Anatomical and morphological changes in Pinus sylvestris and Larix sibirica needles under impact of emissions from a large aluminum enterprise.

Species-specific anatomical and morphological characteristics of Pinus sylvestris and Larix sibirica needles were studied at different levels of tree stand pollution by aluminum smelter emissions. The anatomical characteristics of the needle were studied using light microscopy. The level of tree stand pollution was determined using the cluster analysis outcomes of the pollutant elements content (fluorine, sulfur, and heavy metals) in the needles. Four levels of tree stand pollution were separated: low, moderate, high, and critical, as well as background tree stand in unpolluted areas. It was found that the state of tree phytomass deteriorated with increasing levels of pollution (from low to critical): pine crown defoliation increased to 85%, and larch defoliation increased to 65%. The life span of pine needles was reduced to 2-3 years, with a background value of 6-7 years. The change of morphological parameters was more pronounced in P. sylvestris: the weight and length of the 2-year-old shoot decreased by 2.7-3.1 times compared to the background values; the weight of needles on the shoot and the number of needle pairs on the shoot-by 1.9-2.1 times. The length of the needle and shoot and the number of L. sibirica brachyblasts decreased by 1.8-1.9 times. The anatomical parameters of the needle also changed to a greater extent in P. sylvestris. Up to the high level of tree pollution, we observed a decrease in the cross-sectional area of the needle, central cylinder, vascular bundle, area and thickness of mesophyll, number and diameter of resin ducts by 18-66% compared to background values. At the critical pollution level, when the content of pollutant elements in pine needles reached maximum values, the anatomical parameters of the remaining few green needles were close to background values. In our opinion, this may be due to the activation of mechanisms aimed at maintaining the viability of trees. A reduction in thickness and area of assimilation tissue in the L. sibirica needle was detected only at the critical pollution level. An upward trend in these parameters was found at low, medium, and high pollution levels of tree stand, which may indicate an adaptive nature. The results suggested that at a similar pollution level of trees, the greatest amount of negative anatomical and morphological changes were recorded in pine needles, which indicates a greater sensitivity of this species to technogenic emissions.

Activity of low-molecular weight components of Larix sibirica antioxidant system under exposure to technogenic pollution.

Changes in the antioxidant protection system of Larix sibirica Ledeb at different pollution levels caused by emissions from a large aluminum smelter (BrAS) have been studied. We revealed that the content of peroxide (H2O2) in the needles is a reliable marker of oxidative stress in the trees under pollution. The crucial role of non-enzymatic components, in particular, proline, phenolic compounds, ascorbic acid, glutathione, in reducing the level of free radicals in the needles cells was found. Proline concentration in the needles significantly rises with the increase in pollution levels from low to high. Under critical level pollution, it decreases by 40% compared to the background. The total content of ascorbic acid (ASC) in the needles of polluted trees varies slightly; however, there are significant changes in its various forms. With an increase in pollution to a high level, the content of the reduced form of ASC in the needles increases by 1.5-2.9 times compared to the background content. At a critical level of pollution, the total level of ascorbic acid and its reduced form falls, the content of the oxidized form reaches minimum values. The total content of phenolic compounds in the needles increased by 50-55%, concentration of flavonoids by 1.5-1.8 times, catechins by 1.9-2.5 times, proanthocyanidins by 45% compared to the background level under low, moderate, high pollution, whereas under critical pollution their content decreased. The absolute concentration of the reduced form glutathione in the needles falls by 1.9-3.0 times, the oxidized form increases by 1.5-2.0 times compared to the background. The ratio of reduced glutathione to oxidized glutathione decreased, especially during critical pollution. The data obtained show significant activation of Siberian larch biochemical protection at low, moderate and high levels of pollution by the aluminum smelter emissions. At a critical levels of contamination, a significant depletion of the pool of low-molecular antioxidants was observed.

Changes in the fatty acid composition of pine needle lipids under the aluminum smelter emissions.

Changes in the fatty acid (FA) composition of total lipids of Pinus sylvestris needles at different pollution levels caused by emissions from a large aluminum smelter (BrAS) have been studied. In the needles of trees from unpolluted (background) territories, the FA spectrum is represented by 24 acids with prevalence of unsaturated FAs (71.6%). The main unsaturated FA are represented by oleic (C18: 1ω9), linoleic (C18: 2ω6), and α-linolenic (C18: 3ω3) acids. Under the influence of BrAS emissions, the total amount of identified FAs in the needles and the proportion of unsaturated FAs decrease, while the fraction of saturated FAs, on the contrary, increases from 25.4% in unpolluted needles to 33.2% in polluted ones. The content of palmitic FA (C16:0) in the needles exceeds background values by 1.5 times, behenic acid (C22:0) - by 1.6-2.5 times, arachidic acid (C20:0) - by 1.5 times, palmitic margaric acid (C17:0) - by 1.5-2.3 times. These FAs play the important role in the protection of plant membranes from the effects of abiotic stress factors, making them less permeable. The sum of short-chain saturated FAs (C12:0, C14:0, C15:0) increase by 4.8 times in needles of trees that are highly polluted. Pentadecanoic (C15:0) acid is found in the needles only in the background areas and at the low pollution level. With a more severe pollution, C15:0 is not identified, but lauric acid with the cis-configuration of double bonds in the structure (izo-C12:0) appears. The presence of "relict" ∆5-polymethylene FAs in the composition of pine needle membrane lipids is determined. In the background areas, they account for 12.9% of the total FAs. With the industrial pollution intensification, their total content increases and reaches 14.1%. ∆5-polymethylene FAs are also able to protect membranes against negative influences. Thus, changes in the quantitative and qualitative FA composition of pine needle total lipids indicate the activation of the stabilization mechanisms of membrane lipids due to their tight packing in a bilayer. It is one of the adaptive reactions of Pinus sylvestris in response to the impact of the aluminum industry emissions.

Diversity and negative effect of PM0.3-10.0 adsorbed by needles of urban trees in Irkutsk, Russia.

The study was performed in natural forests preserved within the Boreal zone city, Irkutsk, Russia. Test sites were selected in the forests in different districts of the city, where samples of Scots pine (Pinus sylvestris L.) and Siberian larch (Larix sibirica Ledeb.) needles were taken to study the adsorption on their surface of aerosol particles of different sizes, in microns: PM0.3, PM0.5, PM1, PM2.5, PM5, PM10. Scanning electron microscopy was used to obtain high-resolution photographs (magnification 800- × 2000, × 16,000) and aerosol particles (particulate matter-PM) were shown to be intensively adsorbed by the surface of needles, with both size and shape of the particles characterized by a wide variety. Pine needles can be covered with particles of solid aerosol by 50-75%, stomata are often completely blocked. Larch needles often show areas, which are completely covered with aerosol particles, there are often found stomata deformed by the penetration of PMx. X-ray spectral microanalysis showed differences in the chemical composition of adsorbed PMx, the particles can be metallic if metals predominate in their composition, carbonaceous-in case of carbon predominance-or polyelemental if the composition is complex and includes significant quantities of other elements besides metals and carbon (calcium, magnesium, potassium, sodium, sulfur, chlorine, fluorine). Since the particles contain a large proportion of technogenic pollutants, accumulation by the needles of some widespread pollutants was investigated. A direct correlation of a highly significant level between the concentration of PMx in the air and the accumulation of many heavy metals in pine and larch needles, as well as sulfur, fluorine, and chlorine, has been revealed, which indicates a high cleaning capacity of urban forests. At the same time, the negative impact of PMx particles on the vital status of trees is great, which shows in intense disturbance of the parameters of photosynthesis and transpiration, leading to a significant decrease in the growth characteristics of trees and reduction in the photosynthetic volume of the crowns. We consider that the results obtained are instrumental in developing an approach to improvement of urban forests status and creating a comfortable urban environment for the population.

The effect of aluminum smelter emissions on nutritional status of coniferous trees (Irkutsk Region, Russia).

Element contents in assimilation organs of trees are an essential component of a comprehensive forest condition diagnosis. They allow conclusions about the current nutritional status of trees and estimate the main risks for a sustainable forest ecosystem management in the future. The purpose of this research was to study the effect of highly aggressive fluorine-containing emissions from a large aluminum smelter on the nutritional status of coniferous trees Larix sibirica and Pinus sylvestris. Studies carried out in the background areas showed that the both species have the main part of the elements in optimal quantities. A deficiency is noted for potassium. The content of N, K, Mg, Na, S, F, Cu, Co, and Cd in L. sibirica needles was 1.2-5.2 times higher than in P. sylvestris needles. Under the influence of the aluminum smelter emissions, fluorine concentration in the tree needles increases by 13.8-30.0 times; sulfur by 2.9-3.6 times; heavy metals by 2.0-5.1 times; and nitrogen, calcium, magnesium, and sodium by 1.2-3.6 times, especially in the industrial zone and 5 km far from it. With the increasing distance from the smelter, the content of pollutants in the tree needles decreases. Values close to background are observed at a distance of over 40 km. According to index biogeochemical transformation, the elemental composition of P. sylvestris needles undergoes greater changes than L. sibirica ones under the influence emissions from the aluminum smelter. Changes in the element concentration of the tree needles caused by the impact of industrial emissions lead to a restructuring of the elements accumulation rows, as well as to a violation of the element quantitative ratios. Change of N:P:K, Ca:K, Ca:P, P:S, P:F, Mn:F, and Mn:Fe ratios points to serious nutrient imbalances in coniferous trees, which may reduce their vitality and growth in the long run.

Ecological condition of natural forests located within the territory of a large industrial center, Eastern Siberia, Russia.

Forest surveys were conducted in 2015-2018 on 12 sample plots (SPs), located in different districts of the city of Bratsk, a large industrial center of Eastern Siberia. The ecological state of natural forests preserved within the city's territory was estimated by a set parameters of pine (Pinus sylvestris L.) trees, understory vegetation, moss-and-lichen cover, and soil. Significant changes in the parameters caused by technogenic pollution and a high recreational load on the soil cover have been revealed. The high level of technogenic pollution of urban forests is evidenced by the accumulation of pollutants (sulfur, heavy metals, PAH) in the needles of pine trees and soil horizons, changes in the ratios of elements-pollutants and elements-nutrients in plants and soils, shift in the acid-base balance of the soil solution to alkalinity. A high recreational load on urban forest soils is indicated by many negative changes: a decrease in the thickness of the forest litter or its complete destruction; violation of the natural structure of the upper horizons due to increase in physical clay content, stony content, and anthropogenic inclusions; significant increase in soil density, and decrease in humidity, porosity, and aeration. The impact of a complex of negative factors also leads to a decrease in the species diversity of the understory vegetation, mosses, lichens, and an increase in the number of ruderal species in the herbaceous vegetation. The biggest negative changes in the parameters of forest ecosystems have been found in Tsentralny district of the city, located in close proximity (from 2 to 8 km) to a large aluminum smelter and timber industry complex. Less-pronounced negative changes in parameters were found in samples taken in the Padunsky district, located 25 km from the emission source, and the smallest changes in the parameters were found in Pravoberezhny district, 45 km away from the emission sources. The main recommendations for improving the condition of forests in all areas of the city are as follows: planning a road-path network, restoring the fertile soil layer, sodding open areas of soil with herbaceous vegetation, and selecting an assortment of trees and shrub plants that are resistant to industrial pollution and recreational stress.

Contamination of Scots pine forests with polycyclic aromatic hydrocarbons on the territory of industrial city of Siberia, Russia.

Anthropogenic contamination with polycyclic aromatic hydrocarbons (PAH) coming from a powerful aluminum smelter has been estimated by the accumulation of these substances (17 substances: phenanthrene, fluoranthene, pyrene, chrysene, acenaphthylene, acenaphthene, anthracene, fluorene, benz[а]anthracene, benz[b]fluoranthene, benz[k]fluoranthene, benz[а]pyrene, benz[е]pyrene, perylene, indeno[1,2,3-c,d]pyrene, benz[g,h,i]perylene, dibenz[a,h]anthracene) in needles of Scots pine (Pinus sylvestris L.) in the residential areas of Bratsk, East Siberia, Russia. It has been found that the total PAH amount reaches the maximum values (982 ng/g) in the needles of trees growing in a residential zone, remote from the smelter up to 10 km (Central Urban District), where more than half of the city's population lives. On the territory remote up to 25 km (Padunsky District), PAH needle levels decline, but are still 14.5-17.5 times higher than the background ones and at a distance of 45 km (Pravoberezhny District), they still exceed background levels (30 ng/g) by 4.7-8.1 times. Qualitative analysis of PAH showed the prevalence (up to 90% of the total amount) of 3-4 ring PAHs in pine needles on the entire studied territory. PAH concentrations increase when approaching the smelter with the highest values in the Central City District. Within the urban area, the content of PAHs with 5-6 rings (benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene (B[a]P), benz[a]anthracene, dibenz[a,h]anthracene, indeno[1,2,3-c,d]pyrene, benzo[g,h,i]perylene) is also significantly increased. In the Central District, needle concentration of B[a]P, which is a class 1 carcinogen, exceeds the background one by 22 times, the Padunsky District-by 7 times, and the Pravoberezhny District-by 3 times. In the territories of the Central Districts, needle level of perylene, which is a marker of territory pollution by aluminum smelter emissions, is 18 times, the Padunsky District-by 10 times, Pravoberezhny District-by 2.5-3 times higher than in the background, where the perylene level is below the detection limit (< 0.2 ng/g).

Pinus sylvestris as a bio-indicator of territory pollution from aluminum smelter emissions.

The study demonstrates the efficiency of using Pinus sylvestris L. as a bio-indicator of polluting substances that enter the environment with the emission of a large aluminum smelter. Recent research has demonstrated that pollution from aluminum smelter emissions covers a vast territory. The highest content of polluting elements is registered at a distance of 3 km from the smelter, with maximum concentrations found in the industrial zone (0.5 km from the smelter). The farther from the aluminum smelter, the lower the amount of polluting elements in the needles, although the F level still exceeds the background values at a distance of about 60 km from the source, the levels of Zn, Pb, and Cd up to 50 km, S up to 40 km, and Fe and Cu up to 35 km mostly in north-eastern and south-eastern directions correlating with prevailing atmospheric transfer of the emissions. Pollution with polycyclic aromatic hydrocarbons (PAHs) is also most expressed at a distance of 3 km from the smelter, then it gradually decreases to coincide with background concentrations at a distance of more than 60 km. This is confirmed by changes in overall PAH content and in qualitative and quantitative compositions of individual PAHs. The greatest number of components (17 substances) has been found in samples from the territory of the plant area: phenanthrene, fluoranthene, pyrene, chrysene, acenaphthylene, acenaphthene, anthracene, fluorene, benz[а]anthracene, benz[b]fluoranthene, benz[k]fluoranthene, benz[а]pyrene, benz[е]pyrene, perylene, indeno[1,2,3-c,d]pyrene, benz[g,h,i]perylene, and dibenz[a,h]anthracene. The farther away from the plant, the lower the number of components detected in PAH fraction, mainly due to the fact that the concentrations of most toxic PAHs with five or six aromatic rings (benz[b]fluoranthene, benz[k]fluoranthene, benz[а]pyrene, benz[е]pyrene, perylene, indeno[1,2,3-c,d]pyrene, benz[g,h,i]perylene, dibenz[a,h]anthracene) fall below the method detection limit. High concentrations of benz[а]pyrene and perylene in pine needles at the territories adjacent to the aluminum smelter confirm the technogenic character of forest pollution by PAHs.