Anna Smirnoff

Dendrogeochemical distinction between geogenic and anthropogenic emissions of metals and gases near a copper smelter

For countries where metal resources represent an important economic sector, one of the main challenges of environmental research is to distinguish between natural and anthropogenic accumulations of potentially toxic metals in mining districts. The present work aims to evaluate a new environmental monitoring tool combining dendrochronology with natural (Ca, Ca/Mn, δ13C) and anthropogenic (Cd, Pb, 206Pb/207Pb, 208Pb/206Pb) geochemical tracers in tree rings in such a region. We compare spruce trees sampled at a control site near Hudson Bay, with those sampled near the Horne smelter active since 1928 in Rouyn-Noranda. The first effect of smelter emissions is detected by the tree-ring carbon isotope records. The δ13C values obtained on trees near the smelter show major changes immediately after 1928. This is due to the presence of atmospheric SO2 which generates a rapid response of the foliar system. The Ca/Mn ratios in tree-ring pairs of 1936–1937 and younger suggest a SO2-related soil acidification. The concentrations in Cd and Pb show a major increase starting in 1944 which coincides with a decrease of the 206Pb/207Pb ratios. The smelter activities likely generated this increase and the apparent delay of 14 years may have been generated mainly by the residence time of metals in airborne particulates, the buffering effect of the soils and, to a lesser extent, perhaps by mobility of heavy metals in tree stems. The 206Pb/207Pb and 208Pb/206Pb ratios indicate that the growth rings contain at least three types of Pb: natural, derived from the mineral soil horizons; industrial, from coal burning urban pollution; and mining, typical of the volcanogenic massive sulphides treated at the Horne smelter. This new combination of natural and anthropogenic tracers allows recognition of the succession of atmospheric and pedogeochemical changes related to industrial activities in the Rouyn-Noranda mining area.

Is wood pre-treatment essential for tree-ring nitrogen concentration and isotope analysis?

Tree-ring nitrogen concentrations and isotope ratios (δ(15)N) are gaining in popularity for environmental research although their use is still debated because of nitrogen mobility in tree stems. Modern studies generally present results on wood that is pre-treated to remove soluble nitrogen compounds and to minimize the impact of radial translocation on tree-ring nitrogen environmental records. However, the necessity to use such pre-treatment has never been fully assessed. Here we compare the nitrogen concentrations and δ(15)N values of two wood preparation protocols applied to beech and red spruce tree rings for the removal of soluble compounds from ring pairs with non pre-treated tree rings. For both tree species, pre-treatment did not minimize the radial patterns of tree-ring nitrogen concentrations and the increasing concentration trends that are coincident with the heartwood-sapwood boundary. Therefore, even if the tree-ring nitrogen concentrations are slightly modified by pre-treatment, these concentrations are considered to reflect internal stem processes rather than environmental conditions in both species. The δ(15)N values were similar for untreated and pre-treated ring pairs, suggesting that wood pre-treatment did not substantially change the δ(15)N values and temporal trends in ring series. In addition, tree-ring δ(15)N series of untreated and pre-treated wood did not show any sign of influence of the heartwood-sapwood boundary in either tree species, indicating that nitrogen translocation did not generate significant isotopic fractionation. We therefore suggest that untreated ring δ(15)N values of beech and red spruce trees can be used for environmental research.

Isotopic Evidence for Oil Sands Petroleum Coke in the Peace-Athabasca Delta.

The continued growth of mining and upgrading activities in Canadas Athabasca oil sands (AOS) region has led to concerns about emissions of contaminants such as polycyclic aromatic hydrocarbons (PAHs). Whereas a recent increase in PAH emissions has been demonstrated within around 50 km of the main center of surface mining and upgrading operations, the exact nature of the predominant source(s) and the geographical extent of the deposition are still under debate. Here, we report a century-long source apportionment of PAHs using dual (δ(2)H, δ(13)C) compound-specific isotope analysis on phenanthrene deposited in a lake from the Athabasca sector of the Peace-Athabasca Delta situated ∼150 km downstream (north) of the main center of mining operations. The isotopic signatures in the core were compared to those of the main potential sources in this region (i.e., unprocessed AOS bitumen, upgrader residual coke, forest fires, coal, gasoline and diesel soot). A significant concurrent increase (∼55.0‰) in δ(2)H and decrease (∼1.5‰) in δ(13)C of phenanthrene over the last three decades pointed to an increasingly greater component of petcoke-derived PAHs. This study is the first to quantify long-range (i.e., >100 km) transport of a previously under-considered anthropogenic PAH source in the AOS region.

Combining tree-ring metal concentrations and lead, carbon and oxygen isotopes to reconstruct peri-urban atmospheric pollution

ABSTRACT In this study, we analysed the tree-ring metal concentrations and isotope ratios of five stands located in three contrasted settings to infer the diffuse air pollution history of the northern part of the Windsor–Québec City Corridor in eastern Canada. Tree-ring series show that the Cd and Zn accumulation rates were higher between 1960 and 1986 and that the long-term acidification of the soil (Ca/Al series) was likely induced by NO x and SO x deposition (δ15N and δ13C trends as proxy). The Pb concentrations and 206Pb/207Pb ratios indicate that the dominant source of lead from 1880 to the 1920s was the combustion of north-eastern American coal, which was succeeded by the combustion of leaded gasoline from the 1920s to the end of the 1980s. Our modelling approach allows separating the climatic and anthropogenic effects on the tree-ring δ13C and δ18O responses. Diffuse air pollution caused an enrichment in 13C in all stands and a decrease of the δ18O values only in three of the stands. This study indicates that dendrogeochemistry can show contrasted responses to environmental changes and that the combination of several independent indicators constitutes a powerful tool to reconstruct the air pollution history in the complex context of peri-urban regions.

Chapter 9 Air Quality Changes in an Urban Region as Inferred from Tree-Ring Stable Isotopes

Abstract This chapter constitutes the first assessment of δ 18 O values of stem cellulose as an indicator of stress for trees exposed to pollution, and of δ 13 C combined with δ 18 O values to evaluate the relative impact of changes in climatic conditions and in air quality in a peri-urban region. The results obtained near Montreal (Canada) indicate that δ 13 C and δ 18 O characteristics in pine ( Pinus spp.) trees record changes in air quality, whereas δ 13 C patterns clearly change in beech ( Fagus spp.) trees under stressed conditions. Therefore, dendro-isotopic analyses offer a potential method for detecting past changes in air quality and evaluating forest responses to pollution.

Stable isotopes of nitrate reflect natural attenuation of propellant residues on military training ranges.

Nitroglycerin (NG) and nitrocellulose (NC) are constituents of double-base propellants used notably for firing antitank ammunitions. Nitroglycerin was detected in soil and water samples from the unsaturated zone (pore water) at an active antitank firing position, where the presence of high nitrate (NO3(-)) concentrations suggests that natural attenuation of NG is occurring. However, concentrations alone cannot assess if NG is the source of NO3(-), nor can they determine which degradation processes are involved. To address this issue, isotopic ratios (δ(15)N, δ(18)O) were measured for NO3(-) produced from NG and NC through various controlled degradation processes and compared with ratios measured in field pore water samples. Results indicate that propellant combustion and degradation mediated by soil organic carbon produced the observed NO3(-) in pore water at this site. Moreover, isotopic results are presented for NO3(-) produced through photolysis of propellant constituents, which could be a dominant process at other sites. The isotopic data presented here constitute novel information regarding a source of NO3(-) that was practically not documented before and a basis to study the contamination by energetic materials in different contexts.

Membrane permeation continuous-flow isotope ratio mass spectrometry for on-line carbon isotope ratio determination

Gaseous membrane permeation (MP) technologies have been combined with continuous-flow isotope ratio mass spectrometry for on-line delta13C measurements. The experimental setup of membrane permeation-gas chromatography/combustion/isotope ratio mass spectrometry (MP-GC/C/IRMS) quantitatively traps gas streams in membrane permeation experiments under steady-state conditions and performs on-line gas transfer into a GC/C/IRMS system. A commercial polydimethylsiloxane (PDMS) membrane sheet was used for the experiments. Laboratory tests using CO2 demonstrate that the whole process does not fractionate the C isotopes of CO2. Moreover, the delta13C values of CO2 permeated on-line give the same isotopic results as off-line static dual-inlet IRMS delta13C measurements. Formaldehyde generated from aqueous formaldehyde solutions has also been used as the feed gas for permeation experiments and on-line delta13C determination. The feed-formaldehyde delta13C value was pre-determined by sampling the headspace of the thermostated aqueous formaldehyde solution. Comparison of the results obtained by headspace with those from direct aqueous formaldehyde injection confirms that the headspace sampling does not generate isotopic fractionation, but the permeated formaldehyde analyzed on-line yields a 13C enrichment relative to the feed delta13C value, the isotopic fractionation being 1.0026 +/- 0.0003. The delta13C values have been normalized using an adapted two-point isotopic calibration for delta13C values ranging from -42 to -10 per thousand. The MP-GC/C/IRMS system allows the delta13C determination of formaldehyde without chemical derivatization or additional analytical imprecision.