Fingerprinting Organofluorine Molecules via Position-Specific Isotope Analysis.

Organofluorine substances are found in a wide range of materials and solvents commonly used in industry and homes, as well as pharmaceuticals and pesticides. In the environment, organofluorine molecules are now recognized as an important class of anthropogenic pollutants. Fingerprinting organofluorine compounds via their carbon isotope ratios (13C/12C) is crucial for correlating molecules with their source. Here we apply a 19F nuclear magnetic resonance spectroscopy (NMR) technique to obtain the first position-specific carbon isotope ratios for a diverse set of organofluorine molecules. In contrast to traditional isotope ratio mass spectrometry, the 19F NMR method provides 13C/12C isotope ratios at each carbon position where a C-F bond is present, and does not require fragmentation or combustion to CO2, overcoming challenges posed by the robust C-F covalent bonds. The method was validated with 2,2,2-trifluoroethanol, and applied to analyze heptafluorobutanoic acid, 5-fluorouracil and fipronil. Results reveal distinct intramolecular carbon isotope distributions, enabling differentiation of chemically identical molecules. Notably, the NMR method accurately analyzes carbon isotopes within target molecules despite impurities. Potential applications include the detection of counterfeit products and drugs, and ultimately pollution tracking in the environment.

Variations in water use efficiency and carbon and nitrogen concentrations in red heart Chinese fir.

Temperature can significantly (P < 0.05) affect plant growth by modifying water use strategies, which are determined by intrinsic water use efficiency (WUEi). Red Heart Chinese Fir (Cunninghamia lanceolata) is one of the most important ecological and economic plantation species in China. However, the C. lanceolata water use strategy in response to increased temperatures and uneven temporal distribution of precipitation during the growing season is rarely reported. In a 7-year-old C. lanceolata plantation, differences in WUEi and C and N concentrations in different organs were analysed by anova, and the δ13C stable isotope, C, and N concentrations in stems determined at different tree heights. Stepwise regression and variance inflation factor were used to remove autocorrelated factors, and structural equation modelling was then used to explore relationships between WUEi and climate and biological factors. WUEi differed significantly between leaf and branch at different standardized precipitation evapotranspiration indices (SPEI). WUEi and N concentration decreased with age. The highest WUEi in branches and leaves were 92.7 and 88.4 µmol·mol-1 in 2020 (SPEI = 0.00), respectively. δ13C increased with relative tree height but N concentration and C/N ratio were not affected. Air temperatures has increased in between 2014 and 2020. WUEi and N concentration decreased with increasing branch and leaf age, but C concentration increased. SPEI significantly positively affected WUEi (P < 0.05), and WUEi was significantly negatively related to C concentration, which is consistent with the trade-off between C and water.

GasanalyzeR: advancing reproducible research using a new R package for photosynthesis data workflows.

The analysis of photosynthetic traits has become an integral part of plant (eco-)physiology. Many of these characteristics are not directly measured, but calculated from combinations of several, more direct, measurements. The calculations of such derived variables are based on underlying physical models and may use additional constants or assumed values. Commercially available gas-exchange instruments typically report such derived variables, but the available implementations use different definitions and assumptions. Moreover, no software is currently available to allow a fully scripted and reproducible workflow that includes importing data, pre-processing and recalculating derived quantities. The R package gasanalyzer aims to address these issues by providing methods to import data from different instruments, by translating photosynthetic variables to a standardized nomenclature, and by optionally recalculating derived quantities using standardized equations. In addition, the package facilitates performing sensitivity analyses on variables or assumptions used in the calculations to allow researchers to better assess the robustness of the results. The use of the package and how to perform sensitivity analyses are demonstrated using three different examples.

Isotopic study of honey documents widespread plant uptake of old carbon in North America.

A comprehensive understanding of carbon cycling pathways in the soil-plant system is needed to develop models that accurately predict global carbon reservoir responses to anthropogenic perturbations. Honey is a carbon-rich natural food produced by wild and managed pollinating insects all over the world; the composition of a single sample is a function of millions of pollinator-plant interactions. We studied the 13C/12C and Δ14C of 121 honey samples sourced from the United States, and found a significant older carbon contribution. The effect is observed from 25 to 45° latitude, not correlated with 13C/12C, and consistent with a previously published study on European honeys. In specific cases, the measured values were up to 20 ‰ (Δ14C) higher than the expected atmospheric 14CO2 value for the given year, which shows a significant older carbon contribution. We hypothesize that the older carbon is from plant liquids derived in part from soil carbon or stored nonstructural carbohydrates from plants, which shifts the calibrated age of the sample by 5 years or more. Our work is the first to describe the widespread occurrence of older carbon in honey and shows that radiocarbon measurements can be a powerful tool to trace carbon allocations in terrestrial food webs and detect the atmosphere-soil-plant carbon cycle contributions.

Ebullition dominates methane emissions in stratified coastal waters.

Coastal areas are an important source of methane (CH4). However, the exact origins of CH4 in the surface waters of coastal regions, which in turn drive sea-air emissions, remain uncertain. To gain a comprehensive understanding of the current and future climate change feedbacks, it is crucial to identify these CH4 sources and processes that regulate its formation and oxidation. This study investigated coastal CH4 dynamics by comparing water column data from six stations located in the brackish Tvärminne Archipelago, Baltic Sea. The sediment biogeochemistry and microbiology were further investigated at two stations (i.e., nearshore and offshore). These stations differed in terms of stratification, bottom water redox conditions, and organic matter loading. At the nearshore station, CH4 diffusion from the sediment into the water column was negligible, because nearly all CH4 was oxidized within the upper sediment column before reaching the sediment surface. On the other hand, at the offshore station, there was significant benthic diffusion of CH4, albeit the majority underwent oxidation before reaching the sediment-water interface, due to shoaling of the sulfate methane transition zone (SMTZ). The potential contribution of CH4 production in the water column was evaluated and was found to be negligible. After examining the isotopic signatures of δ13C-CH4 across the sediment and water column, it became apparent that the surface water δ13C-CH4 values observed in areas with thermal stratification could not be explained by diffusion, advective fluxes, nor production in the water column. In fact, these values bore a remarkable resemblance to those detected below the SMTZ. This supports the hypothesis that the source of CH4 in surface waters is more likely to originate from ebullition than diffusion in stratified brackish coastal systems.

The long and tortuous path towards improving photosynthesis by engineering elevated mesophyll conductance.

The growing demand for global food production is likely to be a defining issue facing humanity over the next 50 years. To tackle this challenge, there is a desire to bioengineer crops with higher photosynthetic efficiencies, to increase yields. Recently, there has been a growing interest in engineering leaves with higher mesophyll conductance (gm), which would allow CO2 to move more efficiently from the substomatal cavities to the chloroplast stroma. However, if crop yield gains are to be realised through this approach, it is essential that the methodological limitations associated with estimating gm are fully appreciated. In this review, we summarise these limitations, and outline the uncertainties and assumptions that can affect the final estimation of gm. Furthermore, we critically assess the predicted quantitative effect that elevating gm will have on assimilation rates in crop species. We highlight the need for more theoretical modelling to determine whether altering gm is truly a viable route to improve crop performance. Finally, we offer suggestions to guide future research on gm, which will help mitigate the uncertainty inherently associated with estimating this parameter.

Position-specific carbon stable isotope analysis of glyphosate: isotope fingerprinting of molecules within a mixture.

Glyphosate [N-(phosphonomethyl) glycine] is a widely used herbicide and a molecule of interest in the environmental sciences, due to its global use in agriculture and its potential impact on ecosystems. This study presents the first position-specific carbon isotope (13C/12C) analyses of glyphosates from multiple sources. In contrast to traditional isotope ratio mass spectrometry (IRMS), position-specific analysis provides 13C/12C ratios at individual carbon atom positions within a molecule, rather than an average carbon isotope ratio across a mixture or a specific compound. In this work, glyphosate in commercial herbicides was analyzed with only minimal purification, using a nuclear magnetic resonance (NMR) spectroscopy method that detects 1H nuclei with bonds to either 13C or 12C, and isolates the signals of interest from other signals in the mixture. Results demonstrate that glyphosate from different sources can have significantly different intramolecular 13C/12C distributions, which were found to be spread over a wide range, with δ13C Vienna Peedee Belemnite (VPDB) values of -28.7 to -57.9‰. In each glyphosate, the carbon with a bond to the phosphorus atom was found to be depleted in 13C compared to the carbon at the C2 position, by 4 to 10‰. Aminomethylphosphonic acid (AMPA) was analyzed for method validation; AMPA contains only a single carbon position, so the 13C/12C results provided by the NMR method could be directly compared with traditional isotope ratio mass spectrometry. The glyphosate mixtures were also analyzed by IRMS to obtain their average 13C/12C ratios, for comparison with our position-specific results. This comparison revealed that the IRMS results significantly disguise the intramolecular isotope distribution. Finally, we introduce a 31P NMR method that can provide a position-specific 13C/12C ratio for carbon positions with a C-P chemical bond, and the results obtained by 1H and 31P for C3 carbon agree with one another within their analytical uncertainty. These analytical tools for position-specific carbon isotope analysis permit the isotopic fingerprinting of target molecules within a mixture, with potential applications in a range of fields, including the environmental sciences and chemical forensics.

Effect of light-induced changes in leaf anatomy on intercellular and cellular components of mesophyll resistance for CO2 in Fagus sylvatica.

Mesophyll resistance for CO2 diffusion (rm) is one of the main limitations for photosynthesis and plant growth. Breeding new varieties with lower rm requires knowledge of its distinct components. We tested new method for estimating the relative drawdowns of CO2 concentration (c) across hypostomatous leaves of Fagus sylvatica. This technique yields values of the ratio of the internal CO2 concentrations at the adaxial and abaxial leaf side, cd/cb, the drawdown in the intercellular air space (IAS), and intracellular drawdown between IAS and chloroplast stroma, cc/cbd. The method is based on carbon isotope composition of leaf dry matter and epicuticular wax isolated from upper and lower leaf sides. We investigated leaves from tree-canopy profile to analyse the effects of light and leaf anatomy on the drawdowns and partitioning of rm into its inter- (rIAS) and intracellular (rliq) components. Validity of the new method was tested by independent measurements of rm using conventional isotopic and gas exchange techniques. 73% of investigated leaves had adaxial epicuticular wax enriched in 13C compared to abaxial wax (by 0.50‰ on average), yielding 0.98 and 0.70 for average of cd/cb and cc/cbd, respectively. The rIAS to rliq proportion were 5.5:94.5% in sun-exposed and 14.8:85.2% in shaded leaves. cc dropped to less than half of the atmospheric value in the sunlit and to about two-thirds of it in shaded leaves. This method shows that rIAS is minor but not negligible part of rm and reflects leaf anatomy traits, i.e. leaf mass per area and thickness.

Leakage of old carbon dioxide from a major river system in the Canadian Arctic.

The Canadian Arctic is warming at an unprecedented rate. Warming-induced permafrost thaw can lead to mobilization of aged carbon from stores in soils and rocks. Tracking the carbon pools supplied to surrounding river networks provides insight on pathways and processes of greenhouse gas release. Here, we investigated the dual-carbon isotopic characteristics of the dissolved inorganic carbon (DIC) pool in the main stem and tributaries of the Mackenzie River system. The radiocarbon (14C) activity of DIC shows export of "old" carbon (2,380 ± 1,040 14C years BP on average) occurred during summer in sampling years. The stable isotope composition of river DIC implicates degassing of aged carbon as CO2 from riverine tributaries during transport to the delta; however, information on potential drivers and fluxes are still lacking. Accounting for stable isotope fractionation during CO2 loss, we show that a large proportion of this aged carbon (60 ± 10%) may have been sourced from biospheric organic carbon oxidation, with other inputs from carbonate weathering pathways and atmospheric exchange. The findings highlight hydrologically connected waters as viable pathways for mobilization of aged carbon pools from Arctic permafrost soils.

Major sources of sinking particulate organic matter in the western Bay of Bengal.

Impacts of river discharge on coastal ocean processes are multi-dimensional. Studies on sinking particle fluxes, composition and their seasonal variability in coastal oceans are very limited. In this study, we investigated the impact of river discharge on seasonal variability in sinking fluxes of total mass, biogenic and lithogenic material in a river-dominated continental margin, western coastal Bay of Bengal. Higher POC, lithogenic and total mass fluxes were found during early southwest monsoon, and are decoupled with peak river discharge and elevated primary production. It is attributed to cross-shelf transport of re-suspended surface sediments from shelf region. Peak river discharge followed by elevated chlorophyll-a suggest nutrients supply though river discharge support primary production. Elemental C:N ratios, δ13C and δ15N results likely suggest that both marine and terrestrial sources contributed to sinking POM, . Overall, higher sinking fluxes during southwest monsoon than rest of the year suggest that seasonal river discharge exerts considerable impact on sinking fluxes in the western coastal Bay of Bengal.

Carbon cycle perturbations and environmental change of the middle permian and Late Triassic Paleo-Antarctic circle.

During the middle Permian through the Triassic, Tasmania moved from paleo-latitudes of 78° to 69°S, wedged between Antarctica and Australia, within the paleo-South polar circle. During this time, significant global carbon cycle disturbances triggered major environmental and climatic changes and mass extinction events globally. The Bicheno-5 core from Eastern Tasmania, Australia, provides the opportunity to examine middle Permian and Upper Triassic sediments from the paleo-Antarctic, using high-resolution organic carbon isotope (δ13CTOC) chemostratigraphy, pXRF, and sedimentology, combined with new palynological data integrated with the existing radiometric age model. While there is a significant unconformity in the Upper Permian to the middle Triassic associated with eustatic sea-level fall as a result of regional uplift in eastern Australia, three distinct carbon isotope excursions (CIEs), characterized by negative shifts of up to - 6 ‰ were identified; the middle Permian Guadalupian Carbon Isotope Excursions (G-CIE), the Carnian Pluvial Episode (CPE), and the mid-Norian Event (MNE). These three events highlight a significant climate shift through glacial and interglacial cycles to warmer non-glacial intervals in the Late Triassic, with evidence of the polar record of the Carnian Pluvial Episode and the mid-Norian Event, which are poorly studied in the Southern Hemisphere, specifically within the Paleo-Antarctic circle.

Linking African herbivore community enamel isotopes and environments: challenges, opportunities, and paleoecological implications.

Paleoenvironmental reconstructions of fossil sites based on isotopic analyses of enamel typically rely on data from multiple herbivore taxa, with the assumption that this dietary spectrum represents the community's isotopic range and provides insights into local or regional vegetation patterns. However, it remains unclear how representative the sampled taxa are of the broader herbivore community and how well these data correspond to specific ecosystems. Verifying these underlying assumptions is essential to refining the utility of enamel isotopic values for paleoenvironmental reconstructions. This study explores potential links between modern herbivore community carbon isotopic enamel spectra, biome types, and climate in sub-Saharan Africa. This region is one of the most comprehensively isotopically sampled areas globally and is of particular relevance to hominin evolution. Our extensive data compilation reveals that published enamel isotopic data from sub-Saharan Africa typically sample only a small percentage of the taxa documented at most localities and that some biome types (e.g., subtropical savannas) are dramatically overrepresented relative to others (e.g., forests) in these modern data sets. Multiple statistical analyses, including linear models and cluster analyses, revealed weak relationships of associated mammalian herbivore enamel isotopic values, biome type, and climate parameters. These results confound any simple assumptions about how community isotopic profiles map onto specific environments, highlighting the need for more precise strategic approaches in extending isotopic frameworks into the past for paleoecological reconstructions. Developing more refined modern analogs will ultimately allow us to more accurately characterize the isotopic spectra of paleo-communities and link isotopic dietary signatures to specific ecosystems.

Impacts of elevated CO2 levels and temperature on photosynthesis and stomatal closure along an altitudinal gradient are counteracted by the rising atmospheric vapor pressure deficit.

The efficiency of water use in plants, a critical ecophysiological parameter closely related to water and carbon cycles, is essential for understanding the interactions between plants and their environment. This study investigates the effects of ongoing climate change and increasing atmospheric CO2 concentration on intrinsic (stomata-based; iWUE) and evaporative (transpiration-based; eWUE) water use efficiency in oak trees along a naturally small altitudinal gradient (130-630 m a.s.l.) of Vihorlat Mountains (eastern Slovakia, Central Europe). To assess changes in iWUE and eWUE values over the past 60 years (1961-2020), stable carbon isotope ratios in latewood cellulose (δ13Ccell) of annually resolved tree rings were analyzed. Such an approach was sensitive enough to distinguish tree responses to growth environments at different altitudes. Our findings revealed a rising trend in iWUE, particularly in oak trees at low and middle altitudes. However, this increase was negligible at high altitudes. Warmer and drier conditions at lower altitudes likely led to significant stomatal closure and enhanced efficiency in photosynthetic CO2 uptake due to rising CO2 concentration. Conversely, the increasing intracellular-to-ambient CO2 ratio (Ci/Ca) at higher altitudes indicated lower efficiency in photosynthetic CO2 uptake. In contrast to iWUE, eWUE showed no increasing trends over the last 60 years. This suggests that the positive impacts of elevated CO2 concentrations and temperature on photosynthesis and stomatal closure are counteracted by the rising atmospheric vapor pressure deficit (VPD). These differences underscore the importance of the correct interpretation of stomata-based and transpiration-based WUEs and highlight the necessity of atmospheric VPD correction when applying tree-ring δ13C-derived WUE at ecosystem and global levels.

Variable carbon isotope fractionation of photosynthetic communities over depth in an open-ocean euphotic zone.

Marine particulate organic carbon (POC) contributes to carbon export, food webs, and sediments, but uncertainties remain in its origins. Globally, variations in stable carbon isotope ratios (δ13C values) of POC between the upper and lower euphotic zones (LEZ) indicate either varying aspects of photosynthetic communities or degradative alteration of POC. During summertime in the subtropical north Atlantic Ocean, we find that δ13C values of the photosynthetic product phytol decreased by 6.3‰ and photosynthetic carbon isotope fractionation (εp) increased by 5.6‰ between the surface and the LEZ-variation as large as that found in the geologic record during major carbon cycle perturbations, but here reflecting vertical variation in δ13C values of photosynthetic communities. We find that simultaneous variations in light intensity and phytoplankton community composition over depth may be important factors not fully accounted for in common models of photosynthetic carbon isotope fractionation. Using additional isotopic and cell count data, we estimate that photosynthetic and non-photosynthetic material (heterotrophs or detritus) contribute relatively constant proportions of POC throughout the euphotic zone but are isotopically more distinct in the LEZ. As a result, the large vertical differences in εp result in significant, but smaller, differences in the δ13C values of total POC across the same depths (2.7‰). Vertical structuring of photosynthetic communities and export potential from the LEZ may vary across current and past ocean ecosystems; thus, LEZ photosynthesis may influence the exported and/or sedimentary δ13C values of both phytol and total organic carbon and affect interpretations of εp over geologic time.

Invasive Japanese beetle (Popillia japonica Newman) larvae alter structure and carbon distribution in infested surface soil.

Invasive macrofauna influence the biophysical state and function of soil, helping to drive ecological changes over time. Many soil-dwelling invertebrates affect soil stability by facilitating or hindering the soil aggregation process, changing the availability of plant and soil organic matter (SOM) for aggregate incorporation, and shifting the predominant mechanisms by which carbon is incorporated into soil aggregates. Using mass fractionation and stable carbon isotope techniques, this 17-month experimental study examined silt-clay-loam mesocosms either infested or not infested with soil-dwelling larvae of the invasive Japanese beetle, Popillia japonica Newman (JB). We hypothesized that larval root-herbivory would promote a pathway of large aggregate formation that features the mixing of digested root tissue with mineral soil and subsequent fecal deposition. These newly deposited, large soil aggregates will then grow by agglomeration of particles, thereby occluding a larger pool of fresh organic carbon, or be broken apart, exposing fresh organic inputs to microbial activity and mineralization processes, depending on soil conditions. Findings show a proportional increase of larger soil size fractions (2- 8 mm) in the rhizosphere of infested soil after 1½ life cycles of the beetle, but a decrease in the smaller soil size fractions (0.053-2 mm). In infested bulk surface soil (0-2.5 cm) carbon increased, primarily due to greater carbon content in the largest size fractions. Carbon also increased in all size fractions, although the proportion of total carbon in fractions was greater only in the largest fractions due to their greater relative abundance. There may also be an increase of microbially derived carbon in the largest size fractions, possibly indicating significant priming effects associated with JB larval herbivory. The implications of these findings for relative stabilization of the bulk surface soil carbon pool in JB-infested soil likely depends on the residence time of, and stable microaggregate formation within these large size fractions.

Uncoupling of stomatal conductance and photosynthesis at high temperatures: mechanistic insights from online stable isotope techniques.

The strong covariation of temperature and vapour pressure deficit (VPD) in nature limits our understanding of the direct effects of temperature on leaf gas exchange. Stable isotopes in CO2 and H2 O vapour provide mechanistic insight into physiological and biochemical processes during leaf gas exchange. We conducted combined leaf gas exchange and online isotope discrimination measurements on four common European tree species across a leaf temperature range of 5-40°C, while maintaining a constant leaf-to-air VPD (0.8 kPa) without soil water limitation. Above the optimum temperature for photosynthesis (30°C) under the controlled environmental conditions, stomatal conductance (gs ) and net photosynthesis rate (An ) decoupled across all tested species, with gs increasing but An decreasing. During this decoupling, mesophyll conductance (cell wall, plasma membrane and chloroplast membrane conductance) consistently and significantly decreased among species; however, this reduction did not lead to reductions in CO2 concentration at the chloroplast surface and stroma. We question the conventional understanding that diffusional limitations of CO2 contribute to the reduction in photosynthesis at high temperatures. We suggest that stomata and mesophyll membranes could work strategically to facilitate transpiration cooling and CO2 supply, thus alleviating heat stress on leaf photosynthetic function, albeit at the cost of reduced water-use efficiency.

Sources and transport of CO2 in the karst system of Jiguan Cave, Funiu Mountains, China.

Conveyance and modification of carbon-isotope signals within the karst system remain difficult to constrain, due to the complexity of interactions between multiple components, including precipitation, bedrock, soil, atmosphere, and biota. Cave monitoring is thus critical to understanding both their transport in the karst system and dependence on local hydroclimatic conditions. Jiguan Cave, located in Funiu Mountain in central China, is representative of karst tourist caves with relatively thin epikarst zone. We conducted a comprehensive monitoring program of cave climate from 2018 to 2021 and measured δ13C during 2021 in monthly and heavy-rainfall samples of soil CO2, cave CO2, cave water (drip water and underground river), and underground river outlet. Our results demonstrate synchronous variations between CO2 concentration and δ13CCO2 in both soil and cave air on seasonal time scales. Cave pCO2 and carbon-isotope composition further exhibited a high sensitivity to human respiration with fluctuations of ~2000-3000 ppm within 4 days during the cave closure period in July 2021 without tourists. 13C-depleted isotopic signal of cave air in summer is the mixture of human respiration and soil CO2 which varies as a function of regional hydrological conditions of the summer monsoon during the rainy season with high temperatures and humidity. However, respired CO2 from the overlying soil was expected to be the only principal source of the cave CO2 when the anthropogenic CO2 source was removed. The high seasonal amplitude of cave air δ13CCO2 reflects ventilation dynamics, which leads to a prominent contribution from the external atmosphere during winter. Intriguingly, although the δ13C signal reflects complex vertical processes in the vertical karst profile, a heavy summer rainfall event was related to anomalously high δ13C values of cave water that can be utilized to interpret rainfall intensity and regional hydroclimate.

Neighbourhood species richness and drought-tolerance traits modulate tree growth and δ13 C responses to drought.

Mixed-species forests are promoted as a forest management strategy for climate change adaptation, but whether they are more resistant to drought than monospecific forests remains contested. In particular, the trait-based mechanisms driving the role of tree diversity under drought remain elusive. Using tree cores from a large-scale biodiversity experiment, we investigated tree growth and physiological stress responses (i.e. increase in wood carbon isotopic ratio; δ13 C) to changes in climate-induced water availability (wet to dry years) along gradients in neighbourhood tree species richness and drought-tolerance traits. We hypothesized that neighbourhood species richness increases growth and decreases δ13 C and that these relationships are modulated by the abiotic (i.e. climatic conditions) and the biotic context. We characterised the biotic context using drought-tolerance traits of focal trees and their neighbours. These traits are related to cavitation resistance versus resource acquisition and stomatal control. Tree growth increased with neighbourhood species richness. However, we did not observe a universal relief of water stress in species-rich neighbourhoods. The effects of neighbourhood species richness and climate on growth and δ13 C were modulated by the traits of focal trees and the traits of their neighbours. At either end of each drought-tolerance gradient, species responded in opposing directions during dry and wet years. We show that species' drought-tolerance traits can explain the strength and nature of biodiversity-ecosystem functioning relationships in experimental tree communities experiencing drought. Mixing tree species can increase growth but may not universally relieve drought stress.

Source apportionment of suspended particulate matter (PM1, PM2.5 and PM10) collected in road and tram tunnels in Krakow, Poland.

Here, we present the results of a comprehensive study of air quality in two tunnels located in the city of Krakow, southern Poland. The study comprised three PM fractions of suspended particulate matter (PM1, PM2.5 and PM10) sampled during campaigns lasting from March 14 to April 24, 2016 and from June 28 to July 18, 2016, in the road tunnel and the tram tunnel, respectively. The collected samples had undergone comprehensive chemical, elemental and carbon isotope analyses. The results of these analyses gave the basis for better characterization of urban transport as a source of air pollution in the city. The concentrations of particulate matter varied, depending on the analysed PM fraction and the place of sampling. For the tram tunnel, the average concentrations were 53.2 µg·m-3 (PM1), 73.8 µg·m-3 (PM2.5), 96.5 µg·m-3 (PM10), to be compared with 44.2 µg·m-3, 137.7 µg·m-3, 221.5 µg·m-3, respectively, recorded in the road tunnel. The isotope-mass balance calculations carried out separately for the road and tram tunnel and for each PM fraction, revealed that 60 to 79% of carbon present in the samples collected in the road tunnel was associated with road transport, to be compared with 15-33% obtained in the tram tunnel. The second in importance were biogenic emissions (17-21% and 41-49% in the road and tram tunnel, respectively. Sixteen different polycyclic aromatic hydrocarbons (PAHs) have been identified in the analysed samples. As expected, much higher concentrations of PAHs were detected in the road tunnel when compared to the tram tunnel. Based on the analysed PAHs concentrations, health risk assessment was determined using 3 different types of indicators: carcinogenic equivalent (CEQ), mutagenic equivalent (MEQ) and toxic equivalent (TEQ).

Isotopic measurements of carbon dioxide: the role of measurement science and standards.

Isotopic measurements provide valuable information about the origin of greenhouse gases - as carbon dioxide levels increase, there is a corresponding shift towards lighter isotopic composition similar to that of fossil fuels. Detecting such isotopic shifts, however, requires extremely precise measurements, which must also be globally reproducible in order to make reliable policy decisions. This feature article outlines the collective search for the ideal standard for carbon isotope measurements since the 1950s. This tragicomedy of errors, if you wish, has strengthened the reliability of today's measurements and has taken us from fictional oceans, to toilet seat marbles, and complex mathematical conventions that separate data from reliable results.