Anna-Lea Rantalainen

Does urban vegetation mitigate air pollution in northern conditions

It is generally accepted that urban vegetation improves air quality and thereby enhances the well-being of citizens. However, empirical evidence on the potential of urban trees to mitigate air pollution is meager, particularly in northern climates with a short growing season. We studied the ability of urban park/forest vegetation to remove air pollutants (NO2, anthropogenic VOCs and particle deposition) using passive samplers in two Finnish cities. Concentrations of each pollutant in August (summer; leaf-period) and March (winter, leaf-free period) were slightly but often insignificantly lower under tree canopies than in adjacent open areas, suggesting that the role of foliage in removing air pollutants is insignificant. Furthermore, vegetation-related environmental variables (canopy closure, number and size of trees, density of understorey vegetation) did not explain the variation in pollution concentrations. Our results suggest that the ability of urban vegetation to remove air pollutants is minor in northern climates.

Critical evaluation of screening techniques for emerging environmental contaminants based on accurate mass measurements with time-of-flight mass spectrometry.

Emerging contaminants from wastewater effluent samples were analysed, using posttarget and nontarget analysis techniques. The samples were analysed with an ultra performance liquid chromatograph-time-of-flight mass spectrometer (UPLC-TOF-MS), and the resulting data were processed with commercial deconvolution software. The method works well for posttarget analysis with prior information about the retention times of the compounds of interest. With positive polarity, 63 of 66 compounds and with negative polarity, 18 of 20 compounds were correctly identified in a spiked sample, while two compounds of a total of 88 fell out of the mass range. Furthermore, a four-stage process for identification was developed for the posttarget analysis lacking the retention time data. In the process, the number of candidate compounds was reduced by using the accurate mass of selected compounds in two steps (stages 1 and 2), structure-property relationships (stage 3) and isotope patterns of the analytes (stage 4). The process developed was validated by analysing wastewater samples spiked with 88 compounds. This procedure can be used to gain a preliminary indication of the presence of certain analytes in the samples. Nontarget analysis was tested by applying a theoretical mass spectra library for a wastewater sample spiked with six pharmaceuticals. The results showed a high number of false identifications. In addition, manual processing of the data was considered laborious and ineffective. Finally, the posttarget analysis was applied to a real wastewater sample. The analysis revealed the presence of six compounds that were afterwards confirmed with standard compounds as being correct. Three psycholeptics (nordiazepam, oxazepam and temazepam) could be tentatively identified, using the identification process developed. Posttarget analysis with UPLC-TOF-MS proved to be a promising method for analysing wastewater samples, while we concluded that the software for nontarget analysis will need improvement before it can be used in environmental analytical work with LC-TOF-MS systems.

Urban snow indicates pollution originating from road traffic

Traffic is a major source of pollutants in cities. In this well-replicated study we analysed a broad array of contaminants in snowpacks along roads of different traffic intensities. The majority of pollutants showed a similar pattern with respect to traffic intensity: pH and conductivity as well as concentrations of PAHs, total suspended solids, phosphorus and most heavy metals were higher next to high intensity roads compared to low intensity roads. These pollutant levels also decreased considerably up to 5 m distance from the roads. Furthermore, apart from nitrogen, these variables increased in concentration from control sites in urban forest patches to road bank sites next to roads of low, intermediate and high traffic intensities. The deposition pattern of various traffic-derived pollutants--whether gaseous or particle-bound--was the same. Such information can be useful for the purposes of managing pollutants in urban areas.

Similarities in bioaccumulation patterns of polychlorinated dibenzo‐p‐dioxins and furans and polychlorinated diphenyl ethers in laboratory‐exposed oligochaetes and semipermeable membrane devices and in field‐collected chironomids

Sediment and chironomid samples were collected from a river in the vicinity of and downstream from a closed chlorophenol production plant, and they were analyzed for polychlorinated dibenzo-p-dioxins and furans (PCDD/F) and polychlorinated diphenyl ethers (PCDE). Bioaccumulation of these compounds from the sediments by the oligochaeta, Lumbriculus variegatus, and semipermeable membrane devices (SPMDs) was studied in a 28-d bioaccumulation test. The sum concentrations of PCDD/Fs and PCDEs in sediments varied spatially, peaking at the site below the production plant, but the congener composition remained fairly constant throughout the river. The sum concentrations of chironomids, oligochaetes, and SPMDs all varied independently of sediment concentrations. Both invertebrates accumulated more PCDEs, whereas PCDD/Fs dominated in sediments and SPMDs. Despite the variable sum concentrations, similarities were observed in concentrations and compositions of individual congeners. A significant correlation was found between sediments and oligochaetes, and between oligochaetes and chironomids, for both PCDD/Fs and PCDEs. These results suggest that bioaccumulation of PCDD/Fs and PCDEs in invertebrates is nonselective. Furthermore, the laboratory bioaccumulation tests seem to yield relevant results. The SPMDs were found to give good predictions of the PCDD/F concentrations of sediments and oligochaetes. For PCDEs, the estimates were slightly poorer, but still useful for preliminary concentration assessments.

Anaerobic reductive dechlorination of 1,2,3,4-tetrachlorodibenzofuran in polychlorinated dibenzo-p-dioxin- and dibenzofuran-contaminated sediments of the Kymijoki River, Finland

Sediments of the Kymijoki River are highly contaminated with polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). These persistent PCDD/Fs resist biotic degradation and therefore the potential for microbial reductive dechlorination was assessed to determine how microbes impact the fate of these compounds. Anaerobic sediment microcosms of five different sites in the river were spiked with 1,2,3,4-tetrachlorodibenzofuran (1,2,3,4-TeCDF) as a model compound to determine the dechlorination potential in the sediments. Dechlorinating bacteria were active in all the study sites of the river. The extent of dechlorination over 10 and 29 months corresponded to the levels of aged PCDD/Fs, with sediments of the most contaminated site at Kuusankoski being the most active for reductive dechlorination. The dechlorination activity and levels of aged PCDD/Fs were correlated within the sediment cores at the all sites. The pathway of 1,2,3,4-TeCDF dechlorination was mainly via 1,3,4-trichlorodibenzofuran (TrCDF) to 1,3-dichlorodibenzofuran (DiCDF). Dechlorination via 1,2,4-TrCDF to further dechlorination products was also detected. Lateral reductive dechlorination would decrease the toxicity of 2,3,7,8-substituted PCDD/Fs. Our data suggest that sediments of the Kymijoki River contain indigenous microorganisms that are responsible for dechlorination of PCDD/Fs, especially at the most contaminated site.

Selective toxicity at low doses: experiments with three plant species and toxicants.

During the last decade, the paradigm that low toxicant doses often have stimulatory effects on plants has become widely accepted. At the same time, low toxicant doses of metal salts have been observed to inhibit the growth of the most vigorous seedlings of a population in vitro, although mean plant size has remained unaffected. We hypothesized that this kind of selective low-dose toxicity is not restricted to inorganic contaminants. We exposed annual plants (babys breath Gypsophila elegans, purslane Portulaca oleracea, and duckweed Lemna minor) to 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-γ-2-benzopyran (HHCB) and 4-tert-octylphenol and lead acetate. As compared to unexposed G. elegans roots, 4-tert-octylphenol did not affect the mean root size of all seedlings, but it reduced the average length of roots longer than the 98th percentile. A comparable response was found in case of G elegans roots treated with lead acetate beyond the 90th percentile. The average size of roots beyond the 90th percentile was decreased also when L. minor was exposed to lead acetate though the means of all roots were constant. P. oleracea seemed to be insensitive to selective toxicity. We conclude that selective toxicity at low doses should be considered in parallel with hormesis.

Gaseous polycyclic aromatic hydrocarbon concentrations are higher in urban forests than adjacent open areas during summer but not in winter – Exploratory study

While the potential of plants to uptake polycyclic aromatic hydrocarbons (PAHs) is widely acknowledged, empirical evidence of the effects of this process on local atmospheric PAH concentrations and human health is tenuous. We measured gaseous PAH concentrations using passive samplers in urban tree-covered areas and adjacent open, treeless areas in a near-road environment in Finland to gain information on the ability of urban vegetation to improve air quality. The ability of urban, mostly deciduous, vegetation to affect PAHs was season dependent: during summer, concentrations were significantly higher in tree-covered areas, while in the fall, concentrations in open areas exceeded those in tree-covered areas. During winter, concentrations in tree-covered areas were either lower or did not differ from those in open areas. Results of this study imply that the commonly believed notion that trees unequivocally improve air quality does not apply to PAHs studied here.

Effect of temperature on the reductive dechlorination of 1,2,3,4-tetrachlorodibenzofuran in anaerobic PCDD/F-contaminated sediments

The effect of temperature on the reductive dechlorination in sediments of the PCDD/F-contaminated Kymijoki River, Finland was assessed with 1,2,3,4-tetrachlorodibenzofuran (1,2,3,4-TeCDF) at various temperatures and with co-amendment of 2,3,4,6-tetrachlorophenol (2,3,4,6-TeCP) in laboratory microcosms. The dechlorination rate of 1,2,3,4-TeCDF increased with incubation temperature, with TeCDF half-lives of 2.1 y at 21°C, 3.9 y at 15°C, and 19.0 y at 4°C. Co-amendment with 2,3,4,6-TeCP reduced the TeCDF half-life to 1.8 y at 21°C. 1,2,3,4-TeCDF was dechlorinated mainly in the lateral position to 1,3,4-TrCDF and then to 1,3-DiCDF over 29 months, but incubation temperature affected the relative molar ratios of the dechlorination products. The abundance of the Dehalococcoides-like Chloroflexi community did not substantially change in microcosms over 24 months incubation at the different temperatures. The dechlorination activity of 1,2,3,4-TeCDF was significantly limited at lower temperatures, which should be considered in predicting the environmental fate of aged PCDD/Fs in sediments of the Kymijoki River.

Identification of organic xenobiotics in urban aquatic environments using time-of-flight mass spectrometry.

Qualitative non-target and post-target analysis methods using gas chromatography-time-of-flight mass spectrometry were applied for analysing neutral and acidic organic xenobiotics in urban and suburban water samples. Ten water samples representing wastewater, stormwater and surface water matrices were collected and concentrated using solid phase extraction. Compound identification was performed using a spectral deconvolution program, accurate mass measurements and comparisons with library spectra. The non-target and post-target analyses identified 36 and 18 compounds, respectively. The identification of 10 compounds was afterwards confirmed with standard compounds. Organophosphate esters were the most abundant compound group detected. The combination of non-target and post-target analyses proved a useful tool in the tentative identification of xenobiotics in water samples. Post-target analysis can complement non-target analysis results at low analyte concentrations. Results showed that several organic xenobiotics originate in urban areas and accumulate in the environment. The wastewater sample produced the highest number of identified compounds, but most of these compounds were also found in stormwater samples from the city centre. Nearly all the compounds present in wastewater were additionally detected in the surface water sample taken 3 km downstream from the wastewater effluent discharge point. Only a few xenobiotics were otherwise detected in the surface water samples.

Qualitative nontarget analysis of landfill leachate using gas chromatography time-of-flight mass spectrometry

Nontarget analysis means that a sample is analysed without preselection of the studied analytes. While target analysis attempts to determine whether certain selected compounds are present in the sample, nontarget analysis is performed to explore what unknown compounds can be found. We developed a nontarget method using a landfill leachate sample as a complex test sample. The method was based on the use of a gas chromatograph-time-of-flight mass spectrometer (GC-TOF-MS) for final analysis and a deconvolution computer application for data processing. This nontarget analysis method was tested and validated by applying it to a landfill leachate sample spiked with 11 organic pollutants that were treated as unknowns. Sensitivity was found to be the most critical parameter affecting the success of nontarget analysis. The limit of identification (LOI) was 2500 ng L(-1) for four of the 11 compounds, 500 ng L(-1) for three compounds and 100 ng L(-1) for one compound. Three compounds were not detected in any of the spiked samples. A six-stage identification process was developed based on the spiking experiments. The process was based on the forward fit value of the library hit, the number of deconvoluted ions and the accurate mass scoring of the measured ions. The process was applied to an unspiked leachate water sample. Altogether, 44 compounds were tentatively identified in the sample. Elemental compositions of 36 components were additionally determined for which an unequivocal compound identification could not be given. Nontarget analysis with GC-TOF-MS is a promising method for the qualitative analysis of complex water samples. However, we conclude that the computer application for nontarget analysis needs improvement to decrease the amount of manual work needed in the identification process.