Variation in PAH inputs and microbial community in surface sediments of Hamilton Harbour: implications to remediation and monitoring

Variations in concentrations of polycyclic aromatic hydrocarbons (PAHs) and microbial community indicators were investigated in representative highly contaminated and less contaminated surface sediment sites of Hamilton Harbour. Inputs of PAH to the upper 3cm of sediments up to four times the average upper sediment concentrations were observed. Associated PAH fingerprint profiles indicated that the source was consistent with the PAH source to the industrial region of the harbour. Increased PAH loadings were associated with decreased bacterial populations as indicated by phospholipid fatty acid (PLFA) concentrations. However, relatively minor impacts on overall community composition were indicated. Porewater methane concentrations and isotopic data indicated a difference in the occurrence of methane oxidation between the two sites. This study confirms temporally limited transport of contaminants from highly impacted regions as a vector for contaminants within the harbour and the impact on microbial carbon cycling and bed stability.     

Polycyclic aromatic hydrocarbons (PAH) in different forest humus types

The behavior of 20 PAH in the organic layers of a L mull, an Of mull and a mor was assessed by a combined approach of a soil profile study, and the analysis of particle-size separates. Increasing PAH concentrations with depth in the mor profile (L, 866 μg kg⁻³; Of, 2902 μg kg⁻¹; Oh, 10489 ug kg⁻¹) were assigned to selective enrichment during organic matter decomposition. PAH were further highly enriched within the finer separates. For the L horizons, significant positive correlations were established between the enrichment of individual PAH (as observed from the decomposition gradient between the >2-mm fraction and the < 0.05-mm fraction), and the K_OW for each compound. The slope of the regression line, m, described the degree of differentiation between low- and high-molecular PAH during litter decomposition. Since m was greatest in the most biologically active humus type (L mull, 0.33) and smallest in the most inactive (mor, 0.20), microbial breakdown was assumed as the dominating process for this differentiation. The results also indicated that decomposition processes had already taken place in the L horizons, leading to morphological and chemical changes of organic matter, and to an enrichment of high molecular PAH.     

An experimental set up of a PAH vapour generator and its use to test an annular denuder

The aim of this work is to develop and test a dynamic gas generator for semi-volatile organic compounds (SVOC). A single compound, naphthalene, is used as a surrogate PAH to test the system. The dynamic generation of PAH is based on the permeation technique [Analyst 106 (1981) 817; Am. Ind. Hyg. Assoc. J. 38 (1977) 712]. Monitoring the temperature and measuring the mass of PAH present in the permeation chamber every 48 h gives a direct measurement of the sublimation rate of the PAH. Knowing the flow rate, gives an accurate value of the concentration of PAH from the generator. It was found stable over a period of time under constant operating conditions. This concentration is diluted down to between 0.3 and 30 ppbv by a controlled flow of pure air. The diluting airflow is a mixture of dry and wet air, making it possible to control the relative humidity of the flow from the generator as well as its concentration in PAH. We used this generator to calibrate an annular denuder tube, based on the study by Gundel et al. [Atmos. Environ. 29 (1995) 1719]. Although this technique has been shown to be artefact-free for sampling gaseous PAH [Polycyclic Aromatic Compounds 9 (1996) 67; Atmos. Environ. 28 (1994) 3083], its trapping efficiency still depends on environmental parameters (temperature, relative humidity and sampling duration). Accordingly, we used our generator to calibrate a single annular denuder under controlled conditions (T degrees C, HR%, CPAH, sampling duration). The trapping efficiency of the denuder was calculated by two independent methods. Firstly, by comparing the amount trapped on a denuder with the measured mass sublimated in the generator. Secondly, by putting two denuders in series and comparing the mass collected on the first and the second tube. These two methods gave similar results, within the 10% relative uncertainties of both methods. The first results obtained show that, in environmental conditions, the efficiency ranges between 90 and 100%.     

Sorption of native polyaromatic hydrocarbons (PAH) to black carbon and amended activated carbon in soil

Organic pollutants (e.g. polyaromatic hydrocarbons (PAH)) strongly sorb to carbonaceous sorbents such as black carbon and activated carbon (BC and AC, respectively). For a creosote-contaminated soil (Sigma15PAH 5500 mg kg(dry weight(dw))(-1)) and an urban soil with moderate PAH content (Sigma15PAH 38 mg kg(dw)(-1)), total organic carbon-water distribution coefficients (K(TOC)) were up to a factor of 100 above values for amorphous (humic) organic carbon obtained by a frequently used Linear-Free-Energy Relationship. This increase could be explained by inclusion of BC (urban soil) or oil (creosote-contaminated soil) into the sorption model. AC is a manufactured sorbent for organic pollutants with similar strong sorption properties as the combustion by-product BC. AC has the potential to be used for in situ remediation of contaminated soils and sediments. The addition of small amounts of powdered AC (2%) to the moderately contaminated urban soil reduced the freely dissolved aqueous concentration of native PAH in soil/water suspensions up to 99%. For granulated AC amended to the urban soil, the reduction in freely dissolved concentrations was not as strong (median 64%), especially for the heavier PAH. This is probably due to blockage of the pore system of granulated AC resulting in AC deactivation by soil components. For powdered and granulated AC amended to the heavily contaminated creosote soil, median reductions were 63% and 4%, respectively, probably due to saturation of AC sorption sites by the high PAH concentrations and/or blockage of sorption sites and pores by oil.     

Spatial uncoupling of biodegradation, soil respiration, and PAH concentration in a creosote contaminated soil

Hotspots and coldspots of concentration and biodegradation of polycyclic aromatic hydrocarbons (PAHs) marginally overlapped at the 0.5-100 m scale in a creosote contaminated soil in southern Sweden, suggesting that concentration and biodegradation had little spatial co-variation. Biodegradation was substantial and its spatial variability considerable and highly irregular, but it had no spatial autocorrelation. The soil concentration of PAHs explained only 20-30% of the variance of their biodegradation. Soil respiration was spatially autocorrelated. The spatial uncoupling between biodegradation and soil respiration seemed to be governed by the aging of PAHs in the soil, since biodegradation of added ¹³C phenanthrene covaried with both soil respiration and microbial biomass. The latter two were also correlated with high concentrations of phospholipid fatty acids (PLFAs) that are common in gram-negative bacteria. However, several of the hotspots of biodegradation coincided with hotspots for the distribution of a PLFA indicative of fungal biomass.     

Prediction of complete bioremediation periods for PAH soil pollutants in different physical states by mechanistic models

Mass-transfer models and biodegradation models were developed for three theoretical physical states of polycyclic aromatic hydrocarbons (PAHs) in soil. These mechanistic models were used to calculate the treatment periods necessary for complete removal of the PAH pollutants from the soil under batch conditions. Results indicate that the bioremediation of PAHs in such systems is mainly mass-transfer limited. The potential for bioremediation as a treatment technique for PAH contaminated soils is therefore mainly determined by the mass-transfer dynamics of PAHs. Under mass-transfer limited conditions simplified mathematical models, based on the assumption of a zero dissolved PAH concentrations, can be used to predict the period of time needed for complete bioremediation.     

An experimental study of the dry deposition of gaseous nitric acid to snow

A chamber placed in a constant temperature freezing room was used to study the surface resistance during deposition of HNO₃ to a snow surface. The resistance decreased with increasing temperature from larger than 5 s mm⁻¹ at − 18°C to about l s mm⁻¹ at −3°C. Measurements of gaseous and particulate nitrate concentrations during winter at a rural site in south central Sweden gave concentrations in the range of 0.4–5 μg HNO₃ m⁻¹ and 0.3–3 μg NO⁻₃ m⁻³ with a mean value of 1.3 μg HNO₃ m⁻³ and 0.7 μg NO⁻₃ m⁻³, respectively. The results indicate that for periods with temperatures below − 2°C estimated dry deposition of HNO₃ to snow is at most 4 % of measured wet deposition of nitrate in the area.     

Regional trends in soil acidification and exchangeable metal concentrations in relation to acid deposition rates

The deposition of high levels of reactive nitrogen (N) and sulphur (S), or the legacy of that deposition, remain among the world's most important environmental problems. Although regional impacts of acid deposition in aquatic ecosystems have been well documented, quantitative evidence of wide-scale impacts on terrestrial ecosystems is not common. In this study we analysed surface and subsoil chemistry of 68 acid grassland sites across the UK along a gradient of acid deposition, and statistically related the concentrations of exchangeable soil metals (1 M KCl extraction) to a range of potential drivers. The deposition of N, S or acid deposition was the primary correlate for 8 of 13 exchangeable metals measured in the topsoil and 5 of 14 exchangeable metals in the subsoil. In particular, exchangeable aluminium and lead both show increased levels above a soil pH threshold of about 4.5, strongly related to the deposition flux of acid compounds.     

Oxidation of a PAH polluted soil using modified Fenton reaction in unsaturated condition affects biological and physico-chemical properties

A batch experiment was conducted to assess the impact of chemical oxidation using modified Fenton reaction on PAH content and on physico-chemical and biological parameters of an industrial PAH contaminated soil in unsaturated condition. Two levels of oxidant (H₂O₂, 6 and 65 g kg⁻¹) and FeSO₄ were applied. Agronomic parameters, bacterial and fungal density, microbial activity, seed germination and ryegrass growth were assessed. Partial removal of PAHs (14% and 22%) was obtained with the addition of oxidant. The impact of chemical oxidation on PAH removal and soil physico-chemical and biological parameters differed depending on the level of reagent. The treatment with the highest concentration of oxidant decreased soil pH, cation exchange capacity and extractable phosphorus content. Bacterial, fungal, and PAH degrading bacteria densities were also lower in oxidized soil. However a rebound of microbial populations and an increased microbial activity in oxidized soil were measured after 5 weeks of incubation. Plant growth on soil treated by the highest level of oxidant was negatively affected.     

Assessment of bioavailable PAH, PCB and OCP concentrations in water, using semipermeable membrane devices (SPMDs), sediments and caged carp

Bioavailable water concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were assessed at several freshwater sites in and around the city of Amsterdam. Carp (Cyprinus carpio) were caged for 4 weeks at 10 sites, together with semipermeable membrane devices (SPMDs). In addition, sediment samples were taken at each site. SPMDs and sediments were analysed for PAHs, PCBs and OCPs. Carp muscle tissues were analysed for PCBs and OCP, while PAH metabolites were assessed in fish bile. Contaminant concentrations in the water phase were estimated using three different methods: 1. Using fish tissue concentrations and literature bioconcentration factors (BCFs), 2. Using SPMD levels and a kinetic SPMD uptake model, and 3. Using sediment levels and literature sorption coefficients (K_ocs). Since PAH accumulation in fish is not considered an accurate indicator of PAH exposure, calculated aqueous PAH concentrations from SPMD data were compared with semiquantitatively determined biliary PAH metabolite levels. Contaminant concentrations in the water phase estimated with fish data (Cw_fish) and SPMD data (Cw_spmd) were more in line for compounds with lower K_ow than for compounds with higher K_ow values. This indicates that the assumption of fish–water sorption equilibrium was not valid. At most sites, sediment-based water levels (Cw_sed) were comparable with the Cw_spmd, although large differences were observed at certain sites. A significant correlation was observed between biliary PAH metabolite levels in fish and aqueous PAH concentrations estimated with SPMD data, suggesting that both methods may be accurate indicators of PAH exposure in aquatic ecosystems.     

Description and evaluation of a model of deposition velocities for routine estimates of air pollutant dry deposition over North America.: Part I: model development

This paper describes the development of a detailed dry deposition model for routine computation of dry deposition velocities of SO₂, O₃, HNO₃ and fine particle SO₄²⁻ across much of North America. Four different dry deposition/surface exchange sub-models have been combined with the current Canadian weather forecast model (Global Environmental Multiscale model) with a 3 h time resolution and a horizontal spatial resolution of 35 km. The present model uses the US Geological Survey North American Land Cover Characteristics data to obtain fourteen different land use and five seasonal categories. The four sub-models used are a multi-layer model for gaseous species over taller canopy land-use types, a big-leaf model for gaseous species over lower canopies (including bare soil and water) and for HNO₃ under all surface types and, two different models for SO₄²⁻, one for tall canopies and the other for short canopies. All necessary parameters for each sub-model, chemical species, land-use and seasonal categories have been selected from available data libraries or from the values reported in the literature. The purpose for developing this model (referred to as the Routine Deposition Model (RDM)), when coupled with air concentration data, is to provide estimates of seasonal dry deposition, which can be combined with wet deposition to produce total deposition estimates. Model theory is discussed in this paper and model sensitivity tests and results will be presented in a companion paper.     

Quantification of centimeter-scale spatial variation in PAH, glucose and benzoic acid mineralization and soil organic matter in road-side soil

The aim of the study was to determine centimeter-scale spatial variation in mineralization potential in diffusely polluted soil. To this end we employed a 96-well microplate method to measure the mineralization of ¹⁴C-labeled organic compounds in deep-well microplates and thereby compile mineralization curves for 348 soil samples of 0.2-cm³. Centimeter-scale spatial variation in organic matter and the mineralization of glucose, benzoic acid, and PAHs (phenanthrene and pyrene) was determined for urban road-side soil sampled as arrays (7 × 11 cm) of 96 subsamples. The spatial variation in mineralization was visualized by means of 2-D contour maps and quantified by means of semivariograms. The geostatistical analysis showed that the easily degradable compounds (glucose and benzoic acid) exhibited little spatial variation in mineralization potential, whereas the mineralization was highly heterogeneous for the PAH compounds that require specialized degraders. The spatial heterogeneity should be taken into account when estimating natural attenuation rates.     

Description and evaluation of a model of deposition velocities for routine estimates of dry deposition over North America. Part II: review of past measurements and model results

Numerical sensitivity tests and four months of complete model runs have been conducted for the Routine Deposition Model (RDM). The influence of individual model inputs on dry deposition velocity as a function of land-use category (LUC) and pollutant (SO₂, O₃, SO²⁻₄ and HNO₃) were examined over a realistic range of values for solar radiation, stability and wind speed. Spatial and temporal variations in RDM deposition velocity (V_d) during June – September 1996 time period generated using meteorological input from a mesoscale model run at 35 km resolution over north-eastern North America were also examined. Comparison of RDM V_d values to a variety of measurements of dry deposition velocities of SO₂, O₃, SO²⁻₄ and NHO₃ that have been reported in the literature demonstrated that RDM produces realistic results. Over northeastern NA RDM monthly averaged dry deposition velocities for SO₂ vary from 0.2 to 3.0 cm s⁻¹ with the highest deposition velocities over water surfaces. For O₃, the monthly averaged dry deposition velocities are from 0.05 to 1.0 cm s⁻¹ with the lowest values over water surfaces and the highest over forested areas. For HNO₃, the monthly averaged dry deposition velocities have the range of 0.5 to 6 cm s⁻¹, with the highest values for forested areas. For SO²⁻₄, they range from 0.05–1.5 cm s⁻¹, with the lowest values over water and the highest over forest. The monthly averaged dry deposition velocities for SO₂ and O₃ are higher in the growing season compared to the fall, but this behaviour is not apparent for HNO₃ and sulphate. In the daytime, the hourly averaged dry deposition velocities for SO₂, O₃, SO²⁻₄ and HNO₃ are higher than that in the nighttime over most of the vegetated area. The diurnal variation is most evident for surfaces with large values for leaf area index (LAI), such as forests. Based on the results presented in this paper, it is concluded that RDM V_d values can be combined with measured air concentrations over hourly, daily or weekly periods to determine dry deposition amounts and with wet deposition measurements to provide seasonal estimates of total deposition and estimates of the relative importance of dry deposition.     

Occurrence of PAH in the seasonal snowpack of the Eastern Italian Alps

PAH concentrations have been determined in 47 seasonal snowpack samples collected in the Valbelluna valley and in the Bellunesi Dolomites National Park, in the Italian North-Eastern Alps, during the winter of 2005. The ΣPAH concentration in high-altitude alpine sites (above 1700 m) was 32 ± 20 ng/kg while in valley bottom urban areas it was 165 ± 54 ng/kg with maximum values of 290 ng/kg. The GIS mapping technique was employed to produce a PAH spatial distribution. The urbanized Valbelluna valley, and in particular the SW part, had the highest accumulation of all PAH, with values an order of magnitude more than those in rural and alpine areas. This behaviour is consistent with urban air quality data, and is due to geo-morphological and meteorological factors such as the deeper shape of the valley at the position of the town of Feltre and the low altitude of the boundary layer during the winter season.     

Atmospheric deposition of polycyclic aromatic hydrocarbons near New England coastal waters

Wet and dry deposition of polycyclic aromatic hydrocarbons (PAHs) was measured at Nahant, Massachusetts, a peninsula jutting into Massachusetts Bay and Wolf Neck, a peninsula jutting into Casco Bay, Maine. Wet deposition (rain and snow) was collected in a funnel which drains into a shielded, temperature controlled receiving bottle. Dry deposition of gaseous and particulate PAHs was collected onto an exposed water surface. PAHs were analyzed by solid phase extraction and gas chromatography-mass spectrometry. Sixteen PAH species were analyzed, ranging from acenaphthylene to coronene. The mean wet deposition rate of the sum of the 16 species is 720 ng m⁻² cm⁻¹ precipitation at Nahant, and 831 ng m⁻² cm⁻¹ precipitation at Wolf Neck. Wet deposition is attributed to regional PAH emitting sources. Storm patterns appear to bring somewhat higher wet deposition of PAHs to Wolf Neck than to Nahant. The mean dry deposition rate is 95 ng m⁻² h⁻¹ at Nahant and 9.3 ng m⁻² h⁻¹ at Wolf Neck. The large difference is attributed to the fact that Nahant is close to the urban-industrial metropolitan Boston area and Logan International Airport, whereas Wolf Neck has no major PAH-emitting sources nearby. Individual measurements have an error bracket of ±30%. The Chemical Mass Balance model was used to apportion the dry deposition to source categories. At Nahant, nine samples gave valid statistical attributes with a mean apportionment: jet exhaust 35%, gasoline fueled vehicles 32%, diesel fueled vehicles 17%, wood combustion 13%, others 3%. At Wolf Neck, six samples yielded a mean apportionment: jet exhaust 30%, gasoline vehicles 28%, diesel vehicles 18%, wood combustion 16%, others 8%. There is a considerable variation between the samples. The apportionment is greatly dependent on the quality and selection of the model inputs, i.e. source signatures, which for PAHs are questionable.     

Seasonal patterns of heavy metal deposition to the snow on Lambert Glacier basin,East Antarctica

Al, V, Mn, Fe, Cu, As, Cd, Ba, Pb, Bi and U were determined in a continuous series of 46 snow samples from a 2.3-m snow pit, covering the time period from austral spring 1998 to summer 2002, at a site on the east side of the Lambert Glacier basin in East Antarctica. Concentrations are very low for all metals and differ by orders of magnitude from one metal to another, with the mean concentrations ranging from 0.028 pg g⁻¹ for Bi to 165 pg g⁻¹ for Al. It is estimated that anthropogenic contributions are dominant for Cu, Pb and probably As, in the snow in our study area while the natural contributions from rock and soil dust, sea-salt spray and volcanic emissions account for most of the measured concentrations of the other metals. Our snow profiles show pronounced seasonal variations for Mn, As, Ba, Pb and Bi throughout the year, but a very different situation is observed between different metals. These observations suggest that heavy metals determined in our samples are controlled by different transport and deposition mechanisms related to physical and chemical alterations in the properties and sources of aerosol.     

The effect of oils on PAH, PCDD, PCDF, and PCB emissions from a spark engine fueled with leaded gasoline

The effect of synthetic and mineral oils on the formation of polyaromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and biphenyls (PCBs) in emissions from a spark ignition engine was studied on a Skoda Favorit engine fueled with leaded gasoline. The test cycle simulated urban traffic conditions on a chassis dynamometer, in accordance with the ECC 83.00 test. The data for selected PAHs as well as PCDDs, PCDFs, and PCBs congener profiles are presented. PCDD/Fs emissions for an unused oil and the oil after 10000-km operation varied from 300 to 2000 fmol/m3, PCBs emissions from 75 to 178 pmol/m3, and PAHs emissions from 150 to 420 microg/m3. The content of PCBs in oils varied from 2 to 920 mg/kg.     

Comparison of annual dry and wet deposition fluxes of selected pesticides in Strasbourg, France

This work summarizes the results of a study of atmospheric wet and dry deposition fluxes of Deisopropyl-atrazine (DEA), Desethyl-atrazine (DET), Atrazine, Terbuthylazine, Alachlor, Metolachlor, Diflufenican, Fenoxaprop-p-ethyl, Iprodione, Isoproturon and Cymoxanil pesticides conducted in Strasbourg, France, from August 2000 through August 2001. The primary objective of this work was to calculate the total atmospheric pesticide deposition fluxes induced by atmospheric particles. To do this, a modified one-dimensional cloud water deposition model was used. All precipitation and deposition samples were collected at an urban forested park environment setting away from any direct point pesticide sources. The obtained deposition fluxes induced by atmospheric particles over a forested area showed that the dry deposition flux strongly contributes to the total deposition flux. The dry particle deposition fluxes are shown to contribute from 4% (DET) to 60% (cymoxanil) to the total deposition flux (wet + dry).     

Spatial distribution and source identification of wet deposition at remote EANET sites in Japan

Wet deposition of major ions was discussed from the viewpoint of its potential sources for six remote EANET sites in Japan (Rishiri, Happo, Oki, Ogasawara, Yusuhara, and Hedo) having sufficiently high data completeness during 2000–2004. The annual deposition for each site ranged from 12.1 to 46.6 meq m⁻² yr⁻¹ for nss-SO₄²⁻, from 5.0 to 21.9 meq m⁻² yr⁻¹ for NO₃⁻. The ranges of annual deposition of the two ions for the sites were lower than those for urban and rural sites in Japanese Acid Deposition Survey by Ministry of the Environment, Japan, and higher than those for global remote marine sites. Factor analysis was performed on log-transformed daily wet deposition of major ions for each site. The obtained two factors were interpreted as (1) acid and soil source (or acid source for some sites), and (2) sea-salt source for all the sites. This indicates that wet deposition of ions over the remote areas in Japan has a similar structure in terms of types of sources. Factor scores of acid and soil source were relatively high during Kosa (Asian dust) events in spring in western Japan. Back-trajectories for high-deposition episodes of acid and soil source (or acid source) for the remote sites showed that episodic air masses frequently came from the northeastern area of Asian Continent in spring and winter, and from central China in summer and autumn. This indicates a large contribution of continental emissions to wet deposition of ions over the remote areas in Japan.