Scots pine needle surfaces on radial transects across the north boreal area of Finnish Lapland and the Kola Peninsula of Russia

To gain an understanding of the characteristics of the needle surfaces of naturally regenerated Scots pine (Pinus sylvestris L.) and their geographical distribution, eight physicochemical variables were investigated within the north boreal forest area. The visibly undamaged needles were collected in autumn 1990 from 114 plots (3-5 pines per plot) along radial transects from the Monchegorsk and Nikel smelters, emitting SO2 and heavy metals, on the Kola Peninsula, Russia, to Finnish Lapland. The needles were examined by scanning electron microscopy (SEM) and measured for surface wettability using the droplet contact angle (DCA) method. Significant geographical south-north and west-east patterns could be observed in needle surface characteristics, correlating with emissions from the smelters and to climate. Despite the slightly higher initial DCAs (61.4-87.6 degrees) towards the north, the pine needle surfaces of the northernmost transects exhibited higher annual needle wettability change (ANWC) and wax erosion rate (AWER), expressed as the reduction in DCAs and epistomatal wax tube distribution (WTD) during one year, respectively, but a lower occurrence of particles and fungal hyphae than those of more southern transects. The higher ANWC was related to higher atmospheric SO2 concentration, and to the lower long-term temperature sum, but not clearly to annual precipitation. In the Monchegorsk smelter area, the current needles exhibited, on average, a 15% higher WTD and seven degree larger DCA, resulting in more hydrophobic needle surfaces than in Finnish Lapland, but during their first year, both the AWER and ANWC, were greatly increased. In Finnish Lapland, 30%, of all the epistomatal wax tubes disappeared from the needle surface during the first year, the value being 70% for the pines located 8 km from the smelter. The mineral composition of the particles deposited on the needle surfaces mirrored that of the minerals being produced by the smelters (e.g. FexSx, CuFeS2, NixSx, FexOx). Stomatal densities were in the range of 71.1-141.7 stomata mm(-2). The lower densities of stomata on needles close to the smelters correlated with reduced number of needle age classes of the pines, higher dry weights, higher pollutant accumulation and lower Mn and Zn concentrations in the needles. The AWER and ANWC were able to indicate the most seriously deteriorated needle surfaces on a regional scale, e.g. including the surroundings of both smelters, although the plot-specific relationships between 'needle surface variables' and 'pollution variables' were generally weak. The present study showed that the exposure of pine needles to the combined effects of ambient pollutants and harsh climate led to a deterioration in the physicochemical characteristics of the epicuticular wax, which may have serious ecophysiological consequences in the long term.     

Occurrence and distribution of atmospheric organic micropollutants in conifer needles

The distribution of some chlorinated hydrocarbons(p,p′-DDT, p,p′-DDE,α-HCH,γ-HCH,HCB) in spruce (Picea abies) needles was investigated. A comparision of concentrations in the wax with that of the remaining needle and time-resolved washing of the needle-surface shows the distribution behaviour of these substances.     

Monitoring of air pollution by polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans of pine needles in Korea

The atmospheric contamination levels of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were evaluated from the analysis of pine needles in South Korea. Pine needles were collected from 30 sampling points at five main cities in South Korea (Busan, Daegu, Gwangju, Changwon and Jeju island). The highest concentrations of PCDDs/DFs (2.19–26.88 pg I-TEQ/g of dry weight) were measured at Busan, where is the city of the highest population density and traffic volume among five cities. The lowest concentration was detected at Jeju with 0.62 pg I-TEQ/g dry weight, suggesting Jeju could be an environmental background area in Korea. The dominant homologues of PCDDs/DFs in pine needles were the lower chlorine-substituted compounds such as tetra CDDs and CDFs, and the distribution ratios of PCDDs/DFs decreased with increase of the number of chlorine substituents. Homologue profiles of pine needle samples were similar to PCDDs/DFs profiles of the vapor phase in the ambient air, and thus the pine needles absorbed the vapor phase of PCDDs/DFs from air. Results suggested that pine needles could be used as an indicator of the atmospheric contamination for PCDDs/DFs in Korea.     

Chlorinated short chain aliphatic hydrocarbons in pine needles by purge and trap gas chromatography/mass spectrometry

The concentrations of volatile chlorinated short chain aliphatic hydrocarbons in pine needles have been measured using purge and trap GC/MS. The concentrations of dichloromethane, chloroform, dichloroethene and tetrachloroethene in the needles were calculated. The concentrations of dichloromethane and tetrachloroethene were highest. As a rule the concentrations were higher in the older needles. The needle samples were collected from five sampling points in an area situated in the Southern Finland in the vicinity of a metal scrab plant. Reference needles were collected in the Central Finland. Needles originated from years 1991, 1992 and 1993.     

Phosphorus loads from different urban storm runoff sources in southern China: a case study in Wenzhou City

Storm runoff from six types of underlying surface area during five rainfall events in two urban study areas of Wenzhou City, China was investigated to measure phosphorus (P) concentrations and discharge rates. The average event mean concentrations (EMCs) of total phosphorus (TP), total dissolved phosphorus (TDP), and particulate phosphorus (PP) ranged from 0.02 to 2.5 mg?·?L^?1, 0.01 to 0.48 mg?·?L^?1, and 0.02 to 2.43 mg?·?L^?1, respectively. PP was generally the dominant component of TP in storm runoff, while the major form of P varied over time, especially in roof runoff, where TDP made up the largest portion in the latter stages of runoff events. Both TP and PP concentrations were positively correlated with pH, total suspended solids (TSS), and biochemical oxygen demand (BOD)/chemical oxygen demand (COD) concentrations (p?<?0.01), while TDP was positively correlated with BOD/COD only (p?<?0.01). In addition, the EMCs of TP and PP were negatively correlated with maximum rainfall intensity (p?<?0.05), while the EMCs of TDP positively correlated with the antecedent dry weather period (p?<?0.05). The annual TP emission fluxes from the two study areas were 367.33 and 237.85 kg, respectively. Underlying surface type determined the TP and PP loadings in storm runoff, but regional environmental conditions affected the export of TDP more significantly. Our results indicate that the removal of particles from storm runoff could be an effective measure to attenuate P loadings to receiving water bodies.     

Haloacetic acids,phytotoxic secondary air pollutants

Haloacetic acids are atmospheric oxidation products of airborne C₂-halocarbons which are important solvents and propellants. Levels of trichloroacetate (TCA) in conifer needles from mountain ranges in Germany (Black Forest, Erzgebirge) and from two sites in Finland are compared; TCA is present in conifer needles at concentrations up to 0.7 μmol/kg, MCA up to 0.2 μmol/kg. At the Finnish sites, TCA-concentrations and branch degeneration symptoms of Scots pine are correlated. Monochloroacetate (MCA) has been determined in needle samples from Southern Germany in concentrations exceeding its phytotoxicity threshold towards photoautotrophic organisms. Data on atmospheric chloroacetate levels in Germany are also given; ambient air levels of chloroacetic acids range from about 2 pmol/m³ (TCA) to 390 pmol/m³ (MCA). TCA and dichloroacetic acid (DCA) arise from atmospheric oxidation of airborne C₂-chlorocarbons, while the source of MCA is not yet known; several tentative pathways are suggested.     

Biomonitoring airborne parent and alkylated three-ring PAHs in the Greater Cologne Conurbation I: Temporal accumulation patterns

Polycyclic aromatic hydrocarbons (PAHs) comprise an important group of air pollutants, with three-ring components (PAH-3) often dominating. Spatiotemporal variation in atmospheric PAH-3 can be analyzed by biomonitoring but high vapour pressure and low octanol-air-partitioning of PAH-3 cause dynamic accumulation on plant surfaces. This study for the first time shows that PAH-3 exhibit systematic accumulation trends on pine needles of 3-48 months of exposure time at six sites in Germany. Correlation of needle exposure time with PAH-3 concentration was r² = 0.83 for phenanthrene and methylphenanthrenes, r² = 0.77 for cyclopenta[def]phenanthrene, r² = 0.60 for dibenzothiophene, r² = 0.57 for dimethylphenanthrenes and r² = 0.32 for retene. Variations in PAH-3 for summer and winter collected needles emphasize vegetation-air-partitioning influence on cumulative PAH-3 loads. PAH-3 ratios calculated for needle cohorts indicate persistence of original PAH patterns thus demonstrating the source-diagnostic potential of pine needle biomonitoring, which is utilized in part II of this study where spatial distribution of PAH-3 is investigated and related to emission sources.     

Estimation of the annual scavenged amount of polycyclic aromatic hydrocarbons by forests in the Pearl River Delta of Southern China

Leaves of six main tree species from the Pearl River Delta (PRD) in Southern China were collected to identify the interspecific variability, the spatial variability and the seasonal variations of polycyclic aromatic hydrocarbons' (PAHs) concentrations, and to calculate the amount of PAHs removed by leaves. PAHs concentrations in pine needles were much higher than in broad-leaves and leaves from urban/industrial areas (Baiyunshan and Heshan) exhibited two times greater concentrations than leaves from the rural area (Dinghushan). Seasonal variations of PAHs in leaves occurred with lesser concentrations in September. Leaves in PRD scavenged 3.7 ± 0.9 t PAHs y⁻¹, accounting for about 10% of the total amount emitted in this region. This result suggests that forests play an important role in the fate of PAHs.     

Comprehensive assessment of pine needles as bioindicators of PAHs using multivariate analysis. The importance of temporal trends

The importance of the annual and seasonal trends associated to the polycyclic aromatic hydrocarbons (PAHs) biomonitoring by pine needles are studied with a comprehensive use of univariate and multivariate analysis tools. For this purpose, four pine needle sampling campaigns (winter, spring, summer and autumn 2007) were carried out in 29 sites from Portugal. Needles from Pinus pinaster Ait. and Pinus pinea L. trees were collected from all year-classes available in each tree, corresponding to the different shoots of needles coming out every spring and the results of both species were treated separately. Annual trends of polycyclic aromatic hydrocarbons (PAHs) contamination indicate a general increase from the least to the most exposed year-classes, for all seasons. The mean values for the sum of 16 PAHs ranged from 71 ± 33 ng g⁻¹ (dry weight – dw) for new year (2007) needles in the summer to 514 ± 317 ng g⁻¹ (dw) for 2-year needles (2005) in the spring for P. pinea, and between 90 ± 50 ng g⁻¹ (dw) for new year (2007) needles in the summer and 1212 ± 436 ng g⁻¹ (dw) for 3-year needles (2004) in summer for P. pinaster. The seasonal evolution shows the highest concentrations in the winter, then declining to the lowest levels in the summer and rising again from summer to autumn. Principal component analysis confirmed differences between seasons and needle year-classes, more visible for P. pinea samples. The cooler seasons have more affinity towards the lighter more abundant PAHs, as do the older needles. Differences between both pine species are also evident.     

Particle-size distribution and gas/particle partitioning of atmospheric polybrominated diphenyl ethers in urban areas of Greece

Ambient concentrations, gas/particle partitioning and particle-size distribution of polybrominated diphenyl ethers (PBDEs) were investigated in two urban areas (Athens and Heraklion) of Greece. Atmospheric (gas + particle) concentrations of ∑PBDE varied from 21 to 30 pg m⁻³ in the center of Athens and from 4 to 44 pg m⁻³ in the suburbs of Heraklion. A predominance of particulate PBDEs was observed in Athens (71-76% in particles), whereas the opposite was evident in Heraklion (69-92% in gas phase). In both urban areas, PBDE particle-size distribution featured a distinct enrichment in smaller particles. A similar trend was also observed in aerosols of a background marine site. For all sampling sites, more than 46% of ∑PBDE was associated with particles of <0.57 μm in diameter. Our results imply that particulate PBDEs may have long atmospheric residence time and they may be capable of reaching the deeper parts of the human respiratory system.     

Atmospheric polychlorinated biphenyl concentrations and apparent degradation in coastal New Jersey

To characterize the atmospheric dynamics and behavior of organic compounds in the NY–NJ Harbor Estuary, atmospheric concentrations of polychlorinated biphenyls (PCBs) were measured at coastal, suburban and urban sites in New Jersey in 1997–1999. ∑PCB concentrations at the suburban site varied from 86 to 2300 pg m⁻³ and from 84 to 1100 pg m⁻³ at the coastal site. Although the temporal trends of total concentrations were significantly different at the three sites (p<0.01), PCB congener profiles revealed similar patterns (r²>0.90, p<0.001) implicating a dominant emission type and/or process. Temperature explained >50% of the total variability in ln[PCB] at both sites. Atmospheric concentrations at the suburban site increased when winds blew from an eastnortheast vector, while increased wind speeds led to a slight dilution. Wind speed and direction were not significantly correlated with the concentrations measured at the coastal site. Temporal changes in congener distribution at the suburban site are consistent with the preferential atmospheric removal of 3–5 Cl-biphenyls by hydroxyl radical attack with estimated half-lives of 0.7–1.8 years.     

Biomonitoring of air quality in the Cologne Conurbation using pine needles as a passive sampler – Part III: Major and trace elements

We here report complementary trace element (Fe, Pb, Cd, Zn, Cr, Cu, Ni and sulfur) concentrations and ratios in pine needles collected in the urban area of Cologne, Germany. Potential element sources are discussed in conjunction with enviromagnetic and PAH data to evaluate air quality. Foliar trace element concentrations of Zn, Cr, Cu, Ni and sulfur are close to essential nutrient levels. Median concentrations of foliar Fe, Pb and Cd in Cologne are 132, 1.1, and 0.06 μg g^?1, respectively. Thus these elements are enhanced over biogenic background levels and show significant accumulation with needle exposure time. Foliar sulfur concentrations vary between 868 and 2076 μg g^?1 with a median value of 1409 μg g^?1, except for two locations where 2370 and 2379 μg g^?1 were observed. Cadmium serves as an indicator for local industrial emissions with short transport distances of only a few kilometres in Cologne City. Elevated Fe, Pb and Zn concentrations mark areas with higher traffic loads and agree with enhanced PAH burdens and magnetic susceptibility intensities of pine needles. Isopleths mapping and source differentiation of atmospheric pollutants using foliar trace elements is feasible. For temporal or spatial high-resolution studies more cost-effective environmental magnetics is recommended, which may guide in design of detailed studies aiming at identification and allocation of emission sources. Hereby, a combination of organic tracers (PAH), magnetic properties, and trace metals is considered most reliable.     

Spatial variability of arsenic concentration in soils and plants, and its relationship with iron, manganese and phosphorus

Spatial distribution of arsenic (As) concentrations of irrigation water, soil and plant (rice) in a shallow tube-well (STW) command area (8 ha), and their relationship with Fe, Mn and P were studied. Arsenic concentrations of water in the 110 m long irrigation channel clearly decreased with distance from the STW point, the range being 68-136 μg L⁻¹. Such decreasing trend was also noticed with Fe and P concentrations, but the trend for Mn concentrations was not remarkable. Concerning soil As, the concentration showed a decreasing tendency with distance from the pump. The NH₄-oxalate extractable As contributed 36% of total As and this amount of As was associated with poorly crystalline Fe-oxides. Furthermore only 22% of total As was phosphate extractable so that most of the As was tightly retained by soil constituents and was not readily exchangeable by phosphate. Soil As (both total and extractable As) was significantly and positively correlated with rice grain As (0.296 ± 0.063 μg g⁻¹, n = 56). Next to drinking water, rice could be a potential source of As exposure of the people living in the As affected areas of Bangladesh.     

Monitoring of air pollution by polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans of pine needles in Korea

The atmospheric contamination levels of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were evaluated from the analysis of pine needles in South Korea. Pine needles were collected from 30 sampling points at five main cities in South Korea (Busan, Daegu, Gwangju, Changwon and Jeju island). The highest concentrations of PCDDs/DFs (2.19–26.88 pg I-TEQ/g of dry weight) were measured at Busan, where is the city of the highest population density and traffic volume among five cities. The lowest concentration was detected at Jeju with 0.62 pg I-TEQ/g dry weight, suggesting Jeju could be an environmental background area in Korea. The dominant homologues of PCDDs/DFs in pine needles were the lower chlorine-substituted compounds such as tetra CDDs and CDFs, and the distribution ratios of PCDDs/DFs decreased with increase of the number of chlorine substituents. Homologue profiles of pine needle samples were similar to PCDDs/DFs profiles of the vapor phase in the ambient air, and thus the pine needles absorbed the vapor phase of PCDDs/DFs from air. Results suggested that pine needles could be used as an indicator of the atmospheric contamination for PCDDs/DFs in Korea.     

Relations between Scots pine needle element concentrations and decreased needle longevity along pollution gradients

Scots pine (Pinus sylvestris L.) shoots were sampled along transects near one urban pollution source and two smelters. Needle Mg, P and K concentrations decreased from the second to the fourth age class linearly with needle survival along the urban pollution gradient. Still, over 80% of the average concentration of these nutrients remained in the fourth needle age class. Decreased needle longevity was closely related to the increased heavy metal concentrations near the smelters. Near the urban pollution source, it was related to the increased annual needle mass and the increased needle nutrient concentrations. Decreased Mn accumulation along with needle age was detected near all pollution sources. Leaching of Mn from needles and especially from soil as a cause of decreased needle concentrations is discussed.     

Pine needles as passive bio-samplers to determine polybrominated diphenyl ethers

Eight polybrominated diphenyl ethers (PBDEs) were determined in pine needles of three species (Pinus halepensis, Pinus pinea and Pinus nigra) collected in the NE Spain in an attempt to use this matrix for the biomonitoring of airborne PBDEs. The method used was based in ultrasonic extraction followed by alumina and Florisil clean-up and determination by gas chromatography coupled to mass spectrometry in negative chemical ionization. Recoveries were between 99% and 138%, limits of detection between 0.011 and 0.070 ng g⁻¹-dw (0.232 ng g⁻¹-dw for BDE 209) and repeatability lower than 13%. PBDE levels ranged between 0.027 ng g⁻¹-dw and 13.04 ng g⁻¹-dw, with predominance of BDE 209, followed by BDEs 47. P. halepensis was the species with the highest PBDE levels and P. nigra, the least, according to their widespread and remote distribution, respectively. The presence of PBDEs in pine needles was attributed to the release of in-use PBDEs, transport through atmosphere and adsorption upon lipid rich pine needles. Given the easy collection of pine needles, its ample distribution and its potential to accumulate airborne contaminants, this matrix is proposed as passive bio-sampler to be used in PBDE monitoring programs.

Capsule

Pine needles can be used to biomonitor airborne PBDEs.     

Atmospheric Particulate Matter and Polycyclic Aromatic Hydrocarbons for PM10 and Size-Segregated Samples in Bangkok

Abstract

Air samples of particulate matter (PM) with an aerodynamic diameter less than 10 µm (PM₁₀) were collected from six sites in Bangkok, Thailand, using high-volume air samplers. Daily samples were taken at intervals of 12 days from November 1999 to November 2000. Size-selected sampling using a multislit Andersen size-fractionated cascade impactor was undertaken at one site in central Bangkok to identify particulate size distribution. The annual average PM₁₀ concentration at all six sites exceeded the Thailand National Ambient Air Quality Standard (NAAQS) of 50 µg/m³. The daily PM₁₀ concentrations at heavy traffic roadside areas ranged between 30 and 160 µg/m³. The highest PM₁₀ level occurred during the winter period (November–February), which is the dry season. From our results, which are based on a 1-yr survey, it can be observed that the particulate concentrations are associated with traffic volumes and seasonal factors (temperature and rainfall). The relative importance of size fractions in contributing to PM load is presented and discussed. Twenty polycyclic aromatic hydro-carbons (PAHs) associated with PM have been identified and quantified. The summed PAHs based on the 20 species had an average concentration of 60 ng/m³. Benzo(e)pyrene, indeno(123cd)pyrene, and benzo(ghi)perylene were the major compounds with average concentrations of 8, 10, and 13 ng/m³, respectively. Results indicate that more than 97% of PAHs were found in the small particulate size range of <0.95 µm.     

Rates of particulate pollution deposition onto leaf surfaces: Temporal and inter-species magnetic analyses

Evaluation of health impacts arising from inhalation of pollutant particles <10 μm (PM₁₀) is an active research area. However, lack of exposure data at high spatial resolution impedes identification of causal associations between exposure and illness. Biomagnetic monitoring of PM₁₀ deposited on tree leaves may provide a means of obtaining exposure data at high spatial resolution. To calculate ambient PM₁₀ concentrations from leaf magnetic values, the relationship between the magnetic signal and total PM₁₀ mass must be quantified, and the exposure time (via magnetic deposition velocity (MV_d) calculations) known. Birches display higher MV_d (∼5 cm⁻¹) than lime trees (∼2 cm⁻¹). Leaf saturation remanence values reached ‘equilibrium’ with ambient PM₁₀ concentrations after ∼6 ‘dry’ days (<3 mm/day rainfall). Other co-located species displayed within-species consistency in MV_d; robust inter-calibration can thus be achieved, enabling magnetic PM₁₀ biomonitoring at unprecedented spatial resolution.     

Urban scale modeling of particle number concentration in Stockholm

A three-dimensional dispersion model has been implemented over the urban area of Stockholm (35×35 km) to assess the spatial distribution of number concentrations of particles in the diameter range 3–400 nm. Typical number concentrations in the urban background of Stockholm is 10 000 cm⁻³, while they are three times higher close to a major highway outside the city and seven times higher within a densely trafficked street canyon site in the city center. The model, which includes an aerosol module for calculating the particle number losses due to coagulation and dry deposition, has been run for a 10-day period. Model results compare well with measured data, both in levels and in temporal variability. Coagulation was found to be of little importance in terms of time averaged concentrations, contributing to losses of only a few percent as compared to inert particles, while dry deposition yield particle number losses of up to 25% in certain locations. Episodic losses of up to 10% due to coagulation and 50% due to deposition, are found some kilometers downwind of major roads, rising in connection with low wind speed and suppressed turbulent mixing. Removal due to coagulation and deposition will thus be more significant for the simulation of extreme particle number concentrations during peak episodes.The study shows that dispersion models with proper aerosol dynamics included may be used to assess particle number concentrations in Stockholm, where ultrafine particles principally originate from traffic emissions. Emission factors may be determined from roadside measurements, but ambient temperature must be considered, as it has a strong influence on particle number emissions from vehicles.     

Organohalogenated compounds in pine needles from Beijing city, China

Pine needles collected from 22 sites of six areas in Beijing city, China, were analyzed by instrumental neutron activation analysis (INAA) combined with organic extraction for extractable organohalogens (EOX) and extractable persistent organohalogens (EPOX). The concentrations of EOX (EOX = ECl + EOBr + EOI) were in the order of EOCl > EOBr > EOI. About 1.6-34% of EOCl remained as extractable persistent organochlorine (EPOCl) after treatment with concentrated sulfuric acid, which suggested that major fractions of EOCl in pine needles were an acid-liable or acid-soluble fraction. The fact that pine needle contained higher EOCl contents in chemical industrial and traffic hub areas indicated that chemical industries and exhaust emission from vehicle were the main sources of organochlorines in the Beijing's air. The relative proportions of the known organochlorines (such as HCHs, DDTs, chlordanes, HCB and PCBs) to total EOCl and EPOCl were 0.32-0.76% and 2.5-11.4%, respectively, which implied that a major portion of the EOCl and EPOCl measured in pine needles was unknown. The organochlorinated pesticides (OCPs) and PCBs concentrations in six areas were as follows: sigma HCH (sigma HCH = alpha- + beta- + gamma- + delta-HCH), 11.7-20.8 ng/g; sigma DDT (p,p'-DDT + p,p'-DDE + p,p'-DDD), 12.5-113.3 ng/g; hexachlorobenzene (HCB), 1.1-5.3 ng/g; sigma chlordane (cis-chlordane + trans-chlordane + heptachlor), 1.7-9.5 ng/g, sigma PCB, 41.8-270.5 ng/g, on dry weight basis. The samples from chemical industrial area and residential area nearby chemical industries contained the highest concentrations of sigma DDT, HCB, sigma chlordane and sigma PCB, while the contamination levels of most OCPs and PCBs in iron-steel industrial area were the lowest. The ratios of alpha/gamma-HCH (ranged from 0.9-1.5) and p,p'-DDT/DDTs (ranged from 72.1% to 91.0%) revealed the presence of the recent use of lindane and DDTs or impure dicofol in Beijing.