INTRODUCTION
The isotopes of carbon, radioactive 14C and stable 13C (as 14C/12C and 13C/12C ratios, or Δ14C and δ13C, respectively), are mostly used in global carbon and atmospheric studies, as well as for the study of anthropogenic influence on the environment. Both isotopes originate from natural and anthropogenic sources. Natural 14C production predominantly depends on the Earth’s geomagnetic field and solar activity and it varied significantly in the past (Muscheler et al. Reference Muscheler, Beer, Kubik and Synal2005; Miyake et al. Reference Miyake, Nagaya, Masuda and Nakamura2012; Mekhaldi et al. Reference Mekhaldi, Muscheler, Adolphi, Aldahan, Beer and McConnell2015; Channell et al. Reference Channell, Hodell, Crowhurst, Skinner and Muscheler2018; Heaton et al. Reference Heaton, Bard, Bronk Ramsey, Butzin, Köhler, Muscheler, Reimer and Wacker2021). Natural 14C distribution in the Earth’s atmosphere was anthropogenically disturbed in 19th century when a decrease of 14C concentration in atmospheric CO2 (Δ14CCO2) was recorded in tree rings and correlated with the beginning of the Industrial Revolution and the release of 14C free CO2 into the atmosphere due to fossil fuel combustion (Suess Reference Suess1955). Similarly, δ13C of atmospheric CO2, with pre-industrial value of –7‰, also decreased, since fossil fuels have δ13C values around –26‰ (Graven et al. Reference Graven, Keeling and Rogelj2020; Keeling and Graven Reference Keeling and Graven2021). In the 1950s and 1960s, atmospheric 14C concentration suddenly increased due to atmospheric nuclear bomb testing. 14C activity almost doubled in the Northern Hemisphere and reached a peak in 1963 (Nydal and Lövseth Reference Nydal and Lövseth1965), after which it started decreasing due to the Nuclear Test Ban Treaty and CO2 exchange with other carbon reservoirs, mostly oceans (Levin and Hesshaimer Reference Levin and Hesshaimer2000; Hua et al. Reference Hua, Barbetti and Rakowski2013; Graven et al. Reference Graven, Keeling and Rogelj2020; Heaton et al. Reference Heaton, Bard, Bronk Ramsey, Butzin, Köhler, Muscheler, Reimer and Wacker2021; Kutchera Reference Kutchera2022; Levin et al. Reference Levin, Hammer, Kromer, Preunkert, Weller and Worthy2022). Today, levels of Δ14CCO2 have approached pre-bomb values (Heaton et al. Reference Heaton, Bard, Bronk Ramsey, Butzin, Köhler, Muscheler, Reimer and Wacker2021; Hua et al. Reference Hua, Turnbull, Santos, Rakowski, De Pol-Holz, Hammer, Lehman, Levin, Miller, Palmer and Turney2022) and further decrease of 14C concentration is predicted as well as a decrease in δ13C values stemming from fossil fuel combustion (Heaton et al. Reference Heaton, Bard, Bronk Ramsey, Butzin, Köhler, Muscheler, Reimer and Wacker2021; Hua et al. Reference Hua, Turnbull, Santos, Rakowski, De Pol-Holz, Hammer, Lehman, Levin, Miller, Palmer and Turney2022; Levin et al. Reference Levin, Hammer, Kromer, Preunkert, Weller and Worthy2022). The decrease of Δ14CCO2 and δ13CCO2 in the future can be enhanced by the exchange of CO2 between oceans and the atmosphere (Menviel et al. Reference Menviel, Mouchet, Meissner, Joos and England2015; Skinner et al. Reference Skinner, Primeau, Freeman, de la Fuente, Goodwin, Gottschalk, Huang, McCave, Noble and Scrivner2017; Keeling and Graven Reference Keeling and Graven2021). The oceans may also become a source of 14C release into the atmosphere due to release of bomb 14C from the water column (Gao et al. Reference Gao, Liping, Kexin and Xiaomei2019; Levin et al. Reference Levin, Hammer, Kromer, Preunkert, Weller and Worthy2022). Other sources of man-made 14C, such as various nuclear facilities, can contribute to an increase of Δ14CCO2 locally.
Generally, Δ14CCO2 has a seasonal trend with expected maximum concentration during spring/summer mainly due to vertical mixing between the troposphere and stratosphere (Turnbull et al. Reference Turnbull, Rayner, Miller, Naegler, Ciais and Cozic2009; Graven et al. Reference Graven, Keeling and Rogelj2020). In the autumn and winter seasons Δ14CCO2 values decrease due to a lack of atmospheric mixing. Locally, the winter Δ14CCO2 minima could be observed in urban (Rakowski et al. Reference Rakowski, Nakamura and Pazdur2008; Molnár et al. Reference Molnár, Major, Haszpra, Svetlik, Svingor and Veres2010; Varga et al. Reference Varga, Barnucz, Major, Lisztes-Szabó, Jull, László, Pénzes and Molnár2019) and even clean-air site areas due to fossil fuel burning during heating season (Major et al. Reference Major, Haszpra, Rinyu, Futó, Bihari, Hammer, Jull and Molnár2018). δ13CCO2 also shows seasonality, but for different reason: higher spring/summer values are due to photosynthesis and lower autumn/winter values are due to plant respiration (Turnbull et al. Reference Turnbull, Rayner, Miller, Naegler, Ciais and Cozic2009; Graven et al. Reference Graven, Keeling and Rogelj2020). Since δ13C of fresh plants and respired CO2 are generally similar to that of the fossil fuel, δ13C cannot be used to differentiate bio from fossil carbon. Δ14CCO2 is monitored by several long-term stations (Levin and Hammer Reference Levin and Hammer2021; Levin et al. Reference Levin, Hammer, Kromer, Preunkert, Weller and Worthy2022) of which there are currently 15 stations active in Europe (ICOS 2022). δ13CCO2 is monitored world-wide by the Scripps CO2 Program (Keeling et al. Reference Keeling, Piper, Bacastow, Wahlen, Whorf, Heimann, Meijer, Ehleringer, Cerling and Dearing2005; Keeling and Graven Reference Keeling and Graven2021) and Global Monitoring Laboratory (NOAA – GML 2023; Vaughn et al. Reference Vaughn, Evans, White, Still, Masarie and Turnbull2010).
We present the establishment of three experimental stations for monitoring Δ14CCO2 and δ13CCO2 in the northern coastal area of Croatia: the port of Rijeka and two sites in its surroundings (Gornje Jelenje and Parg). The aim was to determine the influence of fossil fuel combustion on Δ14CCO2 and δ13CCO2 values at different locations with the hypothesis that the urban site is affected by fossil fuel uses. It should be emphasized that there is no previous data on carbon isotopic composition of atmospheric CO2 in the Croatian coastal area and there are scant data from European coastal areas. European monitoring sites included in the ICOS program are mainly continental (Levin et al. Reference Levin, Hammer, Kromer, Preunkert, Weller and Worthy2022; Scripps CO2 Program 2022) and the stations included in Scripps CO2 Program, such as Mauna Loa, Hawaii, are situated on Pacific islands or close to the Arctic and Antarctic (Keeling et al. Reference Keeling, Piper, Bacastow, Wahlen, Whorf, Heimann, Meijer, Ehleringer, Cerling and Dearing2005; Keeling and Graven Reference Keeling and Graven2021; Scripps CO2 Program 2022). A few monitoring programs have analyzed carbon isotopic composition of the atmospheric CO2 above the oceans collected from boats (Dutta et al. Reference Dutta, Bhushan, Somayajulu and Rastogi2006; Longinelli et al. Reference Longinelli, Giglio, Langone, Moggio, Ori, Selmo and Sgavetti2012; Gao et al. Reference Gao, Liping, Kexin and Xiaomei2019) and isotopic composition of dissolved inorganic carbon (DIC) (Becker et al. Reference Becker, Andersen, Erlenkeuser, Humphreys, Tanhua and Körtzinger2016; Gao et al. Reference Gao, Liping, Kexin and Xiaomei2019; Scripps CO2 Program 2023). The Mace Head (MHD) monitoring station situated on west coast of Ireland is exposed to clean marine air nearly 50% of the time but is also under the influence of polluted air masses from the UK and Europe (Yttri et al. Reference Yttri, Simpson, Bergström, Kiss and Szidat2019).
SAMPLING AND METHODS
Sampling Sites Characterization
The characteristics of all three sampling locations are summarized in Table 1. Rijeka is the third largest city in Croatia and has the largest seaport, with 128,600 inhabitants and a population density of 2900 inhabitants/km2. It is located in Primorje-Gorski Kotar County, on the coast of the Kvarner Gulf (Figure 1). The climate of Rijeka is moderately warm and humid with hot summers (Cfa) (Peel et al. Reference Peel, Finlyanson and McMahon2007; Beck et al. Reference Beck, Zimmermann, McVicar, Vergopolan, Berg and Wood2018). It is known for the Bora, the cold and dry north-easterly wind (CMHS 2022; Figure 2a) that sometimes gusts at hurricane speeds (160 km/hr). The annual mean air temperature (T) in 2021 was 15.1°C (seasonal variations in Figure 2b), and the total amount of precipitation (P) was 1161 mm (CMHS 2022). The samples were collected in the center of the city (Figure 1d), near the main railway station, 9 m above ground (0 m a.s.l), on the terrace of an apartment.
Characteristics of the three sampling locations.
(a) Map of Europe with Croatia highlighted; (b) position of the sampling area in Croatia; (c) enlarged map of sampling points, and (d) micro location of sampling point in Rijeka
(a) Wind roses for Rijeka and Parg in 2021. (b) Air temperatures for Rijeka and Parg (CMHS 2022).
Gornje Jelenje is a saddle located 14 km northeast of Rijeka in the foothills of Risnjak National Park and Snježnik Mountain (Figure 1). The area is covered by forests, and the sampling site is located 500 m away from the main road at 882 m a.s.l.; the samples were collected 2 m above the ground. The climate is moderately warm and humid with warm summers (Cfb) (Peel et al. Reference Peel, Finlyanson and McMahon2007; Beck et al. Reference Beck, Zimmermann, McVicar, Vergopolan, Berg and Wood2018). Gornje Jelenje is not a CMHS station and there is no meteorological data for this site.
Parg is a village in Gorski Kotar, 33 km distant from Rijeka. It is located in a wooded, mountainous area far from inhabited zones and roads (Figure 1). The climate is classified as Dfb type (Peel et al. Reference Peel, Finlyanson and McMahon2007; Beck et al. Reference Beck, Zimmermann, McVicar, Vergopolan, Berg and Wood2018) with annual mean air temperature in 2021 of 8.4oC (seasonal variations in Figure 2b), and an annual amount of precipitation 1586 mm with snowfall in the winter period and warm summers. The wind that prevails in the area is SW to SE (CMHS 2022, Figure 2a); samples were collected 2 m above the ground.
Sampling Methods
Sampling for atmospheric CO2 Δ14C and δ13C analyses was performed from January 2 to December 28, 2021. Atmospheric CO2 for Δ14C analyses was sampled by static absorption method on saturated NaOH in plastic pads as a one-month integrated sample. Absorption occurs under highly alkaline conditions (Dietzel Reference Dietzel1997) accompanied by intensive isotope fractionation and the δ13C of absorbed CO2 (in form of Na2CO3) is not representative for atmospheric CO2 (Krajcar Bronić et al. Reference Krajcar Bronić, Vreča, Horvatinčić, Barešić and Obelić2006). Na2CO3 samples were transferred from sampling pads into plastic bottles and thoroughly sealed to avoid isotopic exchange between sample and the atmosphere. For δ13CCO2 analyses, grab air samples were collected by 50 mL plastic syringe and transferred to a 12 mL Labco glass ampoule fitted with a gas-tight septum, flushed using two needles (input and output needle) and filled with air under pressure (Kanduč et al. Reference Kanduč, Sedlar, Novak, Zadnik, Jamnikar, Verbovšek, Grassa and Rošer2021). Three ampoules were filled per location: at 2 m above ground at Parg and Gornje Jelenje, and 9 m above the ground in Rijeka. These samples were taken at the same sampling heights as the samples for the Δ14C analyses and stored at standard atmospheric conditions until analysis. Sampling was performed between 2:00 and 5:00 pm.
The leaves of deciduous trees were collected on August 30, 2021, directly from a plane tree (Platanus) in Rijeka and maple trees (Acer) in Parg and Gornje Jelenje.
Measurement Methods
The majority of the CO2 samples and leaf samples were measured in the form of benzene in a Liquid Scintillation Counter Quantulus 1220 (Horvatinčić et al. Reference Horvatinčić, Barešić, Krajcar Bronić and Obelić2004; Krajcar Bronić et al. Reference Krajcar Bronić, Sironić and Barešić2023). CO2 was released from Na2CO3 by HCl (18%) in an inert N2 atmosphere and cryogenically purified. The obtained CO2 was converted to benzene in vacuum synthesis line (Horvatinčić et al. Reference Horvatinčić, Barešić, Krajcar Bronić and Obelić2004). The leaf samples were carbonized at 650°C and converted to benzene (Horvatinčić et al. Reference Horvatinčić, Barešić, Krajcar Bronić and Obelić2004; Krajcar Bronić et al. Reference Krajcar Bronić, Sironić and Barešić2023). Accelerator mass spectrometry (AMS) was used in the cases when the sample quantity of absorbed CO2 was not enough for benzene synthesis. Samples were prepared in the form of graphite targets: CO2 from Na2CO3 was evolved using acid (4% HCl) and reduced to graphite with Zn reduction on Fe powder (Sironić et al. Reference Sironić, Krajcar Bronić, Horvatinčić, Barešić, Obelić and Felja2013). Graphite samples were measured at the Center for Applied Isotope Studies, University of Georgia (Cherkinsky et al. Reference Cherkinsky, Culp, Dvoracek and Noakes2010). Anthracite and SRM 4990C (OxA II) were used as background and reference samples, respectively, for both techniques. All 14C activities were corrected to the date of sampling and defined as Δ14C (Mook and van der Plicht Reference Mook and van der Plicht1999; van der Plicht and Hogg Reference van der Plicht and Hogg2006).
δ13CCO2 from the air samples was determined on the Europa Scientific 20-20 mass spectrometer with the continuous flow IRMS ANCA-TG preparative module at the Jožef Stefan Institute, Ljubljana in Slovenia. Reference material with a known value of δ13CCO2 (–35.4 ± 0.2‰) calibrated to VPDB (Vienna Pee Dee Belemnite) was used. Additionally, as a working standard, natural gas from emission sources in Sicily with a known δ13CCO2 (–0.87 ± –0.20‰) determined at the Istituto Nazionale di geofisica e vulcanologia, manufacturer: gtp-gas.it, (homepage: https://gtp-gas.it/diassido-liquidi-criogenici-i/9) was used. Two-point normalization was performed for CO2. 0.01 mL of CO2 (reference gas and working standards) was transferred to Labco ampoules. The whole collected sample was used for δ13CCO2 determination. Because concentrations of CO2 in air are low, optimal integral peak area (liquid nitrogen cryo trap) was used. Stable isotopes are reported in the δ notation (Coplen Reference Coplen1996) relative to VPDB and measurement uncertainty was between ±0.3 and ±0.7‰.
Estimation of the Fossil CO2 Component
We estimated the fossil CO2 share in the Rijeka and Gornje Jelenje sampling sites assuming that Parg as a clean-air site had 14C signal only from natural sources (CO2 free from fossil fuel influence, biospheric and sea CO2). Since the shares of the CO2 natural components were unknown, we assumed that Rijeka and Gornje Jelenje differed from Parg only in fossil CO2 share, i.e., we approximated biospheric, sea and fossil-free CO2 components as a background (Levin et al. Reference Levin, Kromer, Schmidt and Sartorius2003). This simplification enabled the estimation of fossil CO2 contribution in Rijeka and Gornje Jelenje from a simple two component mixing relation:
$${\rm{a = - 1000 \times X + b \times (1}} - {\rm{X)}}$$
where “a” represents Δ14CCO2 from Rijeka or Gornje Jelenje, “b” represents the background Δ14C value, –1000‰ is Δ14C of fossil CO2, and “X” is the share of fossil CO2. Such mixing relations are used when data on CO2 concentration are not available (Piotrowska et al. Reference Piotrowska, Pazdur, Pawełczyk, Rakowski, Sensuła and Tudyka2019). As a background Δ14C values, data from JFJ (Jungfraujoch, Switzerland) station are usually used (Levin et al. Reference Levin, Hammer, Kromer and Meinhardt2008). In this paper the Δ14CCO2 values from Parg were used as background, and additional calculation was made using the JFJ data from 2020 as data for entire 2021 were not available.
RESULTS AND DISCUSSION
Results of Δ14CCO2 are shown in Figure 3a, while numerical individual data are presented in Table SM1 of supplementary material. For all three locations the data show similar seasonal patterns (Figure 3), with significant correlation with temperature values (Rijeka r = 0.58, Parg r = 0.70, p < 0.05; Figure 3c). Δ14CCO2 mean values (Table 2) show that Gornje Jelenje represents an approximate middle value (–10 ± 8‰) between Rijeka (–22 ± 12‰) and Parg (0 ± 12‰). Tree leaves should reflect Δ14CCO2 values from the spring/summer period (March–September). This is true for the tree leaves from Gornje Jelenje and Parg: their Δ14C values correspond to Δ14CCO2 values for respective periods (Table 2). The leaves from Rijeka show a higher, but statistically insignificant (z = 0.65; Table SM3) Δ14C value compared to the Δ14CCO2 values determined in Rijeka for the spring/summer period (Table 2), and it is more similar to the Δ14CCO2 from winter season. This could be explained by the altitude difference and coastal position of Rijeka, where the budding period generally starts earlier than in the mountain area. The altitude Δ14C effect has been reported in tree leaves from higher altitudes (Sakurai et al. Reference Sakurai, Tokanai, Kat, Takahashi, Sato, Kikuchi and Tavera2013), but higher Δ14C values were found at above 3000 m a.s.l. The trend of a Δ14C increase from the lowest altitude sampling point in Rijeka, to the highest, through Gornje Jelenje to Parg observed in samples of tree leaves, as well as in respective Δ14CCO2 values (Table 2) is the most likely caused by distance from the expected fossil fuel and marine reservoir carbon sources and climatic differences between sites, rather than altitude effect. The increase in Δ14CCO2 between Rijeka and Gornje Jelenje to Parg (from –22‰, –10‰, to 0‰; Table 2) much better fits the increase in air distance from Rijeka (15 km to Jelenje and 32 km to Parg), than the increase in elevation (0 m a.s.l., 882 m a.s.l., and 863 m a.s.l.; Table 1).
(a) Integrated monthly Δ14C values at the Rijeka, Gornje Jelenje, and Parg stations for 2021, and for leaves sampled in August 2021 at the respective stations; (b) Δ14C difference of atmospheric CO2 for Rijeka and Gornje Jelenje sites compared to the clean-air site Parg; (c) Δ14C vs. monthly temperature.
The observed decrease of Δ14CCO2 from north to south (clean-air to urban site) could be caused by fossil fuel influence in Rijeka, but this signal is not clear throughout the whole year. In January, the coldest month in 2021 (Figure 2b), Δ14CCO2 values are identical for all three sites (Figure 3a; Table SM1), although it is expected that Δ14CCO2 would be lower in Rijeka due to heating with natural gas and oil. In February, when atmospheric temperatures start to increase, we observed a decrease of Δ14CCO2 in Rijeka and an increase in Gornje Jelenje and Parg. In March, Δ14CCO2 values decreased at all three locations, with the largest difference between Rijeka and Parg (Figure 3b; Table SM3). Starting from May when all three locations had same value, Δ14C increased peaking in September (Rijeka and Parg), and October (Gornje Jelenje), showing an increasing difference between Parg and the other two locations (Figure 3b). The minimum Δ14CCO2 value was detected in Rijeka in October, but this cannot be explained solely by start of heating season, because November and December temperatures were lower, and Δ14C values higher than in October (Figure 2b). Rijeka is the main Croatian seaport and a busy tourist destination, so fossil fuel emissions due to heavy traffic should be expected during summer months, but the Δ14C values were almost identical to those from Gornje Jelenje. During the tourism season in 2021, there were no COVID travel restrictions in Croatia and the number of visitors in the Kvarner area was nearly the same as in 2022 (CBS 2022).
Apart from burning of fossil fuels, the observed Δ14CCO2 fluctuations can be explained by several possible processes. Δ14CCO2 values at all three stations simultaneously started increasing in May, which can be attributed to a penetration of stratospheric air masses enriched with 14C into the troposphere (Levin et al. Reference Levin, Naegler, Kromer, Diehl, Francey, Gomez-Pelaez, Steele, Wagenbach, Weller and Worthy2010, Reference Levin, Hammer, Kromer, Preunkert, Weller and Worthy2022; Graven et al. Reference Graven, Guilderson and Keeling2012; McDonald et al. Reference McDonald, Chivall, Miles and Bronk Ramsey2019; Heaton et al. Reference Heaton, Bard, Bronk Ramsey, Butzin, Köhler, Muscheler, Reimer and Wacker2021); this vertical mixing does not occur during the autumn/winter season, resulting in lower Δ14CCO2 values. Wind directions in the investigated areas can also help in data interpretation. Rijeka is under the influence of cold northeast wind that blows from the mountains, i.e., from the direction of Parg and Gornje Jelenje (Figure 2a). Parg is under strong influence of southerly winds, i.e., from the coast toward mountains (Figure 2a). Wind directions imply strong mixing of air masses above Rijeka and Parg, with the influence of the marine air. Due to Marine Reservoir Effect (Faivre et al. Reference Faivre, Bakran-Petricioli, Barešić and Horvatinčić2015) and to the strong vertical mixing processes, especially pronounced in the northern Adriatic during the winter (Vilibić and Supić Reference Vilibić and Supić2005), surface dissolved inorganic carbon (DIC) is 14C depleted, which is reflected in atmospheric CO2 (Skinner et al. Reference Skinner, Primeau, Freeman, de la Fuente, Goodwin, Gottschalk, Huang, McCave, Noble and Scrivner2017; Graven et al. Reference Graven, Keeling and Rogelj2020; Keeling and Graven Reference Keeling and Graven2021); this corresponds to lower Δ14CCO2 values in the autumn/winter period. During summer stratification, Δ14CDIC values are generally higher due to the still present 14C from the bomb peak in marine water column (Fallon et al. Reference Fallon, Guilderson and Caldeira2003; Gao et al. Reference Gao, Liping, Kexin and Xiaomei2019; Guilderson et al. Reference Guilderson, Schrag, Druffel and Reimer2021). The presence of bomb peak residue is exhibited in shells from the northern Adriatic (Δ14C = 25‰ in 2013; Peharda et al. Reference Peharda, Sironić, Markulin, Jozić, Borković and Andersson2019). This corresponds to higher Δ14CCO2 during the spring/summer period. The especially high Δ14CCO2 level at Parg could be attributed to the influence of this 14C enriched marine CO2 that can be transported by strong S and SW winds (Figure 2a), and increased CO2 outgassing due to high summer temperatures (Figure 2b). Mediterranean influence during the summer has been shown on isotopic composition of precipitation (Vreča et al. Reference Vreča, Krajcar Bronić, Horvatinčić and Barešić2006; Krajcar Bronić et al. Reference Krajcar Bronić, Barešić, Borković, Sironić, Lovrenčić Mikelić and Vreča2020), as well as from backward trajectories for July and September (Stein et al. Reference Stein, Draxler, Rolph, Stunder, Cohen and Ngan2015; Rolph et al. Reference Rolph, Stein and Stunder2017; NOAA – HYSPLIT 2023). The photosynthesis/respiration ratio also has a certain role in Δ14CCO2 dynamics, but it complicates the interpretation of our results as photosynthetic activity during spring/summer that overrides respiration should decrease Δ14CCO2 due to CO2 consumption, and the respiration, with no photosynthesis (autumn/winter) should increase Δ14CCO2 due to CO2 production. Nevertheless, photosynthesis vs. respiration could explain the Δ14CCO2 drop in March at all three locations, the most intensive of which was in Rijeka. This corresponded to the observed Δ14C value of tree leaves from Rijeka and start of budding season earlier compared to the two mountain sites Gornje Jelenje and Parg. Maximum values of Δ14CCO2 in September (Rijeka and Parg) and October (Gornje Jelenje) could be due to soil respiration and CO2 release into the atmosphere (Trumbore Reference Trumbore2000).
Generally, Δ14CCO2 values from urban Rijeka site are the lowest (average value –22 ± 12‰, Table 2) compared to ICOS stations, while values from Gornje Jelenje (average Δ14CCO2 is –10 ± 8‰, Table 2) are comparable to STE (Steinkimmen, Germany, average Δ14CCO2 is –9 ± 6‰, Kubistin et al. Reference Kubistin, Plaß-Dülmer, Arnold, Kneuer, Lindauer and Müller-Williams2022a), KRE (Křešín u Pacova, Czechia, average Δ14CCO2 is –8 ± 3‰, Marek et al. Reference Marek, Vítková and Komínková2022). It must be emphasised that clean-air site Parg has higher Δ14CCO2 values (average 0 ± 12‰, Table 2) compared to other EU monitoring stations, but due a huge Δ14CCO2 fluctuation during the year, average value does not show a clear difference. The peak Δ14CCO2 value of 24.8 ± 6.4‰ was observed at Parg in September, and the highest value among the EU stations was 2.6 ± 1.8‰ measured in September at SVB (Svartberget, Sweden, data available until September 2021, Marklund et al. Reference Marklund, Ottosson-Löfvenius and Smith2022). The ICOS station that could be regarded as most similar to Parg and with data available for the whole of 2021 is KRE, but the maximum Δ14CCO2 value determined for this site was –3.5‰ in August. Other ICOS stations with data available for the whole year are STE, PAL (Pallas, Finland; without data for December; Hatakka Reference Hatakka2022) and OPE (Observatoire pérenne de l’environnement, France; without data for December, Ramonet et al. Reference Ramonet, Conil, Delmotte and Laurent2022). The maximum Δ14CCO2 values were –0.2‰ measured in August at STE, 1.3‰ measured at PAL in September, and –2.78‰ at HTM (Hyltemossa, Sweden, Heliasz and Biermann Reference Heliasz and Biermann2022), also in September. There are not data for the whole year from the JFJ, but data for 2019 and 2020 show maxima Δ14C of 6.1 ± 1.5‰ in September and 5.4 ± 1.7‰ in July, respectively (Emmenegger et al. Reference Emmenegger, Leuenberger and Steinbacher2022). Data from Mace Head (MHD) would be interesting as this is European maritime station, but Δ14CCO2 values are available only until March 2016. However, a comparison of MHD data from 2015 with the available data for 2015 from JFJ station, show higher summer Δ14CCO2 values at MHD (maximum was 23‰ in August, while maximum Δ14CCO2 for JFJ was 17.4‰ in February). These two values could imply summer 14C sea CO2 influence onto the atmosphere at MHD, and a similar explanation might be applicable to high summer Δ14CCO2 values at the Parg site. Parg has a Δ14CCO2 range for January–June and October–December, of –18.2‰ to 4.0‰, while between July and September these values are considerably higher within the range from 10.1‰ to 24.8‰. To the best of our knowledge there is no source of anthropogenic 14C in the area, since the contribution of Δ14C from the only nuclear facility in a radius of 100 km from the investigated sites (NPP Krško, Slovenia, NE direction) disappears 15 km from the facility (Krajcar Bronić et al. Reference Krajcar Bronić, Breznik, Volčanšek, Barešić, Borković, Sironić, Horvatinčić, Obelić and Lovrenčić Mikelić2017). Backward trajectories (Stein et al. Reference Stein, Draxler, Rolph, Stunder, Cohen and Ngan2015; Rolph et al. Reference Rolph, Stein and Stunder2017; NOAA – HYSPLIT 2023) indicate travel of air masses from distant areas and that high Δ14CCO2 signals could be transferred from EU nuclear power plants. Investigation of atmospheric pollution in Croatia showed that more than 70% of pollutants have been transferred from other European countries by air masses (Špoler Čanić et al. Reference Špoler Čanić, Vidič and Bencetić Klaić2009). However, much more investigation is needed on this topic. As we discussed earlier, apart from seasonal influence of 14C enriched marine CO2, the high Δ14CCO2 values from Parg could be the result of CO2 originated from organic matter decomposition. The Parg area is covered mainly by coniferous trees and fallen leaves may be several years or decades old, so the CO2 resulting from decomposition has higher Δ14C values compared to the atmosphere of deciduous forest area (Trumbore Reference Trumbore2000).
The approximate shares of calculated fossil CO2 (Table SM5) were 2.1 ± 1.3% at Rijeka and 1.0 ± 0.9% at Gornje Jelenje (yearly averages). The maximum shares were calculated for Rijeka in October (4.5%) and for Gornje Jelenje in September (2.6%) and the minimum, even negative, values of –0.4% (Rijeka) and –0.3% (Gornje Jelenje) in January (Table SM5). The values were also lower compared with data for January from majority of ICOS stations, except the STE (Δ14CCO2 is –15.0‰) and KIT (Karlsruhe, Germany, Δ14CCO2 is –22.3‰, Kubistin et al. Reference Kubistin, Plaß-Dülmer, Arnold, Kneuer, Lindauer, Müller-Williams and Schumacher2022b) while other stations had values between –12.9 and 5.6‰. Although the Δ14CCO2 difference between Rijeka and Parg, and Gornje Jelenje and Parg were non-significant for January (z = 0.37 and 0.31, respectively, Table SM3), negative shares of fossil CO2 values indicate the influence of 14C depleted CO2 at the Parg station, probably transported by SSW wind from the Adriatic Sea (Figure 2a). It is worth mentioning that backward trajectories for January 2021 for three investigated sites as well as for STE and KIT indicate air masses transport from the North Atlantic, detailed investigation on this subject is necessary as well as the 14C analyses of sea DIC to determine the influence of CO2 form the sea. The calculation with JFJ data as a background (from 2020) give very similar yearly averages for both Rijeka and Gornje Jelenje (Table SM5) without negative values in January, which also implies a source of 14C depleted CO2 in the Parg site during winter.
The comparison between clean-air sites and industrial areas based on tree ring 14C analyses show higher fossil CO2 shares in urban European areas compared to Rijeka and Gornje Jelenje: in south-west Slovakia 3.4 ± 1.5% (Kontul’ et al. Reference Kontul’, Svetlik, Povinec, Pachnerova Brabcova and Molnár2020), southern Poland 3.6 ± 0.3% (Rakowski et al. Reference Rakowski, Kuc, Nakamura and Pazdur2005, Reference Rakowski, Nakamura and Pazdur2008; Pazdur et al. Reference Pazdur, Nakamura, Pawelczyk, Pawlyta, Piotrowska, Rakowski, Sensula and Szczepanek2007), and 5.8% in Gliwice, Poland, which is regarded as one of the most fossil CO2 affected region (Piotrowska et al. Reference Piotrowska, Pazdur, Pawełczyk, Rakowski, Sensuła and Tudyka2019). Samples from the Debrecen area, in Hungary, indicate smaller fossil CO2 contribution in tree leaves (0.9 ± 1.2%) compared to grasses (2.5 ± 2.5%), with higher values in the vicinity of busy crossroads (4.7 ± 0.7% and 9.6 ± 0.7% for tree leaves and grasses, respectively, Varga et al. Reference Varga, Barnucz, Major, Lisztes-Szabó, Jull, László, Pénzes and Molnár2019). Dilution of fossil CO2 observed in Debrecen at sites away from busy crossroads may be used as an explanation for our data from Rijeka and Gornje Jelenje. Rijeka, although an urban and touristic place, has many city parks that clearly help to remove produced CO2. This could be valid for the Gornje Jelenje area as well, where the vicinity of the road is heavily forested and therefore rife with photosynthetic activity and CO2 consumption.
CO2 for the determination of δ13C was sampled as a grab sample at the beginning and at the end of the sampling period for Δ14CCO2 determination (Figure 4; Table SM2). δ13CCO2 values have similar seasonal trends for all locations and δ13C values between all three sites are significantly correlated (R-GJ: r = 0.66, p = 0.025; R-P: r = 0.72, p = 0.011; P-GJ: r = 0.72, p = 0.011). Of the three sites, only the clean-air site Parg is significantly correlated to temperature (r = 0.77, p < 0.02), implying the predominant influence of natural processes at Parg (photosynthesis with higher δ13C values and organic matter decomposition with lower δ13C values). A decreasing trend of δ13C values from Parg, through Gornje Jelenje to Rijeka is barely visible, and is the most distinguished in minimal values between Parg and the two other sites (Table 2; Table SM4). Although the mean δ13C values are not significantly different, seasonal fluctuation show differences. Compared to Parg, δ13CCO2 in Rijeka is lower during spring, summer and autumn, but statistically significantly only in September by –1.1‰ (z = 2.6) (Figure 4b; Table SM4). δ13CCO2 values at Gornje Jelenje are also lower compared to Parg within the same period as Rijeka, but none of these differences are significant. It is interesting that both, Rijeka and Gornje Jelenje, have significantly higher δ13CCO2 for 1‰ (z = 2.4 and 2.6, respectively; Table SM4) compared to Parg in March which corresponds to Δ14CCO2 values drop (Figure 3a) explained earlier as CO2 photosynthesis uptake. The minima δ13C values were in January (Parg and Rijeka) and December (Gornje Jelenje) and maxima in September (Parg and Gornje Jelenje) and June (Rijeka) (Figure 4a; Table SM2). The spring and summer δ13C maxima reflect CO2 consumption and discrimination of 13C due to photosynthesis. Higher summer values at Parg and Gornje Jelenje compared to Rijeka may be attributed to geographical differences between sites: Parg belongs to the Dfb climate type, Gornje Jelenje to the Cfb while Rijeka to the Cfa climate. The described differences mean that photosynthetic activity at Parg and Gornje Jelenje begins later than in Rijeka. This trend is observed in Δ14C values of atmospheric CO2 and tree leaves. Decreasing of δ13C values from June to the end of the year could be connected to fossil fuel combustion from more intensive traffic in Rijeka, but contribution of soil respiration cannot be neglected and were confirmed by the maximum Δ14C value in Rijeka in September.
(a) δ13C in grab samples of atmospheric CO2 at three locations; (b) δ13C differences for the Rijeka and Gornje Jelenje sites and the clean-air Parg site; (c) δ13C vs. temperature.
The decrease in δ13C values at Parg and Gornje Jelenje starts later (in September) reflecting a shift in seasonal activity (start of respiration and decrease in photosynthetic activity). High late summer/autumn Δ14CCO2 values (Figure 3a) at Parg and Gornje Jelenje confirm soil respiration influence.
The δ13CCO2 and Δ14CCO2 values of each investigated site do not correlate to each other, however Parg shows the most similar behavior of δ13CCO2 and Δ14CCO2 values in year (Figures 3a and 4a). This corroborates the assumption that Parg is influenced mostly by natural processes. The δ13C and Δ14C differences relative to Parg (Figures 3b and 4b; Table 2) show that Rijeka and Gornje Jelenje are lower than Parg in both values throughout nearly the whole year. All three sites are affected by strong winds and the transport of atmospheric CO2 depleted in 13C from the sea towards the land, which contributes to the decrease in δ13CCO2 during late autumn/winter period (Figure 4a). The possible sea CO2 influence are also confirmed by lower winter Δ14CCO2 values (Figure 3a). However, there are no data for seasonal δ13C and Δ14C values of DIC from the Adriatic Sea necessary for interpretation of this influence. Additionally, the interpretation of CO2 sources on the basis of δ13C is more complicated due to the lack of δ13C differentiation between δ13CCO2 value derived from fossil fuel combustion and from plant respiration (C3 plants dominate in the Kvarner Gulf) and the lack of data for year 2021 for January and February.
A direct comparison of δ13C values with other locations in Europe in 2021 is not possible because there are no numerical data available. However, graphical data from GML indicate that all three investigated Croatian sites have lower δ13C values, ranging from −13.1 ± 0.7‰ to –10.5 ± 0.3‰. For same year, data from HUN (Hegyhatsal, Hungary), and HPB (Hohenpeissenberg, Germany) vary between –8.0‰ during the summer and –9.5‰ during the winter (numerical data were not available, so data were read from the graph from NOAA – GML 2023, Vaughn et al. Reference Vaughn, Evans, White, Still, Masarie and Turnbull2010). The δ13C data for JFJ station for 2017 has a mean value of –11.4 ± 0.7‰ (Levin and Hammer Reference Levin and Hammer2021). The difference in δ13CCO2 from 2017 to 2021 at Mauna Loa, Hawaii, USA (Scripps CO2 Program 2022) is only 0.06‰ (–8.54 ± 0.02‰ in 2017, –8.60 ± 0.02‰ in 2021) so we may approximate δ13C in 2021 for JFJ with the one from 2017. There is no significant difference between δ13C at all three investigated sites and approximate values from JFJ as z values between JFJ and Rijeka, Gornje Jelenje and Parg are 0.24, 0.11, and 0.01 respectively (Table SM6). Similar results of δ13CCO2, from –18.0‰ to –6.4‰, with an average of –11.7‰ were obtained in the Velenje Basin (9 locations) in 2011 and were explained by the influence of the largest thermal power plant in Slovenia (Kanduč Reference Kanduč2015).
CONCLUDING REMARKS
This paper presents the results of δ13C and Δ14C values of atmospheric CO2 at three experimental sites over a one-year period. The aim was to distinguish CO2 sources between the clean-air site Parg, the Gornje Jelenje site (in Risnjak National Park, in the vicinity of a main arterial road), and the port city of Rijeka, as Croatia’s tourism and seaport center of the northern Adriatic. The obtained results showed the trend of descending Δ14CCO2 from Parg through Gornje Jelenje towards Rijeka (from 0 to –22‰). A similar trend in Δ14C values was observed in leaves samples collected at the same locations, with decrease from Parg to Rijeka (2 ± 3‰ to –25 ± 7‰, respectively). Based on the assumption that the investigated area is under the influence of three sources of CO2 (fossil, sea/air exchange and biosphere) and that the difference between Parg and other the two sites is only due to fossil CO2, the approximate share of fossil CO2 in atmospheric CO2 was determined for urban Rijeka site (2.1 ± 1.3%) and Gornje Jelenje (1.0 ± 0.9%) using a Parg as the background level.
Δ14C values showed a seasonal pattern with lower autumn/winter values and higher spring/summer values, especially at Parg. Seasonality is expected due to natural influences. The Parg summer Δ14C values reached rather high peaks, not observed in any other EU monitoring station. A possible explanation for the high summer and autumn values is CO2 enriched with 14C transported from Adriatic Sea and released by soil respiration. The influence of anthropogenically enriched 14C sources cannot be totally excluded, due to the possibility of large air mass transportation from distant nuclear power plants.
There was no significant difference among mean δ13CCO2 values: –11.4 ± 0.7‰ Parg, –11.5 ± 0.8‰ Gornje Jelenje and –11.6 ± 0.7‰ Rijeka. The values are generally quite low, and very similar to those measured at JFJ in 2017. δ13C values for the station nearest to Croatia, Hegyhatsal, Hungary and Hohenpeissenberg, Germany for 2021 are significantly higher and vary between –8.0‰ during the summer and –9.5‰ during the winter. δ13C values showed an increase in spring and summer due to photosynthetic discrimination of isotopically lighter CO2 toward isotopically heavier CO2. Decrease of δ13C during winter is possible due to a 13C depleted CO2 transported from the sea by a strong wind, fossil fuel influence estimated from Δ14C and to soil respiration. However, differentiation of CO2 sources on the basis of δ13C values is not as clear as for Δ14C values as fossil fuel signal is the same as the fresh C3 biomass signal.
The significant differences in δ13C between European clean-air site Jungfraujoch and Mauna Loa indicates that it is very important to compare climatologically similar sites, whenever possible.
At the moment, none of the aforementioned possibilities can be clearly distinguished due to the short investigation period. However, it was shown that, in even a such a small experimental area as this one, investigation of isotopic composition of CO2 has great potential. For future research, clarification of sources of CO2 in atmosphere other phases (DIC(aq) – CO2(g)) of carbon cycling (e.g., vegetation, ocean) should be simultaneously traced. The impact of distant 14C sources from nuclear power plants should also be explored in more detail using transport models.
SUPPLEMENTARY MATERIAL
To view supplementary material for this article, please visit https://doi.org/10.1017/RDC.2023.72
ACKNOWLEDGMENTS
We would like to thank the Croatian Meteorological and Hydrological Service for meteorological data. We would also like to acknowledge the Slovenian Research Agency (ARRS) for Program funding P1-0143: “Cycling of substances in the environment, mass balances, modelling of the environmental processes and risk assessment.” We would also like to give special thanks to Stojan Žigon and Anita Rajtarić for their technical support in the laboratory. Finally, we would like to express gratitude to the two anonymous reviewers for their constructive comments, and to Prof. Zvjezdana Bencetić Klaić for fruitful discussion. The authors gratefully acknowledge the NOAA Air Resources Laboratory (ARL) for the provision of the HYSPLIT transport and dispersion model and/or READY website (https://www.ready.noaa.gov) used in this publication.
