A new moss biomonitoring method for detecting sources of small scale pollution

A new simple method is proposed for identifying sources of small scale pollution, by determining the tissue concentrations of pollutants in terrestrial mosses. The method is based on spatial characterization of the processes that generate accumulation of pollutants in these organisms. The steps involved in implementing and applying the method are: (i) obtaining data on pollutants in moss samples collected at least at 35 pairs of sampling sites (SS) separated by 1 km distance; (ii) study of the distribution of the differences in concentration between the pairs of SS, eliminating pairs affected by foci that generate small scale processes; (iii) characterization of the resulting normal distributions and calculation, for different levels of significance, of the probability of a value lying within these distributions, and (iv) application of the calculated quantiles to data corresponding to the differences in concentrations between pairs of SS in the vicinities of foci of small scale pollution, to determine which elements can be considered as pollutants. Given the small number of data required once the distribution of the differences has been established, the method is an inexpensive, efficient way of establishing the probability that a pollutant is being emitted from a particular source. The method is very useful for verifying the results of pollution inventories, evaluating new technologies and improving the design of regional networks for biomonitoring of air quality with terrestrial mosses.     

Polycyclic aromatic hydrocarbons in ambient air in the Philippines derived from passive sampler with polyurethane foam disk

Passive samplers with polyurethane disks (PUF) were applied in the determination of the concentration of polycyclic aromatic hydrocarbons (PAHs) in ambient air in six residential areas in the Philippines during four simultaneous sampling periods. The uptake profiles of PAHs were determined at one site during one sampling period. Most of the PAHs that were detected in air at concentrations that were significantly higher than their analytical detection limits exhibited a linear uptake trend on the PUF disk. The linear uptake profiles of some high molecular weight (HMW) PAHs were not established and this is attributed to the low concentration of the compounds in air in the gaseous phase. The retention concentrations of phenanthrene-d-10 were determined after depuration in four sampling sites during two sampling periods. The sampling rate for phenanthrene-d-10 was calculated at the linear phase of the uptake using the k_A derived from depuration experiments and the relationship of k_A and sampling rate which was established in a previous passive sampling study. The average sampling rate obtained for phenanthrene d-10 (2.94±0.69 m³ d⁻¹) was applied for derivation of the concentrations of the PAHs in the field samples.The passive sampler with PUF disk and short integration time of 42–56 days is applicable for the derivation of the concentrations of PAHs in ambient air in the Philippines. The concentrations of the organic pollutants derived from the passive sampler showed variability for the six residential areas; reflecting the influence of possible sources of emission of the pollutants at the sites at the different sampling periods. The weather conditions, including the occurrence of a tropical cyclone, increased rainfall and high-relative humidity during the rainy season, had an influence on the concentrations of PAHs derived by the passive sampler.     

Use of semipermeable membrane devices (SPMDs)

Triolein-containing semipermeable membrane devices (SPMDs) were employed as passive samplers to provide data on the bioavailable fraction of organic, waterborne, organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polynuclear aromatic hydrocarbons (PAHs) in streams flowing through a highly polluted industrial area of Bitterfeld in Saxony-Anhalt, Germany. The contamination of the region with organic pollutants originates in wastewater effluents from the chemical industry, from over one-hundred years of lignite exploitation, and from chemical waste dumps. The main objective was to characterise time-integrated levels of dissolved contaminants, to use them for identification of spatial trends of contamination, and their relationship to potential pollution sources. SPMDs were deployed for 43 days in the summer of 1998 at four sampling sites. The total concentration of pollutants at sampling sites was found to range from a low of 0.8 microgram/SPMD to 25 micrograms/SPMD for PAHs, and from 0.4 microgram/SPMD to 22 micrograms/SPMD for OCPs, respectively. None of the selected PCB congeners was present at quantifiable levels at any sampling site. A point source of water pollution with OCPs and PAHs was identified in the river system considering the total contaminant concentrations and the distribution of individual compounds accumulated by SPMDs at different sampling sites. SPMD-data was also used to estimate average ambient water concentrations of the contaminants at each field site and compared with concentrations measured in bulk water extracts. The truly dissolved or bioavailable portion of contaminants at different sampling sites ranged from 4% to 86% for the PAHs, and from 8% to 18% for the OCPs included in the estimation. The fraction of individual compounds found in the freely dissolved form can be attributed to the range of their hydrophobicity. In comparison with liquid/liquid extraction of water samples, the SPMD method is more suitable for an assessment of the background concentrations of hydrophobic organic contaminants because of substantially lower method quantification limits. Moreover, contaminant residues sequestered by the SPMDs represent an estimation of the dissolved or readily bioavailable concentration of hydrophobic contaminants in water, which is not provided by most analytical approaches.     

Temporal trends of polycyclic aromatic hydrocarbons (PAHs) in Dreissena polymorpha specimens from Lake Maggiore (Northern Italy)

The Lake Maggiore (Northern Italy) has been recognized as an aquatic environment heavily contaminated by persistent organic pollutants, mainly organochlorine compounds, but to date limited information is available regarding another class of widespread and hazardous pollutants, such as the polycyclic aromatic hydrocarbons (PAHs). The aim of this study was to investigate seasonal and temporal trends of 18 PAHs accumulated in native Dreissena polymorpha specimens during a 5-year biomonitoring program, as well as to identify the possible PAH emission sources by using isomeric diagnostic ratios. Zebra mussels were sampled both in their pre- (May) and post-reproductive (September) stage over the 2008–2012 period in eight sampling stations covering the whole lake shoreline. PAH concentrations were measured through gas chromatography coupled to mass spectrometry. A notable PAH contamination following an increasing temporal trend was noticed in bivalves from all the sampling stations, with the benzo(α)anthracene as the predominant compound. An overall increase in PAH levels was found in the post-reproductive surveys, indicating a marked seasonality of this contamination probably due to the increase in touristic activity during spring–summer months.     

Polycyclic aromatic hydrocarbon (PAH) contamination of surface sediments and oysters from the inter-tidal areas of Dar es Salaam, Tanzania

Surface sediment and oyster samples from the inter-tidal areas of Dar es Salaam were analyzed for 23 polycyclic aromatic hydrocarbons (PAHs) including the 16 compounds prioritized by US-EPA using GC/MS. The total concentration of PAHs in the sediment ranged from 78 to 25,000 ng/g dry weight, while oyster concentrations ranged from 170 to 650 ng/g dry weight. Hazards due to sediment contamination were assessed using Equilibrium Partitioning Sediment Benchmarks and Threshold Effect Levels. Diagnostic indices and principle component analysis were used to identify possible sources. Interestingly, no correlation between sediment and oyster concentrations at the same sites was found. This is supported by completely different contamination patterns, suggesting different sources for both matrices. Hazard assessment revealed possible effects at six out of eight sites on the benthic communities and oyster populations. The contribution of PAH intake via oyster consumption to carcinogenic risks in humans seems to be low.     

Polycyclic aromatic hydrocarbon (PAH) dispersion and deposition to vegetation and soil following a large scale chemical fire

Polycyclic aromatic hydrocarbons (PAHs) were determined in soil and vegetation following a large scale chemical fire involving 10,000 ton of polypropylene. In comparison with sites outside the plume from the fire, PAH concentrations were elevated in grass shoots (by up to 70-fold) and in soil (by up to 370-fold). The pattern of PAH dispersion under the plume was dependent on the physical-chemical properties of individual PAHs. The lighter, least hydrophobic PAHs were dispersed into the environment at greater distances than heavier, more hydrophobic PAHs. At the most distant sampling point (4.5 km) under the plume, the low molecular weight PAHs were still considerably elevated in vegetation samples compared to control sites. Dispersion appeared to be regulated by the compounds partitioning between the vapour and particulate phase, with dry particulate deposition occurring closer to the fire source than gaseous deposition. For all PAHs, the fire resulted in greater contamination of soils compared to grasses, with the relative ratio of plant/soil contamination decreasing as hydrophobicity increased.     

Airborne pollutants along a roadside: assessment using snow analyses and moss bags

Vertical snow sampling and moss bag transplants were used to estimate the local inorganic and organic pollutant load deposited from traffic along a major highway in Finland. The pH and concentrations of Cl(-), NO(3)(-), SO(4)(2-), Ca(2+), Na(+) and polyaromatic hydrocarbons (PAHs) were determined from snow samples collected in winter at different sites along the highway. In summer, moss bags containing 20 g of fresh red-stemmed feather moss (Pleurozium schreberi) were transplanted at the same sites. The moss bag transplants remained exposed to roadside traffic for a period of one month following which the samples were collected and the PAH profiles and concentrations were analysed. The deposition of inorganic and organic pollutants from road traffic was observed up to 60 m from the road. The prevailing winds had a significant effect on the dispersion of pollutants. Snow appears to be a good collector of inorganic pollutants from the atmosphere and can be used to monitor local airborne pollution from road traffic. Snow packs can also be used as passive collectors of organic pollutant loads from road traffic on a local scale. To monitor organic PAH deposition from the road traffic, moss bags appeared to be better indicators compared to snow sampling. The efficiency of moss bags in accumulating PAH compounds indicate that vegetation may be an important sink for traffic pollution.     

Passive air sampler as a tool for long-term air pollution monitoring: Part 1. Performance assessment for seasonal and spatial variations

The potential of passive air sampling devices (polyurethane foam disks) to assess the influence of local sources on the quality of the surrounding environment was investigated. DEZA Valasske Mezirici, a coal tar and mixed tar oils processing plant, and Spolana Neratovice, a chemical factory with the history of high production of organochlorinated pesticides (OCPs), were selected as the point sources of PAHs, and OCPs, respectively. Levels of PCBs, OCPs and PAHs were determined for all sampling sites and sampling periods. The study brought useful data about the air concentrations of POPs in the investigated regions. More important, it provided information on the transport and fate of POPs in the vicinity of local sources of contamination useful for the estimation of their influence. Very good capability of passive samplers to reflect temporal and spatial fluctuation in concentrations of persistent organic pollutants in the ambient air was confirmed which makes them applicable for monitoring on the local scale.     

Bioconcentration of metals in the moss Scleropodium purum in the area surrounding a power plant. A geotopographical predictive model for mercury

Samples of the moss Scleropodium purum collected in 1995 and 1997 were used to biomonitor the deposition of metals in the area surrounding a thermal power plant. Significantly higher levels of Cu (p<0.05), Fe (p<0.01), As and Hg (p<0.001) were found in the 1997 samples than in the 1995 samples, due to changes in atmospheric conditions. The influence on bioconcentration of the orientation of the sampling sites relative to the source of emission was studied. It was found that the increase recorded in 1997 generally occurred in the sampling sites in the south east of the study area. Analysis of the effect of distance from the source of emission revealed that the increase in metal levels in 1997 took place close to the power station (10–30 km). Finally, multiple regression analysis was used to construct a model that related different topographical variables to the concentrations of Hg in moss. The model, constructed using the data collected in both sampling periods, included the orientation of the sampling sites relative to the source of emission as well as the height of sampling sites in 1995 and the distance from the emission point in 1997. The model allowed us to determine the extent of the area affected by deposition and to establish the magnitude of deposition.     

Seasonal and spatial occurrence and distribution of atmospheric polycyclic aromatic hydrocarbons (PAHs) in rural and urban areas of the North Chinese Plain

Passive air sampling (PAS) was employed to study the occurrence of gaseous and particle-bound PAHs in the North Chinese Plain. The averaged concentrations of gaseous and particle-bound PAHs were 485 ± 209 ng/m³ and 267 ± 161 ng/m³, respectively. The PAHs concentrations at urban sites were generally higher than those at rural ones with ratios <1.5 in spring, summer and fall, but differences between them were not significant for the wintertime and annually averaged concentrations. This urban-rural distribution pattern was related to the PAHs emission sources. PAHs spatial variation can be partially (49%) explained by emission with a simple linear regression method. Both the gaseous and particle-bound PAHs were highest in winter and lowest in summer, with winter/summer ratios of 1.8 and 8, respectively. Emission strength was the most important factor for the seasonality.     

Distribution and sources of polycyclic aromatic hydrocarbons from urban to rural soils: a case study in Dalian, China

To estimate the distribution and sources of soil polycyclic aromatic hydrocarbons (PAHs) in metropolitan and adjacent areas, soil samples were collected from urban, suburban and rural locations of Dalian, China, and concentrations of 14 PAHs were determined. The spatial PAH profiles were site-specific and determined by the sources close to the sampling sites. PAH concentrations decreased significantly along the urban-suburban-rural transect. The gradient implied that the fractionation effect influenced PAH distribution. Bivariate plots of selected diagnostic ratios showed general trends of co-variation and allowed to distinguish samples taken from different areas. An improved method, factor analysis (FA) with nonnegative constrains, was used to determine the primary sources and contributions of PAHs in soils. The FA model showed traffic average (74%) and coal related residential emission (26%) were two primary sources to Dalian soils. In addition, the FA model provided reasonable explanations for PAH contributions in soils from different sites. The results suggest that FA with nonnegative constraints is a promising tool for source apportionment of PAHs in soils.     

Distribution of polycyclic aromatic hydrocarbons in thirty typical soil profiles in the Yangtze River Delta region, east China

Polycyclic aromatic hydrocarbons (PAHs) were quantified in 30 soil profiles from the Yangtze River Delta Region, in east China. Relative concentrations of PAH compounds with different benzene rings and ratios of fluoranthene to fluoranthene plus pyrene and benz(a)anthracene to benz(a)anthracene plus chrysene were used to identify the possible sources of soil PAHs. Total concentrations of 15 PAHs in topsoils ranged from 8.6 to 3881 microg kg(-1) with an average of 397 microg kg(-1). Half of the soil samples were considered to be contaminated with PAHs (>200 microg kg(-1)) and two sampling sites were heavily polluted by PAHs with concentrations >1000 microg kg(-1). Phenanthrene was found in soils below a depth of 100 cm in half of the sampling sites, but the detectable ratio of benzo(a)pyrene decreased sharply from 100% in topsoil to 0 in the 4th horizon.     

Distribution of PAHs in tissues of wetland plants and the surrounding sediments in the Chongming wetland, Shanghai, China

Polycyclic aromatic hydrocarbons (PAHs) concentrations were determined in sediments and three types of wetland plants collected from the intertidal flats in the Chongming wetland. The concentration of total PAHs in sediments ranged from 38.7 to 136.2 ng g⁻¹. Surface sediment concentrations were higher in regions with plant cover than in bare regions. Rhizome-layer sediments (56.8-102.4 ng g⁻¹) contained less PAHs than surface sediments (0-5 cm). Concentrations of PAHs in plant tissues ranged from 51.9 to 181.2 ng g⁻¹, with highest concentrations in the leaves of Scirpus. Most of the PAHs in the leaves and other plant tissues were low molecular weight compounds (LMW, 2-4 rings), and a similar distribution pattern of PAHs in different types of plants was also observed. Source analysis indicated that plants and sediments both came from pyrogenic sources, but plants had additional petroleum contamination. The low ratio of benzo[a]anthracene over chrysene suggests that the wetland PAHs came mainly from long-distance atmospheric transportation. Significant bioaccumulation of PAHs from the sediments into plants was not observed for high molecular weight PAHs (HMW, 5-6 rings) in Chongming wetland. The small RCFs (root concentration factor from sediments) for HMW PAHs and large RCFs for LMW PAHs suggested that roots accumulated LMW PAHs selectively from sediments in Chongming wetland.     

Bioconcentration of metals in the moss Scleropodium purum in the area surrounding a power plant: A geotopographical predictive model for mercury

Samples of the moss Scleropodium purum collected in 1995 and 1997 were used to biomonitor the deposition of metals in the area surrounding a thermal power plant. Significantly higher levels of Cu (p<0.05), Fe (p<0.01), As and Hg (p<0.001) were found in the 1997 samples than in the 1995 samples, due to changes in atmospheric conditions. The influence on bioconcentration of the orientation of the sampling sites relative to the source of emission was studied. It was found that the increase recorded in 1997 generally occurred in the sampling sites in the south east of the study area. Analysis of the effect of distance from the source of emission revealed that the increase in metal levels in 1997 took place close to the power station (10–30 km). Finally, multiple regression analysis was used to construct a model that related different topographical variables to the concentrations of Hg in moss. The model, constructed using the data collected in both sampling periods, included the orientation of the sampling sites relative to the source of emission as well as the height of sampling sites in 1995 and the distance from the emission point in 1997. The model allowed us to determine the extent of the area affected by deposition and to establish the magnitude of deposition.     

PAHs associated with the leaves of Quercus ilex L.: Extraction,GC–MS analysis,distribution and sources: Assessment of air quality in the Palermo (Italy) area

In this study, the leaves of Quercus ilex L. were selected as possible bioaccumulators of polycyclic aromatic hydrocarbons (PAHs). Quercus is an evergreen plant that occurs widely in both urban and rural areas. Several sites (urban roadside, urban, urban park, suburban and rural) in and around Palermo city were investigated.The purpose of this research was to optimize analytical method for quercus leaves, investigate the degree of contamination in the urban area of Palermo by comparing PAH concentration in leaves of quercus from the several sites, establish distribution patterns and relate them to possible sources of PAHs. To this aim, the 16 recommended as priority pollutants by the Environmental Protection Agency (EPA) and perylene were analyzed. PAHs were positively correlated to atmospheric particulate gravimetrically determined on filters aspiring a known volume of air in the various stations.The analyses have been performed by gas chromatography coupled to mass spectrometry (GC–MS) in selected ion monitoring (SIM) mode. The total PAH content in the samples ranged from 92 to 1454 μg kg⁻¹ d.w. The higher amounts of PAHs detected in leaves of quercus from the urban area of Palermo compared with the control site are diagnostic of air contamination, in particular in the zones with heavy traffic. The determination of PAHs in the leaves of quercus allows us, with very simple and fast procedures, to assess the quality of the air over a longer period, since PAHs are accumulated over the whole lifetime of the leaves, irrespective of atmospheric conditions at the moment of sampling.     

Accumulation of polycyclic aromatic hydrocarbons (PAHs) on the spider webs in the vicinity of road traffic emissions

Studies focused on the possible use of spider webs as environmental pollution indicators. This was a first time ever attempt to use webs as indicators of polycyclic aromatic hydrocarbons (PAHs) pollution. The aim of the study was (a) to evaluate whether webs are able to accumulate PM-associated road traffic emissions and be analyzed for organic toxics such as PAHs, (b) to assess if the distance from emission sources could have an influence on the accumulation level of pollutants, and (c) to determine types of pollution sources responsible for a structure of monitoring data set. Webs of four species from the family Agelenidae were sampled for PAHs presence. Data from vehicle traffic sites (i.e., road tunnel, arterial surface road, underground parking) and from railway traffic sites (i.e., two railway viaducts) in the city of Wroclaw (Southwest of Poland) showed a significantly higher mean concentrations of PAHs than the reference site 1 (municipal water supply works). We also found a significant differences at sites differed by the distance from emission sources. The result of PCA analysis suggested three important sources of pollution. We conclude that spider webs despite of some limitations proved useful indicators of road traffic emissions; they could be even more reliable compared to use of bioindicators whose activity is often limited by a lack of water and sun.     

Distribution and characteristics of PAHs in sediments from the marine environment of Korea

To assess the contamination of polycyclic aromatic hydrocarbons (PAHs) in the marine environment of Korea, 117 sediment samples along the coast were collected and analyzed. This study provides perspectives on concentration ranges and on geographic distributions of PAHs. Sum of 16 PAHs concentrations are in the range of 8.80-18500 ng/g dry weight. Industrialized and urbanized region showed high level of PAHs contamination. When compared with nationwide monitoring results of USA and UK, concentration of total PAHs are in the order of UK>US>this study. Major PAHs sources inferred from diagnostic indices and statistical approach were both pyrogenic and petrogenic. In coastal and offshore sediments of Korea, 7.76% sites had a mean PAH ERL quotient >1.0, indicating the potential to cause adverse effects in sensitive species. Youngil Bay was recognized as highly contaminated with PAHs, and recommended to be managed with special plan.     

Influence of roads and inhabited areas on metal concentrations in terrestrial mosses

The guidelines regarding sampling terrestrial mosses for biomonitoring the atmospheric contamination in a region specifically recommend that sampling close to focal points of contamination (i.e. roads, populated areas, etc.) should be avoided for satisfactory characterization of general patterns of contamination. However, these recommendations cannot always be followed in many parts of the world with dense, highly dispersed populations. The aim of the present study was to determine how the distances between sampling sites (SS) and contamination foci such as roads, isolated houses and urban nuclei affect regular, large-scale sampling networks. Metal concentrations obtained in biennial sampling surveys carried out between 2000 and 2006 in Galicia (NW Spain) were used, and the relative proportions of the concentrations corresponding to small-scale and large-scale processes were calculated. The possible relationship between the mean concentrations corresponding to small-scale processes in the different sampling surveys and the distances from SS to roads, buildings and urban nuclei was established by a GIS. Outliers in the data were identified at many of the SS and frequency statistics revealed the absence of any relationship between the distance to these foci and the concentrations of metals in the moss. The method also revealed many instances of the influence of one or more small-scale contamination foci such as airports and railways (often not considered in the sampling recommendations) on SS. Relocation of such SS would improve the representativeness of the sampling grid.     

Heavy metals, polycyclic aromatic hydrocarbons and polychlorinated biphenyls in surface sediments of the Naples harbour (southern Italy)

The Naples's harbour is one of the largest and most important commercial and tourist port of the Mediterranean basin. It is located on the southeast coast of Italy and receives industrial and municipal wastewaters from the city of Naples. Due to its social and economic impact, a comprehensive assessment of levels and sources of contamination of bottom sediments in this area of the Mediterranean basin is essential to identify potential danger due to mobilization of contaminants produced by managing of the same sediments. In this study, superficial sediments collected from 189 sampling sites were analyzed for grain size, heavy metals (Cr, Cu, Ni, Pb, V, Zn, Co, Sn, Cd, Hg, As, Al and Fe), 16 priority polycyclic aromatic hydrocarbons (PAHs) and perylene and 38 individual polychlorinated biphenyl (PCB) congeners. Compared to the estimated local background, Cu, Zn, Pb, Cd, Sn and Hg show enrichment factors >3 and only Hg evidences a median value higher than the NOAA (effects range - median) guidelines. Principal component analysis allowed us to clearly discriminate two areas mainly affected by heavy metals contamination and influenced by different sources related to industrial, commercial and/or urban activities. Priority PAHs are predominantly represented by three-five-ring compounds with concentrations ranging between 9 and 31774 ng g(-1) and frequently higher than the NOAA ER-M index. A prevalent pyrolitic origin of PAH was assessed on the basis of the relative abundance of the different congeners and selected isomer ratios. The concentrations of PCBs, as sum of the 38 congeners, ranged from 1 to 899 ng g(-1), with a predominance of highly chlorinated (tetra- and penta-chlorobiphenyls) congeners. WHO-TEQ values, calculated for the PCDD-like PCB congeners, suggest a relatively high level of toxicity. Generally, the concentration of PAHs and PCBs were higher near the sites of intense industrial, shipping and/or commercial activities suggesting a direct influence of these sources on the pollutant distribution patterns.     

Polychlorinated naphthalenes in urban soils: analysis,concentrations, and relation to other persistent organic pollutants

We determined the concentrations of 35 PCNs, 12 PCBs, and 20 PAHs in 49 urban topsoils under different land use (house garden, roadside grassland, alluvial grassland, park areas, industrial sites, agricultural sites) and in nine rural topsoils. The sums of concentrations of 35 PCNs (sigma35 PCNs) were <0.1-15.4 microg kg(-1) in urban soils and <0.1 to 0.82 microg kg(-1) in rural soils. The PCN, PCB, and PAH concentrations were highest at industrial sites and in house gardens. While rural soils receive PCNs, PCBs, and PAHs by common atmospheric deposition, there are site-specific sources of PCNs, PCBs, and PAHs for urban soils such as deposition of contaminated technogenic materials. The PCN, PCB, and PAH concentrations decreased from the central urban to the rural area. In the same order the contribution of lower chlorinated PCNs and PCBs increased because they are more volatile and subject to increased atmospheric transport. The PCNs 52+60, and 73 were more abundant in soil samples than in Halowax mixtures, indicating that combustion contributed to the PCN contamination of the soils.