Long-term aerosol particle flux observations part I: Uncertainties and time-average statistics

Long-term eddy covariance particle flux measurements for the size range starting from 10 nm were performed at a boreal forest site in Southern Finland. The large variability in turbulent flux estimates is inherent to the particle flux observations and thus long-term particle flux measurements enable to obtain statistically significant results by a suitable averaging. The particle flux random errors were estimated and a parameterisation for the integral time scale of turbulent flux was proposed. Application of flux errors for classification according to statistical significance of single flux values leads to systematically different deposition estimates on ensemble average basis. This must be avoided for determination of unbiased average deposition fluxes. The role of storage term in particle deposition evaluation was analysed. It was empirically determined that the method of storage term estimation discussed by [Finnigan, J., 2006. The storage term in eddy flux calculations. Agric. Forest Meteorol., 136, 108–113.] is not sensitive to the selection of the concentration averaging window in both ends of the flux averaging period. It is argued that the storage change in real atmospheric conditions results from boundary layer development as well as source–sink activity and therefore the filtering effect arising from averaging the concentration is of less importance. Diurnal, seasonal and annual variability of particle fluxes was analysed and it was observed that particle deposition rates are higher in winter. More detailed analysis of functional dependencies of particle deposition on environmental factors as well as dependence on size will be done in the second part of the paper.     

Long-range transport episodes of fine particles in southern Finland during 1999–2007

The frequency, strength and sources of long-range transport (LRT) episodes of fine particles (PM_2.5) were studied in southern Finland using air quality monitoring results, backward air mass trajectories, remote sensing of fire hot spots, transport and dispersion modelling of smoke and chemical analysis of particle samples (black carbon, monosaccharide anhydrides, oxalate, succinate, malonate, SO₄^2?, NO₃^?, K⁺ and NH₄⁺). At an urban background site in Helsinki, the daily WHO guideline value (24-h PM_2.5 mean 25 μg m^?3) was exceeded during 1–7 LRT episodes per year in 1999–2007. The 24-h mean maximum concentrations varied between 25 and 49 μg m^?3 during the episodes, which was 3–6 times higher than the local mean concentration (8.7 μg m^?3) in 1999–2007. The highest particle concentrations (max. 1-h mean 163 μg m^?3) and the longest episodes (max. 9 days) were mainly caused by the emissions from open biomass burning, especially during springs and late-summers in 2002 and 2006. During the period 2001–2007, the satellite remote sensing of active fire hot spots and transport and dispersion modelling of smoke indicated that approximately half of the episodes were caused partly by the emissions from wildfires and/or agricultural waste burning in fields in Eastern Europe, especially in Russia, Belarus and Ukraine. Other episodes were mainly caused by the LRT of ordinary anthropogenic pollutants, e.g. from energy production, traffic, industry and wood combustion. During those ‘other episodes’, air masses also arrived from Eastern Europe, including Poland. The highest concentrations of biomass-burning tracers, such as monosaccharide anhydrides (levoglucosan + mannosan + galactosan) and K⁺, were observed during open biomass-burning episodes, but quite high values were also measured during some winter episodes due to wood combustion emissions. Our results indicate that open biomass burning in Eastern Europe causes high fine particle concentration peaks in large areas of Europe almost every year.     

Screening of halogenated aromatic compounds in some raw material lots for an aluminium recycling plant

Four samples of scrap raw materials for an aluminium recycling plant were screened for the occurrence of persistent halogenated aromatic compounds. The samples contained waste from handling of electric and electronic plastics, filter dust from electronic crusher, cyclone dust from electronic crusher and light fluff from car shredder. In our screening analyses, brominated flame retardants were observed in all samples. Polybrominated diphenyl ethers (PBDE) were identified in all samples in amounts of 245-67450 ng/g. The major PBDE congeners found were decabromo- and pentabromodiphenyl ethers. 1,1-bis(2,4,6-tribromophenoxy)ethane, hexabromobenzene, ethyl-pentabromobenzene, tetrabromobisphenol-A, pentabromotoluene and dimethyl tetrabromobenzene were observed in all scrap samples. The concentrations of PCBs, PCNs (polychlorinated naphthalenes) and nona- to undecachlorinated terphenyls in some of these scrap samples were remarkably high.     

Deposition of gamma emitters from Chernobyl accident and their transfer in lichen-soil columns

Lichen-soil column samples were taken from several locations in the Southern Finland between 1986 and 2006. Columns were divided into three parts, upper lichen, lower lichen and underlying soil, and their gamma emitting radionuclides, (134)Cs, (137)Cs, (103)Ru, (95)Zr, (106)Ru, (110m)Ag, (125)Sb and (144)Ce, were measured with gamma spectrometry. Deposition values were calculated as Bq/m(2) for each sampling site. Distribution of various radionuclides in the three compartments as a function of time was determined. Both effective and ecological half-lives of all radionuclides were calculated for upper lichen, whole lichen and whole lichen-soil column. A linear relation was derived between the physical half-lives and effective half-lives for whole lichen and for whole lichen-soil column. Reindeer meat activity concentrations of various radionuclides and ensuing radiation doses to reindeer-herding people were also estimated for a hypothetical case where a similar high radioactive pollution, as was taken place in the Southern Finland, would have occurred in the reindeer-herding areas in the Finnish Lapland.     

Temperature dependent properties of environmentally important synthetic musks

Environmental fate determining physical properties including their temperature dependence for five nitro musks and for seven polycyclic musks were estimated. The properties evaluated were vapor pressure in a solid and liquid state (PS and PL), solubility in water (S), Henry's law coefficient (H = PL/S) and log octanol-water partition coefficient (log KOW). Gas chromatography for starting values of vapor pressure estimation and HPLC experiments at 5-20 degrees C for comparison of the theoretical versus experimental solubilities in water were performed. The values of temperature (T) dependence coefficients (Ai and Bi) in equations: log (Property)i = Ai - Bi/T were determined. Values of properties were compared with literature-based data, and an example of their use in environmental hazard estimation by fate modeling was given.     

Roadside aerosol study using hygroscopic,organic and volatility TDMAs: Characterization and mixing state

Traffic-related aerosol particles are ubiquitous in the urban atmosphere. As they are produced at ground level, they can also cause adverse health effects to urban dwellers. However, knowledge of the formation, transformation and chemically resolved size distribution of urban ultrafine particles is incomplete. Thus, more of these measurements are needed for better assessment of ambient air quality and its potential health effects. The particle number concentration, aerosol black carbon (BC) concentration and size distribution of traffic-related aerosols were measured near two major roads in Kuopio, Finland, from 16 June to 5 July, 2004. Furthermore, the properties of roadside aerosol particles were examined with the Tandem Differential Mobility Analyzer technique (TDMA). A suite of TDMA instruments relying on water (hygroscopic TDMA) and ethanol (organic TDMA) condensation as well as heating (volatility TDMA) were deployed to study the composition of the nucleation and Aitken mode particles (D_p = 10–50 nm) formed from vehicle exhaust. The results show that a simple three-component model was able to reproduce characteristic insoluble, organic and water-soluble volume fractions. Insoluble constituents were dominant in the Aitken mode particles, whereas organic compounds dominated the nucleation mode sizes. On average, only a small volume fraction was water-soluble, but a clear external mixing was observed particularly when enough time was allowed after the tail pipe emissions. The contribution of the insoluble material was seen to increase as a function of particle size, being typically less than 10% at 10 nm and between 20 and 50% at 50 nm, in contrast to the organic fraction, which decreased from about 80% at nucleation mode size range to 50–60% at 50 nm.     

Aerosol Particle Number Concentration Measurements in Five European Cities Using TSI-3022 Condensation Particle Counter over a Three-Year Period during Health Effects of Air Pollution on Susceptible Subpopulations

Abstract

In this study, long-term aerosol particle total number concentration measurements in five metropolitan areas across Europe are presented. The measurements have been carried out in Augsburg, Barcelona, Helsinki, Rome, and Stockholm using the same instrument, a condensation particle counter (TSI model 3022). The results show that in all of the studied cities, the winter concentrations are higher than the summer concentrations. In Helsinki and in Stockholm, winter concentrations are higher by a factor of two and in Augsburg almost by a factor of three compared with summer months. The winter maximum of the monthly average concentrations in these cities is between 10,000 cm^-3 and 20,000 cm^-3, whereas the summer min is ?;5000–6000 cm^-3. In Rome and in Barcelona, the winters are more polluted compared with summers by as much as a factor of 4–10. The winter maximum in both Rome and Barcelona is close to 100,000 cm^-3, whereas the summer minimum is >10,000 cm^-3. During the weekdays the maximum of the hourly average concentrations in all of the cities is detected during the morning hours between 7 and 10 a.m. The evening maxima were present in Barcelona, Rome, and Augsburg, but these were not as pronounced as the morning ones. The daily maxima in Helsinki and Stockholm are close or even lower than the daily minima in the more polluted cities. The concentrations between these two groups of cities are different with a factor of about five during the whole day. The study pointed out the influence of the selection of the measurement site and the configuration of the sampling line on the observed concentrations.     

Effects of soil phosphorus status on environmental risk assessment of glyphosate and glufosinate-ammonium

The increased use of herbicides poses a risk to the aquatic environment. Easy and economical methods are needed to identify the fields where specific environment protection measures are needed. Phosphorus (P) and organophosphorus herbicides compete for the same adsorption sites in soil. In this study the relationship between P obtained in routine Finnish agronomic tests (acid ammonium acetate [P(AC)]) and adsorption of glyphosate and glufosinate-ammonium was investigated to determine whether P(AC) values could be used in the risk assessment. The adsorption of glyphosate ((N-(phosphonomethyl)glycine) and glufosinate-ammonium (2-amino-4-(hydroxymethylphosphinyl)butanoic acid) was studied in a clay and a sandy loam soil enriched with increasing amounts of P added as potassium dihydrogen phosphate. Desorption was also determined for some P-enriched soil samples. The adsorption of both herbicides diminished with increasing P(AC) value. The correlations between Freundlich adsorption coefficients obtained in the adsorption tests and P(AC) were nonlinear but significant (r > 0.98) in both soils. The exponential models of the relationship between soil P(AC) values and glyphosate adsorption were found to fit well to an independent Finnish soil data set (P < 0.1 for glyphosate and P < 0.01 for glufosinate-ammonium). The desorption results showed that glufosinate-ammonium sorption is not inversely related to soil P status, and the high correlation coefficients obtained in the test of the model were thus artifacts caused by an abnormal concentration of exchangeable potassium in soil. The solved equations are a useful tool in assessing the leaching risks of glyphosate, but their use for glufosinate-ammonium is questionable.