corresponding to its decomposition: CaGO3 CaO + CO2T, at temperatures of 920-950°C (Liptay, 1971). Aragonite should give, on the DTA curve, an additional small endothermic peak at 470-480°C, corresponding to the aragonite-calcite transition. TG curves are identical for both structures (Liptay, 1971). The equilibrium temperature of the decomposition of CaCO3 in air is equal to 787°C (Schultze, 1974). The real equilibrium temperature increases, however, with the increase of the local COl pressure in the pores between the individual grains. Moreover, since the reaction rate at the boundary solid-gaseous phase is limited, decomposition of calcite occurs at higher temperatures. Both effects cause a broadening and shifting of the DTA peaks of calcite decomposition. The parameters of the TG and DTA curves of the investigated shell Contamination Studies on Mollusk Shell Samples 37

Fig 1. An example of differential thermal analysis curves (sample ZO-3RES) with indicated parameters of the DTA and TG curves. samples are listed in table 2. No peak of aragonite-calcite transition was observed in any of the studied samples, even at an increased sensitivity of the DTA curve. All samples show a small decrease of mass below 100°C, interpreted as dehydration.. The loss of mass in the temperature interval from 100°C to T, and small exothermic peak of the DTA curve at T,,, correspond to the burning of organic matter of the shell. The values of TO and T,,, are presented graphically in figure 2. The character of both of these diagrams seems to indicate that organic matter is variously distributed in shells of different species. The lack of a T, peak in three samples is to be attrib- uted to the low content of organic fractions in these shells. Thermal analyses show that organic fraction does not occur in shells subjected to elevated temperatures. Instead, these samples show an endothermic peak and corresponding loss of mass due to the decomposition of Ca(OH)2 : Ca(OH)2 --

CaO + H2O T (Liptay, 1975). The diagrams in figure 3 show the localization of the DTA peak of calcite decomposition and its width, both in time and temperature scales. Two groups of samples were distinguished, separated in table 2 by a broken line. The Student test at the significance level a = 0.001 indicates that only the difference of the mean values of t for both groups is significant. Such 38 Tomasz Goslar and Mieczys-laze F Pazdur

TABLE 2 Parameters of the TG and DTA curves of the studied samples

Sample m mg p% T, T2 ZO-1 MYA 1100 95.5 ZO-1 HIA 1100 95.6 ZO-2MYT 1100 96.5 ZO-2RES 1100 95.9 ZO-3NIEB 1100 94.5 40 ZO-3PERL 1100 94.8 40 ZO-3RES 1100 95.5 ZO-4 1100 95.9 ZO-5MYA 1100 95.6 ZO-5RES 1300 - ZO-6 1300 - J-1-80 1100 93.8 n

M79wap 1100 97.1 430 935 M 79wap* 820 97.3 420 925 ZO-4* 1100 95.9 200 930 ZO-4kwas 1100 94.6 200 925 ZO-4A/500 1100 96.3 n 930 ZO-4/5 00 1000 56.4 ZO-4/9 00 1100 78.9 mass of Ca (OH)2 CaO, G02 mg Parameters: heating rate - 11 °C/min, DTA sensitivity - 1/20, TG sensitivity 500, * - = DTA sensitivity - 1/10; m = mass of the sample; p = CaCO3 content in %; n = no peak results suggest that the supposed differences in the composition of calcite are connected more likely with the reaction rate at the boundary solid-gaseous phase than with the increase of the local CO2 pressure. Crystalline grains are probably greater in samples of the first group.

14C AND `3C MEASUREMENTS Table 3 shows the results of measurements of '4C and '3C for samples used in studies of carbon exchange. 14C dates of other shell samples will be published elsewhere (Goslar & Pazdur, 1984) The b' 3C values of Spits- bergen shells lie in the range from +0.9 to +2.6I()()Oo vs PDB, for the fresh- b'3C water sample, J-1-80, = -6.38 ± 0.04/,o vs PDB, as was to be expected.

00 i 200 300 400 T0N

o 1 1 310 320 330 340 lack Tm[°C

Fig 2. Temperatures of the beginning (Tf,) and the maximum (Tn,) of the burning of shell organic matter. = Mya, Hiatella; U = Mytilus; 0 = Helix; 0 = Lymnaea. Contamination Studies on Mollusk Shell Samples 39

(°Cl 12[°C] T T [°G] et [mini 905° ° ° 40 °°°°°°°° ° 50 °°° 14 °°°° 9100 ° 000 ° 44$ ° 40 000 12 9200000+ ° + + 30 ++ 0 4 30 +++ 10 + 30 ++ +

Fig 3. Location and width of the DTA peak of the decomposition of calcite.

DISCUSSION OF THE CONTAMINATION EXPERIMENTS

Limestone Environment The difference of 14C activity of M79 and M79wap samples is great, which is quite surprising because both samples are of an aragonite structure. The experiment has been repeated on sample M81, and no significant change of 14C activity was found. Also, measurements of b' 3C do not suggest any significant exchange. As the only explanation of this controversy we suggest a temporal inhomogeneity of sample M79, caused by the incorpo- ration of a few shells a dozen or so years older (see fig 4).

Acid Environment The results of 14C activity measurements in samples ZO-4 and ZO- 4kwas give no evidence of carbon exchange in the external part of the shell sample. Exchange degree denotes the fraction of total carbon which is exchanged with those from the surrounding environment causing measured shift of 14C activity without any change of sample mass. Assuming the contamination of the external part of the ZO-4kwas sample with recent soil organic matter of 14C activity equal to 150 ± 20 PM, the estimated exchange degree would be 9 ± 74o. Such a small exchange may have taken place during the dissolution of aragonite and the subsequent reprecipitation of calcite. This hypothesis seems to be confirmed by the lower content of CaCO5 in the sample ZO-4kwas and the small shift of the b' 3C value. As the above small admixture of calcite lies below detection limit of X-ray anal-

TABLE 3 Results of '3C and 14C measurements of the shells used in exchange experiments 14C 14C Sample b'3C; 6o vs PDB activity (PM) Age BP or D ZO-4 OUT + 1.81 ± 0.15 27.28 ± 0.28 10,430 ± 90 ZO-41N same 26.95 ± 0.48 10,530 ± 150 ZO-4kwasOUT +2.46 ± 0.16 28.24 ± 0.32 10,160 ± 90 ZO-4kwasIN same 26.28 ± 0.50 10,730 ± 160 M79 -10.84 ± 0.11 144.51 ± 1.10 445 ± 11 M79wapOUT -10.91 ± 0.11 135.90 ± 1.53 359 ± 16 M79wapIN same 135.45 ± 0.74 355 ± 8 M81 OUT -10.40 ± 0.03 134.48 ± 0.95 345 ± 10 M81IN same 135.87 ± 0.65 359 ± 7 M8IwapOUT -10.89 ± 0.04 134.34 ± 1.08 343 ± 11 M81 wapIN -10.74 ± 0.08 134.65 ± 1.04 347 ± 11 ZO-4A/500 +1.80 ± 0.05 28.51 ± 0.29 10,080 ± 90 ZO-4/500 -4.58 ± 0.08 45.78 ± 0.63 6280 ± 120 ZO-4/900 -1.41 ± 0.14 34.93 ± 0.45 8450 ± 110 40 Tomasz Goslar and Mieczysaw F Pazdur [%] e14C 450 fM79

4001-

M 79II 35( wapOU TJ1 pIN waplN M81//M81 OUT wa OUT

1975 1976 1977 1978 1979 1980 1981 year 14C Fig 4. Results of measurements of shells used in studies of carbon exchange in a calcareous environment. The horizontal bars denote the average annual levels of atmospheric 14C activity estimated from data provided by Levin, Mi nnich, and Weiss (1980) and Segl et al (1983). ysis, it is to be concluded that even a recrystallization undetectable by x-ray analysis may cause a significant error of the 14C age of the shell (in the case of sample ZO-4 > 200 yr). Elevated Temperatures 14C The activity of sample ZO-4A/500 is ca 1% higher than that of sample ZO-4. This is equivalent to an exchange degree equal to 0.46 ± 0.24%o. 14C We suppose, however, that this change of activity is not caused by carbon exchange during recrystallization, but by small adsorption of active CO2 in the shell pores. The changes of 14C activity of the ZO-4/500 and ZO-4/900 samples with respect to the initial sample Z0-4 are equivalent to exchange degrees equal to 5.8 ± 0.6%o and 50.7 ± 9.2%o, respectively. The assumed mechanism of this exchange comprises the decomposition of CaCO3 and recrystallization, according to the model shown in figure 5. This model accounts for the burning of organic matter in the shell, the evolving of some CO2, and the adsorption of H2O and *C02 of high 14C concentration by CaO. For the sake of simplicity, the presence of CaO2 is neglected, which is justified by its small amount estimated from the DTA and TG curves. In order to test if such a model describes correctly the complexity of the reactions involved, the values of the coefficient (13C/' 2C)C02 a (13C/12C)CaCO3 were calculated based on the data obtained in experiments with samples ZO-4/500 and ZO-4/900. The masses of the individual components were calculated from known amounts of CaGO3, CaO, and Ca(OH)2 and the known exchange degree of 14C in both experiments. The values of 513G of initial CO2 surrounding the samples were assumed to be 3 = -20 ± 20%o and b2 = -22 ± 5%o, respectively. The calculated values of a are equal to a1 = 1.0059 ± 0.0008 and a2 = 1.0052 ± 0.0023. The good agreement of Contamination Studies on Mollusk Shell Samples 41

A cot IH2o 15 q 23 rg 41 Ca(OH)2 232 70 93 CciCO3 a 0 Ca0 47 176 CaCO3 b L C

19 b x'34 am Cpr=959 aC03 Cp=679 r cp Cw 645 Fig 5. Simplified model of reactions during the heating of shells in a carbon dioxide 14C atmosphere of high activity. C initial mass of CaCO3; CW = mass of CaCO3 formed with r = 14C b, S*, 8 external *C02 ; CP = final mass of CaCO3; *C = carbon of high activity; f, and Sm = b13C coefficients of the initial sample, external CO2, CaCO3 after the decomposition of some initial carbonate, and final CaCO3, respectively. The upper and lower numbers denote values from the 1st and 2nd experiment (see text). both these values seems to confirm the suitability of the model presented in figure 5, despite relatively large errors caused by low accuracy of the assumed values of b.

CONCLUSIONS The results of differential thermal analyses of shell samples indicate that this technique is unsuitable for determining the crystalline structure of shells. Exchange experiments in an acid environment show, however, that even the results of x-ray analysis cannot completely exclude the recrystallization of shells by dissolution and reprecipitation. No carbon exchange was found in experiments with limestone environment and during thermal recrystallization in solid state. A significant isotopic fractionation was proved during the thermal decomposition of calicte. X-ray analysis shows traces of vaterite in shells of Mya truncata. The dimensions of crystalline grains of mollusk shells were determined to be equal to 102-103nm. The question based on the measurements of the grain size, of the possibility of distinguishing between primary and secondary calcite remains, as yet, open.

REFERENCES Boulton, G S, 1979, Glacial history of the Spitsbergen archipelago and the problem of a Ba- rents Shelf ice sheet: Boreas, v 8, p 31-57. Craig, Harmon, 1954, Carbon-13 in plants and the relationship between carbon-13 and carbon-14 variations in nature: Jour Geol, v 62 p 115-149. Davies, T T and Hooper, P R, 1963, The determination of calcite:aragonite ratio in mollusc shells by X-ray diffraction: Mineralog Magazine, v 33, p 608-612. Goslar, Tomasz and Pazdur, M F, in press, Datowanie muszli metod14C: Kwartalnik Geol, v 28, in press. Keith, M L, Anderson, G H, and Eichler, R, 1964, Carbon and oxygen isotopic composition of 42 Tomasz Goslar and Mieczysiaw F Pazdur

mollusc shells from marine and freshwater environments: Geochim et Cosmochim Acta, v 128, p 1757-1786. Klug, H P and Alexander, L E, 1954, X-ray diffraction procedures for polycrystalline and amorphous materials: New York, John Wiley and Sons, Inc, p 491-537. Levin, Ingeborg, Munnich, K 0, and Weiss, Wolfgang, 1980, The effect '4C of anthropogenic CO2 and sources on the distribution of 14C in the atmosphere, in Stuiver, Minze and Kra, Renee, eds, Internatl radiocarbon conf, 10th, Proc: Radiocarbon, v 22, no.2, p 379- 391. Liptay, G, 1971, Atlas of thermoanalytical curves: Vol 1, Budapest, Akad Kiado. - 1975, Atlas of thermoanalytical curves: Vol 5, Budapest, Akad Kiado. Mangerud, Jan, 1972, Radiocarbon dating of marine shells, including discussion of apparent age of recent shells from Norway: Boreas, v 1, p 143-172. Olsson, I U,1968, Modern aspects of radiocarbon dating: Earth Sci Rev, v 4, p 203-218. -----1974, Some problems in connection with the evaluation of 14C dates: Geol Foren Stokholm Forh, v 96, p 311-320. Polach, H A, 1976, Radiocarbon dating as a research tool in archaeology-hopes and limita- tions, in Barnard, Noel, ed, Symposium on scientific methods of research in the study of ancient Chinese Bronzes and South East Asian metal and other archaeological artifacts, Proc: Melbourne, Australia, Nat! Gallery Victoria, p 255-298. Pazdur, M F, Awsiuk, Romuald, Bluszcz, Andrzej, Pazdur, Anna, Walanus, Adam, and Zas- tawny, Andrzej, 1983, Gliwice radiocarbon dates IX: Radiocarbon, v 25, p 843-866. Schultze, I), 1974, Termiczna analiza roznicowa: Warszawa, Panstwowe Wydawnictwo Nau- kowe. Segl, Monika, Levin, Ingeborg, Schoch-Fischer, Hilla, Munnich, Marianne, Kramer, Bernd, Tschiersch, Jochen, and Munnich, K 0, 1983, Anthropogenic 14C variations, in Stuiver, Minze and Kra, Renee, eds, Internatl radiocarbon conf, 11 th, Proc: Radiocarbon, v 25, p 583-592. Taft, W H, 1967, Modern carbonate sediments: Developments in sedimentology, v 9A, p 29- 50. Thommeret, Jean, 1976, Difficultes d'interpretation des dates 14C mesurees a partir des coquilles marines, in Labeyrie, Jacques and Lalou, Claude, eds, Union Internatl des Sci Prehistoriques et Protohistoriques, Cong, 9th: Col! I, Datations absolues et analyses isoto- piques en prehistoric, methodes et limites: Paris, CNRS, p 160-169. [RADIoCAKBON, Vot, 27, No. 1, 1985, P 43-51] WOODS HOLE OCEANOGRAPHIC INSTITUTION RADIOCARBON LABORATORY: SAMPLE TREATMENT AND GAS PREPARATION SHEILA GRIFFIN and ELLEN R M DRUFFEL Woods Hole Oceanographic Institution, Department of Chemistry, Woods Hole, Massachusetts 02543

INTRODUCTION The purpose of this paper is to present the methodology used for sample preparation at the Woods Hole Oceanographic Institution Radiocar- bon Laboratory. The WHOI lab is dedicated to oceanographic research supported by the National Science Foundation (OCE81-11954). We began operation in March 1982. The methods used for the production of samples are based on those developed previously (Barker, 1953; Suess, 1954; Noakes, Kim, & Stipp, 1969; Linick, 1975). Subsequent changes and refinements to these methods are described. This paper will present detailed descriptions of how various samples are collected and sectioned, then converted to CO2 and to C2H2, the primary counting gas for most of our samples. Use of acetylene as a counting gas for radiocarbon detection was ini- tiated by Suess (1954). He precipitated SrCO in a strong ammonia solution and then produced SrCI by reduction with Mg. Subsequent hydrolysis of SrC9 produced C2H2 gas. Methods were also developed during the early 1950's, that used direct absorption of CO2 into molten Li and subsequent hydrolysis of the Li2C2 (Barker, 1953; Noakes, Kim, & Stipp, 1969; Linick, l 975). The preparation of acetylene from coralline aragonite, the primary oceanographic substrate used in our research, is described here. Acetylene gas is used for two major reasons. First, our past experience at the La Jolla Radiocarbon Laboratory in collaboration with Hans E Suess was with acetylene detection systems (Suess, 1954). Second, higher levels of impurities are tolerated when counting acetylene than with CO2 counting, with no significant alteration of counter pulse height or energy. Thus, it is feasible to use one-channel detection systems for monitoring radiocarbon pulses from acetylene gas. Carbon dioxide gas is counted for samples smaller than 900mg carbon. Research topics of major interest to us are those involving the cycling of carbon between atmosphere and ocean, as well as determination of past ocean circulation. We are particularly concerned with those mixing processes in the upper few hundred meters of the water column. Skeletons of corals are excellent monitors of various physical and chemical processes in the oceans. Hermatypic, or reef-building, corals accrete calcium carbonate using mainly the dissolved inorganic carbon (DIC) extracted directly from the surrounding sea water. They accrete density layers, which are detect- able using X-rays. Plate 1 shows an X-radiograph of a slab of Diploria strig- osa (8mm thick) cut along the vertical axis of growth from a massive (hemi- spherical) head (1.3m diameter) collected from the south shore of Bermuda (33°N, 63°W). Each alternating light and dark density band constitutes one 43 44 Sheila Griffin and Ellen R M Druffel

PLATE 1

X-ray positive of a slab of coralline aragonite, 9mm thick, cut along the axis of growth of Diploria from North Rock in Bermuda. Woods Hole: Sample Treatment and Gas Preparation 45 year's growth, the dark band having been accreted during the warm months (30°C) of July-September. Recorded within known-aged coral bands are time histories of: 1) sea 180/160 surface temperature and salinity from ratios (Weber & Woodhead, 1972; Fairbanks & Dodge, 1979); 2) input of anthropogenic Pb from Pb/ '4C Ca ratios (Shen & Boyle, 1983); 3) fossil fuel CO2 and bomb-produced from '4C/ '2C ratios (Druffel & Linick, 1978; Druffel & Suess, 1983); 4) bomb-produced fallout products, such as 90Sr (Toggweiler, 1983) and 2,240Pu (Purely, Livingston, & Druffel, unpub data). For the results of our research, the reader is referred to other publications (Druffel, 1980, 1981, 1982). It is our purpose here to describe in detail the technical aspects of our methods for sample collection, sectioning, and gas preparation. Attention to detail and inclusion of "tricks of the trade" are important to the scientist who intends to set up his/her own lab. Intercalibration of the counting systems with other labs will appear in a later publication.

METHODS

Sample Description and Preparation Coral for 14C analysis is collected using a hydraulic drill fitted with a diamond bit and a core barrel 3 to 4 inches in diameter. This arrangement is driven by a small hydraulic pump which is operated from aboard ship (Hudson et al, 1976). Using extensions, cores up to 14 feet long have been obtained. The cores are cleaned by placing them under running water for approximately four hours to remove most of the polyps and residual sea salts. The cores are dried and sliced along the vertical growth axes using a diamond rock saw. Slabs, 4 to 10mm thick, are ultrasonically cleaned to remove dust imbedded in the skeleton. The dried coral slabs are X-rayed at the Falmouth Hospital x-ray facility. Yearly growth bands appear as alternating high and low density bands (p11). A map is made from the X-ray by tracing the high density bands onto an acetate sheet, which is then trans- ferred onto the coral slab. It is below this line that the coral is cut into one- year growth bands using a band saw. Bands cut in this manner from Diploria collected off Bermuda represent a September-to-August time interval. These bands are then ground into coarse fragments using a porcelain mortar and pestle. If seasonal growth bands are desired, then the one-year growth bands are sectioned into four equidistant parts. These small bands are sanded off using a Dremel tool. Sanding minimizes the amount of sample lost due to the thickness of the saw blade. Other types of samples are also prepared at the WHOI lab. Cellulose from tree rings, hydrothermal vent samples (shells and tissue), seawater marine biomass and ocean sediments are pre-prepared in accordance with standard techniques described previously.

Preparation of Counting Gas The WHOI lab uses acetylene as the counting gas for most 14C analyses. Initially, each sample is converted to carbon dioxide using either the 46 Sheila Griffin and Ellen R M Druffel

VACUUM LINES FOR CO2 PREPARATION

CO2 STORAGE BULB

FINE PUMP a (<10 TORR) v MANOMETER

iROUGH PUMP L_ (<102 TORR) SAMPLE

FLOW METER

O2 TANK

\__J v u NaOH CO2 H2O H2O P205 (4) (3) (2) (5)

L CuO; HEAT SLEEVE --

Hg MANOMETER MEKER BURNERS

Fig 1. Schematic of vacuum system used for CO2 preparation. Carbon dioxide is produced initially either by acidification with HCl or by heat in a stream of oxygen gas. Subse- quent elimination of water is achieved in traps 1, 2, 3, 5, and 7 (see text for detail). acidification or burning methods (fig 1) and then reduced to acetylene gas via lithium carbide (fig 2). The vacuum lines are constructed of borosilicate glass (Pyrex). The stopcocks are glass barrel o-ring construction; o-ring ball joints are also used to reduce the risk of contamination from stopcock grease.

Acidif cation. Ca 22g of coralline aragonite is acidified in order to gen- erate enough gas (2.35L acetylene) for the 1.5L quartz counter. The sample is placed in a 3L round-bottom flask, and air is evacuated to a pressure of 10 - torr using mercury diffusion and two-stage mechanical pumps (fig 1). Small aliquots of 4N HC1 are then added to the sample over a 30-minute period. The amount of time it takes to complete the reaction is dependent on the weight, grain size, and percent organic carbon content of the sample. Carbon dioxide evolves according to this reaction:

CaCO3 + 2 H+ Ca2 + CO2() + H2O (1) Wendt Hale: Sample Treatment and (at Peepaealtan 47

VACUUM LINES FOR CH2 PREPARATION

Fig 2. temahcnt ac ann aydc nird lee ( 11 pimp ian L'bdmadr

1, 10, 12, md 14 and 4w enltant I II n pinked n nap lb lhr tipk p at rat 00.0a'artyter aim (nc tact ha

The gas passrs tbraugb a series af traps. iraps 1, 2, and 3, snrmannded b5 dewars hued m'itlt isaprapanol (try a e slusbes ( 77 C), collect water bat distills aaer bent tbe reat tian resin!. ( arbot ditataide is fraaen intn trap 4, wlticbissnrronnded by liquid nitrogen ( 192 C). Witen tlt ereac lions hn— shed. as ecident ed bt the cessation of stnall bubbles, the liqntd ntlrogen 5 rrnnnrd I toni trap 4. A stirting bar is tltrn arttsatrd in thr flask fttr a 15 ntinatrs to rid tbr salatntn of tracrs of Co . Mranwltile, tlte 0,0 is etapanded dtrnagh pltttspborttus pentotaide cttrered glass beads (trap 5) and fro,ett intta trap 6. 'I rap 6 is titen isolated and pumped to a pressure 10 tIter. TIte CO0 is titen detect by an additittttal P10 trap (7), and etapatttled ittttt a 121 ltttldittg task attd the pressure recttrded.

Redaetton of carbon dtoatdela aelylene. 'Ilte carbon dittaide is reduced Itt acetylene gas cia lidtiu at car bide (kg 2). Carbon-free litbiuttt it purcltused 48 Sheila Gri, ffin and Ellen R M Druffel from Lithium Corporation of America in rod-form, dry packed in argon gas. The lithium is stored under vacuum and away from direct light in a greaseless o-ring desiccator. We found that these refinements reduced the buildup of white lithium oxide on the surface of the rods, thus increasing the shelf life of the lithium. A 10% stoichiometric excess of lithium is used for each conversion (Linick, 1975):

2CO2 + l OLi -i Li2C2 + 4Li2O (2) The lithium is placed in the bottom of a cylindrical pot. The pot is constructed of 316 stainless steel with an OD of 33cm and 36cm high. The pot is then pumped to a pressure of <10-2 torr. A Meker burner fueled by pro- pane gas is used to heat the lithium to 600°C. An Omega K-199 temperature probe placed 2mm above the inside bottom of the pot is used to monitor the temperature of the lithium. The CO2 gas is ready to be absorbed into the molten lithium when the lithium has a mirror-like finish, visible through dual windows on top of the pot, and the pot is fully degassed (<10-2 torr). The flame under the pot is then reduced slightly so that a 600-650°C temperature is maintained during the absorption, as this reaction is highly exothermic. If the CO2 is added too quickly, the lithium becomes too hot and another reaction is favored (Linick, 1975):

650°C 4Li + CO2 2Li2O + C (3)

After the absorption reaction is complete, the pot is maintained at a temperature of 625-650°C while the pot is vacuum pumped for a period of 90-120 minutes. The purpose of this after-burning is to remove any resid- (222Rn) ual gases, including radon which decays with a half-life of 3.8 days. The afterburning also allows any elemental carbon that may have formed (equation 3) to be converted to lithium carbide. The lithium mixture is then allowed to cool overnight. The lithium carbide is hydrolyzed by the addition of well water to the pot: Li2C2 + 2H2O - 2LiOH + C2H2 (4) The well water is collected at a free-flowing aquifer at Chekika State Recreation Area, Florida. It has been tested by H G Ostlund, RSMAS, Uni- versity of Miami, and is found to contain negligible amounts of tritium (<0.2 TU). We have observed that too low a volume of well water used for hydrolysis reduces the yield of acetylene from Li2C2. We suspect this is a function of the solubility of Li salts in aqueous solution. An average yield of 98% is standard when using 1200ml of well water for Li2C2 equivalent of 10-12L of CO2. The well water is added slowly to the carbide, as the production of acetylene from lithium carbide is violently exothermic. A pressure of 60cm Hg is maintained in the system; most of this pressure is due to hydrogen from the hydrolysis of excess lithium metal. The evolved acetylene is then dried by two slush traps (9 and 10) and frozen (trap 11). Termi- nation of the hydrolysis is indicated when hydrogen production drops markedly and the temperature of the hydrolysis solution is ca 27°C. Pres- Woods Hole: Sample Treatment and Gas Preparation 49 sure in the vacuum system is slowly reduced to 10-2 torr. The acetylene (trap 11) is dried over P2O5 (trap 12), frozen (trap 13) and pumped to 10-3 torr. The acetylene is then dried a second time (trap 14) and frozen (trap 15). The sample is then distilled through activated charcoal (trap 16) which has been cooled to 0°C. This step removes residual gaseous impurities in the sample. After each use, the charcoal trap is vacuum pumped overnight at 500°C. The distilled acetylene is frozen into trap 17. The triple point of the gas is checked to test for impurities. The triple point of pure acetylene occurs at - 80.8°C and 96cm Hg. Ammonia (NH3) may be present if the pot leaked during any part of its heating:

heat N2(air) + 6 Li -- 2Li3N (5)

Li3N + 3H2O -- NH3(g) + 3LiOH (6) thousand of ammonia will not affect the manner in which A few parts per 14C the sample counts, but it will dilute the gas and lower the apparent activity. If the triple point of a sample is depressed by more than 1 cm, the concentration of NH3 most likely exceeds 0.1% in the sample. In this event, the sample is distilled through syrupy phosphoric acid (85%) and then through P2O5 and charcoal traps. When water is present in the sample, visible detection is apparent by a flaky white crust that is present before and during the triple point. Samples are distilled through an isopropanol-dry ice slush trap to remove water. In contrast to acetylene, carbon dioxide as the counting gas is affected by oxygen and to a lesser extent by nitrogen in amounts of a (Brenninkmeijer & Mook, 1979). The sample is stored few parts per million 222Rn in a pyrex flask for at least three weeks to allow for the decay of any that might still be present.

Oxidation by burning. Samples containing organically-bound carbon, (such as wood, animal biomass, ocean sediments, etc) are placed in porcelain boats and then into a large Vycor tube (31mm OD, 24mm ID) (fig 1). Medical grade oxygen, which is free of petroleum products, is passed through a trap filled with sodium hydroxide pellets in order to remove any CO2. Initial heating of certain samples (ie, cholesterol, wood, etc) is performed slowly in order to avoid distillation of volatile organics. Each sample is burned for a period of 1 to 4 hours with an oxygen flowrate of 5-1 Oml/ min, using two Meker burners. The combustion products are passed over wire-form CuO (600°C) in order to oxidize CO and other carbonaceous distillates to CO2. Water is eliminated by using a dry-ice slush (trap 2). The carbon dioxide is then passed through a trap containing chromic acid (trap 3). Subsequently, the samples are treated in the same manner as described above for acidified samples (figs 1, 2). standard. The acetylene prepared from an NBS oxalic NBS oxalic acid 14C acid standard (#SRM 4990-B) is used to monitor the sensitivity of all the counters. We use the wet digestion method for preparation of carbon dioxide from oxalic acid (Valastro, Laud & Varela,1979). The oxalic acid is oxi- dized by potassium permanganate in an acidic aqueous media to produce 50 Sheila Griffin and Ellen R M Druffel CO9:

2MnO4- + 5(COOH)2 + 6H+ --k 2Mn2+ + l OCO2 + 8H20 (7) The reaction vessel is left open to the vacuum line while being stirred for a minimum of 30 minutes after completion. This allows for the decomposition of all oxalate compounds and eliminates significant isotopic fractionation of the collected CO2. The evolving CO2 gas is treated and collected in the same manner as that described above for coral samples (fig 1) and then converted to acetylene gas (fig 2). Preparation of background samples. A carbonaceous compound that con- '4C tains essentially no is used to measure the background activity of each proportional counter. Limestone is converted to calcium carbide by Union Carbide, Inc. The calcium carbide is then converted to acetylene in the laboratory:

CaG2 + 2H20 C2H2(g) + Ca(OH)2 (8) Chekika well water is used to hydrolyze the CaG2 in a 3L round-bottom flask. The evolved acetylene is dried by three slush traps and two P2O5 traps. Other gaseous contaminants are removed by passing the acetylene over activated charcoal cooled to 0°C. The acetylene is then aged for at least six weeks, to allow for the decay of 2222Rn, which is present in significant quantities immediately after preparation.

Cleaning Procedures All the pyrex traps used for acidifying, burning, and reduction are cleaned after each sample. They are rinsed with 6N HC1, tap water, distilled water, and finally with reagent-grade acetone and dried at room temperature. The porcelain boats and vycor tubes used during the burning of samples are cleaned occasionally by soaking them in a dilute solution of HF. After hydrolysis of each sample, the stainless steel pot is cleaned with 6N HC1 and rinsed with tap water, distilled water, and finally with reagent- grade acetone. No additional steps are taken to remove a layer of stainless steel from the pot, as we have determined that no significant memory from previous samples is retained within the walls of the pot, in contradiction to the findings of Radnell and Muller (1980).

CONCLUSIONS Our methods for collection, mapping, and cutting of hermatypic corals are described in detail. Preparation of acetylene from aragonitic coral bands is essentially the same as that described by Linick (1975) for sea water carbonate. We have made refinements to this method, which include: 1) a minimum amount of well water is required to obtain maximum yield during hydrolysis; 2) close monitoring of Li temperature is important for complete conversion to Li2C2; 3) careful storage of lithium, under low light conditions in a vessel free from all carbon-based stopcock grease (o-ring type) reduces dramatically the degradation of lithium metal. It is necessary to stress that checking the triple point of the acetylene (George Bien, pers Woods Hole: Sample Treatment and Gas Preparation 51 commun; Linick, 1975) is an important step in determining the purity of the resultant sample gas.

ACKNOWLEDGMENTS We sincerely thank members of the Woods Hole Oceanographic Insti- tution for their moral and financial support: Geoff Thompson, Susan Kadar, I)erek Spencer, John Steele, Jim Mitchell, Cliff Winget, and Ed Phares. We are indebted to two talented glassblowers, Paul Yeager and Bob Anderson. We thank Greg 1)insmore and the staff of the Falmouth Hospital x-ray facility. We are grateful to C Eben Franks, Terri Jackson, Tim Linick, I)empsey Lott, Rindy Ostermann, and Hans Suess for reviewing the manuscript. We also thank Margaret Harvey for typing the manuscript. Special thanks go to those who guided us in our earlier years at the La Jolla Radio- carbon Laboratory: George Bien, Terri Jackson, Carol Hutto, Tim Linick, Bob Michel, Mike Stenhouse and last, but certainly not least, Hans Suess. This is contribution no. 5787 from the Woods Hole Oceanographic Institution.

RF:FF:RENCES Barker, H, 1953, Radiocarbon dating: large-scale preparation of acetylene from organic material Nature, v 172, p 631-633. Brenninkmeijer, C A and Mook, W G, 1979, The effect of electronegative impurities on CO2 proportional counting: An on-line purity test counter, in Berger, Rainer and Suess, H E, eds, Radiocarbon dating, Internat radiocarbon conf, 9th, Proc: Berkeley/Los Angeles, Univ California Press, p 181-196. Druffel, Fl M, (ms), 1980, Radiocarbon in annual coral rings of the Pacific and Atlantic Oceans: Ph D dissertation, Univ California San Diego, 213 p. ----- 1981, Radiocarbon in annual coral rings from the eastern tropical Pacific. Geo- phys Research Letters, v 8, p 59-62. ----- 1982, Banded corals: Changes in oceanic carbon-14 during the Little Ice Age: Science, v 218, p 13-19. Druffel, E M and Linick, T W, 1978, Radiocarbon in annual coral rings of Florida: Geophys Research Letters, v 5, no. 11, p 913-916. Druffel, E M and Suess, H E, 1983, On the radiocarbon record in banded corals: Exchange parameters and net transport of 14CO2 between atmosphere and surface ocean: Jour Geo- Research, v 88, no. C2, 1271-1280. phys p 180/160 Fairbanks, R G and Dodge, R E, 1979, Annual periodicity of the and 3C/12C ratios in the coral Montastrea annularis: Geochim et Cosmochim Acta, v 43, p 1009-1020. Hudson, H, Shinn, E, Halley, R, and Lidz, B, 1976, Sclerochronology: a tool for interpreting past environments: Geology, v 4, p 361-364. Linick, T W, (ms), 1975, Uptake of bomb-produced radiocarbon in the surface water of the Pacific Ocean: Ph D dissertation, Univ California San Diego, 255 p. M, Chemical counting advances in liquid scintilla- Noakes, J E, Kim S and Stipp, J J, 1969, and tion age dating, in Chatters, R M and Olson, E A, eds, Internatl conf on radiocarbon and tritium dating, 6th, Proc: Clearinghouse for fed sci tech inf, Natl Bureau of Standards, Washington, I)C. Radnell, C J and Muller, A B, 1980, Memory effects in the production of benzene for radiocarbon dating, in Stuiver, Minze and Kra, Renee, eds, Internatl radiocarbon conf, 10th, Proc: Radiocarbon, v 22, no. 2, p 479-486. Shen, (;T and Boyle, E A, 1983, Reconstruction of aeolian anthropogenic lead fluxes through coral ring chronology: EOS, v 64, p 738. Suess, H E, 1954, Natural radiocarbon measurements by acetylene counting: Science, v 120, p 5-7. Toggweiler, J R, (ms), 1983, A six zone regionalized model for bomb radiotracers and CO2 in the upper kilometer of the Pacific Ocean: Ph D dissertation, Columbia Univ, 421 p, Valastro, S, Jr, Land, L S, and Varela, A G, 1979, An improved procedure for wet oxidation of the 19C NBS oxalic acid standard, in Berger, R and Suess H E, eds, Radiocarbon dating, Internatl radiocarbon conf, 9th, Pro: Berkeley/Los Angeles, Univ California Press, p 125-134. Weber, J N and Woodhead, P M j, 1972, Temperature dependence of oxygen-18 concentration in reef coral carbonates: Jour Geophys Research, v 77, p 463-473. [RAV1ocARBoN, VOL 27, No. 1, 1985, P 52-73]

GLIWICE RADIOCARBON DATES X MIECZYSLAW F PAZDUR, ROMUALD AWSIUK, ANDRZEJ BLUSZCZ, TOMASZ GOSLAR, ANNA PAZDUR, ADAM WALANUS, and ANDRZEJ ZASTAWNY Institute of Physics, Silesian Technical University Krzywoustego 2, PL-44-100 Gliwice, Poland The following list contains all age measurements of paleoenvironmental samples made from 1978 to the end of 1982 for the IGCP 158 Project "Paleohydrological changes in the temperate zone in the last 15,000 years," Subproject B "Lake and mire environments" (Berglund,1979), ii- dated by Bjorn Berglund and Leszek Starkel in 1976. The aim of this project was to reconstruct environmental changes related to climate and human activity in the temperate zone of Asia, Europe, and North America. Broad environmental reconstructions will be based upon a network of reference sites representing the natural geographic regions, distinguished by their geology, climate, vegetation, and other natural factors, according to Ber- glund (1979). The subdivision of Poland into 29 paleoecological units according to Ralska Jasiewiczowa (1982) is presented in table 1, and in fig- 14C ure 1 where reference sites dated by in our lab are also indicated. In this paper, we present a list of 14C dates from 12 reference sites (figure 1). The site at Lake Wielkie Gacno (subregion 1la, fig 1; Hjelmroos, 1981 a,b;1982) was 14C dated in Lund (Hakansson,1980). A brief report on the activities of the Polish Group of the IGCP 158B Project was given by RalskaJasiewiczowa (1981). 14C Ages are reported as conventional dates in years before Al) 1950, uncorrected for isotopic fractionation and based on the Libby half-life of 5568 yr. Errors quoted (± 1a) include estimated overall standard deviations of count rates of the unknown sample, contemporary standard and background (Pazdur & Walanus, 1979). The ANU Sucrose Secondary Radiocar- bon Dating Standard was used as the modern reference standard, corre- 14C 3130 lated with 95% of activity of NBS Oxalic Acid, normalized to = - 19%o wrt PDB, according to Polach (1979) and Currie and Polach (1980). Laboratory equipment and techniques have been described (Pazdur et al, 1982; 1983), the only exception being chemical pretreatment of peat samples. Unless otherwise stated, peat samples were pretreated only with HCI, as suggested by Hakansson (1976). Sample descriptions and comments are based on information provided by submitters.

ACKNOWLEDGMENTS The authors are indebted to Henry A Polach, Australian Nat! Univ, Canberra, for submitting ANU Sucrose Standard. Significant financial support from the Committee of Quaternary Research, Polish Academy of Sciences, Warsaw, is acknowledged. Thanks go to Helena Skorupka for her technical assistance during sample pretreatment.

52 Gliwice Radiocarbon Dates X 53

TABLE 1 Subdivision of Poland into paleoecological regions and subregions

1. Carpathians-Polish Carpathians a. Western Carpathians a,. Western Beskids a2. Tatra Mts a3. jasl'o-Sanok Depression and Dynow Foreland a4. Low Beskid b. Bieszczady Mts 2. Sudetes a. Central Sudetes b. Eastern Sudetes 3. Silesia Lowland 4. Silesia-Little Poland Uplands a. Silesia-Cracow Upland b. Nida Basin and Miechow Upland c. Holy Cross Mts 5. Sandomierz Basin 6. Lublin-Wolhynia Uplands a. Lublin Upland b. Roztocze 7. Lublin Polesie 8. Mazovia-Podlasie Lowlands a. Mazovia-South Podlasie Lowlands b. North Podlasie Lowland 9. Northern Foreland of Little Poland Upland 10. Great Poland-Kujawy Lowlands a. Lubusz Lake District b. Poznan-Gniezno-Kujawy Lake Districts 11. Western Pomerania a. West Pomerania Lake District b. Szczecin Lowland c. Baltic Coastal Zone d. Baltic Shore e. Vistula Deltaic Area 12. Eastern Pomerania a. DobrzyIi Lake District b. Olsztyn Lake District c. District of Masurian Great Lakes d. Suwalki-Augustw Lake District

SAMPLE DESCRIPTIONS

PALEOENVIRONMENTAL SAMPLES

Region 1. Carpathians (fig 1)

a2. Tatra Mts

Puscizna Rekowianska profile PR series Peat from Puscizna Rekowianska bog, Orawa-Nowy Targ Basin, ca 12km W of Nowy Targ (49° 29' N,19° 49' E), alt 654 to 658m asl; toll June 1980 and subm 1980 and 1982 by Andrzej Obidowicz, Inst Bot, Pol Acad Sci, Cracow. Earlier pollen studies of this site were made by Koperowa (1962); present palynol age determinations are by AO. 54 Mieczysiaw F Pazdur et al

Fig 1. Subdivision of Poland into palaeoecological regions (RalskaJasiewiczowa, 1982). 1 0-boundaries of main regions, 2 E and 3 s-boundaries of sub-regions, 4 -location of ref sites.

Gd-1565. PR VII 3670 ± 70 Brown medium decomposed Sphagnum peat, depth 3 to 3.lm, Sub- atlantic/Sub-boreal boundary.

Gd-2050. PR VI 4540 ± 150 Same, depth 3.8 to 3.9m, Sub-boreal/Atlantic boundary.

Gd-1570. PR V 4890 ± 60 Brown medium decomposed Eriophorum-Sphagnum peat, depth 4.4 to 4.5m, Atlantic period.

Gd-985. PR IV 7350 ± 160 Dark-brown strongly decomposed Eriophorum peat, depth 5.6 to 5.7m, Atlantic period.

Gd-1501. PR III 8570 ± 90 Dark-brown strongly decomposed fen peat with fragments of wood, depth 6.7 to 6.8m, Boreal period.

Gd-986. PR II 8800 ± 160 Same, depth 6.8 to 6.9m, Boreal/Pre-boreal boundary. Gd-1500. PR I 8960± 80 Same, depth 7.1 to 7.15m, Pre-boreal period. Gliwice Radiocarbon Dates X 55 a3. Jaslo-Sanok Depression and Dynbw Foreland Ref area in Jasiolka R valley comprises 2 sites with lacustrine sediments, consisting of marl, peat, clay, and gyttja, studied by Antoni Wojcik, Geol Inst, Carpathian Branch, Cracow, and Krystyna Harmata and Kazim- ierz Szczepanek. Previous paleobot studies of this area by Szafer (1948) indicate late glacial and Holocene sediments. Tarnowiec profile TAR series Peat and wood from fossil lake sediments in Tarnowiec (49° 44' N, 21° 32' E), Jasiolka R terrace, alt 230m as!. Coll Aug 1979 and subm 1982 by Antoni Wojcik. Gd-1483. TAR VIIA 2040 ±50 Clayey peat, depth 25 to 30cm. Comment (KS): deforestation of area, beginning of Sub-atantic period.

Gd-966. TAR VIIB 1950 60 Duplicate run on same sample.

Gd-1484. TAR VI 3930 ± 60 Brown peat, depth 56 to 60cm. Comment (KS): highest values of Fagus and Abies pollen, Sub-boreal period.

Gd-964. TAR V 4240 ± 90 Peat with fragments of wood, depth 96 to l 00cm. Comment (KS): pollen spectrum shows presence of beech and hornbeam forest, beginning of Sub- boreal period.

Gd-1482. TAR IV 5230 ± 80 Peat with wood fragments, depth 1.3m. Comment (KS): large amounts of Corylus, Tilia, and Ulmus pollen, typical for Atlantic period, with unexpectedly large amounts of Fagus pollen.

Gd-1481. TAR III 9380 ± 80 Peat, depth 1.55m. Comment (KS): pollen spectrum indicates pine forest with elm and spruce, typical for younger Pre-boreal period.

Gd-962. TAR II 9840 ± 100 Wood fragments from marl layer at depth I.8m. Comment (KS): presence of larch and Swiss stone pine (Pinus cembra) forests with pine, Pre-boreal period.

Gd-967. TAR! 11,190 ± 140 Peat with marl and fauna! remains, depth 2m. Comment (KS): pollen spectrum containing large amounts of Pinus pollen with Pinus cembra, Larix, Betula nana, and Gramineae, and Cyperaceae confirms Allerod age. Comment (MFP): peat from depth 1.4 to 1.45m, this profile, was dated to 7930 ± 110; Gd-767 (R, 1983, v 25, p 854). 56 Mieczysiaw F Pazdur et al Region 2. Sudetes

b. Eastern Sudetes

Zieleniec profile ZL series Peat from continuous profile at ref site Zieleniec (50° 21' N, 16° 25' E), Klodzko Basin, 8km S of Duszniki Zdroj, S part of Lower Silesia, Bystr- zyckie Mts, E Sudetes, alt 750m asl (Kuzniewski, 1959). Core taken Oct 1978 by Andrzej Obidowicz; samples subm 1979 by Magdalena Ralska- Jasiewiczowa; preliminary pollen analysis by Ewa Madeyska. Site was previously studied by Stark (1936) and Kuzniewski (1962). Gd-658. ZL VI 2720 ± 80 Undecomposed Eriophorum peat, depth 2.45 to 2.55m, end of Sub- boreal or beginning of Sub-alantic period. Gd-661. ZL V 3700 ± 60 Light brown peat, medium decomposition, depth 3.25 to 3.35m, Sub- boreal period. Gd-1092. ZL IV 5370 ± 70 Well-decomposed Eriophorum peat, depth 5.05 to 5.15m, Atlantic period. Gd-1091. ZL III 8390 ±80 Transitional peat layer with bark fragments, medium decomposition, depth 6.85 to 6.95m, younger part of Boreal period. Gd-1090. ZL II 8700 ± 80 Well-decomposed dark brown peat with wood fragment, depth 7.19 to 7.29m, older part of Boreal period. Gd-1089. ZL I 8740 ± 100 Well-decomposed dark brown peat, depth 7.29 to 7.38m, Pre-boreal period.

Region 4. Silesia-Little Poland Uplands

c. Holy Cross Mts Slopiec profile II series Peat from continuous profile Slopiec II taken from bog in small trough, probably oxbow lake, in Belnianka R valley, Slopiec village (50° 47' N, 20° 47' E), near Daleszyce, ca 20km E of Kielce, Daleszyce Basin, Holy Cross Mts, alt 248m asl. Coll Nov 1978 and subm 1979, 1980, and 1982 by Kazimierz Szczepanek, Inst Bot, Bot Garden, Jagellonian Univ, Cracow. Gd-768. Slopiec II/7 <120 Light brown Sphagnum-Eriophorum-Ericaceae peat, depth 27.5 to 32.5cm, local pollen assemblage zone (PAZ) Rumex-Cerealia. Gliwice Radiocarbon Dates X 57

Gd-774. Slopiec II/18 370 ± 60 Transition between Sphagnum-Eriophorum-Ericaceae and Sphagnum- Eriophorum peat with distinct layer of Ericaceae shoots at 85cm, depth 82.5 to 87.5cm, PAZ Cannabis-Fagus-Pinus, overlying boundary with PAZ Pinus- Betula-Quercus.

Gd-701. Slopiec II/23 480 ± 70 Sphagnum-Eriophorum peat with pieces of wood, depth 107.5 to 112.5cm, PAZ Pinus-Betula-Quercus.

Gd-1157. Slopiec II/29 1090 ± 60 Brown swamp peat, depth 137.5 to 142.5cm, boundary of PAZ Pinus- Betula-Quercus and Carpinus-Fagus-Abies. Gd-983. Slopiec II/33 1940 60 Same, depth 162.5 to 167.5cm, PAZ Capinus-Fagus-Abies.

Gd-1241. Slopiec II/40 2710 ± 60 Same, depth 192.5 to 197.5cm, boundary of PAZ Carpinus-Fagus-Abies and Alnus-Carpinus, Sub-atlantic/Sub-boreal boundary.

Gd-775. Slopiec II/45 3450 ± 80 Same, depth 217.5 to 222.5cm, PAZ Alnus-Carpinus.

Gd-1158. Slopiec II/49 3650 ± 50 Same, depth 237.5 to 242.5cm, same PAZ, overlying boundary with PAZ Corylus-Tilia-Picea.

Gd-1505. Slopiec II/52 4660 70 Same, depth 252.5 to 257.5cm, PAZ Corylus-Tilia-Picea. Gd-1506. Slopiec II/55 5710 80 Same, depth 267.5 to 272.5cm, same PAZ.

Gd-1507. Slopiec II/60 6690 ± 80 Same, depth 292.5 to 297.5cm, same PAZ, overlying boundary with PAZ Corylus-Alnus.

Gd-776. Slopiec II/70 9090 ± 100 Same, depth 342.5 to 347.5cm, boundary of PAZ Corylus-Alnus and Pinus-Ulmus, Atlantic/Boreal boundary.

Gd-703. Slopiec II/80 9330 ± 150 Brown swamp peat with numerous rhizomes and shoots of swamp plants and pieces of wood; depth 392.5 to 397.5cm,"boundary of PAZ Pinus-Ulmus and Salix-Betula.

Gd-700. Slopiec II/81 9620 ± 120 Same, adjacent layer, depth 397.5 to 400cm, PAZ Salix-Betula. 58 Mieczyslaw F Pazdur et al Gd-702. Slopiec II/85 10,080 ± 160 Same, depth 417.5 to 422.5cm, same PAZ, overlying boundary with PAZ Populus-Polypodiaceae, overlying Pre-boreal/Younger Dryas boundary. Gd-1508. Slopiec II/95 10,090 ± 120 Blackish-brown swamp peat with rhizomes of swamp plants and numerous seeds of Menyanthes and single pieces of wood; depth 467.5 to 472.5cm, PAZ Larix Juniperus-Pinus. Gd-704. Slopiec 11/ 104 10,280 ± 210 Same, depth 512.5 to 515cm, basal layer of peat at contact with fine sands, same PAZ.

Region 7. Lublin Polesie

Reference site: Lukcze Lukcze in W part of Lcczno Lake Dist, SW part of Lublin Polesie (Wil- gat, 1953; Maruszczak, 1966) comprises small eutrophic Lake Lukcze and mire at W shore of lake (51 ° 30' N, 23° E). Two profiles (TL & LIII), ca l Om apart and ca 20m from shore, were taken in May 1979, subm 1979 and 1981 by Krystyna Balaga, Inst Earth Sci, Maria Curie Sklodowska Univ, Lublin. Lake Lukcze has two parts linked by channel (Balaga, 1982, fig 1, p 10-11), with NE, E, and Slake shores covered with alder, and fragments of devastated pine Vaccinio myrtilli-Pinetum forest and mixed Pino-Quercetum forest in SE part. From SW and NW, community of Salici-Franguletum con- nects lake with mire covered by fragments of Caricetum lasiocarpae, C limo- sae, C diandrae, and Sphagnetum med io-rubelli. Eleven local pollen assemblage zones were defined, 5 based on data from Lukcze TL and Lukcze III profiles. Lukcze profile TL series Profile TL consists of well-decomposed black-brown sedge-moss peat, max thickness 3.5m. Gd-1175. Lukcze TL-1 980 ± 50 Depth 50 to 55cm, local PAZ L-10, transition between subzones e and f, with decreases of Car pinus, Quercus, Plantago lanceolata, Rumex, and Urtica pollen, and first appearance of Secale cereale pollen. Gd-1178. Lukcze TL-2 6420 ± 70 Depth 90 to 95cm, local PAZ L-8 with dominance of Ulmus, Quercus, and Corylus, and first appearance of Plantago lanceolata and cereals. Dates first appearance of Carpinus and Fagus. Gd-1179. Lukcze TL-3 7790 ± 70 Depth 165 to 170cm, boundary of local PAZs L-7 and L-8 with increase of Quercus and Alnus and decrease of Pinus pollen, and first appearance of Pteridium aquilinum spores. Gliwice Radiocarbon Dates X 59

Gd-1181. Lukcze TL-4 10,900 ± 100 Depth 250 to 255cm, boundary of local PAZs L-3 and L-4, with decrease in Artemisia pollen and empirical limit of Ulmus (after Baaga, 1982, p 15), end of Younger Dryas period.

Gd-1182. Lukcze TL-5 10,930 ± 90 Depth 280 to 285cm, boundary of local PAZs L-2 and L-3 with increase of Artemisia and decrease of Gramineae pollen. Comment (KB): beginning of Younger Dryas period; date younger than expected. Lukcze profile L-III series Core L-III is composed of silt with some gray brown gyttja at base, overlain by sedge-moss peat, peaty gyttja, calcareous gyttja, and at top, sedge-moss brown peat of varying degrees of decomposition; max depth of organic sediments, 450cm.

Gd-1180. Lukcze L-III-1 9080 ± 90 Black-brown peaty gyttja, organic matter 91%, depth 250 to 260cm, boundary of local PAZs L-5 and t-6, at max rise of Corylus, end of calcareous gyttja sedimentation, beginning of Boreal period.

Gd-822. Lukcze L-III-2 10,660 ± 210 Black-gray detritus-calcareous gyttja, depth 340 to 350cm, organic matter content 52%, carbonate 9%, local PAZ L-3 with max rise of Artemi- sia pollen up to 30%. Comment (MFP): undersized, diluted, date is probably too old 1)ecause of hard-water effect, indicated by presence of Potamogeton and Myrio phyllum (Pazdur, 1982).

Gd-824. Lukcze L-III.3 10,680 ± 190 Black-brown peaty gyttja, depth 380 to 390cm, underlying calcareous gyttja, organic matter 72%, no carbonates. Local PAZ L-3, sample dates transition between peaty gyttja and detritus-calcareous gyttja and beginning of carbonate sedimentation. Comment (M FP): undersized, diluted.

Gd-825. Lukcze L-III-4 11,160 ± 110 Black-brown peaty gyttja, organic matter ca 70%, no carbonates, depth 400 to 410cm. Boundary of local PAZs L-2 and L-3. Comment (MFP): corre- lates fairly well with Gd-1182: 10,930 ± 90, and dates beginning of Younger Dryas period.

Gd-1183. Lukcze L-III-5 12,330 ± 160 Black-brown sedge moss peat with gyttja and silt, organic matter 35%, depth 425 to 430cm, boundary of local PAZs L-0 and L-1 with decrease in Betula and Salix pollen and increase in Pinus and Gramineae percentages, beginning of organic matter sedimentation and mire development.

Region 10. Great-Poland-Kujawy Lowlands

b. Poznan-Gniezno-Kujawy Lake District 60 Mieczysi aw F Pazdur et al Goplo profile GI series Peat and gyttja from core taken in bog in subglacial channel, 500m SW of Goplo Lake shore, in Mielnica Duza village (52° 33' N,18° 30' E), Kujawy Uplands, alt 78m asl. Organogenic sediments, 10.25m thick, overlying Pleistocene sands, are composed of detrital gyttja and basal peat layer, overlain by ca 8.5m thick series of calcareous gyttja with shells and upper peat layer. Coll March 1980 and subm by Barbara Jankowska, Inst Biol, Mikolaj Kopernik Univ, Torun (Jankowska, 1981). Gd-1263. Goplo G1 460 ± 50 Slightly decomposed peat, depth 20cm, 1.67% CaCO3, weight loss on ignition (LWI) 76.8%. Gd-1264. Goplo G2 1010 ± 50 Slightly decomposed peat, depth 60cm, 6.2996 CaCO3, LWI 83.3%. Gd-798. Goplo G3 1370 ± 60 Well-decomposed black-brown peat, depth 120cm, 10.07% CaCO3, LWI 52.8%. Gd-799. Goplo G10 13,040 ± 140 Organic matter with fine sand, depth 10.15 to 10.25m, 2.51% of CaCO3, LWI 0.19%. Comment (MFP): undersized, diluted. General Comment (BJ): preliminary results of pollen analysis indicate Sub- atlantic age for upper peat layer and Oldest Dryas age for lowermost organic layer (Jankowska, 1981).

Region 11. Western Pomerania

c. Baltic Coastal Zone

Reference site: Zarnowiec Zarnowiec covers three loci in neighborhood of Lake Zarnowiec, chosen to obtain pollen material representative of past local and regional plant cover. Two loci lie in extensive Lake Zarnowiec channel surrounded by moraine hills covered by beech and oak forest, representing regional features. Third locality representing local features is in Darzlubie Forest in 14C tunnel valley of Lake Dobre (Latal'owa, 1981a). For pollen analysis and dating 2 cores were taken with Russian "Instorf" corer 10cm diam. Eight pollen assemblage zones were distinguished, which can probably be applied regionally (Latal'owa, 1981 a,b; 1982a,b). Zarnowiec profile Zar/76 series Highly decomposed peat from core Zar/76, loc 1 (Lataowa, 1982a, p 51, fig 3) ca 2km S of lake shore in bog in Lake Zarnowiec tunnel valley (54° 43' N, 18° 7' E), alt 5m asl, Kaszuby Coast. Coll 1976 and subm 1978 by Malgorzata LataTowa, Dept Plant Ecol, Inst Biol, Gdansk Univ, Gdynia. Present peatbog vegetation is devastated, meadow communities of Cirsio- Gliwice Radiocarbon Dates X 61 Polygonetum type are dominant, with swamp spp and some low-moor sp occurring in places.

Gd-685. Zar/76/45-50 2400 ± 60 From depth 45 to 50cm, Iron age settlement phase, pollen assemblage zone (PAZ) Quercus-Carpinus.

Gd-598. Zar/76/107-112 3230 ± 70 From depth 107 to 112cm, settlement phase of Early Bronze age, PAZ Quercus-Corylus.

Gd-1030. Zar/76/142-152 4030 ± 60 From depth 142 to 152cm, rational Carpinus limit, settlement phase of Neolithic period, PAZ Quercus-Corylus.

Gd-595. Zar/76/191-200 5460 ± 60 From depth 191 to 200cm, overlying first pollen of Plantago lanceolata and first settlement phase, PAZ Quercus-Corylus, close to boundary with PAZ Tilia-Ulmus-Pinus.

Gd-686. Zar/76/245-250 6460 ± 100 From depth 245 to 250cm, distinct increase of Quercus, Atlantic period, PAZ Tilia-Ulmus-Pinus.

Gd-596. Zar/76/288-298 8090 ± 70 From depth 288 to 298cm, somewhat below rational Tilia limit, Bo- real/Atlantic boundary, just above boundary of PAZs Tilia-Ulmus-Pinus and Corylus-Pinus.

Gd-1029. Zar/76/343-352 9070 ± 70 From depth 343 to 352cm, rational Corylus limit, Pre-boreal/Boreal boundary, boundary of PAZ Corylus-Pinus and Pinus sub-zone of PAZ Pinus-Betula.

Gd-1031. Zar/76/387-397 10,130 ± 120 From depth 387 to 397cm, Late Glacial/Holocene boundary, decline of Juniperus and NAP marking boundary of PAZ Juniperus-Pinus-Betula with sub-zone Pinus-Betula-Filipendula of PAZ Pinus-Betula. Darzlubie Forest profile PDarz/78 series Slightly decomposed peat from loc 3 in Darzlubie Forest, peat bog in tunnel valley of Lake Dobre, core PDarz/78 taken ca 1 km SW of lake shore (54° 42' N, 18° 10' E), ca 6km SE of loc 1, alt 80m asl. Coll and subm 1978 by Mal'gorzata Latalowa. Lake valley is ca 100m wide with slopes somewhat raised and grown over with pine and oak-pine woods, wet meadow communities of order Molinietalia cover surface of peat bog with typical low-moor and transition bog sp. 62 Mieczysiaw F Pazdur et al Gd-1032. PDarz/78/23-33 1120 ± 50 From depth 23 to 33cm, decrease of Carpinus and expansion of Fagus, expansion of Early Medieval settlement, PAZ Pinus-Fagus Juniperus, overlying boundary with PAZ Quercus-Carpinus. Gd-599. PDarz/78/87-98 2310 ± 60 From depth 87 to 98cm, below rational Fagus limit, Sub-boreal/Sub- atlantic boundary PAZ Quercus-Carpinus. Gd-1033. PDarz/78/113-123 2770 ± 60 From depth 113 to 123cm, expansion of Carpinus, distinct decrease of Quercetum Mixtum, first appearance of Lusation culture settlement indicators, PAZ Quercus-Carpinus. Gd-1058. PDarz/78/183-193 4030 ± 70 From depth 183 to 193cm, rational Carpinus limit (?), first pollen of Plantago lanceolata, Neolithic settlement phase, PAZ Quercus-Corylus. Gd-1124. PDarz/78/201-205 5070 ± 70 From depth 201 to 205cm, decrease of Ulmus, distinct increase of Quercus and Corylus, PAZ Tilia-Ulmus-Pinus.

Gd-1125. PDarz/78/220-225 6780 ± 80 From depth 220 to 225cm, distinct change in local vegetation, very strong increase of concentration of sporomorphs, PAZ Tilia-Ulmus-Pinus. Gd-625. PDarz/78/253-263 7900 ± 110 From depth 253 to 263cm, just below rational Tilia limit and Boreal Atlantic boundary, PAZ Corylus-Pinus, underlying boundary with PAZ Tilia-Ulmus-Pinus, marked by fall in Corylus percentage. Gd-626. PDarz/78/303-313/a 8890 ± 100 From depth 303 to 313cm, changes in local vegetation, PAZ Corylus- Pinus, Boreal period.

Gd-1113. PDarz/78/303-313/b 8780 ± 90 Duplicate run on 2nd portion of same sample. Gd-1126. PDari/78/327-332 9170 ± 110 From depth 327 to 332cm, increase of Ulmus and Quercus, decrease of heliophytes, Pinus sub-zone of PAZ Pinus-Betula, underlying boundary with PAZ Corylus-Pinus. Comment (ML): upper boundary of PAZ Pinus-Betula is synchronous in profiles Zar/76, PDarz/76 and PDari778 and falls at 9100 BP.

Gd-1154. PDarz/78/332-337 8990 ± 90 From depth 332 to 337cm, control run on sample from adjacent level. Gliwice Radiocarbon Dates X 63

Gd-1059. PDarz/78/350-358 9080 ± 90 From depth 350 to 358cm, rational Corylus limit, Pre-boreal/Boreal boundary.

Gd-1060. PDarz/78/373-381 9840 ± 110 From depth 373 to 381cm, decrease of,Juniperus, boundary of PAZ Pinus-Betula and Juniperus-Pinus-Betula. Comment (ML): this boundary in profile Zar/76 is dated to 10,130 ± 120 BP; Gd-1031, above. General Comment (ML): pollen diagrams from Lake Zarnowiec area differ considerably despite fact that loci are within 5km of one another. This results from local (loc 3) vs regional (loc 1) types of pollen spectra. Nev- ertheless, pollen assemblage zones are parallel and should have regional applications. Seven settlement phases were distinguished based on cultural indicators and plants related to human activity. First 3 phases correspond to Neolithic, 4th to II/I11 period of Bronze age, phases 5 and 6 correspond to Kaszubian Group of Lusatian and East Pomeranian cultures (Halstatt C and D). Last, 7th phase corresponds to Early Middle age habitation.

d. Baltic Shore

Reference site: Niechorze Niechorze, in W part of Western Pomerania, consists of two profiles with peat and peaty slime deposits; 1st in cliff ca 1.7km W of Niechorze village (54° 5' N, 15° 3' E), 2nd in small bog ca 1.8km SW of 1st profile. Samples colt April 1978 and subm by Krystyna Kopczynska-Lamparska, Inst Fundamental Geol, Warsaw Univ, Warsaw.

Niechorze Cliff I series Peat and peaty slime deposits from small lake basin exposed in cliff cut mainly in two horizons of Vistulian tills (Kopczynska-Lamparska, 1974). Organic deposits overlying fluvioglacial sands and silts continue 30m along cliff and about same distance to S, their thickness in cliff is 2.85m and decreases to 0.5m at lake shore, 17m S of cliff. Present samples taken from profile ca 1 m from profile studied in 1974 (Kopczynska-Lamparska, 1976, figs 2 & 3; Pazdur, Pazdur, & Zastawny, 1979, p 168-169; Brykczynska, 1978).

Gd-1111. Niechorze I-1 3340 60 Peat, depth 32 to 37cm.

Gd-1099. Niechorze I-3 5910 ± 80 Peaty silt, uppermost layer overlain by peat, depth 42 to 49cm.

Gd-1112. Niechorze I-7 9330 ± 120 Peaty silt overlying series of silts with mollusk shells, depth 72 to 79cm. 64 Mieczys1aw F Pazdur et al Gd-782. Niechorze I-8:sol 13,430 ± 150 Peaty silt with mollusk shells, lowermost part of layer, depth 160 to 164cm. Comment (MFP): alkali-soluble fraction dated.

Gd-1245. Niechorze I-8:ins 12,260 120 Same sample, insoluble fraction.

Gd-1107. Niechorze I-9 11,880 ± 110 Peat, uppermost part of peat layer overlying peaty silt, depth 191 to 193cm.

Gd-1108. Niechorze I-10 11,980 130 Peaty, lowermost part of same layer.

Gd-1109. Niechorze I-11 12,150 100 Peaty silt, depth 195 to 201 cm.

Gd-673. Niechorze I-12 12,010 ± 150 Peaty silt, lowermost part of same layer, depth 201 to 210cm. General Comment (MFP): Gd-782 and -1245 older than expected probably due to hard-water effect. Niechorze profile sl series Peat from profile s 1 from bog developed above lacustrine deposits in small basin on morainic plateau.

Gd-1096. Niechorze sl-2 3660 60

Depth 1 to 1.15m.

Gd-1097. Niechorze s l-4 4330 80 Depth 2 to 2.15m.

Gd-1098. Niechorze s 1-5 4600 ± 70 Depth 2.55 to 2.7m.

Reference area: Gardno-Leba Lowlands Gardno-Leba Lowlands are separate, morphologically and genetically differentiated physiographic unit in central part of Western Pomerania, bordered in N part by Baltic Sea shoreline and in S part by diluvial plateau, with three coastal lakes in N part, where sand bars are partly covered by migrating dunes. Gardno-Leba Lowlands are under supervision of Slowinski Nat! Park. Ref area is represented by 5 sites, 3 in coastal sand bars and 2 in large mires SW of Lebsko Lake, studied by Kazimierz Tobolski, Inst Quaternary Research, Adam Mickiewicz Univ, Poznan (Tobolski, 1982, fig 1, p 132). Gliwice Radiocarbon Dates X 65 Sarbsko Bay Bar series Wood from individual trunks (Quercus sp, id by Kazimierz Tobolski) from top series of organic sediments on beach or in dune cliff on Sarbsko Bay Bar near Leba-Neptun (54° 46' N, 17° 34' E), ca 1 km E of Leba R mouth to Baltic. Coll May 1978 and subm by Kazimierz Tobolski for studies of post-Littorina succession of local vegetation in Sarbsko Bar (Tobolski, 1979;1981, p 104-106;1982; Tobolski et al, 1980). Gd-573. Leba-Neptun 1/78 1220 ± 50 From outer part of horizontal oak trunk, 55cm diam, with 160 annual rings, lying on oak forest humus horizon containing 62% of Quercus pollen grains, overlain by coastal dune sands, depth ca 85cm. Comment (KT): date confirms earlier dating of humus horizon, thought to be rejuvenated due to younger humic acids penetration or rootlets (1430 ± 140: Gd-418, R, 1979, v 21, p 165). This horizon was previously expected to be of late Sub- boreal age or slightly younger.

Gd-1008. Leba-Neptun 2/78 1060 ± 50 From outer part of horizontal root of oak trunk with ca 120 annual rings found on surface of organic sediments, ca 10m W of trunk 1/78.

Gd-1006. Leba-Neptun 3/78 1120 ± 50 From outer part of root of oak trunk with ca 100 annual rings, from surface of organic sediments, ca 5m E of trunk 1/78. General Comment (KT): dating of Leba-Neptun oak trunks proves that destruction of oak forest occurred in 9th century AD. Decay of primary oak forests was gradual and took place at different times, which, compared with fossil soils in area, argues for anthropogenic causes of changes within primary vegetation of bar areas. Gardno Bay Bar series Wood from outer part of individual trunks of Quercus sp forming two oak cemeteries related to subfossil peat layers on beech in E part of Gardno Bay Bar (54° 41' N, 17° 8' E). Coll May 1978 and subm by Kazimierz Tobolski.

Gd-1005. MG-1/78 2130 ± 50 From in situ trunk, diam 70cm.

Gd-1004. MG-2/78 2860 ± 50 From in situ trunk, diam 120cm, found ca 350m W of trunk 178. General Comment (KT): dates indicate non-uniform decay of oak forests over this area. First date refers to period when oak trees were destroyed in central part of Leba Bar; 2nd one is related to older events from earlier period of Bronze age (Tobolski et al, 1980). Other date of interest to problem was obtained on oak charcoals from fossil soil near Czolpino, same area (Gd- 421; 3340 ± 130, R,1979, v 21, p 165; Borowka & Tobolski, 1979). 66 Mieczyslaw F Pazdur et al Leba Bay Bar series Wood and bark fragments related to fossil soil levels in area of mobile coastal dunes, central part of Leba Bay Bar (54° 45' N, 17° 24' E). Coil and subm 1978 by Kazimierz Tobolski. Dated as part of complex systematic studies including paleo- and phytogeography of Gardno-Leba Lowlands (Tobolski, 1981, p 93-100), evolution of coastal dunes (Tobolski, 1975; 1980;1981, p 100-103), decay of pine and beech forests (Wojterski,1964; Tobolski, 1979), partly in connection with IGCP 158B project.

Gd-570. ML-4/78 290 ± 50 Wood from outer part of partly rotten trunk (Pinus silvestris) found in situ in vertical position in tree cemetery ca 800m NE of Lcka Dune culmi- nation, Div 7 of Protection Circle. Trunk had 21 cm diam, 20 annual rings, with insect burrows; most of surface had no remaining bark.

Gd-571. ML-5/78 250 ± 50 Wood from outer part of trunk (Pinus silvestris) found in situ in vertical position, E part of tree cemetery On Lcka Dune, Div 7 of Protection Cir- cle. Trunk had 20cm diam, 30 annual rings; outer rings had insect burrows.

Gd-572. ML-6/78 210 ± 50 Wood from outer part of trunk of Pinus silvestris found in situ in vertical position in NE part of tree cemetery, Div 9 of Protection Circle, ca 200m W of tourist rte from Lebsko Lake to seashore. Trunk had 26cm diam, 42 annual rings; outer rings had insect burrows to 3 cm depth.

Gd-1034. ML-7/78 390 ± 50 Wood from outer part of basal fragment of Quercus robur, id by Kazim- ierz Tobolski, found at surface of fossil soil level no. 14, according to Tobolski (1975). Outcrops of this level occur in Divs 8 and 9 of Protection Circle.

Gd-1038. ML-8/78 250 ± 50 Bark from basal part of highly rotten trunk (Fagus silvatica), same fossil soil level. General Comment (KT): results of 14C dating of pine tree cemeteries agree with historical documents cited by Kobendzina (1976) which indicate increasing human activity from beginning of 17th century AD. Other dates confirm earlier opinions (Tobolski,1975) concerning occurrence in historical time of pine and broad leaf forests with Fagus sp dominating. Kluki profile 74 series Peat from coastal bog belonging to vast peatland complex extending throughout N area of Gardno-Leba Lowlands, profile Kluki/74 in Slowinski Natl Park, 0.5km E of Kluki village (54° 40' N, 17° 19' E) in mar- shy forest Vaccinio uliginosi-Pinetum, alt 2.l m asl. Organic deposits, 6.7m thick, overlie medium-grained sands with thin layer of detritus gyttja at base Gliwice Radiocarbon Dates X 67 of organic series. N part of Gardno-teba Lowlands is ref area representative of geobot unit defined by Czubinski (1950) as Coastal Region (To- bolski, 1981, p 90-93). Core Kluki/74 studies include palynol, carpol, geo- chem analyses, and physical sediment analysis. Core 74 coil 1974; samples subm 1978 to 1982 by Kazimierz Tobolski.

Gd-1305. Kluki/74/25-30cm 230 ± 50 Sphagnum-wood peat.

Gd-565. Kluki/7460-65cm 860 ± 60 Sphagnum peat.

Gd-1306. Kluki/74/80-85cm 1350 ± 60 Carex peat.

Gd-1307. Kluki/74100-105cm 1530 ± 50 Carex peat.

Gd-564. Kluki/74/120-125cm 1750 ± 50 Carex peat.

Gd-1308. Kluki/74/170-174cm 2120 ± 50 Transition peat.

Gd-1321. Kluki/74/190-195cm 3080 ± 50 Carex peat.

Gd-563. Kluki/74/240-245cm 3860 ± 70 Carex peat.

Gd-1330. Kluki/74/275-280cm 4680 ± 60 Carex peat.

Gd-1315. Kluki/74/310-315cm 4910 ± 90 Juncus peat.

Gd-1331. Kluki/74/340-345cm 5050 ± 50 juncus peat.

Gd-562. Kluki/74/380-385cm 5300 ± 70 Transition between Cladium and Juncus peat.

Gd-855. Kluki/74/430-435cm 6050 ± 120 Carex peat.

Gd-1323. Kluki/74/460-465cm 6670 ± 60 Carex peat. 68 Mieczystaw F Pazdur et al

Gd-1587. Kluki/74/505-510cm 7400 ± 60 Cladium peat.

Gd-1322. Kluki/74/540-545cm 8130 ± 80 Cladium peat.

Gd-547. Kluki/74/575-580cm 8370 ± 110 Cladium peat.

Gd-1329. Kluki/74/630-635cm 9110 ± 70 Cladium peat.

Gd-548. Kluki/74/660-665cm 9870 ± 110 Carex peat with gyttja. General Comment (KT): according to palynol and 14C data, beginning of organic deposition can be assigned to older part of Pre-boreal period. Since then, few distinctive minerotrophic phytocenoses contributed to deposition of various peat layers. Oligotrophication began ca 1000 yr BP. Modern bog pine forests phytocenosis growing on bog is estimated to be very young; most probably this pine stand constitutes first tree generation (Tobolshi,1982, p 133). Kluki KL/2 series Peat from supplementary profile taken ca 2.5km N of profile Kluki/ 74. Coll and subm 1981 by Kazimierz Tobolski.

Gd-1291. Kluki KL/2/2/150-155cm 3790 ± 60

Gd-830. Kluki KL/2/ 1/205-210cm 5950 ± 130

e. Vistula Deltaic area

Druzno profile 1 a series

Peat and gyttja from basal series of organogenic sediments, profile 1 a, in Druzno Lake basin (54° 10' N, 19° 30' E), ca 10km SSE of Elblg, Zul'awy. Coll March 1979 by Kazimierz Wigckowski and Joanna Zachowicz; subm 1979 by JZ, Inst Meteorol and Water Management, Gdynia. Lake Druzno is in central part of catchment basin of Elblig R, surrounded by Malbork Zuawy, Vistula Lagoon, and Elbltg Upland, in depression 1.8m below sea level. Lake is shallow, max depth 3m, lake basin filled with layer of gyttja, 6 to 8m thick (Mikulski,1955). Present studies include palynol, diatom, physical and chemical analyses (PrzybyIowska-Lange, 1976; Zachowicz, 1981; Zachowicz, Przybylowska-Lang & Nagler, 1982).

Gd-1131, Druzno la-1 6440 ± 50 Black-brown peat with fragments of undecomposed leaves and twigs, depth 625 to 635cm. Gliwice Radiocarbon Dates X 69 Gd-1128. Druzno la-2 6390 ± 140 Wood from tree trunk, I0cm diam, depth 646 to 655cm. Gd-1132. Druzno la-3:sol 7050 ± 70 Brown-gray coarse detritus gyttja, depth 679 to 688cm, alkali-soluble fraction. Gd-715. Druzno la-3:ins 6430 ± 180 Same sample, insoluble fraction. Comment: undersized, diluted. Gd-1136. Druzno la-4:sot 8990 ± 80 Well-decomposed brown peat, depth 712 to 722cm, alkali-soluble fraction.

Gd-716. Druzno 1 a-4:ins 8760 ± 220 Same sample, insoluble fraction. Comment: undersized, diluted. Gd-1137. Druzno la-5 11,290 ± 110 Black-brown peat with sand, lowermost layer, depth 858 to 866cm. Region 12. Eastern Pomerania

a. Dobrzyn Lake District

Reference site: Lake Steklin Steklin is in SW part of Dobrzyn Lake dist (Dobrzyn Moraine Plateau), ca 23km ESE of Torun, comprising Lake Steklin (52° 58' N, 19° E) and peat bog in W part of Lake channel (Noryskiewicz,1982). Gd-1115. Lake Steklin 920-928 11,630 ± 110 Silt with plant detritus, depth 920 to 928cm, lowermost part of basal deposits of total thickness, 940cm, W part of Lake Steklin. Coil Feb 1978 and subm 1979 by Boiena Noryskiewicz, Inst Bioi, Mikolaj Kopernik Univ, Torun. Steklin peatbog series Peat from profile taken at W part of Lake Steklin channel. Coil and subm 1980 by Boiena Noryskiewicz. Gd-840. Steklin 110cm 750 ± 90 Gd-841. Steklin 230cm 1870 ± 60 Gd-842. Steklin 340cm 2330 ± 120 Gd-1303. Steklin 420cm 4470 ± 60

b. Olsztyn Lake District

Reference site; Woryty 70 Mieczystaw F Pazdur et al Woryty profile 80s series Gyttja and peat from continuous profile of organic sediments with variable content of CaCO3 filling bipartite overgrown channel lake in Woryty village (53° 45' N, 20° 10' E), center of subregion 12b, ca 17km WSW of Olsztyn, 2km WNW of Gietrzwald, hilly area bordered by Paslgka, Old Paslcka, and Gi1wa Rivers, close to settlement complex of Lusatian culture from IV-VI periods of Bronze age (Dbrowski, 1981; Dbrowski & Mogielnicka-Urban, 1976). Core Woryty 80 coil 1974 by Kazimierz Wigckowski and Magdalena Ralska Jasiewiczowa (Ciesla, Ralska-Jasiewic- zowa, & Stupnicka, 1978), and core Woryty 80s coll 1979 by G Digerfeldt and T Persson and MRJ. Six samples from core 80 were subm and dated in Cambridge (Ralska Jasiewiczowa et al, ms in preparation), chronology of '4C core 80s is based on 17 dated samples, 5 dated in Lund (R,1981, v 23, p 392-393; Pawlikowski et al, 1982) and 12 in Gliwice. Thirteen local pollen assemblage zones (PAZ) were distinguished, some with subzones based on cluster analysis (Gordon & Birks, 1972).

Gd-1190. Woryty 80s/136-139cm 2080 ± 80 Swamp peat with gyttja, PAZ W-12, high Carpinus pollen percentage, subzone W-12b, decrease in pollen concentration and increase in NAP pollen percents with predominant Gramineae, Artemisia, Plantago lanceolata, and Rumex acetosella. Comment (MRJ): this subzone reflects entry of new cultural group into Woryty area.

Gd-1192. Woryty 80s/176-179cm 2320 ± 60 Same, just below upper boundary of PAZ W-11. Comment (MRJ): lower boundary of PAZ W-11 can be dated to ca 3500 BP. Pollen spectrum shows long-lasting settlement phase of Late Bronze Lusatian culture with dominance of pastoral economy.

Gd-1191. Woryty 80s/316-319cm 3960 70 I)ark brown peaty gyttja with some silt, PAZ W-10.

Gd-1193. Woryty 80s/406-409cm 5120 ± 80 Dark-brown gelatinous sapropelic sediment, lower boundary of PAZ W-10. Comment (MRJ): first pollen grains of cereals indicate presence of human settlement near lake, deciduous forest became more open, domi- nated by oak with abundant hazel understory.

Gd-727. Woryty 80s/426-429cm 5890 ± 90 Same, PAZ W-9. Comment (MRJ): rise in pollen concentration, probably resulting from decreased sedimentation rate.

Gd-1194. Woryty 80s/476-479cm 6460 ± 70 Same, PAZ W-10. Comment (MRJ): slow decrease in Ulmus and increase in Quercus pollen values between 6460 BP and 5120 BP with change in sediment suggest lowered water level in lake and indicate phase of warm but drier climate. Gliwice Radiocarbon Dates X 71 Gd-731. Woryty 80s/586-589cm 8040 ± 170 Gray-olive slightly porous detritus gyttja with calcium carbonate, PAZ W-8 with dominant pollens of Pinus and Alnus. Comment (MFP): undersized, diluted. Gd-1198. Woryty 80s/616-619cm 8440 ± 110 Dark-brown dy-like silty sediment, overlying lower boundary of PAZ W-8. Gd-800. Woryty 80s/665-678cm 10,320 ± 220 Gray-olive silty gyttja with some CaCO3 and patches of partly disinte- grated shells, PAZ W-7. Comment (MRJ): older than expected. Gd-1265. Woryty 80s/810-820cm 11,210 ± 90 Dark-brown gelatinous calcareous gyttja, top of layer. Comment (MRJ): older than expected. Gd-801. Woryty 80s/868-885cm 10,450 ± 300 Black ferruginous gyttja with mollusk shells. Comment (MFP): undersized, diluted. Gd-802. Woryty 80s/920-930cm 10,430 ± 300 Gray ferruginous gyttja, top of layer. Comment (MFP): undersized, diluted. General Comment (MRJ): dates Gd-800, -801, and -1265 were not taken into account in establishing absolute chronology of profile 80s.

RF:FEKENCF;s Bataga, Krystyna, 1982, Vegetational history of the Lake X ukcze environment (Lublin Polesie, E Poland) during the Late Glacial and Holocene: Acta Palaeobot, v 22, no. 1, p 7-22. Berglund, B E, ed,1979, Palaeohydrological changes in the temperate zone in the last 15,000 years. Subproject B. Lake and mire environments: Proj Guide 1,1)ept Quaternary Geol, Univ Lund, Lund, Sweden, 123 p. Borbwka, R K and Tobolski, Kazimierz, 1979, Nowe znaleziska archeologiczne na Mierzei x.ebskiej i ich znaczenie dla paleogeografii tego obszaru: Bad Fizjogr nad Polski Zach, ser A, v 32, p 21-29. Brykczynska, Ewa, 1978, Proba odtworzenia rozwoju roslinnosci w pbznym glacjale i holoce- nie w okolicach Niechorza na Pomorzu Zachodnim: Kwart geol, v 22, p 361-377. Ciesla, A, Ralska-Jasiewiczowa, Magdalena, and Stupnicka, Ewa, 1978, Paleobotanical and geochemical investigations of the lacustrine deposits at Woryty near Olsztyn (NE Poland): Pol Arch Hydrobiol, v 25, p 61-73. Currie, I. A and Polach, H A, 1980, Exploratory analysis of the international radiocarbon cross-calibration data: consensus values and interlaboratory error. Preliminary note, in Stuiver, Minze and Kra, Renee, eds, lnternatl radiocarbon conf, 10th, Proc: Radiocar- bon, v 22, no. 3, p 933-935. Czubinski, Zygmunt, 1950, Zagadnienia geobotaniczne Pomorza: Bad Fizjogr nad Polsk-- Zach, v 2, no. 4, p 439-658. D browski, Jan, ed, 1981, Woryty-studium archeologiczno-przyrodnicze zespolu osadniczego kultury Xuyckiej: Pol Bad Archeol, v 20, p 1-256. I)browski, Jan and Mogielnicka-Urban, M, 1976, Wyniki prat wykopaliskowych na stanowis- kach zespolu osadniczego kulturyTuzyckiej we wsi Woryty, wok Olsztyn: Spraw Archeol, v 22,p 145-167. I. Gordon, A D and Birks, H J B, 1972, Numerical methods in Quaternary palaeoecology. Zonation of pollen diagrams: New Phytol, v 71, p 961-979. Hakansson, Soren,1976, University of Lund radiocarbon dates IX: Radiocarbon, v 18, p 290- 320. 72 Mieczysaw F Pazdur et al

Hakansson, Soren, 1980, University of Lund radiocarbon dates XIII: Radiocarbon, v 22, p 1045-1063. ----- 1981, University of Lund radiocarbon dates XIV: Radiocarbon, v 23, p 384- 403. Hjelmroos, Mervi, 1981a, Holocene history of Lake Wielkie Gacno and its surroundings, in Kozarski, Stefan and Tobolski, Kazimierz, eds, Paleohydrology of the temperate zone, symposium: Guide-book of excursion; Poznan, Adam Mickiewicz Univ, p 76-88. ----- 1981 b, The Post-Glacial development of Lake Wielkie Gacno, NW Poland. The human impact on the natural vegetation: Acta Palaeobot, v 21, no. 2, p 129-144. ----- 1982, The Holocene development of Lake Wielkie Gacno, NW Poland, a palaeoecological study. Preliminary results: Acta Palaeobot, v 22, no. 1, p 23-46. Jankowska, Barbara, 1981, History of vegetation and settlement development at the Gopfo Lake in the light of pollen analysis, in Paleohydrology of the temperate zone, symposium: Abs of papers, Poznan, Adam Mickiewicz Univ, p 68-69. Kobendzina, Jadwiga, 1976, Z geografii historycznej teby i okolicy: Przegld geog, v 48, p 689-701. Kopczynska-Lamparska, Krystyna, 1974, Genesis and stratigraphy of tills of the cliff near Rewal: Uniw Adama Mickiewicza, zesz nauk, ser geog, v 10, p 167-176. ----- 1976, Radiocarbon datings of the Late Glacial and Holocene deposits of West- ern Pomerania: Acta geol pol, v 26, p 413-418. Koperowa, Wanda, 1962, Poinoglacjalna i holocenska historia roslinno"sci Kotliny Nowotars- kiej: Acta Palaeobot, v 2, no. 3, p 3-57. Kuzniewski, Edward, 1959, Torfowisko Zieleniec kolo Dusznik: Rocznik Kfodzki, v 3, p 169- 211. ----- 1962, Analiza palinologiczna torfowiska Zieleniec kofo Dusznik: Kwart Opolski, zesz przyrodn, no. 2, p 115-143. Latafowa, Mafgorzata, 1981 a, Local and regional aspects of paleobotanical material from the Lake Zarnowiec area, in Kozarski, Stefan and Tobolski, Kazimierz, eds, Paleohydrology of the temperate zone, symposium: Guide-book of excursions, Poznan, Adam Mickiewicz Univ, p 116-120. -----1981 b, The vegetational history of the Lake Zarnowiec area (eastern part of the Baltic coastal zone in Poland), in Paleohydrology of the temperate zone, symposium: Abs of papers, Poznan, Adam Mickiewicz Univ, p 70-71. ----- 1982a, Major aspects of the vegetational history in the eastern Baltic coastal zone of Poland: Acta Palaeobot, v 22, no. 1, p 47-63. ----- I982b, Postglacial vegetational changes in the eastern Baltic coastal zone of Poland: Acta Palaeobot, v 22, no. 2, p 179-249. Maruszczak, Henryk, 1966, Zagadnienia genezy i wieku jezior ..gczynsko-Wodawskich: Folia D, Soc Sci Lubliniensis, ser no. 5/6, p 31-37. Mikulski, J S, 1955, Jezioro Druzno-proba charakterystyki limnologicznej: Ekologia Polska, ser A, v 3, no. l , p 1-31. Noryskiewicz, Boiena, 1982, Lake Steklin-a reference site for the Dobrzyn-Chefmno Lake District, N Poland. Report on palaeoecological studies for the IGCP Project No. 158B: Acta Palaeobot, v 22, no. 1, p 65-83. Pawlikowski, M, Ralska Jasiewiczowa, Magdalena, Schonborn, W, Stupnicka, Ewa, and Szeroc- zynska, Krystyna, 1982, Woryty near Gietrzwal"d, Olsztyn Lake District, NE Poland- vegetational history and lake development during the last 12,000 years: Acta Palaeobot, v 22, no. 1, p 85-116. Pazdur, Anna, Awsiuk, Romuald, Bluszcz, Andrzej, Pazdur, M F, Walanus, Adam, and Zas- tawny, Andrzej, 1982, Gliwice radiocarbon dates VII: Radiocarbon, v 24, p 171-181. Pazdur, Anna, Pazdur, M F, and Zastawny, Andrzej, 1979, Gliwice radiocarbon dates V: Radiocarbon, v 21, 165-170. p '4C Pazdur, M F, 1982, Badanie dokladno"sci datowania metod poinoplejstocenskich i holocenskich osadow organogenichznych: Pol Slska, zesz nauk, ser mat-fii, no. 41, p1-81. Pazdur, M F, Awsiuk, Romuald, Bluszcz, Andrzej, Pazdur, Anna, Walanus, Adam, and Zas- tawny, Andrzej, 1983, Gliwice radiocarbon dates IX: Radiocarbon, v 25, p 843-866. Pazdur, M F and Walanus, Adam, 1979, Statistical analysis of data and age calculation in Gli- wice Radiocarbon Laboratory: Muz Archeol i Etnogr w todzi, prace i materiafy, ser archeol, v 26, p 283-289. Polach, H A, 1979, Correlation of 14C activity of NBS oxalic acid with Arizona 1850 wood and ANU sucrose standards, in Berger, Rainer and Suess, H E, eds, Radiocarbon dating, Internatl radiocarbon conf, 9th, Proc: Berkeley/Los Angeles, Univ California Press, p 115-124. Przybyfowska-Lange, Weis awa, 1976, Diatoms of the lake deposits from the Polish Baltic Coast. I. Lake Druzno: Acta Palaeobot, v 17, no. 2, p 35-74. Gliwice Radiocarbon Dates X 73 Ralska-Jasiewiczowa, Magdalena, 1981, Polish working group IGCP 158B. Report on the results of research 1978-1981, in Paleohydrology of the temperate zone, symposium: Abs of papers, Poznan, Adam Mickiewicz Univ, p 39-40. -----1982, Introductory remarks: Acta Palaeobot, v 22, no. 1, p 3-6. Stark, L, 1936, Zur Geschichte der Moore and Walder Schlesiens in postglazialer Zeit: Englers Bot Jahrb, v 67, p 493-640. Szafer, Wladysfaw, 1948, Pony lacjatw Roztokach pod Jaslem: Starunia, no. 26, p 1-29. Szczepanek, Kazimierz, 1961, Poznoglacjalna i holocenska historia rcslinnosci Gor Swigtokr- zyskich: Acta Palaeobot, v 2, no. 2, p 1-45. -----1982, Development of the peat-bog at Sl'opiec and the vegetational history of the Swigtokrzyskie (Holy Cross) Mts in the last 10,000 years. Preliminary results: Acta Palaeo- bot, v 22, no. l, p 117-130. Tobolski, Kazimierz, 1972, Wiek i geneza wydm przy pol'udniowowschodnim brzegu jeziora .[ebsko: Bad Fizjogr nad Polsk Zach, ser B, v 25, p 135-146. ----- 1975, Studium palinologiczne gleb kopalnych Mierzei .Lebskiej w Sl'owinskim Parku Narodowym: Pozn Tow Przyj Nauk, kom biol, prace, v 41, p 1-76. ----- 1979, Zmiany lokalnej szaty roslinnej na podstawie badan subfosylnych osadow biogenicznych w strefie play kofo x eby: Bad Fizjogr nad polsk Zach, ser A, v 32, p 151- 168. ----- 1980, The fossil soils of the coastal dunes on the'f eba Bar and their paleogeo- graphical interpretation: Quaestiones Geog, v 6, p 83-97. ----- 1981, The Gardno-Leba Plain, in Kozarski, Stefan and Tobolski, Kazimierz, eds, Paleohydrology of the temperate zone, symposium: Guide-book of excursions, Poznan, Adam Mickiewicz Univ, p 89-115. ----- 1982, Anthropogenic changes in vegetation of the Gardno-Leba Lowland, N Poland. Preliminary report: Acta Palaeobot, v 22, no. 1, p 131-139. Tobolski, Kazimierz, Pazdur, M F, Pazdur, Anna, Awsiuk, Romuald, Bluszcz, Andrzej, and Walanus, Adam, 1980, Datowanie metod 14C subfosylnych drewien wystgpuj cych na mierzejach Niziny Garniensko-.Lebskiej: Bad Fizjogr nad Polski Zach, ser A, v 33 p 133- 148. Wilgat, T,1953, Jeziora'[,gczynsko-Wl'odawskie: Ann UMCS, ser B, v 8, no. 3, p 1-121. Wojterski, Teofil, 1964, Bory sosnowe na wydmach nadmorskich na Polskim Wybrzeiu: Pozn Tow Przyj Nauk, kom biol, prace, v 28, no. 2, p 1-217. Zachowicz, Joanna, 1981, The Late-Glacial and Holocene vegetational history of the Zulawy Region (North Poland) in the light of a biostratigraphic study of Lake Druzno, in Paleohy- drology of the temperate zone, symposium: Abs of papers, Poznan, Adam Mickiewicz Univ, p 88. Zachowicz, Joanna, Przybyfowska-Lange, Wiestawa, and Nagler, J,1982, The Late-Glacial and Holocene vegetational history of the Zul"awy Region, N Poland. A biostratigraphic study of Lake Druzno sediments: Acta Palaeobot, v 22, no. 1, p 141-161. [RADIOcARBON, Vol. 27, No. 1, 1985, P 74-94] HARWELL RADIOCARBON MEASUREMENTS IV A J WALKER and R L OTLET Isotope Measurements Laboratory, Nuclear Applications Centre Atomic Energy Research Establishment, Harwell, Oxfordshire 0X11 ORA, UK The dates in this list follow, in approximately chronologic order, those reported in Harwell III (R, 1979, v 21, p 358-383). It is confined to archaeologic samples from the United Kingdom only, most of which origi- nate from "rescue" type operations supported by the Historic Buildings and Monuments Commission for England, (formerly a section of the Dept. of the Environment) and submitted through the Ancient Monuments Labo- ratory, London. As in previous lists, all samples were measured by liquid scintillation counting following the procedures reported elsewhere (Otlet & Warchal, 1978). The error term quoted is the 1 standard deviation, an estimate of the full replicate sample reproducibility of the laboratory process which takes into account all variations, not just counting statistics alone. The procedures by which these are computed is given in Otlet (1979). As recommended, all calculations are based on the Libby half-life of 5568 years, using NBS oxalic acid standard (x 0.95) as "modern," both values treated as constants, with Al) 1950 as the reference jyear. All results are corrected for fractionation according to the quoted b' C (wrt PDB) values measured in this laboratory. This is the first list produced from data stored on the Harwell main frame computer (IBM 3083) using the assembly programs described in Otlet & Walker (1981).

ACKNOWLEDGMENTS We wish to acknowledge the work of G A Bradburn and D G Humph- reys with the laboratory measurements, R S Keyzor, C F Linacre, and N J Metcalfe in the production of the data in computer readable form and in the final word processing. The financial support and co-operation of the staff of the Historic Buildings and Monuments Commission for England (Ancient Monuments Laboratory), through which most of the samples (those additionally referenced with AML numbers) were submitted, is also gratefully acknowledged.

ARCHAEOLOGIC SAMPLES

British Isles England Killibury series Samples from multiple-enclosure Iron Age hillfort at Killibury, Wade- bridge, Cornwall (50° 31' 36" N, 4° 48' 39" W, Natl Grid Ref SX 008735). Except for HAR-745, all samples coil Aug 1976 and subm Dec 1976 by H 74 Harwell Radiocarbon Measurements IV 75 Miles, Dept Extra-Mural Studies, Univ Exeter. For description of site, see Miles (1977).

2210 ± 70 HAR-745. KILLIB b13C = -24.8 oo Soil from early soil level in hillfort interior. Coll and subm Aug 1974 by T P F Trudgian. Comment (HM): this conforms well with other determinations from similar levels on site (HAR-1950 to -1953, below).

2180 ± 70 HAR-1950. 82368 b13C= -27.7%,, Charcoal. Comment (HM): sample from large pit expected to be from early Iron Age. Pit was sealed by ca 1 m of deposits. Date is entirely acceptable in confirming back-dating of multiple-enclosure hillforts and SW style of British La Tene-decorated pottery into third century BC.

2180 ± 70 b`3C HAR-1951. 236466 = -25.8)() Charcoal. Comment (HM): sample came from stratified soil deposit which should date early use of site, earlier than HAR-1953, but possibly contemporary with HAR-1950.

2880 ± 70 b13C HAR-1952. 430513 = -24.3 Charcoal from pit immediately antedating hillfort rampart now largely ploughed away; pit sealed by 0.2m of deposits below plough soil. A single sherd from interior suggests that core of rampart may have been constructed during later Bronze age.

2110 ± 70 13C HAR-1953. 6221 b = -25.2() Charcoal. Comment (HM): sample came from stratified soil level which should be comparatively late in hillfort occupation. Sealed by ca 0.8m of other deposits. Consistent with sequence suggested by other dates from site.

MARC 3 R4 series Samples from triple barrow with three cremations and later flint indus- ° try at Marc 3, Site R4, Micheldever Wood, Hampshire (51 7' 30" N, 1° 14' 56" W, Natl Grid Ref SU 52553653). Coll and subm Nov 1974 by P J Fasham, M3 Archaeol Rescue Comm. For description of site, see Fasham (1979) and Fasham and Ross (1978).

3100 ± 90 '3C HAR-1041. R4-3 b = -25.4 Charcoal, AML 749324, from oval barrow ditch which sealed flint working deposits. Comments: small sample accounts for larger than normal error term; (PJF): sample was taken from layer yielding date for fine, prob- 76 A J Walker and R L Otlet ably windblown, soil overlying flint industry. Samples also coll for detrital magnetic remanent dating by A J Clark, Ancient Monuments Lab.

3670 ± 80 13C HAR-1042. R4-144 b = -23.7 %o Charcoal, AML 749327, from flint layers of Western Mound.

6900 ± 170 b13C HAR-1043. R4-167 = -16.9 % Soil with charcoal, AML 749332, assoc with feature that antedates barrow construction. Comment: sample was very small and needed topping-up with 14C dead CO2 before benzene synthesis. 8'3C value is extremely unlikely for charcoal; contamination with ground carbonate is suspected and result should, therefore, not be accepted.

3370 ± 90 HAR-1044. R4-5 b13C = -24.7%o Charcoal with soil, AML 749325, from layer in ditch which sealed possible windblown soil (cf HAR-1041, R4-3, 3100 ± 90). Comment (PJF): strat- igraphically below flint industry. Samples also coll for detrital remanent magnetic dating by A J Clark. Baynard Castle series Wood from timbers which supported Roman stone wall at Baynard Castle, London (Hill, 1975; Hill, Millett, & Blagg, 1980). First 3 samples form part of dendrochronol series from 2 oak piles. All subm Jan 1976 by R Morgan, Dept Archaeol,Univ Sheffield, except HAR-1590.

1700 ± 70 513C HAR-1456. BC! = -26.4 %o AML 750334. Colt by S Hill. Comment (RM): rings 30 to 50 of 116-yr floating tree-ring sequence; 50 yr growth allowance to be added.

1740 ± 60 s13C HAR-1457. BC2 = -26.1 %o AML 750335. Comment (RM): rings 55 to 75 of 116-yr floating tree- ring sequence; 50 yr growth allowance to be added.

1640 ± 70 HAR-1464. 1724 BC3 '3C= -26.7%o AML 750336, taken from sapwood and outer area of piles. Comment (RM): rings 55 to 75 of 116-yr floating tree-ring sequence; 30 yr growth allowance to be added. General Comment (RM): archaeol evidence points to mid-4th century AD date for wall's construction. HAR-1456 and -1464 agree well with this date with necessary growth allowances added. HAR-1457 is, however, earlier than expected. Harwell Radiocarbon Measurements IV 77

1770 ± 80 bJ3C HAR-1590. BC4 = -26.4 %o Wood, AML 750855, from plank forming part of wooden revetment on S side of wall. Subm Feb 1976 by R Morgan. Comment (RM): sample comprises 20 annual rings from end of 129-yr sequence; no sapwood was' present. Result confirms suspected dendrochronol date in late 2nd century. Somerset Levels series The following 19 dates are of samples cull during excavations in 1976 and 1978 at Somerset Levels sites. For brief introduction to this ongoing project, see Harwell II (R, 1977, v 19, p 415-416). Within major Somerset Levels series are three sub-series (Meare Heath, Tinney's, and Meare Lake Village), dates for which are reported at end of general dates for Somerset Levels. Except where noted, all samples were coll and subm by J Coles, Dept Archaeol, Univ Cambridge. 1710±80 b13C HAR-1842. SLP7610 = -28.2 %o Wood from young timbers from lowest deposit of structure buried in ° pool peat at Difford's Site 1 (1.116) Shapwick (51 9' 45" N, 2° 47' 15" W, Natl Grid Ref ST 44954073). Comment (JC): agrees well with HAR-1854 and with series for highest levels of peat in which structure lay (Coles & Orme, 1978c).

1730 ± 70 b13C HAR-1854. 5LP769 = -29.4 %o Wood from young timbers of structure buried in pool peat at Difford's Site 1, Shapwick (51° 9' 45" N, 2° 47' 15" W, Natl Grid Ref ST 44954073). Subm July 1976. Comment (JC): agrees well with HAR-1842. 3770 ± 80 '3C HAR-1843. 5LP764 b = -27.7 %o Peat adjacent to hoard of flint flakes (Coles & Orme,1978d) preserved in grasses and container at Skinner's Wood, Shapwick (51 ° 9' 34" N, 2° 50' 7" W, Natl Grid Ref ST 416404). Subm,July 1976.

6520 ± 90 b13C HAR-1855. SLP767 = -29.8 %o Peat from lower peat deposit beneath clay 2m thick at Durston's Works, Sharpham (51 ° 8' 32" N, 2° 46' 26" W, Natl Grid Ref ST 45873846). Subm July 1976. Comment (JC): early peat formation in trough of Somerset Levels prior to marine inundation.

5600 ± 70 b13C HAR-1856. 5LP766 = -27.3 %o Peat from interface between lower marine clay and peat formation at Garvin's Factory, Walton Heath (51 ° 8' 32" N, 2° 46' 27" W, Nail Grid Ref 78 A J Walker and R L Otlet ST 45853845). Subm July 1976. Comment (JC): dates transition to freshwater conditions in Levels.

5290 ± 80 HAR-1857. SLP765 S13C= -27.6)o Peat from interface between lower marine clay and peat formation at Sweet Railway, Shapwick (51 ° 9' 54" N, 2° 49' 19" W, Natl Grid Ref ST 42534103). Subm July 1976. Comment (JC): dates transition to freshwater conditions in Levels.

3480 ± 90 HAR-2243. SLP772 b13C = -29.1%)o Peat found underlying lowest wooden structure at Tinney's Ground, Sharpham (51 ° 8' 24" N, 2° 45' 28" W, Natl Grid Ref ST 470382). Coll by S Coleman and subm July 1977. Comment (,JC): lowest structures in complex field with upper trackways dated ca 1050 be (Coles & Orme, 1978b).

2920 ± 60 HAR-2429. SLP774 o'3C = -29.6/)o Wood from lowest roundwood of major Bronze age track at Tinney's ° Ground (TIN B), Sharpham (51 8' 24" N, 2° 46' 14" W, Natl Grid Ref ST 46103820). Coll by S M Fordham and Subm Sept 1977. Comment (,JC): HAR-947 (1010 ± 70bc) and HAR-684 (1070 ± 70bc) relate to other exposures of same track; cf also HAR-2243, above. 4560 ± 80 11C HAR-2224. SLP771 = -28.6'x) Peat from Meare Heath (51 ° 9' 40" N, 2° 46' 30" W, Natl Grid Ref ST 45824054). Coll Feb 1977 and subm Mar 1977. Comment (JC): peat was assoc with flint axe of Neolithic type, closely comparable to Early Neolithic Sweet Track finds 3km away. I)ate seems slightly young (c/ Sweet Track ca 3200 bc: Coles & Orme, 1979). Peat was exactly contemporary with axe or slightly older.

4580 ± 60 HAR-2428. SLP773 '3C= -27.9%x Wood from terminal area of Meare Heath Bronze age track at Meare Heath Field 12.3, Meare (51 ° 9' 59" N, 2° 47' 30" W, Natl Grid Ref ST 44654115). Colt by SC Beckett and subm Sept 1977. Comment (JC): date is older than series from track timbers to S including HAR-943(1030 ± 70bc) (Coles & Orme, 1978a). Sample consisted of small piece of wood from terminal area, but was not part of construction.

2900 ± 80 513C HAR-2619. SLP7807 = -27.8/ o Peat, AML 780684, from burned peat horizon overlying Meare Heath track at Meare Heath Drove (51 ° 9' 35" N, 2° 47' 48" W, Natl Grid Ref ST 443404). Subm Apr 1978. Comment (JC): date fits stratigraphy in placing Harwell Radiocarbon Measurements IV 79

burned horizon at slightly later date than Meare Heath track (eg, I OObc) which closely underlies it (Beckett, 1978). Meare Heath series Wood, from dendrochronol series of 3 samples from 118-yr floating tree-ring sequence at Meare Heath Trackway, Somerset Levels (Coles & Orme, 1976; Morgan 1978a). Coil 1974-5 and subm Jan 1976 by R Mor- gan, I)ept Archaeol, Univ Sheffield.

3200 ± 80 HAR-1489. SPL761 b13C = -26.8 (o AML 760301, from rings 30 to 50. Comment (RM): sample taken from two timbers. Growth allowance of > 100 yr to be added. 3000 ± 80 HAR-1627. SLP762 b13C = -26.8 AML 760302, from rings 60 to 80. Comment (RM): sample includes sees from four timbers. Growth allowance of > 70 yr to be added. 3060 ± 80 b13C HAR-1494. SLP763 = -27.2() AML 760303, from rings 90 to 110. Comment (RM): sample includes sees from > two timbers. Some root intrusion. Growth allowance of > 40 yr to be added. General Comment (RM): in all cases, wood was quite decayed due to peat drying out. With necessary growth allowances added, HAR-1489 and -1494 are consistent with series but -1627 is rather later. Tinney's series Two samples of wood, (waterlogged oak) from tree-ring sequence on planking of track TIN A at Tinney's Ground, Sharpham (51 ° 8' 27" N, 2° 45 33" W, Natl Grid Ref ST 469383). Coll Sept 1977 by R A Morgan. For description of site, see Morgan (1978b). 3050 ± 70 b13C HAR-2538. SLP7801 = -25.4 %o AML 780339, from rings 120 to 140. Subm Feb 1978. 2990 ± 60 HAR-2544. SLP7802 b13C = -26.3 AML 780340, from rings 220 to 240. Subm May 1978. General Comment (RAM): both dates fall neatly into series from track. HAR- 2538 has growth allowance of 100 yr. HAR-2544, with slight allowance for sapwood only, provides date close to time of felling of trees used in track. Meare Lake Village series Samples from Meare Lake Village West MVW W10, Somerset (51° 10' 33" N, 2° 47' 38" W, Natl Grid Ref ST 445422). For a description of the site, see Orme et al (1981). 80 A J Walker and R L Otlet 5210 ± 80 b13C HAR-2616. SLP7803 = -29.5 %o Peat, AML 780680, from peat-clay interface beneath fen peat. Coil by S C Beckett and subm Apr 1978. Comment (JC): date is comparable with, but slightly younger than, those dates (HAR-1831 and -1856) from equivalent marine clay/upper peat interface further S in Somerset Levels.

2340 ± 80 b13C HAR-2620. SLP7804 = -26.4 %o Peat, AML 780681, from raised bog peat underlying settlement. Coil by S C Beckett and subm Apr 1978. Comment (JC): stratigraphic relationship between establishment of settlement and environmental conditions in Levels seems secure on basis of this date and HAR-2654.

2200 ± 70 b13C HAR-2654. SLP7806 = -27.6 %o Wood, brushwood, AML 780683, from lowest level of settlement. Coll by C R Sturdy and subm Apr 1978. Comment (JC): dates lowest horizon of lake village in general agreement with archaeol dating (Orme et al, 1981).

2130 ± 90 b13C HAR-2668. SLP7805 = -27.7 %o Oak wood from stake in construction. Coil by S C Beckett and subm Apr 1978. Comment (JC): dates major constructional phase of settlement. Hereford series

950 ± 70 b'3C HAR-1620. HE75B583 = -22.2 %o Bone, AML 757647, from layer in front of Saxon stone revetment wall to earlier bank at Cantilupe St, Hereford (52° 3' 11" N, 2° 42' 32" W, Nail Grid Ref SO 514397). Coll Nov 1975 and subm Feb 1976 by R Shoesmith. Comment (RS): layer was deposited after stone wall was built and probably before it was disused. Layer contained much mortar (from wall) and snails, as well as animal bone (Shoesmith, 1982).

1020 ± 70 513C HAR-1875. HE73IS83 = -19.8 %o 14C Bone, one series of dates already pub (R, 1977, v 19, p 406-407), from cemetery at Castle Green, Hereford (52° 3' 4" N, 2° 42' 40" W, NGR SO 513395). Coll 1973 and subm Oct 1976 by R Shoesmith. Comment (RS): series of burials from ca AD 700 to 1150 include charcoal and coffin burials (Shoesmith, 1980).

1570 ± 70 b13C HAR-1623. CIRENC30 = -23.7 %o Bone from Late Roman farmyard or barn (Reece, 1974) at Beeches Rd, Cirencester, Gloucestershire (51 ° 42' 22" N, 3° 24' 25" W, Natl Grid Ref 50 028018). Subm May 1976 by R Reece. Harwell Radiocarbon Measurements IV 81 Gloucester series

Samples from 1 Westgate St, Gloucester. Subm Feb 1976 by C M Heighway, Gloucester Excavation Unit.

1540 ± 70 b13C HAR-1652. 49751 = -25.3 %o Wood, id as oak by C A Keepax, AML 750870, from fairly large timbers from charred sill beams of Late Roman bldg postdating demolition of major bldgs in town center. Coil Nov 1975. Comment (CH): bldg was dated from coin evidence to late 4th century or early 5th century AD.

1190 ± 70 HAR-1655. 4975V130 b13C = -27.9'00 Charcoal, AML 750874, from stake from wattle fence in aceramic levels. Subm Feb 1976 by C Heighway. Comment (CH): HAR-1788 was taken from same sample and HAR-1658 and --1787 came from another stake in same fence.

1260 ± 80 b13C HAR-1656. 49753 = -28.3 %o Wood, AML 750871, part of complete oak post from possible Saxo- Norman undercroft at frontage of site. Comment (CH): pottery assoc with sample dates to early 11th century or earlier.

910 ± 60 b13C HAR-1657. 49759 = -29.4 10 Wood, AML 750872, part of stake from pit (F21) containing wooden artifacts. Comment (CH): pit postdates preserved Saxon wooden bldgs dated by HAR-1658, -1655, and -1788; it contained late 11th century pottery and artifacts. Dendrochronol date of same sample is after AD 1110 (R Mor- gan, Univ Sheffield, pers commun).

1040 ± 60 HAR-1658. 497527 b13C = -28.4 Wood, AML 750873, from Saxon bldg, 1 of 2 stakes of same wattle fence as HAR-1655 and -1788.

1000 ± 70 HAR-1787. 497527 b13C = -28.7 Wood, Hawthorn type, id by C A Keepax, AML 750873, from stake from wooden Saxon bldg, 1 of 2 stakes of wattle fence. Comments: replicate check measurement on HAR-1658; (CH): sample came from well-preserved aceramic bldgs and antedates HAR-1657.

1170 ± 80 b'3C HAR-1788. 497530 = -25.05 0 Wood, AML 750874, part of stake from aceramic Saxon levels. Com- ments: replicate check measurement of HAR-1655; (CH): stake came from same wattle fence as HAR-1658 and -1787. 82 A J Walker and R L Otlet Bishopstone series Charcoal samples from Bishopstone, Sussex (50° 47' 15" N, 0° 4' 53" E, Natl Grid Ref TQ 467008). Coll Sept 1975 by M Bell and subm by P L Dre- wett, Inst Archaeol, Univ London. For description of site, see Bell (1977). 4460 ± 70 b13C HAR-1662. B1357L4 = -25.6 4o AML 750326, from fill of Neolithic Pit 357. Subm Feb 1976. Comment (PLD): pit was cut into chalk and contained early Neolithic artifact assemblage assoc with food refuse. 1630 ± 70 HAR-1663. BIKXXXV b13C = -26.2 Oak, id by C A Keepax, AML 750861, from fairly large timbers of rec- tangular structure XXXV, which was thought to be of Anglo-Saxon date. Subm May 1976. Nazeingbury series Bone, from Christian cemetery at Nursery Rd, Nazeingbury, Essex (51 ° 44' 26" N, 0° 0' 27" E, Natl Grid Ref TL 386066). Cemetery is middle Saxon and unlikely to be later than Al) 870 (Huggins, 1978). 180 graves were seen oriented E to W and without grave goods. Preponderance of females (80) to males (32) and pathology leads to idea of hospice run by nuns. All samples coil and subm May 1976 by P J Huggins. 1280 ± 80 13C HAR-1666. NZ76GR54 b = -22.4 o AML 760789, from primary grave. Comment (PJH): grave was of very old female buried at F end of church, oriented E-W without grave goods, middle Saxon. 1120 ± 80 11C HAR-1681. N275GR26 = -22.7 %o AML 760790, from secondary grave. Comment (PJH): sample overlay Roman 1 st to 2nd century and Belgic occupation. Foulness series Oak wood from wooded structure in ancient earth wall, embedded in clay, 1.Im below surface at Old Wall, NW Shelford, Foulness, Essex (51° 34' 51" N, 0° 51' 8" E, Nat! Grid Ref TQ 976908). Subm by E Hyde, AWRE Archaeol Soc. 500 ± 70 HAR-1689. FBMO11 b'3C = -26.2)() AML 760495, subm July 1976. 360 ± 80 b13C HAR-1690. FBM021 = -27.1 "/r,o AML 760496, subm May 1976. General Comment (EH): tree-ring age dates felling at Al) 1490. Harwell Radiocarbon Measurements IV 83 Little Bay series Charcoal from Bldg 2 at Little Bay, St Martins, Isles of Scilly (49° 58' 9" N, 6° 17' 26" W, Natl Grid Ref SV 924166). Subm May 1976 by H Keeley, Ancient Monuments Lab. For description of site, see Butcher (1974).

3190 ± 110 HAR-1715. 1792E16 b' 3C = - 25.3 / Ca 25% of sample id by C A Keepax as oak from fairly large timbers and hazel, from Hearth Ic. Coll Sept 1974 by S A Butcher.

2780 ± 80 b'3C HAR-1726. 43-14E-F = -25.9 AML 756490 from upper fill. Coil June 1974 by S A Butcher.

960 ± 70 b13C HAR-1728. BH2046A = -28.1 'H) Charcoal, AML 760236, wood fragments derived from sec of long beam (originally entire), at Bishophill, Skeldergate, York. Subm Feb 1976 by H K Kenward. Comment (HKK): may have been subject to contamination by humates from later layers. Winklebury series Charcoal samples from Winklebury Camp, Basingstoke, Hampshire. Subm Sept 1976 by G Wainwright and K Smith. For description of site, see Smith (1979).

2200 ± 60 HAR-1764. 13690 b' 3C = -27.3 AML 766708, from remains of charred post found in post hole, part of porch of round house. Coll F McAvoy. Comments: extensive rootlet contamination separated as much as possible; (GW): date slightly later than that suggested by pottery, which belongs to early phase, 6th to possibly 4th centuries BC.

1980 ± 90 HAR-1778. 13961 b' 3C = -25.8/±) AML 766706, from layer of burned material in top half of beehive storage pit. Coil by F McAvoy and subm Sept 1976 by K Smith. Comment (GW): layers above and below sample produced saucepan pots (3rd to 1st centuries BC). 2020 ± 80 13C HAR-1794. 13961 b = -25.6()/rr AML 766705, from layer of burned material in top half of pit. Coll by D Batchelor. Comment (GW): date is consistent with assoc pottery. Wootton Wawen series Bone from early medieval cemetery sealed by domestic bldgs of small alien priory at Wootton Wawen, Warwickshire. Subm Sept 1976 by H Bar- nie, Dyfed Archaeol Trust. 84 A J Walker and R L Otlet 790 ± 70 S13C HAR-1820. A62 = -20.3 %o

790 ± 80 HAR-1821. A61 b13C = -19.8/ o

900 ± 70 b13C HAR-1822. A21 = -20.9 %o General Comment (HB): cemetery is only datable by 14C measurement, and resulting dates are vital for dating earliest priory bldgs on site. New Fresh Wharf series Wood samples, all waterlogged oak, part of dendrochronol series of 4 samples from 282-yr floating tree-ring sequence (Morgan, 1977) from Roman waterfront at New Fresh Wharf, London (51 ° 30' 31" N, 0 5' 2" W, Natl Grid Ref TQ 32958066). Subm Aug 1976 by R Morgan.

1660 ± 60 HAR-1864. NFW3 b13C = -26.2 oo Third sample (rings 190-210) from 3 timbers, growth allowance ca 90 yr.

1800 ± 60 b13C HAR-1865. NFW2 = -26.3 %o Second sample (rings 140-160), from 2 timbers, growth allowance ca 140 yr.

'3C- 1840 ± 60 HAR-1867. NFW3 -26.8 4o Earliest sample (rings 90-110), from 2 timbers, growth allowance ca 190 yr.

1760 ± 60 '3C= " HAR-1868. NFW4 -26.1 o Latest sample (rings 240-260), from 2 timbers, growth allowance ca 40 yr. General Comment (RM): 282-yr chronology is now dated from 73 BC to AD 209. With allowances quoted, HAR-1865 and -1867 fit well into series but -1864 is slightly later than expected and -1868 rather earlier.

1590 ± 80 b13C HAR-1837. F75BK = -22.6 %o Bone, AML 760777, from rubbish deposit at Flaxengate, Lincoln (53° 13' 49" N, 0° 32' 16" W, Natl Grid Ref SK 976714). Coll by R H ones and subm Sept 1976 by C Colyer, Lincoln Archaeol Trust. Comment (CC): date confirms late Roman origin of this material, which was in secondary context of later date. Harwell Radiocarbon Measurements IV 85 Hambledon Hill series Samples from Hambledon Hill, Neolithic causewayed enclosure, Dor- set (50° 54' 34" N, 2° 12' 38" W, Nat! Grid Ref ST 852123). Samples HAR- 3058, -3060, and -3062, although part of Hambledon Hill series, come from Stepleton enclosure (Natl Grid Ref ST 856125). All samples coil and subm by R Mercer and pub in Mercer (1980).

4560 ± 90 HAR-1882. HH752134 b13C = -24.9%o Charcoal, ashy gray wash, 50% id by C A Keepax as Hawthorn type, not twiggy, AML 760800, from ditch segment II, Layer 11. Coil Oct 1975 and subm Feb 1976. Comment (RM): interpretation of layer is problematic- possibly dumped organic deposit similar to that in Site F, or richer, more organic silt deposit that incorporated cultural material in its formation. 4480 ± 130 HAR-1885. HH741245 (b13C = -25.0 %)o) Charcoal, 50% id by C A Keepax as Hawthorn type and Prunus sp from fairly large timbers plus one twig fragment of Blackthorn, AML 760792, from ditch area II. Subm Sept 1976. Comments: b'3C assumed; (RM): ditch was filled with gray organic soil, charcoal flecks, and some burned bone, 1 pot, and burned flint. Feature I is roughly oval and cuts into middle fill, overlain by secondary silt deposits.

4840 ± 150 HAR-1886. HH75846 b13C = -26.4%o Charcoal, 50% id by C A Keepax as Sorbus sp and hazel, not twiggy, AML 760795, from ashy, dark gray, silty soil with small chalk lumps and some charcoal in ditch segment B, Layer 12. Coil Sept 1975 and subm Sept 1976. Comment (RM): this band of silting abuts causeway separating seg- ments A and B of causewayed enclosure ditch in Site D.

4110 ± 80 HAR-2041. HH75545 b13C = -23.4 o/r)o Antler from Site B, Feature 57, Layer 1 (see below). Subm Sept 1976. Comment (RM): Feature 57 is pit with fill of rich black loam, orange brown loam with orange pea chalk and chalk lumps, and chalk wash. Layer 1, in particular, contained rich assemblage of material including antler, 1 pot, bone, and stone rubber fragments. 4520 ± 80 '3C HAR-2368. HH7626 b = -25.2 %o Charcoal, id by C A Keepax as oak, AML 777002, from bank outwork Ditch 2, Feature 8, Site M, HH 76. Coil Sept 1976 and subm Sept 1977. Comment (RM): feature was filled with dark brown, almost black, soil with granular chalk and flint. Texture was grittier towards edges with loamier central filling. At depth of ca 12cm, fill was browner more compact soil. Feature produced charcoal fragments and unabraded sherds. 86 A J Walker and R L Otlet 4630 ± 80 HAR-2372. HH7646 o13C = -27.2%ro Charcoal, id by C A Keepax as oak and hazel/alder, not twiggy, AML 777005, from HH 76, Site L, outwork Ditch 1, Layer 7. Coll 1976 and subm Sept 1977. Comment (RM): layer was composed of large vacuous chalk and flint nodules overlying Layers 8 and 9 of primary silt. Charcoal fragments were contained within other burned material. Bone, flint, and human skeletal material was incorporated in deposit.

4670 ± 100 b'3C HAR-2375. HH7682 = -25.8 Charcoal, id by C A Keepax as oak, hazel/alder and possibly Hawthorn type, not twiggy, AML 777012, from HH 76, Site G, ditch segment 3, Layer 9A. Coll Oct 1976 and subm Sept 1977. Comment (RM): layer came from deep pit, bowl-shaped in cross-sec, characterized by gray charcoal stained silt. It cut into Layer 10, vacuous rubble fill overlying ditch floor.

4350 ± 80 HAR-2379. HH7650 o13C = -26.3 Charcoal, id by C A Keepax as oak and hazel/alder, some twiggy, AML 777007/8/9, from HH 76, Site L, outwork Ditch 1, Layer 7. Coll Sept 1976 and subm Sept 1977. Comments: Samples HH7648, HH7649, and HH7650 combined; (RM): layer was composed of large vacuous chalk lumps and flint nodules overlying Layers 8 and 9 of primary silt. Deposit incorporated bone, flint, and human skeletal material. HH7648 and HH7649 were closely assoc with skeletal material.

4700 ± 90 HAR-3058. ST7883 o13C = -24.9)4() Charcoal, id by C A Keepax as Quercus sp, Corylus sp Rosaceae subfamily Pomoideae (eg, Hawthorn) all from mature timbers, AML 790530, from main enclosure, Ditch 1, Segment A, Quad 2, Layer 5. Coll Sept 1978. Com- ment (RJM): represents accumulation of silt overlying natural chalk. Sample consisted of admixture of charcoal and ash.

4570 ± 90 HAR-3060. ST78121 b13C = -25.4)() Charcoal, id by C A Keepax as Quercus sp and Corylus sp from mature timbers, AML 790534, from main enclosure, Ditch 1, Segment A, Quad 2, Layer 4. Coil Sept 1978. Comment (RJM): layer represents initial accumulation of rubble from unstabilized bank, sample from burned area assoc with human skeletal material.

4850 ± 70 5130 HAR-3062. ST78118 = -25.6% Charcoal, id by C A Keepax as Corylus sp, Quercus sp Rosaceae subfamily Pomoideae (eg, Hawthorn) all from mature timbers, AML 790531, from Harwell Radiocarbon Measurements IV 87 main enclosure, Ditch 1, Segment A, Quad 2, Layer 3a. Coil Oct 1978. Comment (RJM): layer is composed of chalk gravel in matrix of chalk wash with little humic material, representing erosion of bank material. Finds included bone and antler picks. Bedford St Johns series Samples from St John's St, Bedford (52° 7' 53" N, 00 27' 50" W, Natl Grid Ref TL 05144929). Coll and subm Nov 1976 by Jane Hassall. For description of site, see Hassall (1979).

1010 ± 70 b13C HAR-1896. BSJ76C1 = -25.9 °'/o Charcoal, id by C A Keepax as mainly oak (large timbers) with a few fragments hazel and Hawthorn type, AML 766971, from one of large pits in backyard area. Comment (JH): sample came from largest rubbish pit uncovered. It seems likely that domestic rubbish was thrown into this pit and burned in situ.

1110 ± 70 HAR-1897. B5J76C3 b13C = -26.2 o/)O Charcoal, id by C A Keepax as mainly oak (large timbers) with some ash (branch), hazel (twiggy), Hawthorn type (large timbers) and maple (large timbers), AML 766972, from Saxo-Norman or Early Medieval rubbish pit. Comment (JH): pit seems archaeol contemporary with that of Sample BSJ76C1 (HAR-1896).

480 ± 70 b'3C HAR-1930. BSJ76W1 = -26.0'00

Wood, oak, AML 766969, from 1 of 4 timbers which outlined square well; timbers underlay well housing and overlay present-day water table.

1170 ± 70 b13C HAR-1898. SFII/ 1 = -26.24 Charcoal from floor level of small, stone house at Simy Folds, Upper Teesdale, Co Durham (54° 38' 39" N, 2° 10' 25" W, Natl Grid Ref NY 888277). Subm Oct 1976 by K J Fairless. Comment (KJF): it is hoped that further excavation at site will produce evidence to confirm this date.

3420 ± 100 b13C HAR-1899. BDI = -25.9 % Charcoal, id by C A Keepax as Hawthorn type, oak and blackthorn, from large timbers, AML 766984, from silts of first phase ditch at Weekley, Northamptonshire (52° 25' 36" N, 0041P 38" W, Nail Grid Ref SP 888818). Coll May 1976 and subm July 1976 by D A Jackson. Comment (DAJ): this could be boundary ditch mentioned in Anglo-Saxon literature but is thought to be of Roman or Iron age. 88 A J Walker and R L Otlet St Mark's, Lincoln series Bone samples, from burials at St Mark's, Lincoln (53° 15' 7" N, 00 32' 24" W, Nat! Grid Ref SK 974738). Coil by B Gilmour and subm Sept 1976 by C Co!yer, Lincoln Archaeol Trust. For interim report on site, see Jones (1981).

870 ± 70 HAR-1961. SMASSI 5130= -19.9%o AML 766556. Comment (CC): burial is post-Roman but antedates earliest Medieval church. Later than another two graves.

1040 ± 60 513C HAR-2010. SMAUJB = -21.0 0/0 AML 766558, from complete skeleton. Comment (CC): primary burial which antedates earliest Medieval church.

980 ± 70 5130 HAR-2011. SMAWK4 = -20.4 %o AML 766559, from deepest burial N of and antedating earliest Medi- eval church.

1110 ± 70 HAR-2012. SMATP2 Y3C = -20.1 %o AML 766557, from post-Roman burial antedating earliest Medieval church. Comment (CC): burial was sealed by two more graves and cut away above waist by porch foundations. General Comment (CC): dates of these samples confirm 10th century dating for origin of cemetery. Curbridge series Bone samples, from small cemetery overlying Romano-British settle- ° ment at Curbridge (Coral Springs) Oxfordshire (51 46' 38" N, 10 30' 41" W, Natl Grid Ref SP 337089). Coil 1975 and subm Apr 1976 by R Cham- bers, Oxford Archaeol Unit. For description of site, see Chambers (1976; 1978).

1840 ± 80 513C HAR-2005. GRAVEF27 = -21.4 %o AML 760234. Comment (RC): AD 110 appears a little early for inhuma- tion burial in Roman Britain; archaeol evidence also suggests that this small cemetery is 3rd or 4th century AD at earliest.

1640 ± 70 5130 HAR-2006. GRAVEF8 = -21.9 % AML 760233. Comment (RC): from archaeol evidence, cemetery appeared to be 3rd century. Fourth century date for this skeleton is quite acceptable. Harwell Radiocarbon Measurements IV 89

2940 ± 80 b13C HAR-2091. AYTON02 = -26.1 %o Charcoal from pit inside enclosure added to long cairn with two collared urns at Great Ayton Moor (Barrows and Enclosures) N Yorkshire (54° 29' 43" N,1 ° 4' 58" W, Nat! Grid Ref NZ 594115). Coil 1959 by R H Hayes and subm Jan 1977 by S Pierpoint. Comment (SP): result is archaeoi unsatis- factory, 300-700 yr later than other comparable dates for collared urns. Charcoal had been kept for some time in suspect container before being submitted.

1140 ± 70 HAR-2209. WAGR876 b13C = -23.7/o Bone, AML 770870, from grave in Christian cemetery at Waltham Abbey (S E Transept) Essex (51° 41' 12" N, 0° 0' 2" W, Natl Grid Ref TL 382006). Coil Apr 1977 and subm June 1977 by P J Huggins. Comment (P]H): cemetery antedates S E Transept of Augustinian Abbey at Waltham founded in AD 1177 (Huggins, 1979). Shaugh Moor series Charcoal samples from Cairn site, Shaugh Moor, Devon (50° 27' 10" N, 40 2' 19" W, Nat! Grid Ref SX 553635), coil from charcoal-filled pits beneath cairns. All subm July 1977 (except HAR-2214 and -2216) by N D Balaam. For description of site, see Wainwright, Fleming, and Smith (1979).

3430 ± 80 HAR-2213. CAIRN71 b13C = -25.9 /x, AML 772507, from charcoal deposit beneath small cairn. Coil June 1977.

3240 ± 80 13C HAR-2214. 10/150 b = -25.7°,/ o AML 773294, from charcoal pit. Coil by K Smith and subm June 1977.

3520 ± 70 13C HAR-2216. 10/175 b = -25.6 AML 773292, from fill of charcoal pit. Coil by K Smith and subm June 1977.

3430 ± 80 '3C HAR-2219. 10/153 b = -25.3 %o AML 773283, from fill of charcoal pit, sealed by capping stone which was covered by small cairn. 3430 ± 90 b13C HAR-2220. 10/145 = -25.5 %o AML 773289, from fill of charcoal pit which contained faience beads. 90 A J Walker and R L Otlet 3350 ± 70 HAR-2221. 10/168 ('3C= -25.0)) AML 773287. Comment: 513C assumed.

3400 ± 90 b'3C HAR-2285. 10/193 = -25.2 %x) AML 773299, from charcoal pit.

1980 ± 70 513C HAR-2227. TRG 105 = -25.0 ¶/o Charcoal, AML 776291, from alongside base of presumed oven at Tre- gilders near Killibury, Cornwall (50° 31' 57" N, 4° 47' 48" W, Nat! Grid Ref SX 01837410). Coll Sept 1976 and subm Feb 1977 by T P F Trudgian. Com- ment (TPFT): presumably derived from or connected with neighboring remains of oven (Trudgian, 1977).

100 ± 70 HAR-2260. BR! Y3C = -27.7 )o Wood, waterlogged oak, AML 775740, from possible mill structure at Springs Bridge, Bradbourne, Derbyshire (53° 3' 56" N, 1° 41' 44" W, Natl Grid Ref SK 204521). Coil Oct 1975 by J R Collis and subm June 1977 by R A Morgan. Comment (RM): outermost 20 sapwood rings used. Although unexpectedly late, result is possible archaeol and has since been confirmed dendrochronol by date, Al) 1836, for outermost growth ring. See Morgan, Wildgrove and Collis (1980).

480 ± 60 HAR-2261. BILBYI o13C = -26.1 Wood, id by C A Keepax as oak, from pier of bridge spanning R Ryton, retrieved during maintenance work and not in situ at Bilby, Nottingham- shire (53° 20' 30" N, 1° 2' 30" W, Natl Grid Ref SK 638832). Coil by M Dolby and subm Dec 1976 by R Morgan. Comment (RM): sample covers outer 20 heartwood rings of bridge pier. Date was unknown previously, so it is useful guide to locating possible matches for 228-yr tree-ring sequence from bridge timbers. Bilby is deserted Medieval village site and stone bridge, possibly 17th century, spans river some 100m W.

270 ± 70 b13C HAR-2262. 124/47 = -25.2 ¶?/)o Wood, conifer, AML 775743, pine plank of late 17th century date from Queen St, Hull, Humberside (53° 44' 26" N, 0° 19' 54" W, Nati Grid Ref TA 10022844). Coil by A Whitwell and subm June 1977 by R Morgan. Comment (RM): sample originally subm for wood id only but 14C determination agrees well with archaeol evidence. Droitwich series Wood samples, all waterlogged oak, from Friar St, Droitwich, Cheshire (52° 16' 9" N, 2° 9' 1" W, Nat! Grid Ref SO 89746349). Coll July 1975 byA Hunt and subm by R Morgan. Harwell Radiocarbon Measurements IV 91

1950 ± 70 b13C HAR-2263. DF 1 = -27.1 %o From board, measuring 0.55 x 0.364 x 0.047m, deposited with broken stakes in ashy fill of timber and clay-lined pit, which probably func- tioned as brine storage and settling tank. Subm Dec 1976. Comment (RM): function of board is uncertain but it was possibly part of superstructure to pit. Finds include early 2nd century AD pottery and briquetage. Sample was taken from outermost 20 sapwood growth rings of board 262112, very close to felling year. Annual rings have now been dated absolutely to AD 25-45. 800 ± 70 HAR-2264. DF2 b13C = -27.1 /,o AML 775739, from stake driven into base of cess-pit with waterlogged fill containing pottery of 12th century . Stake probably supported seat or shelter over pit. Subm June 1977. Comment (RM): sample was taken from outermost 15 sapwood rings of young stake 13873 close to year of felling. Date supports archaeol evidence. Wales 2800 ± 80 HAR-1385. NANT MELYN b13C = -25.8 Charcoal from part of layer apparently relating to Mesolithic occupa- ° tion with microliths at Nant Melyn, Blaenrhondda, Mid Glamorgan (51 42' 14" N, 30 34' 18" W, Natl Grid Ref SN 914018). Coil Oct 1975 and subm Nov 1975 by H N Savory, Nail Mus Wales. Comment (HNS): sample seems to provide terminus post quern for formation of blanket peat over thin ancient soil, affected by rainwash, in which microliths were present (Savory, 1976).

Scotland Iona series Samples from Old Guest House, Iona (56° 20' S" N, 6° 23' 30" W, Natl Grid Ref NM 286245). Coli July 1974 and subm May 1975 by R Reece, Inst Archaeol, Univ London. 1260 ± 130 HAR-1229. IONASP21 b13C = -22.7/o Bone from top burning level. Comment: result has large uncertainty 14C due to insufficient sample material, which required topping-up with dead CO, after collagen extraction and combustion. 1190 ± 70 b13C HAR-1241. IONASP25 = -22.8 %o Bone from below burning level. 1130 ± 80 b13C HAR-1276. IONASP24 = -25.8 %o Charcoal. 92 A f Walker and R L Otlet General Comment (RR): HAR-1229, -1241, and -1276 over- and underlying deposit of rubbish and burned material all seem to date to ca Al) 800, thus making sequence of 16 layers a short one. For first time, this destruction can be linked to Viking raids that eventually destroyed monastery of Iona early in ninth century (Reece, 1973; 1981). Berrybrae series Charcoal from Pit 9 at Berrybrae recumbent stone circle, near Fraser- burgh, Aberdeenshire (570 36' 15" N, 10 57' 17" W, Natl Grid Ref NK 027571). Both samples coil and subm Aug to Sept 1976 by H A W Burl.

3450 ± 80 b13C HAR-1894. S/11 1 = -25.4 %o

3310 ± 90 b'3C HAR-1893. S/112 = -25.2k General Comment (HAWB): Pit 9 contained soil, some small quartzite stones, and charcoal which was thickest near rim of late beaker placed amongst disturbed cairn stones. Balloch series Charcoal samples from Balloch Hillfort, Argyll (55° 23' 49" N, 5° 40' 8" W, Natl Grid Ref NR 677176). Subm Oct 1976 (except HAR-2043) by E,J Peltenburg.

3360 ± 70 '3C= HAR-1902. 75DP1 -26.8 %o Charcoal (Corylus sp) from cremation burial. Coil June 1975. Comment (EJP): charcoal assoc with cremation Burial 1.

2270 ± 80 HAR-1903. 74B3 513C = -26.6/)o From initial occupation deposits sealed by Rampart 2 collapse. Coil July 1974.

2240 ± 120 5'3C HAR-1904. 74D2AF 1 = -25.0 %o Charcoal (mainly Corylus sp) immediately underlying external collapse of Rampart 2. Coil July 1974. Comments: small sample accounts for larger than normal error term; (EJP): dates collapse of rampart superstructure or debris cast out from fort interior.

2240 ± 70 '3C= HAR-1905. 76J3 -26.4 %o From base of post-fort occupation level. Coil June 1976. Comment (EJP): date suggests occupation period of fort.

2120 ± 70 HAR-1907. 75C5F1 b13C = -25.7 Charcoal (Corylus, Salix spp) from open area and gully assoc with pit. Harwell Radiocarbon Measurements IV 93 2130 ± 90 b13C HAR-2043. 74D2 = -26.7 %o From surface onto which Rampart 2 collapsed. Coil July 1974 and subm May 1977. Comment (EJP): date suggests external material belongs to later period of fort. Port Charlotte series Charcoal samples from Neolithic chambered cairn at Port Charlotte, Islay, Argyll (55° 43' 56" N, 6° 23' 9" W, Natl Grid Ref NR 247575).

4540 ± 70 b13C HAR-2084. PC76C301 = -26.0 9'bo Coil and subm Feb 1977 by S J Pierpoint and P Harrington. Comment (SP & PH): material belongs to fire lit on old ground surface inside sealed part of main chamber (c3) using large side stone as back. Thus, sample dates construction. Date compares well with limited number of determinations from British chambered cairns. It conforms to and confirms some of more recent models of "Clyde Cairn" development.

1860 ± 70 b'3C HAR-2405. PC76F402 = -25.8 %o From pit in forecourt antedating erection of large sill stone. Sample antedates Neolithic pottery and construction of chambers and presumably PC76C301 (HAR-2084). Pit was sealed by facade collapse, but not by blocking. Coil Aug 1976 by S J Pierpoint and P Harrington and subm Aug 1977. Comment (SP): date is much later than expected. Material was undis- turbed although against side of sill.

4710 ± 70 b13C HAR-2406. PC76C303 = -26.2 %o Deposited on old ground surface under monolith in chamber. Coil by S j Pierpoint and P Harrington and subm Sept 1977 by S J Pierpoint. Com- ments: 1st sample measured as HAR-2084, above; (SP): context dates erection of chambers at site and antedates Scottish Neolithic pottery and flints.

REFERENCES Beckett, S C, 1978, The environmental setting of the Meare Heath Track: Somerset Levels Papers, v 4, p 42-46. Bell, M, 1977, The excavation of prehistoric, Romano-British and Anglo-Saxon settlements on Rookery hill, Bishopstone, Sussex: Sussex Archaeol Collns, v 115. Butcher, S A, 1974, Excavation news 1973-1974 at Little Bay, St Martin's, Scilly: Cornish Archaeol, no. 13, p 55. Chambers, R A, 1976, A Romano-British settlement at Curbridge: Oxoniensia, v 41, p 38- 55. ----- 1978, 2 radiocarbon dates from the Romano-British cemeteries at Curbridge: Oxoniensia, v 42, p 252-253. Coles, J M and Orme, B J, 1976, The Meare Heath Trackway: Prehist Soc Proc, v 42, p 293- 318. ----- 1978a, The Meare Heath Track: Somerset Levels Papers, v 4, p 11-39. ----- 1978b, Multiple trackways from Tinney's Ground: Somerset Levels Papers, v 4, p47-8l. ----- 1978c, Structures south of Meare Island: Somerset Levels Papers, v 4, p 90- 100. 94 A J Walker and R L Otlet Coles, J M and Orme, B J, 1978d, Bronze age implements from Skinner's Wood, Shapwick: Somerset Levels Papers, v 4, p 114-121. ----- 1979, The Sweet Track: Drove site: Somerset Levels Papers, v 5, p 43-64. Fasham, P J, 1979, The excavation of a triple barrow in Micheldever Wood, Hampshire: Hants Field Club Archaeol Soc Proc, v 35, p 5-40. Fasham, P J and Ross, J M, 1978, A Bronze age flint industry from a barrow site in Michel- dever Wood, Hampshire: Prehist Soc Proc, v 44, p 47-67. Hassall, J M, 1979, Excavations in Bedford 1967-1977: Bedfordshire Archaeol Jour, v 13, App C. Hill, 0,1975, The Roman riverside wall in the city: London Archaeologist, v 2, no.10, p 260- 261. Hill, C, Millett, M, and Blagg, T, 1980, The Roman riverside wall and monumental arch in London: London Middlesex Archaeol Soc spec paper 3. Huggins, P J, 1978, Excavation of Belgic and Romano-British Farm with Middle Saxon cemetery and churches at Nazeingbury, Essex, 1 975-6: Essex Archaeol Hist, v 10, p 29-118. - 1979, South Precinct excavations, Waltham Abbey, Essex, 1974-77: Essex Archaeol Hist, v 11. Jones, M J, 1981, Excavations at St Mary's Church Lincoln: Antiquaries Jour, v 61, p 83- 114. Mercer, R J, 1980, Hambledon Hill, a Neolithic landscape: Edinburgh, Edinburgh Univ Press. Miles, H, 1977, Excavations at Killibury Hillfort, Egloshayle, 1975-6: Cornish Archaeol, v 16. Morgan, R A, 1977, Tree-ring dating of the London waterfronts: London Archaeologist, v 3, p 40-45. -----1978a, Tree-ring studies in the Somerset Levels: The Meare Heath Track: Som- erset Levels Papers, v 4, p 40-41. - 1978b, Tree-ring studies in the Somerset Levels, Tinney's Ground: Somerset Levels Papers, v 4, p 82-85. Morgan, R A, Wildgrove, M, and Collis, J R, 1980, Some Post Medieval timbers from Brad- bourne, Derbyshire: Derbyshire Archaeol Jour, v 100, p 43-49. Orme, B J, Coles, J M, Caseldine, A E, and Bailey, G N, 1981, Meare Lake Village West 1979: Somerset Levels Papers, v 7, p 12-69. Otlet, R L, 1979, An assessment of laboratory errors in liquid scintillation methods of 140 dating, in Berger, Rainer and Suess, H E, eds, Radiocarbon dating, Internatl radiocarbon conf, 9th, Proc: Berkeley/Los Angeles, Univ California Press, p 256-267. Otlet, R I. and Walker, A J, 1983, The computer writing of radiocarbon reports and further developments in the storage and retrieval of archaeological data, in Mook, W G 14C and Waterbolk, H T, eds, and Archaeology, Internatl symposium, 1st, Proc: PACT 8, p91-106. Otlet, R L and Warchal, R M, 1978, Liquid scintillation counting of low-level 14C, in Crook, M A and Johnson, P, eds, Liquid scintillation counting, vol 5: London, Heyden, 210- 218. p Reece, R, 1973, Recent work on lona: Scottish Archaeol Forum, v 5, p 36-46. -----1974, Roman Britain in 1973: Britannia, v 5, p 448. --- -1981, Excavations on Iona 1964 to 1974: London, Inst Archaeol occasional pub 5, p 103-110. N, Savory, H 1976, Archaeological notes, prehistoric period: Morgannwg, v 20, p 69. Shoesmith, R, 1980, Excavations at Castle Green: Hereford City excavations, vol 1: London, Council Br Archaeol, Research Rept 36. -1982, Excavations on and close to the Defences: Hereford City excavations, vol 2: London, Council Br Archaeol, Research Rept 46. Smith, K, 1979, The excavation of Winklebury Camp, Basingstoke Hants: Prehist Soc Proc, v 43. Trudgian, P, 1977, Excavations at Tregilders, St Kew, 1975-1976: Cornish Archaeol, v 16, 122-128. p Wainwright, G J, Fleming, A, and Smith, K, 1979, The Shaugh Moor project, first report: Prehist Soc Proc, v 45. [RADIOCARBON, VOL 27, No. 1, 1985, P 95-110] PHYSICAL RESEARCH LABORATORY RADIOCARBON DATE LEST V D P AGRAWAL, R V KRISHNAMURTHY, and SHEELA KUSUMGAR Physical Research Laboratory, Ahmedabad 380009, India We report here dates on archaeologic and geologic samples. The samples were counted as methane in gas proportional counters. The techniques used have been described earlier (R, 1971, v 13, p 442-449). Dates are expressed in years BP, taking Al) 1950 as the reference year. Modern standard was NBS oxalic acid. Quoted errors are based on counting statistics alone and are equivalent to ± 1 standard deviation for samples younger than 10,000 years and ± 2 standard deviations for older samples. Descrip- tions and references regarding the samples have been supplied by the submitters of the samples. Most important are the series from the Batadomba cave, Sri Lanka, where the Upper Paleolithic dates go back to ca 28,000 BP. These are the first early dates from Sri Lanka. The CaCO3 based dates from Bhimbetka, Madhya Pradesh, are all very young and indicate the contamination potential of such deposits. The Didwana Salt Lake series dates climatic changes inferred both from pollen and chemical variation through the sediment profile. ARCHAEOLOGIC SAMPLES India PRL-931. Arara, Black and Red Ware (BRW) deposit 2780 ± 120 Charcoal from Arara (23° 76' N, 88° 10' E), Dist Burdwan, Tr 1, Layer 5, depth 1.91m; subm by D K Chakrabarti, Delhi Univ; submitter's Sam- p1 e5. Bagor series, Madhya Pradesh Samples are from Bagor (24° 35' 5" N, 82° 18' 2" E), Dist Sidhi; subm by G R Sharma, Allahabad Univ, Allahabad. + 220 Middle Paleolithic culture 12,450 PRL-711. - 210 Calcareous sand, layer of cross-bedded river sand, 16m above river level. Comment: carbonate assoc with rolled Middle Paleolithic tools and fresh fossils. PRL-714. Middle Paleolithic(?) culture 6460 ± 180 Charcoal, Tr 1, Layer 3, depth 0.54m. Comment: assoc with chert flakes, blades, and chalcedony nodules. PRL-715. Mesolithic culture 8090 ± 220 Charcoal, overlying Layer 2a, depth 0.61 to 0.69m. Comment: assoc with geometric tools. 95 96 D P Agrawal, R V Krishnamurthy, and Sheela Kusumgar Bahiri series, West Bengal Bahiri (23° 60' N, 88° 10' E), Dist Birbhum; subm by D K Chakrabarti, Delhi Univ, Delhi.

PRL-866. Chalcolithic culture 2770 ± 140 Charcoal, Tr BHR II, Layer 5, depth 2.1 to 2.35m; submitter's Sam- ple 1.

PRL-867. Chalcolithic culture 2490 ± 150 Charcoal, Tr BHR IV, Layer 4, depth 2.25m; submitter's Sample 2. Bhimbetka series, Madhya Pradesh Bhimbekta (22° 65' N, 77° 57' E), Dist Raisen; subm by V N Misra, Dec- can Coll, Pune. Comment: samples assoc with Late Mesolithic and Middle Paleolithic industry in Central India.

PRL-534. Cave deposit (Late Mesolithic culture) 2780 ± 150 Charcoal, Tr G, Sq 5, Layer 2, depth 0.66 to 0.7m; submitter's Sample BTK II-B-33.

PRL-535. Cave deposit (Late Mesolithic culture) 1160 ± 150 Charcoal, Tr G, Sq 5, Layer 2, depth 0.66 to 0.7m; submitter's Sample BTK II-B-33.

PRL-536. Cave deposit (Late Mesolithic culture) 950 ± 110 Charcoal, Tr G, Sq 5, Layer 2, depth 0.61 to 0.65m; submitter's Sam- ple BTK II-B-33. 570 PRL-787. Cave deposit (Middle Paleolithic culture) 15,370 + - 530 Calcium carbonate, Tr BTK III F 23, Loc I 7, depth 0.86 to 0.9m; submitter's Sample BTK 18. 480 PRL-788. Cave deposit (Middle Paleolithic culture) 17,230 + - 440 Calcium carbonate, Tr BTK III F 23, Loc 16, Layer 4, depth 0.81 to 0.85m; submitter's Sample BTK 17. 490 PRL-789. Cave deposit (Middle Paleolithic culture) 17,670 + - 460 Calcium carbonate, Tr BTK III F 23, Loc I 6, Layer 2, depth 0.31 to 0.35m; submitter's Sample BTK 16. Daimabad series, Maharashtra Daimabad (19° 13' N, 74° 41' E), Dist Ahmednagar, subm by S A Sali, Archaeol Survey India (ASI), Southwestern Circle, Aurangabad. Comment: samples were measured to date Sawalda, Buff and Cream Ware, Jorwe, and Late Harappan cultures. Physical Research Laboratory Radiocarbon Date List V 97

PRL-654. Sawalda culture 3460 ± 100 Charcoal, Tr GZ63, House No. 12, Rm no. A15, depth 4.1m; submitter's Sample DMD/42/1977-78.

PRL-655. Buff and Cream Ware 3490 ± 110

Charcoal, Tr Z'4, Layer 1 OA, depth 2m; submitter's Sample DMD/43/ 1977-78.

PRL-656. Jorwe culture 3050 ± 150

Charcoal, Tr Y'2, Kiln no. 1 sealed by Layer 1, depth O.lm; submitter's Sample DMD/46/1977-78.

PRL-657. Late Harappan culture 3140 ± 100 Charcoal, Tr ZD60, hearth sealed by Layer 11 and cut into Layer 12, depth 2.3m; submitter's Sample DMD/53/1978-79. Dangwada series, Madhya Pradesh Dangwada, Dist Ujjain, subm by M P Khare, Dept Archaeol, Madhya Pradesh, Bhopal. Comment: samples date Malwa culture in area.

PRL-686. Malwa culture 3110 140 Charcoal grains, Tr IV, Layer 9, depth 2.58m.

PRL-690. Malwa culture 3400 150 Charred rice, Tr VII, Layer 8A, depth 2.2m.

PRL-691. Malwa culture 3200 120 Charcoal, Tr VII, Layer 8B, depth 2.3m.

PRL-692. Malwa culture 2900 140 Charred wheat, Tr VII, Layer 4, depth 2.2m.

PRL-693. Malwa culture 3280 100 Charcoal, Tr VII, Layer 6, depth 3m.

800 PRL-710 . Gerwa well Middle Paleolithic deposit 090 , , 720 Calcium carbonate cement from Gerwa well (24° 33' N, 82° 17' E), Dist Sidhi, well sec, depth 10.5m; subm by G R Sharma, Allahabad Univ; submitter's Sample AU/Sidhi-S/16 B-1.

PRL-907. Kauvakhoh, Microlithic(?) deposit 1040 ± 130 Soil from Kauvakhoh (24° 28-30' N, 83° 4-11' E), Dist Mirzapur, Layer 1, depth 0.4m; subm by S Rai, Dept Ancient Indian Hist Archaeol, Banaras Hind Univ; submitter's Sample I. 98 D P Agrawal, R V Krishnamurthy, and Sheela Kusumgar Khetri series, Rajasthan Khetri (28° 58' N, 75° 16' 10" E), Dist Jhunjhunu; subm by K K Tewari, Hind Copper Ltd, Khetrinagar. Comment: samples found close to ancient mining area and were dated to study ancient mining activity in area. PRL-684. Ancient copper working Modern Dry wood from Khetri copper complex. PRL-685. Ancient copper working Modern Dry wood from Khetri copper complex. PRL-549. Kumbharia, old copper working 670 ± 110 Charcoal from ancient working at Kumbharia (24° 20' N, 72° 51' E), Dist Banaskantha; subm by C A Sastry, GSI, Calcutta, submitter's Sample 8. Comment: dates mining activity at Ambaji. Mahagara series, Uttar Pradesh Mahagara (24° 54' 50" N, 82° 3' 20" E), Dist Allahabad, subm by G R Sharma, Allahabad Univ, Allahabad. Comment: samples date Upper Paleo- lithic culture in area. PRL-602. Upper Paleolithic culture 10,980 ± 190 Shell, Loc XXX-XXXVI, Tr L/6, Layer Upper Level cemented by Gravel III, depth 0.17 to 0.33m; submitter's Sample AU/ALLD/MGR- 78/5. + 400 PRL-603. Upper Paleolithic culture 13,740 - 380 Shell, Loc XXX-XXXVI, Tr L/6, Layer Upper Level cemented by Gravel III, depth 0.73 to 1.3m; submitter's Sample AU/ALLD/MGR- 78/6.

PRL-538. Moirang, grave deposit 750 ± 130 Wood from Moirang (24° 3' N, 74° 5' E), Dist Central Manipur, depth 1.5m; subm by K Singh, Antiquities Unit, Imphal. Comment: sample from coffin containing bronze artifacts. PRL-609. Nirgudsar, Middle Paleolithic culture >31,000 Carbonized wood from Nirgudsar (18° 31' 30" N, 74° 22' 30" E), Dist Poona, depth 6m; subm by S N Rajaguru, Deccan Coil, Poona. Oriyo Timbo series, Gujarat Oriyo Timbo (21 ° 54' N, 71 ° 32' E), Dist Bhavnagar; subm by M H Ravel, Gujarat State Dept Archaeol and G L Possehl, Univ Mus, Univ Penn- sylvania, Philadelphia.

PRL-876. Lustrous Red Ware culture (Rangpur III) 4080 ± 160 Charcoal, Loc SE Qd, Tr F'2, Layer 3, depth 0.35m; submitter's Sam- ple 6096. Physical Research Laboratory Radiocarbon Date List V 99 PRL-886. Lustrous Red Ware (R.angpur III) culture 4160 ± 170 Charcoal, Loc NW Qd, Tr G'3, Layer 3, depth 0.85m; submitter's Sample 5045. PRL-889 + 888. Microlithic culture 4720 ± 160 Charcoal, Loc SE Qd, Tr F'3, Layer 5, depth 1.1 m; submitter's Sample 10043. Ramapuram series, Andhra Pradesh Ramapuram (15° 05' N, 78° 05' E), Dist Kurnool, subm by B Narasim- haiah, Archaeol Survey India, Nagpur. Comment: samples date Chalcolithic settlement pattern in region. PRL-761. Chalcolithic culture(?) 690 ± 100 Charcoal, Loc Qd 1, Tr XA, hearth sealed by Layer 2, depth 0.45 to 0.55m; submitter's Sample CS-17. PRL-762. Chalcolithic culture 3810 ± 110 Charcoal, Loc Qd III, Tr XB, Layer 5, depth 0.9m; submitter's Sample CS-15. PRL-768. Chalcolithic culture(?) 860 ± 130 Charcoal, Loc Qd III, Tr XB, layer pit sealed by Layer 1, depth 0.27m; submitter's Sample CS-5. Singh-Bagwantpur series, Panjab Singh-Bagwantpur (30° 53' N, 76° 33' E), Dist Rupnagar, subm by Y I) Sharma, Panjab Univ, Chandigarh. PRL-780. Early historic deposit 3610 ± 100 Charcoal, Loc XI-XII, Tr 30T, Pit 4 sealed by Layer 6, depth 2.2m; submitter's Sample SBP-30-T-III. Comment: assoc with early historic and NBP pottery. PRL-782. Medieval deposit 1420 ± 100 Charcoal, Loc V-X, Tr 30R, Pit 4 sealed by Layer 5, depth 2.1 m; submitter's Sample SBP-30-R-113. PRL-783. Medieval deposit 1750 ± 100 Charcoal, Loc IX-10, Tr 30R, Pit 4 sealed by Layer 5, depth 1.9m; submitter's Sample SBP-30-R-112. PRL-784. Medieval deposit 1740 ± 120 Charcoal, Loc VIII-IX, Tr 30R, Pit 4 sealed by Layer 5, depth 2.32m; submitter's Sample SBP-30-R-110. Sringaverapura series, Uttar Pradesh Sringaverapura, Dist Allahabad; subm by B B Lal, Indian Inst Advanced Study, Simla. 100 D P Agrawal, R V Krishnamurthy, and Sheela Kusumgar

PRL-669. BRW deposit 2620 ± 130 Charcoal, Loc Tr YA 3, Qd 3, Layer 18, depth 8.47 to 8.65m; submitter's Sample 2.

PRL-671. Red Ware deposit 2070 ± 140 Charcoal, Tr ZB1, Qd 2, Layer 1OE, depth 4.95 to 5.05m; submitter's Sample 5. Thapli series, Uttar Pradesh Thapli, Dist Tehri; subm by K P Nautiyal, Garhwal Univ, Srinagar. Comment: samples date Painted Grey Ware culture (PGW) in Garhwal region.

PRL-731. PGW culture 2030 + 140 Charcoal, Tr TPL 1, Layer 1, 2, 3, depth 0.1 to 1 m; submitter's Sample TPL-1/80.

PRL-732. PGW culture 2070 ± 120 Bone collagen, Tr TPL-l, Layer 1, depth 0.3 to 0.8m. Veerapuram series, Andhra Pradesh Veerapuram (16° N, 78° 15' E), Dist Kurnool, subm by T V G Sastry, Birla Archaeol Cultural Research Inst, Hyderabad. Comment: dates Black and Red Ware and Black Ware of Megalithic period assoc with iron objects.

PRL-725. Megalithic culture(?) 1780 140 Charcoal, Tr B1 1, Layer 9, depth 1.7m.

PRL-727. Megalithic culture 2090 140 Charcoal, Tr B15, Layer 10, depth 2.3m.

PRL-728. Megalithic culture 2870 140 Charcoal Tr C13, Layer 13, depth 3.04m.

PRL-729. Megalithic culture 2830 140 Charcoal, Tr B14, Layer 14, depth 3.1 m.

PRL-730. Megalithic culture 3150 140 Charcoal, Tr B14, Layer 15, depth 3.4m.

PRL-932. Zawar, ancient mining works 2410 ± 100 Charcoal from Zawar Mala Mine (24° 19-45' N, 73° 40' E), Dist Udai- pur; subm by V L Upadhyaya, Hind Zinc Ltd, Zawar; submitter's Sample ZM/I. Comment: sample dated to establish antiquity of mining activity in area. Physical Research Laboratory Radiocarbon Date List V 101 Rivona series Rivona (15° 10' N, 74° 5' E), Dist Goa; subm by VT Gune, Panaji. Com- ment: samples date monastery and Buddha image.

PRL-545. Historic deposit 290 ± 130 Charcoal, Tr C, Loc SN-0.2m, WE 4.25m, Layer 2, depth 0.85m; submitter's Sample 7. PRL-546. Historic deposit Modern Charcoal, Tr C, SN-0.56m, WE-0.3m, Layer 2, depth 0.9m; submitter's Sample 8.

PRL-548. Historic deposit 180 ± 130 Charcoal, Tr C, extension SN 2.15m, WE 0.35m, Layer 2, depth 0.8m; submitter's Sample 10. Pakistan Rehman Dheri series Rehman Dheri, Dist Dik; subm by Chairman, Univ Peshawar, Pesha- war. Comment: samples were measured to date Kot Dijian culture.

PRL-673. Kot Dijian culture 3900 ± 130 Charcoal, Tr BIV/9, Layer 5, depth 1.2m.

PRL-674. Early Kot Dijian 4000 ± 150 Charcoal, Tr BIV/9, Layer 10, depth 1.8m.

PRL-675. Pre-Kot Dijian 4400 ± 110 Charcoal, Tr BIV/9, Layer 15, depth 3.3m.

PRL-676. Pre-Kot Dijian 4520 ± 110 PRL-679. Kot Dijian(?) >31,000 Charcoal, Tr BIV/4, Layer 7, depth 1.5m. Sri Lanka Batadomba Cave series Batadomba (8° N, 82° E), Dist Ratnapura; subm by S U Deraniyagala, Archaeol Dept, Colombo. Comment: samples date Upper Paleolithic and Mesolithic cultures assoc with non-geometric microlithic artifacts.

+ 330 PRL-855. Late Upper Paleolithic deposit 11,200 - 320 Charcoal, Tr 16K, Layer 4A, depth 6m; submitter's Sample BD 16K- 4A. 102 D P Agrawal, R V Krishnamurthy, and Sheela Kusumgar + 470 PRL-856. Late Upper Paleolithic deposit 12,770 - 450 Charcoal, Tr 16K, Layer 4B, depth 1 m; submitter's Sample Bd 16K- 4B.

+ 2090 PRL-857. Late Upper Paleolithic deposit 27,700 - 1660 Charcoal, Tr 16, Layer 7C, depth 2.8m; submitter's Sample Bd 16- 70.

+ 610 PRL-858. Late Upper Paleolithic deposit 15,390 - 570 Charcoal, Tr 16H, Layer 6B, burial depth 2.15m; submitter's Sample Bd 16H-6B.

740 PRL-920. Late Upper Paleolithic deposit + 20,150 - 680 Charcoal, Tr 17, Layer 7B, depth 2.4m; submitter's Sample Bd 17- 7B.

430 PRL-861. Beli Cave, Paleolithic deposit 11,910 + - 410 Charcoal from Beli Cave (8° N, 82° E), Dist Kitulgala, lOG, Layer 4, depth 0.4m; submitter's Sample KB IOG-4; subm by S U Deraniyagala. Comment: sample dates Late Upper Paleolithic culture and possibly domes- tication of cereals. Iran Tepe Gaz Tavileh series Tepe Gaz Tavileh: R37 (28° 20' N, 56° 35' E), Dist Fermand, Balt Baksh Orzuyeh; subm by M Prickett, Harvard Univ, Cambridge, Massachusetts. Comment: samples date Yahya Pd VII-earliest stage of Neolithic settled village agric communities identified so far in SE Iran.

PRL-744. Yahya Pd VII 6670 ± 150 Charcoal, Loc TT1, Rm 1, Layer 4.3, depth 0.96 to lm; submitter's Sample 2.

PRL-748. Yahya Pd VII 6640 ± 180 Charcoal, main sec, Layer 14, depth 3.4 to 3.5m; submitter's Sam- ple 6.

PRL-749. Yahya Pd VII 6650 ± 180 Wood twig charcoal from main sec, Layer 19.1, depth 4.44m; submitter's Sample 7. Physical Research Laboratory Radiocarbon Date List V 103

GEOLOGIC SAMPLES Arabian Ocean sediment series Box cores of calcareous sediments from Arabian Sea (8°-21 ° N, 67°- 71 ° E), subm by N Hussain and B L K Somayajulu, PRL, Ahmedabad. Com- ment: samples measured to study sedimentation rate (table 1).

PRL-721. Arctic Ocean, USA 4370 ± 160 Organic sediment, Dist Seinpoon Lagoon, Alaska, Core V-49, depth 1.45 to 1.5m; subm by B L K Somayajulu. Comment: samples dated for accumulation rate studies. Atlantic Ocean sedimentation rate series Atlantic Ocean core of calcareous sediments (32° N, 42° W) 3500m water depth; subm by B L K Somayajulu.

PRL-741. Core sediment 7470 ± 160 Calcium carbonate, depth 0.08 to 0.1 m; submitter's Sample INMD Box 50, 10th sample.

710 PRL-742. Core sediment 16,910 + - 660 Calcium carbonate, depth 0.17 to 0.2m; submitter's Sample INMD Box 50, 14th sample.

+ 1600 PRL-743. Core sediment 24,110 - 1300 Calcium carbonate, depth 0.24 to 0.29m; submitter's Sample INMD Box 50, 16th sample. India Awai series, Rajasthan Calcium carbonate, 1km upstream from village Awai (27° 30-35' N, 71 ° 50-55' E), Dist Jaisalmer; subm by R P Dhir, Central Arid Zone Research Inst, Jodhpur. Comment: samples dated to study land formation processes in area (table 2).

PRL-921. Bandapara, valley-fill sediment 3520 ± 100 Wood fragments from pit sec near Bandapara (25° 57' N, 91 ° 6' E), Dist Kamrup, depth 1 m; subm by K K Sinha, Geol Survey India, Shillong; submitter's Sample GSI/LB/7/82. Comment: sample dated to study Quater- nary strat of Lower Brahmaputra valley. Barasenchal accumulation rate series, West Bengal Barasenchal (26° 31' and 27° 13' N, 87° 59' and 88° 53' E), Dist Darjee- ling; subm by B B Mukherjee, Bose Inst, Calcutta. 104 D P Agrawal, R V Krishnamurthy, and Sheela Kusumgar

TABLE 1 Arabian Ocean sediments Sample Core depth no. Core no. (mm) date PRL-550 65-1 100 to 200 170 -551 65-2 400 to 500 160 -620 65-H 850 to 950 130 -552 54-1 100 to 200 210 -553 54-2 400 to 500 220 2300 800 to 29 , -621 54 900 - 1800 -554 46-1 100 to 200 180 -555 46-2 400 to 500 190 -662 46 700 to 800 140 -556 52-1 100 to 200 200 380 970 -557 52-2 300 to 400 , - 360 770 to , 970 -558 52-3 500 600 - 700 430 to 900 550 -619 52 800 , - 410 650 330 to 335 , 970 -718 RC-18-130 - 600 1200 450 to 490 22 -737 RC-18-130 , - 1100 2000 to 1970 -719 RC-17-120 1900 27 , - 1600 -720 RC-17-120 20 to 50 120 -733 RC-17-120 120w 150 170 440 to , 500 -734 RC-17-120 210 250 - 420 -735 RC-17-119 60 to 100 230 330 to 640 -736 RC-17-119 250 290 , - 310 -738 RC-17-119 160 to 190 210 -739 RC-17-117 50 to 70 170 360 to 10 -740 RC-17-117 210 230 , - 340 -752 RC-17-117 360 to 390 210 -753 RC-17-125 450 to 470 350 RC-17-125 100 to 120 10 -754 , - 390 -755 RC-17-125 0 to 20 150 -757 RC-17-121 70 to 90 170 Physical Research Laboratory Radiocarbon Date List V 105

TABLE 2 Awai, Rajasthan, calcium carbonates Sample Submitter's no. sample no. (m) date

PRL-890 Nachna-12/3 1.25 to 1.34 19,260 ± 840 -891 Nachna-12/5 1.8 to 2 -892 Nachna-12/7 2.3 to 2.4 -893 Nachna-12/9 2.5 to 2.6 440 3 420 , -420 480 -895 Nachna-13/3 3.37 730 , - 460 1800 -896 Nachna-13/4 3.7 450 , - 1500 -897 Nachna-13/5 4.3 1900 , 430 - 1500 -898 Nachna-13/6 4.6 010 3200 , - 2300 -899 Nachna-15 4.5

PRL-673. Peat 740 100 Peat from 1 m depth.

PRL-638. Peat 550 130 Peat from 2m depth.

PRL-639. Peat 1720 100 Peat from 2.5m depth.

PRL-640. Peat 3180 ± 150 Peat from 3m depth. Budha Pushkar series, Rajasthan Budha Pushkar (26° 30' N, 74° 36' F;), ca 15km NW of Ajmer; subm by R V Krishnamurthy, PRL, Ahmedabad. Comment: samples dated to study paleoclimate of region (Krishnamurthy et al, 1981, p 155-160). PRL-562. Root Cast formation 4890 ± 170 Root cast (calcium carbonate) from surface; submitter's Sample C- 32a.

PRL-563. Root Cast formation 6300 ± 130 Root cast (calcium carbonate), depth 0.2m; submitter's Sample C-33.

PRL-564. Root Cast formation 6020 ± 170 Root cast (calcium carbonate), depth lm; submitter's Sample C-33.

PRL-565. Root Cast formation 3420 ± 220

Root cast (calcium carbonate), depth 1 to 1.5m; submitter's Sample C-34. 11 )6 D P Agrawal, R V Krishnamurthy, and Sheela Kusumgar PRL-566. Root Cast formation 3600 ± 160 Root cast (calcium carbonate), depth 1.5 to 1.75m; submitter's Sample C-35. PRL-567. Root Cast formation 2900 ± 100 Root cast (calcium carbonate), depth 1.75 to 2m; submitter's Sample C-36. PRL-568. Root Cast formation 4420 ± 140 Root cast (calcium carbonate), depth 2.25 to 2.75m; submitter's Sam- ple C-37. PRL-569. Root Cast formation 3780 ± 150 Root cast (calcium carbonate), depth 1.5 to 2.5m; submitter's Sample C-38. PRL-570. Root Cast formation 4160 ± 110 Root cast (calcium carbonate), depth 1.5m; submitter's Sample C-39. Continental shelf series, Gujarat Limestone samples dredged from Gulf of Kutch Continental Shelf, Gujarat; subm by R R Nair, Natl Inst Oceanog, Panaji, Goa. Comment: all samples are 95-97% aragonite. Samples were measured for geol mapping of continental shelf and Quaternary sea-level studies. + 430 PRL-485. Limestone 12,150 - 410 Limestone from Gulf of Kutch (20° 20' N, 70° 18' E), water depth 78m; submitter's Sample G/2/29. 590 14,320 + PRL-486. Algal limestone - 550 Algal limestone from Gulf of Kutch (21 ° 03' N, 69° 01' E), water depth 173m; submitter's Sample G/2/30. PRL-487. Coral 7490 ± 200 Coral from Gulf of Kutch (22° 40.5' N, 69° 18.6' E), water depth 25m; submitter's Sample G/2/45(a). PRL-488. Limestone 4290 ± 160 Limestone from Gulf of Kutch (22° 40.5' N, 69° 18.6' E), water depth 25m; submitter's Sample G/2/45(b). + 520 PRL-489. Limestone 13,460 - 480 Limestone from Gulf of Kutch (22° 38.3' N, 69° 27.2' E), water depth 46m; submitter's Sample G/2/47(a). Physical Research Laboratory Radiocarbon Date List V 107

PRL-490. Limestone 9220 ± 210 Limestone from Gulf of Kutch (22° 26.9' N, 67° 57.5' F), water depth 80m; submitter's Sample G/2/61. Didwana salt lake series, Rajasthan Didwana salt lake (27° 20' N, 74° 35' E), Dist Nagaur; subm by R J Was- son, Australian Natl Univ (644 to 651) and R Hema, Deccan Coil, Pune (9 11 to 913). Comment: samples dated to study paleo-lake levels and paleoclimate.

PRL-644. Lacustrine deposit 4060 ± 130 Organic matter, Tr DIAI well, layer top of Fm III, depth 1.12 to 1.17m.

PRL-645. Lacustrine deposit 5990 ± 190 Organic matter, Tr DIAI well, layer middle of Fm III, depth 2.07 to 2.12m.

PRL-646. Lacustrine deposit 5840 ± 170 Organic matter, Tr DIAI well, layer bottom of Fm III, depth 2.88 to 2.93m.

PRL-647. Lacustrine deposit 6690 ± 250 Organic matter, Tr DIAI well, layer top of Fm V, depth 3.42 to 3.47m.

PRL-648. Lacustrine deposit 7250 ± 150 Organic matter, Tr DIAI well, layer bottom of Fm V, depth 3.55 to 3.6m.

PRL-649. Lacustrine deposit 9110 ± 210 Organic matter, Tr DIAI well, layer top of Fm VII, depth 4.15 to 4.18m. + 360 PRL-650. Lacustrine deposit 12,450 - 340 Organic matter, Tr DIAI well, layer bottom of Fm VII, depth 4.5 to 4.55m. Didwana carbonate series, Rajasthan 1200 PRL-651. Soil carbonate 24 010 , - 1100 Fine carbonate from railway cutting, depth 9 to 9.2m. 2200 PRL-911 . Soil carbonate 26 210 , - 1700 Soil carbonate nodules from Site 16R, Tr A-10, Layer 1, depth 5.5 to 5.55m; submitter's Sample 1. 108 D P Agrawal, R V Krishnamurthy, and Sheela Kusumgar + 930 19,940 PRL-912. Soil carbonate - 830 Soil carbonate nodules from Site RCD, Layer 1, depth 0.46 to 0.66m; submitter's Sample 3. + 450 15,340 PRL-913. Soil carbonate - 430 Soil carbonate nodules from Site RCD, depth 0.98 to 1 m; submitter's Sample 4. Great Rann series, Gujarat Shells from Great Rann (24° 01' 30" N, 69° 41' S" E), Dist Kutch; subm by A K Das Gupta, Geol Survey India, Jaipur. PRL-475. Shells from surface 1360 ± 140 Submitter's Sample S/13. PRL-476. Shells from bore hole 3860 180 Depth 1.5m; submitter's Sample R/8/2. PRL-925. Jira, Terrace deposit 590 110 Charcoal from pit sec near Jira (25° 57' N, 90° 38' E), Dist Golpara, depth 3m; subm by K K Sinha, Geol Survey India, Shillong, submitter's Sample GSI/LB/9/82. Comment: sample dated to study Quaternary strat of lower Brahmaputra basin. Laccadives storm beach series Storm beach at Chetlat (11° 41' N, 72° 11' E); subm by H N Siddiqui, Natl Inst Oceanog, Panaji, Goa. Comment: sample studied to date storm beach. PRL-478. Dead coral 550 ± 130 Dead coral from N end of Chetlat; submitter's Sample CHT-15. PRL-480. Dead coral 220 ± 190 Dead coral from S end of Chetlat I; submitter's Sample CHT-27. PRL-482. Dead coral 150 ± 120 Dead coral from N end of Bitra I; submitter's Sample BR-8. Lopchu series, West Bengal Lopchu (26° 31' and 27° 13' N, 87° 59' and 88° 53' E), Dist Darjeeling; subm by B B Mukherjee, Bose Inst, Calcutta. Comment: samples dated to study sedimentation rate in area. PRL-641. Peat 360 ± 110

Peat from 1 m depth. Physical Research Laboratory Radiocarbon Date List V 109 PRL-642. Peat 1650 210 Peat from 2m depth. Riasa cave series, Jammu and Kashmir Stalactite from Riasa cave in Jammu and Kashmir; subm by K K Sharma, Wadia Inst Himalayan Geol, Dehradun. Comment: samples dated to study growth rate of stalactite.

PRL-612. Stalactite 900 ± 90 Stalactite, submitter's Sample IA(1).

PRL-613. Stalactite 670 ± 100 Stalactite, submitter's Sample IA(2).

PRL-614. Stalactite 750 ± 140 Stalactite, submitter's Sample IA(3).

PRL-615. Stalactite Modern Stalactite, submitter's Sample IA(4). PRL-908. Son at Chopan, terrace deposit >31,000 Shells from left bank fm of Son at Chopan (24° 26-30' N, 83° 4-11' E), Dist Mirzapur, depth 5m; submitter's Sample II. Comment: sample dated for age of deposit. West coast beach series, Maharashtra Calcareous mud from coast beaches; subm by K S Powar, Inst Petrol Exploration, Dehradun. Comment: samples dated to study geomorphic evolution of Indian coast.

PRL-604. Thal Beach 3270 110 Shells, 2m alt MSL; submitter's Sample 1/PN5.

PRL-605. Akshi Nagaon Beach 3080 110 Shells, 2.5m alt MSL; Submitter's Sample 2/PN5.

PRL-606. Borlai Beach 1970 100 Shells, 2m alt MSL; submitter's Sample 3/PN5.

PRL-607. Kasid Beach 1880 140 Shells, 3m alt MSL; submitter's Sample 4/PN5.

PRL-608. Agar Panchaitan Beach 3190 ± 150 Shells, 2.5m alt MSL; submitter's Sample 5/PN5. 110 D P Agrawal, R V Krishnamurthy, and Sheela Kusumgar Scotland

Lake Fyne sediment rate series Lake sediments from Lake Fyne (56° 15' N, 5° 15' W); subm by B L K Somayajulu, PRL, Ahmedabad. PRL-501. Lake sediment 6020 ± 200 Carbonate from lake sediment, depth 20 to 25cm; submitter's Sample P6 20-25. + 320 PRL-503. Lake sediment 12,360 - 310 Carbonate from lake sediment, depth 55 to 60cm; submitter's Sample P6 55-60. PRL-506. Lake sediment >31,000 Carbonate from lake sediment, depth 65 to 80cm; submitter's Sample P6 65-80.

REFERENCES Agrawal, D P, Gupta S K, and Kusumgar, Sheela, 1971, Tata Institute date list IX: Radiocar- bon, v 13, p 442-449. Krishnamurthy, R V, Agrawal, D P, Misra, V N, and Rajaguru, S N, 1981, Palaeoclimatic infer- ences from the behaviour of radiocarbon dates of carbonates from sand dunes of Raja- sthan: Indian Acad Sci Proc, v 90, no. 2, p 155-160. [RArH0CARB0N, Vol. 27, No. 1, 1985, P 111-115] NOTES, COMMENTS, AND REMARKS

AMPLITUDE OF SUNSPOT-DEPENDENT RADIOCARBON VARIATIONS: DATA FROM CORALS AND WINE MORDECKAI MAGARIT7, ISRAEL CARMI, and 7IV SIRKES Department of Isotope Research The Weizmann Institute of Science, 76100 Rehovot, Israel It has been suggested that the sunspot cycle modulates the production rate of radionuclides in the atmosphere and that these modulations can be traced in various parts of the earth surface system. On the basis of a theoretical analysis, Damon, Sternberg, and Radnell (1983) have concluded that the effects of the 11-yr cycle of sunspots should be observable in 14C data provided the measurements are done at a 2 permil (sd) level. This conclu- sion is based on calculations using models discussed by Lingenfelter and Ramaty (1970) and by O'Brien (1979) and on the ' 4C inventory modified from Damon, Lerman, and Long (1978). In this note we compare the amplitude estimate of Damon, Sternberg, and Radnell (1983), who calculated a 14C representative peak-to-peak variation of 1.74 o in for the sunspot cycle between 1848 and 1856, with experimental values derived from recently published data. We find the experimental value to be larger by a significant factor from the theoretical calculation. '4C One set of data is measurements of samples of wine grown in Tbilisi between 1909 to 1952. Burchuladze et al (1980) and Povinec, Burchuladze, and Pagava (1983) have found in this set of data an l l-yr cycle indirectly, by correlation with the data of sunspot numbers. The average 014C peak-to-peak variation of in the wine samples was 14C Another set of data is the activity in growth bands of a single coral given by Druffel (1982). Figure I shows the data of core TRII between 1712 and 1781. Within the existing time resolution, there is an interval of 9 to 15 yr between consecutive max- ima or minima in the time series, the most common value being 12 yr; the peak-to-peak variation is at least 6%o. We applied an objective method of time series analysis to the two series of data to uncover their periodicities. Our method is objective because it does not require any a priori assumptions on the relationship between 14C data and sunspot cycles. Time-series analyses of increasing sophistication 14C have been applied to data sets to discover their characteristics. Lately, the method of Maximum Entropy Spectral Analysis (MESA) (Ulrych & Bishop, 975) has been used to advantage in the analysis of such data. MESA has many useful characteristics, among which is the ability to identify long periods in relatively short time series. Using the data set of Suess (1978), we calculated the period of the grand trend with MESA (Carmi, Sirkes, & Magaritz, 1984) to be 13,200 yr. The same data set was used to show a correlation between the spectra of 14C activity and the width of tree rings for periods between 100 and 2000 yr (Sonnet & Suess, 1984). Our MESA program is based on Barrodale and Erickson (1980a, b). In 111 112 Mordeckai Magaritz, Israel Carmi, and Ziv Sirkes - 30 r r

15 12 9 12 r

r f

r H rO -40 a uaw r$ r .y - 50 \ejL01

- 60 1720 1740 1760 1780 YEAR 14C Fig 1. activity in core TRII of a banded coral (Druffel, 1982)

our procedure the length of the filter (order of autoregression) was determined by Akaike's Final Prediction Error (FPE) criterion (Ulrych & Bishop, 1975) and this, in turn, determined the maximal number of peaks in the spectrum (Jensen & Ulrych,1973). The order of the autoregressive process for the data sets analyzed was half the number of the data points in the time series, ie, the maximal allowable value. In the Tbilisi wine series, there are two duplicate values for which we used average values. We detrended the time series for the Suess effect and calculated its spectrum with MESA, using 44 data points and a filter length of 22. A period of 10.4 yr, which is quite close to that of the sunspot cycle, is very prominent in the spectrum of this time series (fig 2). The coral core data from TRII between 1712 and 1781 are equally spaced (as is required by MESA) in 3-yr intervals, except that three data points are missing (fig 1). A data set with no gaps is required for the applica- tion of MESA, and we generated values for the missing data points by linear 14C interpolation. Druffel (1982) interpreted the higher levels of in the coral data between ca 1700 and 1730 as evidence for the Maunder minimum, and we detrended the data set linearly to account for this effect. Fig- ure 3 shows the spectrum of this data set, obtained using MESA (24 data points, filter length of 12 and 7 maximum possible peaks). The peak at 11.7 yr is close to the period of the sunspot cycle, and we conclude that Druffel's (1982) data of 14C activity in banded corals contain direct evidence of the short-term cycle of sunspots. Amplitude of Sunspot-Dependent Radiocarbon Variations 113 1.0

l 10.4 y N

ti 0.8 . N .

. .V . 0.6 .

N . .I . 0.4 . . . . r 0.2

. H

. H . 26.5 y 7.0 y 0.0 1 y/ Y. I 0 0.05 0.1 0.15 FREQUENCY [Cycles/Year] '4C Fig 2. MESA Power Density Spectrum of activity in wines (Burchuladze et al, 1980)

We also attempted an analysis of a third data set (Lavrukhina & Alex- eev, 1977) of 14C activity in growth rings of a Sequoia from Crimea. The series is in half year intervals between 1890 and 1915.5 with three data points missing. The authors claim to have found an 11-yr cycle in their series by correlation with the sunspot cycle. We applied MESA to the same series (after estimating the missing values), but were unable to identify any period remotely resembling the period of sunspots. The only explanation we can offer is that the resolution in the measurements is insufficient for MESA. This result stresses the necessity of applying objective methods of analysis on the time series. In the wine and in the coral series we found periodicities very similar to those of the sunspots. The two series of data were collected from completely different locations under very different climatic regimes. The Tbilisi samples were exposed to the atmosphere and grew in a temperate region; the corals grew in the tropics and below the surface of the sea. On the face of it, the corals represent a marine environment where the variations in 14C are expected to be damped, in contradiction to the magnitude of the peak- to peak-difference observed (fig 1). However, the habitat of the corals is in very shallow water (<1 Om) with very high wave energy and frequent break- ers; for wavelengths of a few l Os m, the mixing reaches the bottom of the sea. The corals are, therefore, in equilibrium with the atmosphere and the '4C variations in them are undamped. Data on sunspot numbers is available only for the last 300 yr (Eddy, 114 Mordeckai Magaritz, Israel Carmi, and Ziv Sirkes

1.0

lily N 0.8 H

r ti

N 0.6

0.4 r 8.5 y 15.6 y 0.2

53 y 0.0 /ll JL 0.15 0 0.05 0.1 FREQUENCY [Cycles/Year]

Fig 3. MESA Power Density Spectrum of the data set derived from core TRII (Druffel, 1982)

1977). The short-term 11-yr cycle of sunspot numbers is predominant in this data set and has been verified with MESA (Cohen & Lintz, 1974; Son- net, 1982). This cycle modulates the production rate of 14C in the stratosphere and subsequently in the atmosphere. The atmospheric modulation can be expected to be found in specimens of living organisms with well- defined annual growth phases, or in a consecutive set of discrete specimens of annual plants or organisms from the same locality. The 14C signature implanted in such a specimen makes possible, in principle, determination of the sunspot cycle when reliable observations of sunspot numbers are not available (ie, before Al) 1600). In the two cases in which we have shown the 11-yr cycle to be present, the amplitude of the '4C variation was > 4 times the value calculated theo- retically by Damon, Sternberg, and Radnell (1983). The disparity should be investigated in two ways: one is by re-examining the model and the other is by the very accurate remeasuring of, eg, coral samples. The recent achieve- 14C ment of Suter et al (in press) in the very precise measurements of in large numbers of minute samples holds promise of a possible breakthrough in resolving the disparity between the theoretical calculation and the experimental data. It also opens the intriguing possibility of determining the period of sunspot cycles long before AD 1600.

RF.FF:RENCF.S Barrodale, I and Erickson, R E, 1980a, Algorithms for least-squares linear prediction and maximum entropy spectral analysis-part I: theory: Geophysics, v 45, p 420-432. Amplitude of Sunspot-Dependent Radiocarbon Variations 115 Barrodale, I and Erickson, F, R 1980b. Algorithms for least-squares linear prediction and maximum entropy spectral analysis-part II: fortran program: 476. Geophysics, v 45, p 433- Burchuladze, A A, Pagava, S V, Povinec, P, Togonidze, G I, and Usacev, S, 1980, Radiocarbon variation with the I 1-year solar cycle during the last century: Nature, v 287, Carmi, I, Sirkes, Z, and p 320-325. Magaritz, M,1984, Radiocarbon-a direct calculation of the period of the grand trend: Radiocarbon, v 26, 149-151. Cohen, p T j and Lintz, P R, 1974, Long term perioclicities in the sunspot 398. cycle: Nature, v 250, p 1)amon, P E, Lerman J C, and Long, Austin, 1978, Temporal fluctuations of atmospheric14C: causal factors and implications, in Annual review of earth and planetary sciences: Ann Rev Inc, Palo Alto, California, 457-494. I)amon, p P E, Sternberg, R S, and Radnell, C 1983, Modeling of atmospheric fluctuations for J, radiocarbon the past three centuries, in Stuiver, Minze and Kra, Renee, eds, Internatl radiocarbon conf, 11 th, Proc: Radiocarbon, v 25, no 2, 249-258. I)ruffel, E M, 1982, Banded p corals: changes in oceanic carbon-14 during the little ice age:

Science, v 218, p 13-19. Eddy, A, 1977, J The solar output and its variation: Boulder, Colorado Assoc Univ Jensen, 0 G and Ulrych, T, Press.

1973, An analysis of the perturbations of Barnard's Star: The Astronom Jour, v 78, p 1104-1114. Lavrukhina, A K and Alexeev, V A, 1977, Laboratory of cosmochemistry radiocarbon measurements production, I: Radiocarbon, v 19, p 12-18. I.ingenfelter, R E and Ramaty, R, 1970, Astrophysical and geophysical variations in 14C in Olsson I U, ed, Radiocarbon variations and absolute radiocarbon chronology, Internatl conf, 7th, Proc: New York, John 'Wiley & Sons, 513-537. O'Brien K 1979, p J, Secular variations in the production of cosmogenic isotopes: Jour Geophys Research, v 73, p 2057-2067. Povinec, P, Burchuladze, A A, and Pagava, S V, 1983, Short-term concentration variations in radiocarbon with the 11-year solar cycle, in Stuiver, Minze and Kra, Renee, eds, Inter- natl radiocarbon conf, 11th, Proc: Radiocarbon, v 25, no. 2, Sonnet, P, p 259-266. C 1982, Sunspot time series: spectrum from square law modulation cycle: of the Hale Geophys Research Letters, v 9, p 1313-1316. Sonnet, C P and Suess, H E, i4C 1984, Correlation of bristlecone pine ring widths with atmospheric variations: a climate-sun relation: Nature, v 307, 141-143. Suess, H E, 1978, p La Jolla measurements of radiocarbon in tree-ring dated wood: Radiocar- bon, v 20, p 1-18. Suter, M, Balzer, G, Hofman, H J, Morenzoni, E, Wolfli, W, Beer, Oeschger, H, J, Andree, M, and in press, Precision measurements of rare isotopes-results and prospects, in Internatl symposium on accelerator mass spectrometry 3rd: Geophys ters, in press. Research Let- Ulrych, T J and Bishop, T N, 1975, Maximum entropy spectral analysis decomposition: and auto regressive Rev Geophys Space Phys, v 13, p 183-200.

NOTICE TO CONTRIBUTORS TO THE PROCEEDINGS OF THE 12TH INTERNATIONAL, RADIOCARBON CONFERENCE The editors of RADIOCARBON announce the publication of the Pro- ceedings of the 12th International Radiocarbon Conference to be held in Trondheim, Norway, June 24-28, 1985. The Proceedings will appear in one of the three regular numbers of Volume 28, 1986 and will be offered as part of the subscription for that year. Presentation of a paper at the Conference will not guarantee publication in the Proceedings issue. If'a paper is accepted but will not fit into the Proceedings, it will be considered fir publication in one of RADIOCARBON'S regular issues. Only those manuscripts, submitted in proper form (in three typewritten copies) at the Conference will be considered for publication. Articles may not exceed 10 pages including references, illustrations, and tables. No more than four illustrations per paper are recommended, reducible to no more than two pages. Figures should be reduced as much as possible. It is recommended that the author submit camera-ready tables and drawings. Preference will be given to shorter articles. No discussions will be published. The regular review system will be employed. Style guidelines follow the previous Proceedings issues and the STYLF. GUIDE (R, 1984, v 26, 152- 158). p We will not be using the same method of printing as we did for the last Proceedings issue (Vol 25, no. 2, 1983). The author will not be responsible for final preparation of the manuscript. RADIOCARBON will print the Pro- ceedings in the usual manner. Each institution sponsoring research reported in an article will be asked to pay a charge of $80.00 per printed page. Institutions paying such charges will be entitled to 100 free reprints without covers. Publication of an article in the Proceedings is not, conditional on the payment of page charges, as payment can be waived for those institutions unable to pay par- tially or completely. The Norwegian Institute of Technology has offered partial support for the publication of the Proceedings. Pre-publication orders for the Proceedings will be offered at the Con- ference for $25.00 per issue. Only one copy per participant will be available at this reduced price. We look forward to this project and our renewed associations.

1'IIF, f:I)ITORS OF RADIOCARBON Vol 27, No. I Radiocarbon 1985

CONTENTS

14C 25 Years of Tropospheric Observations in Central Europe Ingeborg Levin, Bernd Kromer, Hildegard Schoch-Fischer, Michael Bruns, Marianne Miinnich, Dietrich Berdau, John C Vogel, and Karl Otto Miinnich ...... 1 La Jolla Measurements of Radiocarbon in South German Oak Tree-Ring Chronologies T W Linick, H E Suess, and Bernd Becker ...... 20 Contamination Studies on Mollusk Shell Samples Tomasz Goslar and Mieczyslaw F Pazdur ...... 33 Woods Hole Oceanographic Institution Radiocarbon Laboratory: Sample Treatment and Gas Preparation Sheila Griffin and Ellen R M Druffel ...... 43

DATE LISTS Gd Mieczystaw F Pazdur, Romuald Awsiuk, Andrzej Bluszcz, Tomasz Goslar, Anna Pazdur, Adam Walanus, and Andrezej Zastawny Gliwice Radiocarbon Dates X ...... 52 HAR A J Walker and R L Otlet Harwell Radiocarbon Measurements IV ...... 74

PRL D P Agrawal, R V Krishnamurthy, and Sheela Kusumgar Physical Research Laboratory Radiocarbon Date List V 95

NOTES, COMMENTS, AND REMARKS Amplitude of Sunspot-Dependent Radiocarbon Variations: Data from Corals and Wine Mordeckai Magaritz, Israel Carmi, and Ziv Sirkes ...... 111