Barbara Sensuła

Carbon Isotopes in Tree Rings: Climate and the Suess Effect Interferences in the Last 400 Years

New records of δ13C and ∆14C values in annual rings of pine and oak from different sites around the world were obtained with a time resolution of 1 yr. The results obtained for Europe (Poland), east Asia (Japan), and South America (Peru) are presented in this paper. The δ13C and radiocarbon concentration of α-cellulose from annual tree rings of pine and of the latewood of oak were measured by both accelerator mass spectrometry (AMS) and liquid scintillation spectrometry (LSC). The values of 14S, which represent decreasing 14C concentrations caused by the emission of CO2 from fossil fuel use (Suess effect; Suess 1955), were calculated for each site. Low average 14S (about -0.4 to 0.8%) values for clean areas and high values (about 3.4-3.6%) for industrial and/or urbanized areas were noted. Records of the δ13C values obtained for pine and oak from Poland were used to reconstruct climate changes during the last 400 yr. The results clearly indicate the climate cooling during the periods of the Maunder minimum (1645-1715) and the Dalton minimum (1790-1820). The anti-correlation between the δ13C and ∆14C records during those 2 periods is clear if the 14C record is shifted toward older ages by 24 yr.

First application of mass spectrometry and gas chromatography in investigation of α-cellulose hydrolysates: the influence of climate changes on glucose molecules in pine tree-rings.

We present the first results of the quantitative and qualitative gas chromatographic and isotope ratio mass spectrometric analysis of monosaccharides derived from acid hydrolysis of α-cellulose extracted from annual pine tree-rings. The conifers investigated in this study grew in the Niepolomice Forest in Poland, and the annual rings covered the time span from 1940 to 2000 AD. The main components of the α-cellulose samples were two saccharides: glucose and mannose. The amount of glucose in the annual rings varied between 17 and 44%. The δ(13)C of glucose was found to be less negative than that of α-cellulose and the δ(18)O values in glucose were less positive than those in α-cellulose. The content of monosaccharides in the α-cellulose samples has an influence on the isotope fractionation factors. The values of the carbon isotope fractionation factor increase with an increase in the monosaccharides concentration in α-cellulose, while the values of the oxygen isotope fractionation factor decrease with an increase in monosaccharides concentration in α-cellulose. The challenge is to establish, with respect to climate changes and environmental conditions, the significance of the interannual variations in the observed monosaccharide concentration.

Tree Growth and Climate Relationship: Dynamics of Scots Pine (Pinus Sylvestris L.) Growing in the Near-Source Region of the Combined Heat and Power Plant During the Development of the Pro-Ecological Strategy in Poland.

Since the 1990s, the emission of pollutants was reduced in a majority of Polish and developing country factories whereas the level of energy production was similar to that prior to the 1990s. The conifer investigated in this study has grown for many years under the stress of industrial pollution. Despite this, the trees are preserved, to a large extent, sensitive to the natural climatic factors. We present a complex analysis of the climatic (sunshine, temperature, precipitation, humidity, and wind circulation) and anthropogenic factors influencing the radial increment dynamics of Scots pine (Pinus sylvestris L.) growing in the vicinity of the combined heat and power station in Łaziska (Poland). We analyzed the spatiotemporal distribution of growth reductions, the depth of reduction with respect to the distance from the emitter, the relationship between tree growth and climate during the industry development period and during proecological strategy application . Samples of carbon isotopic composition in pine needles from 2012 to 2013 were additionally determined. Pines series of 3 positions indicate that they have a similar sensitivity to most climatic elements of the previous and given year, but there is also a different rhythm between the studied populations of incremental growth of pines. The causes of diversity are due to the different types of habitat (site types) and industrial pollution. The variation in carbon stable isotopic composition in pine needles was connected with an increase of CO2.

Carbon Isotope Composition of Atmospheric Carbon Dioxide in Southern Poland: Imprint of Anthropogenic CO2 Emissions in Regional Biosphere

Southern Poland is home to numerous large mining and energy industry facilities, which consume relatively great amounts of fossil fuels. Temporal and spatial distribution of CO2 emissions to the atmosphere were estimated on the basis of 13C and 14C isotope measurements in atmospheric CO2 and in -cellulose from pine tree rings. The Suess effect was evaluated in the atmospheric CO2 from the High Tatra Mountains (Kasprowy Wierch) and the urban area (Kraków), as well as in tree rings from Niepo≥omice Forest near Kraków. Two different models were used to estimate the emission component recorded in tree ring 13C on the background of climatic changes.

Influence of climate change on carbon and oxygen isotope fractionation factors between glucose and α-cellulose of pine wood

We present the first analysis of the influence of climate change on carbon and oxygen isotope fractionation factors for two saccharides (glucose and α-cellulose) of pine wood. The conifers grew in the Niepołomice Forest in Poland and the annual rings covered a time span from 1935 to 2000 AD. Glucose samples from acid hydrolysis of α-cellulose were extracted from annual tree rings. The carbon and oxygen isotope fractionation factors between glucose and α-cellulose were not stable over time. The mean value for the carbon isotope fractionation factors between glucose and α-cellulose was greater than unity. The mean value for the oxygen isotope fractionation factors between glucose and α-cellulose was lower than unity. We established, with respect to climate change, the significance of the interannual and intraannual variation in the carbon and oxygen isotope fractionation factors between both saccharides. We used moving interval correlation results for May of the previous year through September of the current year using a base length of 48 years. The relationship with summer temperature is the main climate signal in the carbon isotope fractionation factor between glucose and α-cellulose. The relationship with autumn sunshine is the main climate signal in the oxygen isotope fractionation factor between glucose and α-cellulose for the tree ring chronology.

Stable carbon isotopes of glucose received from pine tree-rings as bioindicators of local industrial emission of CO2 in Niepołomice Forest (1950–2000)

The mass spectrometric investigations of carbon isotope composition of glucose received from α-cellulose samples derived from Scots pine (Pinus sylvestris L.) growing in Niepołomice Forest were the main aim of this study. The annual rings covered the time span from 1950 to 2000. α-Cellulose samples were extracted from increment cores of four representative trees, and then acid hydrolysis was performed. The number of sunshine hours, thermal and pluvial conditions of the growing season and in the preceding months had a significant effect on pine. Also non-climatic factors, most likely by industrial pollution signal, have been recorded in the isotopic composition of glucose. The relationship between climatic conditions, carbon dioxide emission and annual tree-rings carbon isotopic composition was analysed, using methods of correlation and response function, and multiple regression function.

Spatial and Short-Temporal Variability of δ13C and δ15N and Water-Use Efficiency in Pine Needles of the Three Forests Along the Most Industrialized Part of Poland

In this study, stable carbon and nitrogen isotope ratios in the samples of pine needles collected in 2013 and 2014 from heavily urbanized area in close proximity to point-source pollution emitters, such as a heat and power plant, nitrogen plant, and steelworks in Silesia (Poland), were analyzed as bio-indicators of contemporary environmental changes. The carbon isotope discrimination has been proposed as a method for evaluating water-use efficiency. The measurement of carbon and nitrogen isotopes was carried out using the continuous flow isotope ratio mass spectrometer. The isotope ratio mass spectrometer allows the precise measurement of mixtures of naturally occurring isotopes. The δ15N values were calibrated relative to the NO-3 and USGS34 international standards, whereas the δ13C values were calibrated relative to the C-3 and C-5 international standards. The strong year-to-year correlations between the δ13C in different sampling sites, and also the inter-annual correlation of δ15N values in the pine needles at each of the investigated sampling sites confirm that the measured δ13C and δ15N and also intrinsic water-use efficiency (iWUE) trends are representative of the sampling site. Diffuse air pollution caused the variation in δ 13C, δ15N, and iWUE dependent on type of emitter, the localization in the space (distance and direction) from factories and some local effect of other human activities. The complex short-term variation analysis can be helpful to distinguish isotopic fractionation, which is not an effect explainable by climatic conditions but by the anthropogenic effect. Between 2012 and 2014, an increase in iWUE is observed at leaf level.

The Impact of Climate, Sulfur Dioxide, and Industrial Dust on δ18O and δ13C in Glucose from Pine Tree Rings Growing in an Industrialized Area in the Southern Part of Poland

The mass spectrometric analysis of the impact of sulfur dioxide and dust emission on carbon and oxygen stable isotopic compositions of glucose hydrolysed from α-cellulose samples extracted from Scots pine growing in the vicinity of “Huta Katowice” steelworks was the main aim of this study. The annual rings covered the time span from 1975 to 2012 AD. The relationships between climatic conditions, sulfur dioxide, and industrial dust emission and oxygen and carbon isotopic compositions were analyzed using correlation function methods. This study shows the first analysis of carbon and oxygen stable isotopes in glucose as the bio-indicators of CO2, sulfur dioxide, and industrial dust emission. The anticoincidence trend of δ18O and δ13C and dust and sulfur dioxide confirms that the decreases of dust and sulfur dioxide industrial emission increase δ18O and δ13C values in glucose.

Mass spectrometric study of glucose and cellobiose produced during enzymatic hydrolysis of α-cellulose extracted from oak late-wood annual rings

We present the first results concerning interannual variations in concentrations of glucose and cellobiose, obtained through enzymatic hydrolysis of alpha-cellulose. The alpha-cellulose was extracted from late-wood of oak. The tree-ring chronologies, wood components and their physical and chemical properties provide information about the ecosystem in which the tree grew, and thus information regarding climate variability and the impact of human activity in the past. The large molecular size and insolubility make it difficult to determine precisely the chemical and physical properties of the intact cellulose polymer. Enzymatic hydrolysis is the principal method of degradation of cellulose. In this study the feasibility has been examined of characterizing alpha-cellulose through analysis by mass spectrometry (MS) of the degradation products from hydrolysis. Degradation of alpha-cellulose was possible without using alkaline or acid buffers. Analysis by MS provided the opportunity to obtain information on the biodegradation of saccharides. The presence of cellobiose and glucose in the degradation product was evidenced by the mass spectra. We have compared the abundances of these glucose and cellobiose ions with carbon isotope ratios, the efficiency of extraction of alpha-cellulose from the wood and tree-ring width indices. The challenge is to establish, with respect to climate changes and environmental conditions, the significance of the variations from one year to another in the observed abundances of glucose and cellobiose ions.

VARIATIONS OF TREE RING WIDTH AND CHEMICAL COMPOSITION OF WOOD OF PINE GROWING IN THE AREA NEARBY CHEMICAL FACTORIES

Abstract This study reports the variation of tree-ring widths and annual variation of concentration of metals (Na, Mg, Fe, Ni, Cu, Zn, Pb) in pine growing nearby chemical factories. The conifers (Pinus silvestris L.) investigated in this study covered the time span from 1920s to 2010 AD. Tree-ring widths were measured, dated and rechecked using the COFECHA. Radial trace-element profiles were determined by Laser Ablation Inductively Coupled Plasma Mass Spectrometry. The combined usage of tree ring width and chemical composition of wood provides historic records of anthropogenic impact on the environment and allows identifying the behavior adaptation of trees to the pollution. Data of pine tree cores collected from the sites nearby chemical factories show increasing levels of pollution linked to the increasing of industrial activities in Poland and subsequent dust fallout around the site. This study evidences that tree rings can be used as archives of past environmental contamination.