Radiocarbon Analysis of Elemental and Organic Carbon in Switzerland during Winter-Smog Episodes from 2008 to 2012 – Part I: Source Apportionment and Spatial Variability

While several studies have investigated winter-time air pollution with a wide range of concentration levels, hardly any results are available for longer time periods covering several winter-smog episodes at various locations; e.g., often only a few weeks from a single winter are investigated. Here, we present source apportionment results of winter-smog episodes from 16 air pollution monitoring stations across Switzerland from five consecutive winters. Radiocarbon (14C) analyses of the elemental (EC) and organic (OC) carbon fractions, as well as levoglucosan, major water-soluble ionic species and gas-phase pollutant measurements were used to characterize the different sources of PM10. The most important contributions to PM10 during winter-smog episodes in Switzerland were on average the secondary inorganic constituents (sum of nitrate, sulfate and ammonium = 41 ± 15%) followed by organic matter (OM) (34 ± 13%) and EC (5 ± 2%). The non-fossil fractions of OC (fNF,OC) ranged on average from 69 to 85 and 80 to 95% for stations north and south of the Alps, respectively, showing that traffic contributes on average only up to ~ 30% to OC. The non-fossil fraction of EC (fNF,EC), entirely attributable to primary wood burning, was on average 42 ± 13 and 49 ± 15% for north and south of the Alps, respectively. While a high correlation was observed between fossil EC and nitrogen oxides, both primarily emitted by traffic, these species did not significantly correlate with fossil OC (OCF), which seems to suggest that a considerable amount of OCF is secondary, from fossil precursors. Elevated fNF,EC and fNF,OC values and the high correlation of the latter with other wood burning markers, including levoglucosan and water soluble potassium (K+) indicate that residential wood burning is the major source of carbonaceous aerosols during winter-smog episodes in Switzerland. The inspection of the non-fossil OC and EC levels and the relation with levoglucosan and water-soluble K+ shows different ratios for stations north and south of the Alps (most likely because of differences in burning technologies) for these two regions in Switzerland.

Wet deposition of fossil and non-fossil derived particulate carbon: insights from radiocarbon measurement

Radiocarbon (14C) measurements of both organic carbon (OC) and elemental carbon (EC) allow a more detailed source apportionment, leading to a full and unambiguous distinction and quantification of the contributions from non-fossil and fossil sources. A thermal-optical method with a commercial OC/EC analyzer to isolate water-insoluble OC (WIOC) and EC for their subsequent 14C measurement was applied for the first time to filtered precipitation samples collected at a costal site in Portugal and at a continental site in Switzerland. Our results show that WIOC in precipitation is dominated by non-fossil sources such as biogenic and biomass-burning emissions regardless of rain origins and seasons, whereas EC sources are shared by fossil-fuel combustion and biomass burning. In addition, monthly variation of WIOC in Switzerland was characterized by higher abundance in warm than in cold seasons, highlighting the importance of biogenic emissions to particulate carbon in rainwater. Samples with high particulate carbon concentrations in Portugal were found to be associated with increased biogenic input. Despite the importance of non-fossil sources, fossil emissions account for approximately 20% of particulate carbon in wet deposition for our study, which is in line with fossil contribution in bulk rainwater dissolved organic carbon as well as aerosol WIOC and EC estimated by the 14C approach from other studies.

Source apportionment of elemental carbon in Beijing, China: insights from radiocarbon and organic marker measurements

Elemental carbon (EC) or black carbon (BC) in the atmosphere has a strong influence on both climate and human health. In this study, radiocarbon (14C) based source apportionment is used to distinguish between fossil fuel and biomass burning sources of EC isolated from aerosol filter samples collected in Beijing from June 2010 to May 2011. The 14C results demonstrate that EC is consistently dominated by fossil-fuel combustion throughout the whole year with a mean contribution of 79% ± 6% (ranging from 70% to 91%), though EC has a higher mean and peak concentrations in the cold season. The seasonal molecular pattern of hopanes (i.e., a class of organic markers mainly emitted during the combustion of different fossil fuels) indicates that traffic-related emissions are the most important fossil source in the warm period and coal combustion emissions are significantly increased in the cold season. By combining 14C based source apportionment results and picene (i.e., an organic marker for coal emissions) concentrations, relative contributions from coal (mainly from residential bituminous coal) and vehicle to EC in the cold period were estimated as 25 ± 4% and 50 ± 7%, respectively, whereas the coal combustion contribution was negligible or very small in the warm period.

Effects of sample mass and macrofossil type on radiocarbon dating of arctic and boreal lake sediments

Dating lake sediments by accelerator mass spectrometry (AMS) 14C analysis of terrestrial plant macrofossils overcomes one of the main problems associated with dating bulk sediment samples, i.e., the presence of old organic matter. Even so, many AMS dates from arctic and boreal sites appear to misrepresent the age of the sediment. To understand the nature of these apparent dating anomalies better, we conducted a series of 14C dating experiments using samples from Alaskan and Siberian lake-sediment cores. First, to test whether our analytical procedures introduced a sample-mass bias, we obtained 14C dates for different-sized pieces of single woody macrofossils. In these sample-mass experiments, statistically equivalent ages were found for samples as small as 0.05 mg C. Secondly, to assess whether macrofossil type influenced dating results, we conducted sample-type experiments in which 14C dates were obtained for different macrofossil types sieved from the same depth in the sediment. We dated materials from multiple levels in sediment cores from Upper Capsule Lake (North Slope, northern Alaska) and Grizzly Lake (Copper River Basin, southern Alaska) and from single depths in other records from northern Alaska. In several of the experiments there were significant discrepancies between dates for different plant tissues, and in most cases wood and charcoal were older than other macrofossil types, usually by several hundred years. This pattern suggests that 14C dates for woody macrofossils may misrepresent the age of the sediment by centuries, perhaps because of their longer terrestrial residence time and the potential in-built age of longlived plants. This study identifies why some 14C dates appear to be inconsistent with the overall age-depth trend of a lake-sediment record, and it may guide the selection of 14C samples in future studies.

Development of a method for fast and automatic radiocarbon measurement of aerosol samples by online coupling of an elemental analyzer with a MICADAS AMS

A fast and automatic method for radiocarbon analysis of aerosol samples is presented. This type of analysis requires high number of sample measurements of low carbon masses, but accepts precisions lower than for carbon dating analysis. The method is based on online Trapping CO2 and coupling an elemental analyzer with a MICADAS AMS by means of a gas interface. It gives similar results to a previously validated reference method for the same set of samples. This method is fast and automatic and typically provides uncertainties of 1.5–5% for representative aerosol samples. It proves to be robust and reliable and allows for overnight and unattended measurements. A constant and cross contamination correction is included, which indicates a constant contamination of 1.4 ± 0.2 μg C with 70 ± 7 pMC and a cross contamination of (0.2 ± 0.1)% from the previous sample. A Real-time online coupling version of the method was also investigated. It shows promising results for standard materials with slightly higher uncertainties than the Trapping online approach.

Radiocarbon dating of modern peat profiles: Pre- and post-bomb C-14 variations in the construction of age-depth models

We present studies of 9 modern (up to 400-yr-old) peat sections from Slovenia, Switzerland, Austria, Italy, and Finland. Precise radiocarbon dating of modern samples is possible due to the large bomb peak of atmospheric 14C concentration in 1963 and the following rapid decline in the 14C level. All the analyzed 14C profiles appeared concordant with the shape of the bomb peak of atmospheric 14C concentration, integrated over some time interval with a length specific to the peat section. In the peat layers covered by the bomb peak, calendar ages of individual peat samples could be determined almost immediately, with an accuracy of 23 yr. In the pre-bomb sections, the calendar ages of individual dated samples are determined in the form of multi-modal probability distributions of about 300 yr wide (about AD 16501950). However, simultaneous use of the post-bomb and pre-bomb 14C dates, and lithological information, enabled the rejection of most modes of probability distributions in the pre-bomb section. In effect, precise age-depth models of the post-bomb sections have been extended back in time, into the wiggly part of the 14C calibration curve.

Gaseous radiocarbon measurements of small samples

Radiocarbon dating by means of accelerator mass spectrometry (AMS) is a well-established method for samples containing carbon in the milligram range. However, the measurement of small samples containing less than 50 lg carbon often fails. It is difficult to graphitise these samples and the preparation is prone to contamination. To avoid graphitisation, a solution can be the direct measurement of carbon dioxide. The MICADAS, the smallest accelerator for radiocarbon dating in Zurich, is equipped with a hybrid Cs sputter ion source. It allows the measurement of both, graphite targets and gaseous CO2 samples, without any rebuilding. This work presents experiences dealing with small samples containing 1-40 lg carbon. 500 unknown samples of different environmental research fields have been measured yet. Most of the samples were measured with the gas ion source. These data are compared with earlier measurements of small graphite samples. The performance of the two different techniques is discussed and main contributions to the blank determined. An analysis of blank and standard data measured within years allowed a quantification of the contamination, which was found to be of the order of 55 ng and 750 ng carbon (50 pMC) for the gaseous and the graphite samples, respectively. For quality control, a number of certified standards were measured using the gas ion source to demonstrate reliability of the data.

THEODORE, a two-step heating system for the EC/OC determination of radiocarbon (14C) in the environment

Measurements of 14C in the organic carbon (OC) and elemental carbon (EC) fractions, respectively, of fine aerosol particles bear the potential to apportion anthropogenic and biogenic emission sources. For this purpose, the system THEODORE (two-step heating system for the EC/OC determination of radiocarbon in the environment) was developed. In this device, OC and EC are transformed into carbon dioxide in a stream of oxygen at 340 and 650 �C, respectively, and reduced to filamentous carbon. This is the target material for subsequent accelerator mass spectrometry (AMS) 14C measurements, which were performed on sub-milligram carbon samples at the PSI/ETH compact 500 kV AMS system. Quality assurance measurements of SRM 1649a, Urban Dust, yielded a fraction of modern fM in total carbon (TC) of 0.522 ±0.018 (n ¼ 5, 95% confidence level) in agreement with reported values. The results for OC and EC are 0.70± 0.05 (n ¼ 3) and 0.066 ± 0.020 (n ¼ 4), respectively.

Source apportionment and dynamic changes of carbonaceous aerosols during the haze bloom-decay process in China based on radiocarbon and organic molecular tracers

Fine carbonaceous aerosols (CAs) is the key factor influencing the currently filthy air in megacities in China, yet few studies simultaneously focus on the origins of different CAs species using specific and powerful source tracers. Here, we present a detailed source apportionment for various CAs fractions, including organic carbon (OC), water-soluble OC (WSOC), water-insoluble OC (WIOC), elemental carbon (EC) and secondary OC (SOC) in the largest cities of North (Beijing, BJ) and South China (Guangzhou, GZ), using the measurements of radiocarbon and anhydrosugars. Results show that non-fossil fuel sources such as biomass burning and biogenic emission make a significant contribution to the total CAs in Chinese megacities: 56±4 in BJ and 46±5% in GZ, respectively. The relative contributions of primary fossil carbon from coal and liquid petroleum combustions, primary non-fossil carbon and secondary organic carbon (SOC) to total carbon are 19, 28 and 54% in BJ, and 40, 15 and 46% in GZ, respectively. Non-fossil fuel sources account for 52 in BJ and 71% in GZ of SOC, respectively. These results suggest that biomass burning has a greater influence on regional particulate air pollution in North China than in South China. We observed an unabridged haze bloom-decay process in South China, which illustrates that both primary and secondary matter from fossil sources played a key role in the blooming phase of the pollution episode, while haze phase is predominantly driven by fossil-derived secondary organic matter and nitrate.

Foraminifer counts in core JM01-1199, and review of radiocarbon ages in the Norwegian-Barents Sea-Svalbard margin

We compare six high-resolution Holocene, sediment cores along a S-N transect on the Norwegian-Svalbard continental margin from ca 60°N to 77.4°N, northern North Atlantic. Planktonic foraminifera in the cores were investigated to show the changes in upper surface and subsurface water mass distribution and properties, including summer sea-surface temperatures (SST). The cores are located below the axis of the Norwegian Current and the West Spitsbergen Current, which today transport warm Atlantic Water to the Arctic. Sediment accumulation rates are generally high at all the core sites, allowing for a temporal resolution of 10-102 years. SST is reconstructed using different types of transfer functions, resulting in very similar SST trends, with deviations of no more than +- 1.0/1.5 °C. A transfer function based on the maximum likelihood statistical approach is found to be most relevant. The reconstruction documents an abrupt change in planktonic foraminiferal faunal composition and an associated warming at the Younger Dryas-Preboreal transition. The earliest part of the Holocene was characterized by large temperature variability, including the Preboreal Oscillations and the 8.2 k event. In general, the early Holocene was characterized by SSTs similar to those of today in the south and warmer than today in the north, and a smaller S-N temperature gradient (0.23 °C/°N) compared to the present temperature gradient (0.46 °C/°N). The southern proxy records (60-69°N) were more strongly influenced by slightly cooler subsurface water probably due to the seasonality of the orbital forcing and increased stratification due to freshening. The northern records (72-77.4°N) display a millennial-scale change associated with reduced insolation and a gradual weakening of the North Atlantic thermohaline circulation (THC). The observed northwards amplification of the early Holocene warming is comparable to the pattern of recent global warming and future climate modelling, which predicts greater warming at higher latitudes. The overall trend during mid and late Holocene was a cooling in the north, stable or weak warming in the south, and a maximum S-N SST gradient of ca 0.7 °C/°N at 5000 cal. years BP. Superimposed on this trend were several abrupt temperature shifts. Four of these shifts, dated to 9000-8000, 5500-3000 and 1000 and ~400 cal. years BP, appear to be global, as they correlate with periods of global climate change. In general, there is a good correlation between the northern North Atlantic temperature records and climate records from Norway and Svalbard.