Results are presented on the comparative characteristics of the Packard 2000 CA/LL liquid scintillation counter with and without the low-level option on line. An initial performance assessment using 14C labeled benzene with butyl-PBD as the scintillant revealed that although the background count rate decreased by approximately a factor of 3 using the low-level option, a substantial decrease in efficiency was also observed. However, subsequent investigations have indicated that, by careful manipulation of both scintillant composition and concentration, this loss in efficiency can largely be overcome with little or no concurrent increase in background count rate. The introduction of an active vial sample holder and a new light-guide system proved to be significant advances on the standard 2000 CA/LL.

The University of Arizona Radiocarbon Laboratory purchased a state-of-the-art LKB Quantulus LSC and placed it into a new underground counting chamber. We have investigated the performance of the Quantulus in this setting comparing different vial types, checking background sources and experimenting with sample size.

A Packard 2260 XL liquid scintillation counter was placed in an underground counting chamber to test performance under immense physical shielding. Results from the Packard 2260 XL are compared with two other counters under the same conditions, the LKB Quantulus, which has operated for two years in this laboratory, and the LKB 1219 SM, in use since January 1988.

We have replaced the original control electronics and added remote computer control to our Packard Instrument Tri-Carb 460C LSC. The total cost of materials to achieve this was <$1200; ca 200 hr were spent on design and programming, and installation was complete in 30 min. Our system has spectral analysis in 1/2 Kev resolution utilizing the existing 4096 channel multi-channel analyzer, and user-friendly error checking for the mechanical systems. The computer collects spectral information, saves two channels of raw data, plots spectral information and produces data files of the standards, backgrounds and samples used in LOTUS to calculate the age of the sample.

Low-level radiocarbon measurements were made using two liquid scintillation (LS) counters, both with passive lead shields of approximately the same dimensions. The first one had a conventional background reduction with low-activity lead and “high-low” coincidence bias selection, and the second one had a spectrum analysis background reduction based on the different three-dimensional pulse-height signal of background and beta pulses.

The performance of commercial teflon-copper and glass vials were compared with both LS counters. Optimum counting conditions for the two detectors studied were also established. From results obtained, quality parameters and characteristics of quench curves were studied. Performances of each counter in the working conditions established were also compared.

Results of intercomparison tests are presented on samples analyzed using gas and liquid scintillation techniques to study the capability of the LKB Quantulus to count an organic solution used for direct absorption of CO2 and samples with low carbon content. Good agreement was obtained for small samples compared to standard sample size and for the direct absorption compared with the traditional techniques.

At the 12th International Radiocarbon Conference held in Trondheim, the potential of the London Underground as a site for liquid scintillation counting was considered (Bowman, 1986). This was discussed in light of a survey of three possible locations using a portable gamma-ray spectrometer. Two liquid scintillation counters, a Packard 3255 and an LKB “Kangaroo”, have now been successfully installed in a vault which is some 30m below ground. The reduction in background count rates achieved is discussed, together with other improvements made to the counting system.

A multicounter radiocarbon dating system was developed applying the experiences of the previous one-channel low-level counting facility. The counter system consists of nine electrolytic copper proportional counters of identical diameters with sensitive volumes of 0.35–0.7dm3 and filled with either methane at high pressure (6 bar) or CO2 at 1 bar. The inner counters are surrounded by an anticoincidence shield consisting of five multiwire proportional flat counters filled with propane. The pulses of the detectors are handled by integrated amplifiers, discriminators and anticoincidence units interfaced to a microprocessor-controlled data evaluation unit. Software is written in BASIC using ASSEMBLER sub-routines. The overall precision of the system for modern carbon samples using high-pressure methane-filled counters (B ≍ 0.7 cpm, S ≍ 14 cpm) is better than 4 after a counting period of seven days.

Sample materials issued to participants in the interlaboratory calibration exercise are defined and in context of their intended interpretational significance. Preparation of the benzene and calcium carbonate standards as issued for stage 1 is described in detail; likewise, the source and pretreatment/extraction of the environmental samples dispatched for stages 2 and 3.

We report in this paper on a preliminary analysis of Stages 1 and 2 of the International Collaborative program. We have chosen to concentrate on the internal and external consistencies of the participating laboratories. The two stages so far completed have dealt only with the processes of sample synthesis and counting, and results indicate that the major component of variability lies in the counting process. Outlying laboratories are observed at each stage. A third stage is in progress which will allow an assessment of any further variability due to sample pretreatment. With the inclusion of duplicate samples in each stage, we are able to report that laboratories are remarkably consistent internally, ie, the differences between duplicates generally agree with the laboratory's claimed precision.

The need for and means of achieving a 14C dating quality assurance service are debated.

Observations of 14C in atmospheric CO2 at four different sites in central Europe, Heidelberg, Westerland, Schauinsland and Jungfraujoch have enabled us to determine individual fossil-fuel contributions to atmospheric CO2 concentration. The data clearly show a decrease of fossil-fuel CO2 with distance from anthropogenic source regions. At Heidelberg during winter we observe 14C/12C ratios up to 10% lower than at the clean air mountain station Jungfraujoch in the Swiss Alps, corresponding to an anthropogenic CO2 contamination level of ca 10% at the Heidelberg site. The Schauinsland and Westerland winter fossil-fuel CO2 concentrations are only ca 1.5 and 2% of the mean concentration, respectively. Our results indicate a strong seasonality in the European fossil-fuel CO2 source with ca 50% lower CO2 emissions during summer if compared to winter fossil-fuel CO2 release. This effect may significantly contribute (by 1–2 ppm) to the observed annual cycle of atmospheric CO2 concentration in northern mid-latitudes.

The Krakow Radiocarbon Laboratory has been measuring isotope composition of atmospheric CO2 and its natural concentration in the Kraków region for the last five years. We have been sampling on a continuous basis in two-week intervals at ca 20m above ground level, close to the center of Kraków. CO2 was sorbed while slow pumping atmospheric air through a molecular sieve. After recovery by heating, the CO2 was converted to benzene and 14C measured in a liquid scintillation spectrometer. In a small portion of CO2 δ13C was determined in a mass spectrometer. Concentration of CO2 was assessed by measurement of the volumes of the sorbed CO2 and the pumped air. A five-year record (1983–1987) reveals a multi-annual linear trend and winter-summer oscillations. Calculated parameters of the regression line (intercept and slope) for the measured δ14C, δ13C and concentration are: 222 (Jan 1983) and −15.5/yr, −9.57% (Jan 1983) and −0.042/yr, 336ppm (Jan 1983) and 1.4ppm/yr, respectively.

The depth and reliability of archaeological and environmental information on ages, sources and pathways of carbon are being greatly enhanced through a new synergism between advances in “micro 14C dating” and advances in micro-organic analytical chemistry and individual particle characterization. Recent activities at the National Institute of Standards and Technology (NIST, formerly NBS) involving this linkage include dating individual amino acids isolated from bone collagen and the apportionment or tracing of individual carbon compounds derived from anthropogenic sources. Important knowledge has been gained through “direct” (sequential) and “indirect” (parallel) links between microchemistry and 14C measurement. The former is illustrated by 14C measurements on specific amino acids and on the polycyclic aromatic hydrocarbon (PAH) class of compounds. Isolation of the respective molecular fractions from far greater quantities of extraneous carbon held the key to valid dating and source apportionment respectively. Parallel data on 14C and molecular patterns promises new knowledge about the identity of sources of environmental carbon at the nanogram level through multivariate techniques such as principal component analysis and multiple linear regression. Examples are given for atmospheric particulate carbon, using PAH molecular patterns and laser microprobe mass spectral patterns.

Air was sampled with 5L flasks at Kitt Peak (2100m elev) from 1983 through 1984 at approximately monthly intervals, occasionally supplemented with air samples from urban Tucson ca 75km away (760m elev). The Kitt Peak CO2 concentrations, represented by a yield measurement, fluctuated ca 25% over the monitoring period. The δ13C values (uncorrected for N2O) varied from ca −7.6 to −9.0, with high values (and low CO2 yields) in the late summer consistent with hemispheric seasonal biosphere effects. Tucson air has lower δ13C values and possibly greater CO2 yield suggesting a local fossil-fuel effect. 14C activity of four Kitt Peak samples range from 1.158±.007 to 1.223±.008 as uncorrected fraction of modern, below free air activity of ca 1.250 for 1984 even after correcting for fractionation. The slightly low 14C activity and δ13C values suggest the Kitt Peak air is not quite 100% clean and there may be a local/regional fossil-fuel contribution, but CO2 concentrations are similar to background atmospheric values.

We have developed a master δ13C chronology from 14 pinyon pine sites in 6 states of the southwestern U S. Two of the individual isotopic chronologies, reported here for the first time, and 10 of those previously reported (Leavitt & Long, 1986; 1988) are from sites where cores from 4 trees were pooled prior to analysis, and the other 2 are merged from groups of 4 single-tree chronologies (sites) developed in an earlier phase of research (Leavitt & Long, 1985). Regressions of first differences of ring-width indices and δ13C values from each site were used to “correct” individual δ13C chronologies for climate effects which appear primarily related to high-frequency δ13C fluctuations, many of which are common among sites. These climate-corrected chronologies were normalized as deviations from their respective 1800–1849 δ13C means, and these normalized chronologies were averaged into the master. The overall δ13C drop from 1600 to the present is ca 1.2–1.4, consistent with recent ice-core data showing a drop of 1.14 ± 0.15% from 1740 to present (Friedli et al, 1986). However, the δ13C decline in the late 19th and early 20th centuries is greater in the pinyon chronology than that of the ice cores, thus supporting a greater biospheric CO2 input to the atmosphere than that indicated in the ice-core data.

14C concentrations in the stem cellulose of a Sitka spruce from the Pacific coast of Washington respond to changes in atmospheric 14CO2 concentration within 5–6 weeks. δ14C values for cellulose were consistently lower than those of the corresponding clean troposphere during rapid increase in atmospheric 14C caused by nuclear weapons tests (1962–64). Possible reasons for this include: 1) a delay of days or weeks in incorporation of recent photosynthate, 2) the use of stored photosynthate, and 3) photo-assimilation of biospheric decay CO2. We estimate that the influence of process 1 is small or negligible. The respective contributions to the total carbon deposited as radial stem growth in our Sitka spruce then are 2) < 15% (possibly 0), and 3) 10%–23% (13%–28% if the possible effect of root respiration is included in the biosphere decay component). We plan to test this concept by looking for a vertical 14C gradient in the 1963 growth ring of a tree located in a dense forest canopy; we do not expect to find such a gradient in a similar tree from a strongly wind-washed location.

Changes in the ocean ventilation rate may be one of the causes for a net decrease of 100‰ Δ 14C in atmospheric CO2 over the last 8000 years. Ocean ventilation rates of the past can be derived from the 14C record preserved in planktonic and benthic foraminifera in deep-sea sediments. Results of 14C dating using accelerator mass spectrometry on deep sea sediments from the South China Sea show that the age differences between planktonic (G sacculifer) and benthic foraminifera increase from 1350 yr ca 7000 yr ago to 1590 yr at present. An 11-box geochemical model of global ocean circulation was used for this study. Both tree-ring-determined atmospheric 14C values and foraminifera 14C age differences are used as constraints to place limits on patterns of changes in ocean ventilation rates and in atmospheric 14C production rates. Results indicate: 1) 14C production rates in the atmosphere may have decreased by as much as 30% between 7000 and 3000 yr ago, and may have increased again by ca 15% in the past 2000 yr, and 2) the global ocean ventilation rate may not have been at steady state over the last 7000 yr, but may have slowed by as much as 35%.

14C analysis of monospecific samples of planktonic and benthic foraminifera were performed in deep-sea sediment cores from the Atlantic and Pacific Oceans by Accelerator Mass Spectrometry (AMS). These measurements demonstrate that the Younger Dryas cold event, first described in the north Atlantic, is also present at the same time in the north Pacific Ocean. The comparison of the 14C ages of planktonic and benthic foraminifera from the same sediment level in two Pacific cores shows that the ventilation time of the Pacific Ocean was greater than today during the last ice age, but significantly less than today during the deglaciation.

We model the exchange of carbon between the different reservoirs (atmosphere, ocean mixed layer, deep ocean and biosphere). The influence of the biosphere is investigated using two extreme assumptions: 1) no net biospheric effect and 2) biospheric uptake of CO2 proportional to the atmospheric content of CO2 and time-dependent deforestation. Observations of atmospheric CO2 at Mauna Loa and the South Pole may be fit by both these assumptions.